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diff --git a/.gitattributes b/.gitattributes new file mode 100644 index 0000000..d7b82bc --- /dev/null +++ b/.gitattributes @@ -0,0 +1,4 @@ +*.txt text eol=lf +*.htm text eol=lf +*.html text eol=lf +*.md text eol=lf diff --git a/LICENSE.txt b/LICENSE.txt new file mode 100644 index 0000000..6312041 --- /dev/null +++ b/LICENSE.txt @@ -0,0 +1,11 @@ +This eBook, including all associated images, markup, improvements, +metadata, and any other content or labor, has been confirmed to be +in the PUBLIC DOMAIN IN THE UNITED STATES. + +Procedures for determining public domain status are described in +the "Copyright How-To" at https://www.gutenberg.org. + +No investigation has been made concerning possible copyrights in +jurisdictions other than the United States. Anyone seeking to utilize +this eBook outside of the United States should confirm copyright +status under the laws that apply to them. diff --git a/README.md b/README.md new file mode 100644 index 0000000..0548c67 --- /dev/null +++ b/README.md @@ -0,0 +1,2 @@ +Project Gutenberg (https://www.gutenberg.org) public repository for +eBook #50531 (https://www.gutenberg.org/ebooks/50531) diff --git a/old/50531-0.txt b/old/50531-0.txt deleted file mode 100644 index 9b1f34b..0000000 --- a/old/50531-0.txt +++ /dev/null @@ -1,1473 +0,0 @@ -The Project Gutenberg EBook of On Sulphonfluoresceïn and some of its -Derivatives, by C. Willard Hayes - -This eBook is for the use of anyone anywhere in the United States and most -other parts of the world at no cost and with almost no restrictions -whatsoever. You may copy it, give it away or re-use it under the terms of -the Project Gutenberg License included with this eBook or online at -www.gutenberg.org. If you are not located in the United States, you'll have -to check the laws of the country where you are located before using this ebook. - - - -Title: On Sulphonfluoresceïn and some of its Derivatives - -Author: C. Willard Hayes - -Release Date: November 22, 2015 [EBook #50531] - -Language: English - -Character set encoding: UTF-8 - -*** START OF THIS PROJECT GUTENBERG EBOOK SULPHONFLUORESCEÏN *** - - - - -Produced by Paul Marshall and the Online Distributed -Proofreading Team at http://www.pgdp.net (This file was -produced from images generously made available by The -Internet Archive) - - - - - - -Transcriber's Notes: - Illustration has been moved so it does not break up the paragraph. - - As this was a hand-written thesis, the spelling, punctuation and - hyphenation is very inconsistent. The original spelling, hyphenation - and punctuation have been left unchanged. - - Subscripts appears as _{X} where X is an integer. - - Multi-line curly brackets have been replaced with multi-line - square brackets. - - - - - ON - SULPHONFLUORESCEÏN - AND SOME OF ITS DERIVATIVES. - - DISSERTATION - - Presented for the Degree - of - Doctor of Philosophy - at the - Johns Hopkins University - - by - C. Willard Hayes, - - 1887. - - - - - Contents. - p. - - Introduction 3. - I Ortho-sulpho-benzoic acid. - Preparation from toluene and H_{2}SO_{4} 7. - ” ” para-nitro-toluene and H_{2}SO_{4} 8. - Oxidation of toluene-o-sodium sulphonate 12. - Preparation of Sulphinide from ” ” 14. - ” ” ” by chlorsulphonic acid. 17. - Conversion of sulphinide into o-sulphobenzoic acid. 25. - Analysis of and crystallography of ” ” ” 28. - II Sulphonfluoresceïn--previous attempts 29. - Preparation and purification of s-fluoresceïn 30. - Analyses of ” 34. - Properties of ” 35. - Salts. Ba. and Ca. of ” 37. - Acetyl derivative of ” 41. - Br substitution products of ” 42. - Action of H_{2}SO_{4} on ” 44. - Action of HCl on ” 45. - Reduction of ” 46. - Conclusion. 47. - - - - -On Sulphonfluoresceïn and some of its Derivatives. - - -Introduction. - - -The close analogy in composition and structure between phthalic acid -and ortho-sulpho-benzoic acid suggests the possibility of obtaining -from the latter, by its action on phenols, substances analogous to -the phthaleïns. If such compounds could be made they would afford -a favorable opportunity of studying the effects produced in the -properties of a compound by the replacement of CO by SO_{2}. It was -with a view to such study that the following discussed work was -undertaken at the suggestion of Prof. Remsen and carried on under his -constant guidance. - -Some experiments previously performed by Remsen and Palmer (A.G.) -indicated the possibility of the formation of a fluorescent substance -by the action of ortho-sulpho-benzoic acid on resorcin but they did -not succeed in obtaining any definite crystallized compound from the -reaction. - -The chief obstacle to be overcome in the work is the difficulty in -obtaining the o-sulpho-benzoic acid and a large proportion of the -work here described was applied in that direction. - - -Ortho-sulpho-benzoic acid: Methods for its preparation. - - -1. From toluene and H_{2}SO_{4}. - -A method employed by Remsen and Fahlberg (Am. Ch. Jour. Vol. 1. -p __ ) for getting the sulphonic acid group in the ortho position to -methyl was; (a) treat toluene with fuming H_{2}SO_{4} forming thus -ortho- and para- toluene sulphonic acids, (b) make the calcium salt -of the sulphonic acids thus formed and from this the potassium -salt. (c) treat this mixture of potassium toluene sulphonates -with phosphorous penta-chloride forming the corresponding -sulphonchlorides. One of these (para) being a solid and the other -(ortho) an oily liquid a nearly complete separation could be -effected. The difficulty with this method is however that the larger -part of the product is the para and only a comparatively small -proportion of the ortho compound is formed. - - -2. From p-nitro-toluene and H_{2}SO_{4}. - -A second method employed consists in starting with p-nitro-toluene. -This when treated with H_{2}SO_{4} forms toluene p-nitro o-sulphonic -acid. If now a method could be obtained for removing the nitro group -the desired result would be attained. - -The attempt was made by Remsen and Palmer (A.G.) to accomplish this -by (a) reducing the nitro compound to the amide, (b) making the diazo -compound and (c) boiling this with absolute alcohol. According to -generally accepted views this should effect the removal of the diazo -group and its replacement by hydrogen. - -Experiments however showed that the replacement was made not by -hydrogen but by the ethoxy group -OC_{2}H_{5}. This method was -therefore impracticable. - -A modification of this method was suggested by an observation of -Baeyer and Liebermann that if phenyl hydrazine be boiled with a -dilute solution of copper sulphate the hydrazine group is replaced -by hydrogen and benzene thus formed. Hence it was believed that if -the hydrazine compound should be made from diazo compound mentioned -above, the corresponding hydrocarbon, i.e. toluene o-sulphonic acid -could be obtained. The results of experiments showed that this -afforded a practicable method of preparing toluene ortho-sulphonic -acid. - -After experimenting with various modifications of the method the -following was found to be the best adapted to the purpose. - -The potassium salt of toluene p-nitro-o-sulphonic acid is easily -obtained, as already stated, by heating p-nitro toluene on the water -bath with three times its weight of fuming H_{2}SO_{4}, neutralizing -with chalk and to the solution of calcium salt thus obtained adding -a slight excess of K_{2}CO_{3}. On filtering from. the precipitated -CaCO_{3} and evaporating slightly, the salt is obtained in long -needle shaped crystals of a pale straw yellow color. This is - - ┌─ - │CH_{3} - C_{6}H_{3}┤SO_{2}OH (o) - │NO_{2} (p). - └─ - -The reduction of the nitro group is best effected by means of tin and -HCl, in the proportion, salt 5 parts, tin 6 parts and concentrated -HCl 30 parts. - -The amido acid forms a compound with tin which crystallizes from the -HCl together with stannous chloride. This compound may be broken up -and the tin removed by continued boiling with water. - -A better method of removing the tin is by dissolving the compound in -Na_{2}CO_{3}. This forms a salt with the amido acid and throws down -the tin as Sn(OH)_{2}, a white flocculent precipitate. On filtering -and adding to the solution conc. HCl, the free amido acid is -deposited in characteristic colorless, rhombic crystals, having the -formula - - ┌─ - │CH_{3} - C_{6}H_{3}┤SO_{2}OH (o) - │NH_{2} (p) - └─ - -The method at first employed for preparing the hydrazine compound -consisted in treating the amido acid, suspended in HCl, with -potassium nitrite and then with stannous chloride. The tin was then -removed from the solution by the addition of sodium carbonate and the -hydrazine compound thrown down with HCl. This method however gave -poor results the yield being only about 50% of the theoretical. - -Another method was accordingly substituted for the above, namely that -of Strecker and Römer (Ber. IV. s 784.) By this the diazo compound -is made first and isolated. This is done by suspending the finely -powdered acid in absolute alcohol, cooling and passing a current of -the oxides of nitrogen through in the ordinary way. The acid changes -in appearance, becoming more crystalline and slightly darker and -settles quickly on being shaken. The reaction here may be expressed -thus-- - - ┌─ ┌─ - │ CH_{3} │ CH_{3} - C_{6}H_{3} ┤ SO_{2}OH + HNO_{2} = C_{6}H_{3} ┤ SO_{3} + 2H_{2}O - │ NH_{2} │ \ - └─ │ N=N - └─ - -When the reaction is completed as shown by the appearance of the -suspended powder it is filtered and while still fresh is added to a -solution of acid sodium sulphite as long as it continues to dissolve -readily. - -To this solution there is added a quantity of solution of acid -sodium sulphite equivalent to that already used and the solution is -then boiled. It has at first a deep red color but in a few moments -becomes light reddish yellow. The reaction of HNaSO_{3} on the diazo -compound may be represented in two stages, the first portion forming -an addition product and the second acting as a reducing agent. Thus, - - ┌─ ┌─ - │ CH_{3} │ CH_{3} - 1. C_{6}H_{3} ┤ SO_{3} + HNaSO_{3} = C_{6}H_{3}┤ SO_{2}ONa - │ \ │ - │ N═N │ N═NSO_{3}H - └─ └─ - ┌─ - │ CH_{3} - 2. C_{6}H_{3} ┤ SO_{2}ONa + HNaSO_{3} + H_{2}O - │ N═NSO_{3}H - └─ ┌─ - │ CH_{3} - = C_{6}H_{3} ┤ SO_{2}ONa + HNaSO_{4}. - │ NH-NHSO_{3}H - └─ - -To the hot solution an excess of conc. HCl is added when the -hydrazine compound separates in a few moments in lustrous yellow -scales which completely fill the solution. On the addition of the HCl -a large amount of SO_{2} is given off from the excess of HNaSO_{3} and -the solution becomes deep red. When the hydrazine has separated the -mother liquor is again yellow. - -The reaction is represented as follows: - - ┌─ - │CH_{3} - C_{6}H_{6}┤SO_{2}ONa + HCl + H_{2}O - │NH-NHSO_{3}H - └─ - ┌─ - │CH_{3} - = C_{6}H_{3}┤SO_{2}OH + H_{2}SO_{4} + NaCl - │NH-NH_{2} - └─ - -The yield of hydrazine when both the diazo and the NaHSO_{3} are -freshly prepared is practically quantitative. - -The hydrazine thus prepared was treated with a hot 10% solution of -copper sulphate till a permanent blue color was obtained in the -solution. Nitrogen is evolved and the copper sulphate is reduced to -cuprous oxide which is precipitated as a red powder. The reaction is -as follows. - - ┌─ - │CH_{3} - C_{6}H_{3}┤SO_{2}OH + 2CuSO_{4} + H_{2}O - │NH-NH_{2} - └─ - ┌─ - = C_{6}H_{4}┤CH_{3} + Cu_{2}O + N_{2} + 2H_{2}SO_{4} - │SO_{2}OH - └─ - -Chalk was added to the solution to precipitate the H_{2}SO_{4} and -form a calcium salt of toluene-o-sulphonic acid. From this the -sodium salt was made by adding a slight excess of Na_{2}SO_{3} and -evaporating to dryness. The salt is very soluble being deliquescent -in the air while the corresponding potassium salt is not. From 1538 -gr. of para-nitro-toluene, 655 gr. of toluene ortho-sodium sulphonate -were obtained. - -Having thus obtained the toluene ortho-sulphonic acid the next -step in the problem was to find a convenient method for converting -this into ortho-sulph-benzoic acid. Two ways present themselves -for accomplishing this end. (1) direct oxidation of this salt and -(2) conversion into benzoic sulphinide from which the acid may be -obtained. Both of these methods were tried. - - -Oxidation of toluene-o-sodium sulphonate. - - ┌─ - C_{6}H_{4}─┤CH_{3} - │SO_{2}ONa - └─ - -The sodium salt of toluene-o-sulphonic acid is oxidized to -ortho-sulphobenzoic acid with considerable difficulty by KMnO_{4} in -neutral solution. - -Thus two experiments showed that the oxidation was not complete after -24 hours boiling with excess of permanganate. If the solution be made -alkaline however, the oxidation is completed in a few hours, yet the -greatest difficulty still remains in the separation of the free acid -from the products of oxidation in the solution. If HCl be added to -the solution the acid salt - - COOH - ╱ - C_{6}H_{4} - ╲ - SO_{2}OK - -is formed and this has nearly the same solubility as the KCl also -present. A better method therefore is to add a slight excess of -H_{2}SO_{4} and evaporate nearly to dryness. In this way are formed -sulphates and the free acid presumably. The mixture is heated with -alcohol (95%) which extracts the acid leaving the greater part of -the manganese salts. This extract is evaporated and reextracted -with alcohol. To this solution BaCO_{3} is added to precipitate the -H_{2}SO_{4} and form the Barium salt of the o-sulphobenzoic acid. The -solution is filtered from the BaSO_{4} and just enough H_{2}SO_{4} -is added to exactly precipitate the barium. The solution should -thus contain only the free acid sought, which crystallizes out on -evaporating to a small volume. While the method is theoretically -possible it presents so many difficulties that it is practically -useless. The yield is extremely small; only enough acid being -obtained in this way to show that it was possible. - - -Formation of Sulphinide from toluene-o-sodium sulphonate. - -The second method for obtaining free o-sulphobenzoic acid from -toluene-ortho-sulphonic acid is by the conversion of the latter first -into benzoic sulphinide and then into the free acid. The sulphinide -was made essentially as described by Remsen (Am. Ch. Jour. Vol. I. -p. 428) with a few changes in the details as follows. - - ┌─ -The salt C_{6}H_{4}┤CH_{3} finely pulverized and in portions - │SO_{2}ONa - └─ - -of from 10 to 50 gr. was placed in a Florence flask; an equivalent -quantity of PCl_{5} added; An inverted condenser was then attached -and the flask shaken. The action takes place at once and involves -sufficient heat to distill off the oxychloride formed in the -reaction. This being returned to the flask by the condenser furnishes -a liquid medium in which the reaction takes place more readily and -completely than when it is not present. It is best to cool the flask -at first and afterwards heat gently on the water bath. The reaction -which takes place may be represented as follows. - - ┌─ ┌─ - │CH_{3} │CH_{3} - C_{6}H_{4}┤SO_{2}ONa + PCl_{5} = C_{6}H_{4}┤SO_{2}Cl + POCl_{3} + NaCl. - └─ └─ - -On the addition of water the chloride separates as a light yellow -oil. This is washed with water and concentrated aqueous ammonia -added, which forms toluene-o-sulphonamide thus. - - CH_{3} CH_{3} - ╱ ╱ - C_{6}H_{4} + NH_{3} = C_{6}H_{4} + HCl. - ╲ ╲ - SO_{2}Cl SO_{2}NH_{2} - -The reaction is accompanied by a slight evolution of heat and the -formation, apparently, of an intermediate product having a yellowish -color, which passes over on longer standing into the white amide. -After standing several hours the excess of ammonia was driven off -by very gentle heating on the water bath. If the heat is too high -a large amount of a tarry product is formed and the yield of amide -is correspondingly small. In any case some of this tarry product is -formed. When nearly all the ammonia had been driven off the mass was -boiled with water which dissolves everything except the tar. The -hot solution was filtered through charcoal and on cooling the amide -separated in white feathery crystals which melt at 155°-156°. - -The amide thus obtained was oxidized as described by Remsen (loc. cit.) -with potassium permanganate in neutral solution. The proportions are -10 gr amide. 40 gr KMnO_{4} and 1 L. water. The oxidation was usually -effected in from four to six hours. - -To obtain the sulphinide from this solution after oxidation, the -latter, after filtration from the precipitated oxides of manganese, -was slightly acidified with HCl and evaporated to about one fourth -its original volume. On the addition of concentrated HCl to this -solution, the sulphinide separated out in white or slightly yellowish -feather shaped crystals melting at 212° and having the characteristic -intensely sweet taste. - - -Formation of Sulphinide from Toluene by means -of the chlorsulphonic acid reaction. - -Before passing on to the methods used for converting the sulphinide -into free acid another method should be described by which -the former was obtained in larger quantities and much more easily -than by the one above described. - -Beckurts and Otto (Ber. XI. 2061) found that by treatment of toluene -with sulphuryl hydroxy-chloride or chlorsulphonic acid, ClSO_{2}OH, -both o- and p- and as they supposed also m-toluene sulphonchlorides -were formed together with the corresponding sulphonic acid. - -Claesson and Wallin (Ber. XII. p. 1848) repeated the work reaching -practically the same results and finally Noyes (Am. Ch. Jour. Vol. -VIII. p. 176) employed the reaction as a convenient method for -obtaining toluene o-sulphon-chloride. - -Chlorsulphonic acid is made by passing dry HCl over solid sulphuric -acid so long as it continues to be absorbed. Since no solid sulphuric -acid was at hand, ordinary fuming Nordhausen acid was taken and -from one of two equal portions the SO_{3} was driven over into -the other. HCl was passed into the latter and the resulting -chlorsulphonic acid distilled off at about 156°. - -This was placed in a flask, provided with a drop funnel and exit -tube, in portions of 150 gr. and to each portion 60 gr. of toluene -was added, very slowly, with constant shaking, the temperature -being kept near 10°. The action is violent and if any toluene is -allowed to collect on the surface of the liquid it is apt to produce -disastrous results. Large quantities of HCl are given off and the -liquid in the flask assumes a brown color. When all the toluene has -been added, it is poured into a large quantity of ice water, when -the sulphon-chlorides separate out, the ortho- as a heavy oil and -the para- as a white crystalline solid. After allowing to stand some -time in order that as much of the para-chloride might crystallize as -possible the ortho- was drawn off and subjected to a freezing -temperature for several hours. By this means more of the p-chloride -was removed and the operation was replicated as long as any crystals -continued to form, generally two or three times. In this way the -greater part of the para- may be removed, though some still remains -dissolved in the liquid chloride, which cannot be removed by repeated -freezings. - -The chloride thus obtained was treated with strong aqueous ammonia. -The conversion to the sulphamide does not take place so readily as -in case of the pure o-chloride obtained from the sulphonic acid and -phosphorus pentachloride. - -After standing about two days the whole of the oily chloride had -solidified to a yellowish brown mass. The excess of ammonia was -driven off by gentle heating on the water bath and the mass then -boiled with water. Not enough water was added at first for complete -solution but when the first portion was saturated it was poured -off through a filter and from it the amide separated in yellowish -feathery crystals which melted at 105°-125° and consisted therefore -as shown by Fahlberg (Am. Ch. Jour. Vol. I. p. 170) of a mixture -of o- and p-sulphonamides. It was recrystallized and from it was -obtained a portion melting at 153°-5° and one at 108°-20°. - -Since this mixture cannot be completely separated by -recrystallization another method was suggested. Remsen has shown that -K_{2}Cr_{2}O_{7} in acid solution does not oxidize the methyl group in - - - CH_{3} - ╱ - C_{6}H_{4} - ╲ - SO_{2}NH_{2} (o) - -but does oxidize that in - - CH_{3} - ╱ - C_{6}H_{4} - ╲ - SO_{2}NH_{2} (p). - -It was thought that in a mixture of the two the former might be left -unchanged while the latter was oxidized to p-sulphamine benzoic acid. - -To test this 15 gr of the mixture, melting at 105°-125°, was heated -with 40 gr K_{2}Cr_{2}O_{7}, 55 gr H_{2}SO_{4} and 2 vols. of water -for about two hours. It was then tested and shown to be still a -mixture of p-& o-amides, since it was again heated for several -hours with half the original quantity of oxidizing mixture, then -diluted, filtered and washed. The white crystalline residue was -treated with sodium carbonate to dissolve the benzoic para-sulphamide -and the residue was found to be pure toluene o-sulphonamide melting -at 153°-155°. The small quantity remaining, 3 gr., indicated that -part of the o-amide had been completely broken down by the strong -oxidizing agent, though the proportion of o-& p-amides in the -original mixtures was known only approximately. The evolution of gas -during the oxidation would point to the same conclusion. - -Although this effects a complete separation it is hardly economical -since it will be shown later that a separation can be conveniently -effected after the oxidation with KMnO_{4} so that the o-amide -contained in the mixture need not be lost. - -The original mass was treated with successive portions of water -till nothing remained but a black tarry substance. The amide which -separated from these extracts was perfectly white and melted at -153-5°. It was therefore regarded as practically pure o-amide. The -yield in amide melting above 153° was a little over one sixth the -weight of toluene used. - -The amide obtained in this way was oxidized in the manner already -described. It was found however that there was always some benzoic -p-sulphamide in the solution of the oxidation, due to the slight -admixture of p- with the o-amide used. This is thrown down with -the sulphinide on acidifying the solution and may be removed by -re-crystallization since it is somewhat less soluble in hot and cold -water than sulphinide. - -A better way to effect the separation, however, was found to be -the following. After having evaporated the solution containing the -products of oxidation, nearly neutralized with HCl, to about one -fifth its original volume, it is made very slightly acid and allowed -to cool. In this way very nearly all the benzoic p-sulphamide is -separated from the solution and none of the sulphinide. After -filtering, strong HCl is added and the sulphinide then separates -in its characteristic form. This indicates that sulphinide forms -an alkaline salt which is not decomposed by diluted HCl while the -p-sulphamide does not. - -The mixture of amides meeting at 105°-120° was oxidized and the -products separated in this way gave about equal quantities of -sulphinide and benzoic p-sulphamide. - -When toluene is treated with chlorsulphonic acid there are formed -besides the ortho- and para- chlorides also ortho and para sulphonic -acids. These of course are in solution in the water from which the -chlorides separated. In order to recover the ortho-acid, the solution -was neutralized with chalk forming the calcium salt: this converted -into the potassium salt which by evaporating the solution to dryness -was obtained as a white crystalline powder. When treated with PCl_{5} -in the manner already described this gave a mixture of ortho and para -sulphonchlorides consisting of about ⅓ ortho and ⅔ para. - - -Formation of Orthosulphobenzoic acid from Sulphinide. - -Benzoic sulphinide may be converted into a sulpho-benzoic -acid (1) by boiling with Ba(OH)_{2}, (2) by heating in a closed tube -with conc. HCl or (3) by evaporating on the water bath with HCl. - -1. Three gramms of sulphinide were boiled in a flask connected -with an inverted condenser for about two days with an excess of -Ba(OH)_{2}. There was formed in the flask a hard mineral-like mass -which was insoluble in water and cold diluted HCl but dissolved in -hot HCl with effervesence. This was a Barium salt, probably basic (?) -of ortho sulphobenzoic acid. There was also formed an easily soluble -barium salt of that acid. The former was dissolved in H_{2}SO_{4} -and treated with BaCO_{3}; the filtrate from the BaSO_{4} which -contained a soluble barium salt was added to that above mentioned and -the barium exactly precipitated with H_{2}SO_{4} and the filtrate -evaporated to dryness giving the free acid but not in a perfectly -pure condition. - -2. 2.75 gr. of sulphinide was sealed up in a tube with pure conc. HCl -and heated two hours to 150°. On cooling nothing separated; the liquid -was evaporated to dryness giving 3.2 gr of acid and ammonium -chloride. The reaction taking place here may be represented thus: - - CO COOH - ╱ ╲ ╱ -C_{6}H_{4} NH + 2H_{2}O + HCl = C_{6}H_{4} + NH_{4}Cl. - ╲ ╱ ╲ - SO_{2} SO_{2}OH - -3. A more convenient method for obtaining the acid than either of -the above, is to heat the sulphinide with conc. HCl on the water -bath for two days. Then evaporate to dryness and dissolve the -residue in a small quantity of water. If the sulphinide contained -any para-sulphamide, as is usually the case, this will be left -undissolved and most of the NH_{4}Cl will crystallize on standing. -This solution by slow evaporation deposits large colorless crystals -of the free acid. - -This acid is soluble in about two parts of cold water, very -difficultly soluble in absolute alcohol and almost completely -insoluble in ether. It does not melt under 250° but considerably -above that it melts, at first apparently without change and then -with slight sublimation of a very deliquescent substance, probably -the anhydride. - -Two determinations of the S. made by Mr. A. F. Linn, gave the -following results. - -I ·1358 gr substance gave ·1855 gr BaSO_{4} representing 15·72% S. - -II ” ” ” ” ” ” - - COOH - ╱ -Calculated for the formula C_{6}H_{4} = 15·84% S. - ╲ - SO_{2}OH - - -[Illustration] - -A crystallographic examination of the acid showed it to belong to the -orthorhombic system. Axial ratio: a: b: c = ·8507: 1: ·8121. -Planes. Ρ and αΡὰ. - - ┌─ - ┌─ │ Edge X = 131° 8' - │ Ρ ^ Ρ ─┤ ” Y = 82° 18' - │ │ ” Z = 118° 40' - Angles measured ─┤ └─ - │ - │ Ρ ^ αΡὰ = 114° 38' - └─ - -The crystals are up to 8 mm in length. The pyramidal faces are -generally etched so that the image is poor. - - - - -Sulphonfluoresceïn. - - -Several attempts had already been made to obtain from the action -of o-sulphobenzoic acid and resorcin a substance analogous to the -fluoresceïn obtained by Baeyer[1] from phthalic anhydride and -resorcin but while a strongly fluorescent substance was easily -obtained, no definite compound could be separated from it. Thus -Palmer obtained, by heating together the above named substances to -160°(?) a solid mass, part soluble in water and part insoluble as a -dark brown amorphous powder. Both parts gave a strong fluorescence -with alkalis. He was unable however to obtain the substance itself or -any derivative in a crystalline form. - -[1] Annalin. No. 183. S. 1. No. 202. S. 36 & S. 153. - Berichte. No. IV. S. 457. 555. 658. 662. - ” ” VIII. S. 66. 146. - -The first experiments in this series gave the same negative results. -The mixture of acid and resorcin was heated in a sulphuric acid -both for several hours to 150°-170°, and as it showed no sign of -solidification the temperature was raised to 200° and then to 235° -where it was kept several hours longer. The black viscous mass -obtained in this way became vitreous on cooling, and in all respects -resembled that described by Palmer. This however is not the normal -course of the reaction as shown later but is probably due to a -decomposition of the normal product produced by too high heating. - -An experiment was made with the acid salt of ortho-sulphobenzoic acid. - - COOH - ╱ - C_{6}H_{4} - ╲ - SO_{2}OK, - -resorcin and H_{2}SO_{4} heating the mixture to 150°-170°. A solid -black mass was obtained strongly fluorescent in alkaline solution and -in all other respects like the substance obtained above. - - -Preparation of Sulphonfluoresceïn. - -As the result of a number of experiments the following method of -preparing and purifying the sulphonfluoresceïn was found to give the -best results. - -The free acid is mixed with resorcin in the proportion of 1 part acid -to 1.2 parts resorcin, or a slight excess over two molecules of the -latter to one of the former. The mixture is placed in a deep vessel, -a test tube or beaker, which is placed in a sulphuric acid bath, a -thermometer being suspended in the mixture. The bath is heated and at -about 100° the resorcin melts and the acid slowly dissolves in the -liquid. No action appears to take place till the temperature reaches -175° where water begins to be given off and the liquid slowly assumes -a darker color. White crystals of resorcin collect on the sides of -the vessel. After the heating has been continued for about seven -hours at 178°-185° the liquid has a clear deep red color but shows no -signs of becoming viscous. At length lustrous yellow crystalline -plates appear in the liquid and soon the whole mass becomes a thick -nearly solid yellow paste. Continuous heating at the same temperature -causes no further apparent change. This mass, which on cooling is -made up of yellow crystals imbedded in a red vitreous matrix, is then -dissolved in hot water forming a clear red solution or at most one -containing but a small quantity of a brown flocculent precipitate. -This solution is filtered if necessary and evaporated to a small -volume from which the substance separates on cooling in reddish -yellow radial crystals. These are filtered and washed with ether -till the washings are perfectly colorless. The substance on repeated -crystallization from water has a pale straw yellow color and when -deposited slowly forms transparent crystal blocks from 2·6 mm long, -arranged in radial groups. - -A considerable amount of resorcin is lost by sublimation during -the reaction especially if the operation is carried on in a beaker -so that some excess should be added. But even when the resorcin -is present in excess at the end of the reaction some free acid is -always left which may be obtained from the mother liquid in the -characteristic colorless orthorhombic crystals. - -The water of crystallization and sulphur were determined in the -new compound. In estimating the water, the substance was heated to -106°-123° for about ten hours till it attained a constant weight. -On standing in the air it quickly regains its original weight. When -heated to 130°-140° for some time it turns slightly reddish and loses -over 10% of its weight which is not regained by standing in the air. - -Estimation No. I. was made by fusion with KOH and KNO_{3}. Nos. II -and III were made by Mr. Mindileff by Morse’s method, oxidizing with -KMnO_{4} in KOH solution. - - ·3882 gr. heated to 106°-123° lost ·0302 gr. = 8·5% - - Calculation for 2H_{2}O - C_{19}H_{12}O_{6}S+2H_{2}O = 8·9% water. - - I. ·2007 gr sub. gave ·1286 gr BaSO_{4} = 8·77% S. - II. gr ” ” ” gr ” = 7·91” ” -III. gr ” ” ” gr ” = 7·89” ” - - Calculation for C_{19}H_{12}O_{6}S+2H_{2}O = 7·92% S. - -These analyses show with but little doubt that the substance has the -composition indicated above i.e. C_{19}H_{12}O_{6}S+2H_{2}O. The -reaction therefore which takes place between ortho-sulpho benzoic -acid and resorcin from its analogy to that taking place between -phthalic anhydride and resorcin may be represented thus, as shown by -Baeyer in his second paper (Ann. 202. S. 43) - -Representing the formation of the anhydride as the first action. - - COOH CO - ╱ ╱ ╲ - C_{6}H_{4} = C_{6}H_{4} O + H_{2}O - \ ╲ ╱ - SO_{2}OH(o) SO_{2} - -and the action of resorcin on this anhydride thus. - - CO OH - ╱ ╲ ╱ - C_{6}H_{4} O + 2C_{6}H_{4} - ╲ ╱ ╲ - SO_{2} OH (m) - - O - ╱ ╲ - (HO)H_{4}C_{6} C_{6}H_{4}(OH) - ╲ ╱ - = C + 2H_{2}O - ╱ ╲ - C_{6}H_{4} O - ╲ ╱ - SO_{2} - -The substance thus formed would naturally receive the name -Sulphonfluoresceïn from its analogy with Fluoresceïn. - - ┌─ - │ OH - │ ╱ - │ C_{6}H_{3} - │ ╲ - │ O - │ ╱ - C ─┤ C_{6}H_{3} - │ ╲ - │ OH - │ - │ C_{6}H_{4}SO_{2} - │ ╱ - │ O - └─ - Sulphonfluoresceïn. - - - ┌─ - │ OH - │ ╱ - │ C_{6}H_{3} - │ ╲ - │ O - │ ╱ - C ─┤ C_{6}H_{3} - │ ╲ - │ OH - │ - │ C_{6}H_{4}CO - │ ╱ - │ O - └─ - Fluoresceïn. - - -Properties of S.fluoresceïn. - -This compound shows a marked similarity to the fluoresceïn described -by Baeyer as would naturally be expected from its great similarity of -composition and constitution, but it also shows decided differences -which may be attributed to the replacement of CO by SO_{2}. - -Dissolved in water it shows a weak green fluorescence which in -alkaline solution becomes much deeper but not by any means so strong -as that of fluoresceïn. The dilute alkaline solution by transmitted -light is almost perfectly colorless and by reflected light a clear -green. Unlike fluoresceïn it is extremely soluble in water, about -one part in two or three of hot and five or six of cold water. It -is also soluble in absolute alcohol forming a yellow solution with -weak fluorescence. It is soluble with difficulty in ether but when in -solution is deposited only on evaporating to a small volume. - -It does not melt at 250° but if held at a lower temperature for a -long time becomes red undergoing some decomposition. If quickly -heated somewhat above 300° it melts to a deep red liquid and then -solidifies. If the mass is treated with water it partly dissolves -leaving a dark brown flocculent precipitate which dissolves on the -addition of an alkali, the solution having an intense fluorescence, -nearly if not quite equaling that of fluoresceïn. This change -produced by heating was not further studied. - -The crystals are very thin blades, apparently monoclinic, showing the -clinopinacoid αΡὰ and a very narrow prism αΡ and clinodome Ρὰ. The -angle β = 75° and the extinction angle against the ϲ axis = 20°. -The axial ratio could not be accurately determined. - - -Salts of sulphonfluoresceïn. - -The influence of the SO_{2} group is shown by the fact that the -substance acts as an acid decomposing carbonates and forming salts -which is not the case with fluoresceïn. - - -Barium salt. - -The substance was boiled with an excess of carefully purified -BaCO_{3} for two hours. The filtrate from the BaCO_{3} evaporated -to a small volume deposited yellow crystals resembling the original -substance but in shorter and thicker prisms. These were twice -recrystallized and had then a light straw yellow color. - -A determination of the Ba gave the following results. The salt was -dried in the air. - -[Transcriber’s Note: - The following table was crossed out on the original. - A note on the previous page beside the table was: - - All these calculations are wrong. - J.R.] - - I ·1078 gr salt gave ·0304 gr BaSO_{4} = 15·73% Ba. - II ·1641 ” ” ” ·0457 ” ” = 15·53” ” - III ·2425 ” ” ” ·0680 ” ” = 15·65” ” - IV ·2860 ” ” ” ·0798 ” ” = 15·54” ” - V ·1843 ” ” ” ·0498 ” ” = 15·08” ” - VI ·2620 ” ” ” ·0708 ” ” = 15·08” ” - VII ·3230 ” ” ” ·0906 ” ” = 15·65” ” - VIII ·2875 ” ” ” ·0807 ” ” = 15·66” ” - - Calculated for C_{19}H_{13}O_{7}SBa = 15·10% Ba. - -In the above determinations the salt analysed was taken from -specimens made at three different times and purified in slightly -different ways, Nos 1, 2, & 3 being washed with absolute alcohol. Nos -V and V were made by precipitating the Ba with H_{2}SO_{4} from a -solution of the salt. - -The water was determined by heating at 110° till constant weight was -reached. Part only of the weight lost was regained on standing in the -air. - - ·3943 gr salt lost at 110° ·0286 gr = 7.25% - - Water calculated for C_{19}H_{13}O_{7}SBa+2H_{2}O = 7.35% - -Although these analyses show a per cent. of Ba somewhat above that -required by a compound having the formula C_{19}H_{13}O_{7}SBa still -this appears to be the most probable formula which can be assigned to -the substance. If this is the true composition of the salt, then in -sulphonfluoresceïn the anhydride condition must be broken up by -boiling with BaCO_{3} forming the salt thus. - - ┌── ──┐ ┌── ──┐ - │ │ │ │ - │ ┌─ OH │ │ ┌─ OH │ - │ │ / │ │ │ / │ - │ │ C_{6}H_{3} │ │ │ C_{6}H_{3} │ - │ │ \ │ │ │ \ │ - │ │ O │ │ │ O │ - │ │ / │ │ │ / │ - │ C ┤ C_{6}H_{3} │ │ │ C_{6}H_{3} │ - │ │ \ │ + H_{2}O = │ C ┤ \ │ - │ │ OH │ │ │ OH │ - │ │ │ │ │ │ - │ │ C_{6}H_{4}SO_{2} │ │ │ C_{6}H_{4}SO_{2}OH │ - │ │ / │ │ │ │ - │ └─ O │ │ └─ OH │ - │ │ │ │ - └── ──┘ └── ──┘ - - ┌── ──┐ ┌── ──┐ - │ │ │ │ - │ ┌ OH │ │ ┌ OH │ - │ │ / │ │ │ / │ - │ │ C_{6}H_{3} │ │ │ C_{6}H_{3} │ - │ │ \ │ │ │ \ │ - │ │ O │ │ │ O │ - │ │ / │ │ │ / │ - │ │ C_{6}H_{3} │ │ │ C_{6}H_{3} │ - 2 │ C ┤ \ │ + BaCO_{3} = │ C ┤ \ │ Ba. - │ │ OH │ │ │ OH │ - │ │ │ │ │ │ - │ │C_{6}H_{4}SO_{2}OH │ │ │ C_{6}H_{4}SO_{2}O │ - │ │ │ │ │ │ - │ └ OH │ │ └ OH │ - │ │ │ │ - └── ──┘ └── ──┘_{2} - -By treating the salt with H_{2}SO_{4} the original -substance is reformed. - - -Calcium Salt. - -Attempts were made to prepare the calcium salt but without success. -The S-fluoresceïn was boiled several hours with very finely powdered -calcite, and some salt was formed as shown by the CO_{2} evolved -but on evaporating the solution and recrystallizing the substance -deposited it was found to be the unchanged S-fluoresceïn. Some Ca. -salt was in the mother liquors but its extreme solubility prevented a -separation being made. - - -Acetyl derivative of S.fluoresceïn. - -S.fluoresceïn was boiled with an excess of acetic anhydride for about -three hours. The solution became quite dark and when evaporated on -the water bath left a black tarry residue. This was treated with -water which dissolved a part leaving a dark flocculent precipitate. -The solution was boiled with animal charcoal and evaporated nearly -to dryness. On cooling there separated a light yellow flocculent -precipitate very soluble in hot water and but slightly less so in -cold. This was dissolved in a small quantity of alcohol from which -it separated on evaporation in small radial crystals having a light -lavender color & satiny luster. They also have a peculiar odor -resembling slippery elm which is not removed by recrystallization. -They show a tendency to decompose, becoming yellow on exposure to -the air. The substance does not melt or change in appearance under -245°. With alkalis it gives a slight greenish fluorescence. From the -method of its formation this was taken to be an acetyl derivative -of S.fluoresceïn but whether the mono-or di-acetyl could not be -determined without analysis for which the substance did not suffice. - - -Bromine substitution products of S-fluoresceïn. - -It was especially interesting to see what influence the SO_{2} group -would exert upon the introduction of Bromine into the compound. In -the case of fluoresceïn four Bromine atoms enter easily and special -precautions are necessary to obtain a product containing a smaller -number. The case however is different with S.fluoresceïn. - -The latter was dissolved in glacial acetic acid in which it is -soluble with some difficulty and to the solution was added a 20% -solution of bromine in acetic acid, in sufficient quantity to make -eight atoms of bromine to one molecule of S.fluoresceïn. This -solution was evaporated on the water bath and while still having a -considerable volume, small, red, sharply defined crystals began to -separate. The solution was evaporated to a small volume and allowed -to cool but nothing further separated. These crystals are difficultly -soluble in water, alcohol and ether. The alkaline solution shows a -green fluorescence and slight red color by transmitted light. These -crystals were dissolved in a large quantity of alcohol which on -evaporation gradually deposited very small yellow crystals, which -were dried in the air and taken for analysis. The Br. was determined -by Carius method. - - I. ·2345 gr sub. gave ·1718 gr AgBr = 31·17% Br. - II. ·2786 gr ” ” ·1815 gr ” = 27·72% Br. - - Calculated for C_{19}H_{10}Br_{2}O_{6}S = 30·42% Br. - -These results, though not conclusive, indicate that under the -given conditions it is the di-bromsulphonfluoresceïn which is -formed. Whether this is due to the presence in the compound of the -SO_{2} group or simply to the greater insolubility of the di-than -of the tetra-brom product cannot be definitely stated. When the -original acetic acid mother liquor was evaporated to dryness, a red -non-crystalline substance remained which more closely resembled rosin -than the crystals. The concentrated alkaline solution had a deep red -color without fluorescence and acted as a red dye stuff. The dilute -alkaline solution showed the characteristic delicate pink of rosin. - - -Action of H_{2}SO_{4} on S.fluoresceïn. - -A test tube in which S.fluoresceïn was being made just at the end -of the reaction broke and allowed the contents to run out into the -sulphuric acid bath, which had a temperature of 175°. On standing -several days the solution deposited a heavy precipitate which was -separated by filtering through glass wool. When dry it formed a light -yellow powder extremely soluble in water, alcohol and ether. - -The alkaline solution had an intense green fluorescence with -delicate shades of pink by transmitted light. On account of its -great solubility it was impossible to purify it by crystallization, -hence the Ba salt was made. The substance decomposed BaCO_{3} with -great ease forming an easily soluble salt. When it was attempted to -evaporate the solution of this salt to crystallization the latter -came out in a hard insoluble granular form and on continuous boiling -of the solution turned brown. To avoid this undesirable form it was -converted into the Ca. salt by treatment with H_{2}SO_{4} and then -CaCO_{3}. This also formed a hard granular insoluble mass on boiling -but did not change in color. As there was no guarantee as to its -purity and only a small quantity was obtained it was not analyzed. - - -Action of HCl on S.fluoresceïn. - -Hydrochloric acid does not dissolve S.fluoresceïn but converts it -into a light yellow granular powder. When recrystallized from water -in which it is quite easily soluble it melts partially at 130° -apparently with some decomposition. This compound was not further -studied. - - -Reduction of S.fluoresceïn. - -When treated with zinc dust in a strong alkaline solution -sulphonfluoresceïn is reduced to a colorless substance probably -analogous to fluoresceïn which is formed in the same manner. On -account of its great solubility it could not be obtained in the free -state. It is quickly oxidized to s.fluoresceïn by oxidizing agents -as KMnO_{4} and HNO_{3} and passes back spontaneously on standing in -the air. The latter action is however much slower than in case of -fluoresceïn. - - -Conclusion. - -The principal results relating to s.fluoresceïn which have been -reached in this work may be briefly summarized as follows. -Orthosulphobenzoic acid acts on resorcin at a temperature of -about 180° giving off water and forming a substance analogous -to fluoresceïn but having the CO group replaced by SO_{2}. -This substance sulphonfluoresceïn crystallizes from water -in light yellow monoclinic crystals having the composition -C_{19}H_{12}O_{6}S+2H_{2}O. It is very soluble in alcohol and water -and with difficulty in ether. It does not melt under 250° but above -300° melts with decomposition. It shows in alkaline solution -a clear green fluorescence. It acts as an acid, decomposing -carbonates and forming salts, the Ba salt having the composition -C_{19}H_{13}O_{7}SBa. It forms an acetyl compound when boiled -with acetic anhydride. It forms substitution products with Br, -probably the dibrom-product most easily. It forms a compound with -H_{2}SO_{4}, probably a substitution product, whose composition was -not determined. It is reduced by zinc dust and KOH to a colorless -substance analogous to fluoresceïn. - -Finally in terms of the prevalent theory the substance itself may be -represented thus-- - - H H ┌─ - C O C │ - ╱ ╲ ╱ ╲ ╱ ╲ │ OH - (HO)C C C C(HO) │ ╱ - │ │ │ │ │ C_{6}H_{3} - HC C C CH │ ╲ - ╲ ╱ ╲ ╱ ╲ ╱ │ O - C C C = C ──┤ ╱ - H ╱ ╲ H │ C_{6}H_{3} - HC ╱ ╲ │ ╲ - ╱ ╲ ╱ ╲ │ OH - HC C O │ - │ │ ╱ │ C_{6}H_{4}SO_{2} - HC C ╱ │ ╱ - ╲ ╱ ╲ ╱ │ O - C SO_{2} │ - H └─ - - - - - -End of the Project Gutenberg EBook of On Sulphonfluoresceïn and some of it - Derivatives, by C. 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Willard Hayes - -This eBook is for the use of anyone anywhere in the United States and most -other parts of the world at no cost and with almost no restrictions -whatsoever. You may copy it, give it away or re-use it under the terms of -the Project Gutenberg License included with this eBook or online at -www.gutenberg.org. If you are not located in the United States, you'll have -to check the laws of the country where you are located before using this ebook. - - - -Title: On Sulphonfluoresceïn and some of its Derivatives - -Author: C. Willard Hayes - -Release Date: November 22, 2015 [EBook #50531] - -Language: English - -Character set encoding: UTF-8 - -*** START OF THIS PROJECT GUTENBERG EBOOK SULPHONFLUORESCEÏN *** - - - - -Produced by Paul Marshall and the Online Distributed -Proofreading Team at http://www.pgdp.net (This file was -produced from images generously made available by The -Internet Archive) - - - - - - -</pre> - - -<p><span class="pagenum"><a name="Page_1" id="Page_1">[Pg 1]</a></span></p> -<hr class="r5" /> -<h1><span class="h_subtitle">ON</span><br />SULPHONFLUORESCEÏN<br /> -<span class="h_subtitle">AND SOME OF ITS DERIVATIVES.</span></h1> - -<p class="f150 space-above2"><b>DISSERTATION</b></p> - -<p class="center space-above2">Presented for the Degree<br />of<br />Doctor of Philosophy<br /> -at the<br />Johns Hopkins University</p> - -<p class="center space-above2">by<br />C. Willard Hayes,<br /><br />1887. -<span class="pagenum"><a name="Page_2" id="Page_2">[Pg 2]</a></span></p> -<hr class="tb" /> - -<table border="0" cellspacing="2" summary="Table of Contents." cellpadding="0"> - <caption><big><b>CONTENTS</b></big></caption> - <tbody><tr> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdr">p.</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">Introduction</td> - <td class="tdr"><a href="#Page_3"> 3.</a></td> - </tr><tr> - <td class="tdl"><b>I</b>  </td> - <td class="tdl">Ortho-sulpho-benzoic acid.</td> - <td class="tdr"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">Preparation from toluene and H<sub>2</sub>SO<sub>4</sub></td> - <td class="tdr"><a href="#Label_1"> 7.</a></td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">   ”   ” para-nitro-toluene and H<sub>2</sub>SO<sub>4</sub></td> - <td class="tdr"><a href="#Label_2"> 8.</a></td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">Oxidation  of  toluene - o - sodium sulphonate</td> - <td class="tdr"><a href="#Label_3">12.</a></td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">Preparation of Sulphinide from ”   ”</td> - <td class="tdr"><a href="#Label_4">14.</a></td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">  ”   ”   ”  by chlorsulphonic acid.</td> - <td class="tdr"><a href="#Label_5">17.</a></td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">Conversion of sulphinide into o-sulphobenzoic acid.  </td> - <td class="tdr"><a href="#Label_6">25.</a></td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">Analysis of and crystallography of  ”  ”   ”</td> - <td class="tdr"><a href="#Label_7">28.</a></td> - </tr><tr> - <td class="tdl"><b>II</b>  </td> - <td class="tdl">Sulphonfluoresceïn—previous attempts</td> - <td class="tdr"><a href="#Page_29">29.</a></td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">Preparation and purification of s-fluoresceïn</td> - <td class="tdr"><a href="#Label_8">30.</a></td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">Analyses of          ”</td> - <td class="tdr"><a href="#Label_9">34.</a></td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">Properties of          ”</td> - <td class="tdr"><a href="#Label_10">35.</a></td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">Salts. Ba. and Ca. of       ”</td> - <td class="tdr"><a href="#Label_11">37.</a></td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">Acetyl derivative of        ”</td> - <td class="tdr"><a href="#Label_12">41.</a></td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">Br substitution products of    ”</td> - <td class="tdr"><a href="#Label_13">42.</a></td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">Action of H<sub>2</sub>SO<sub>4</sub> on       ”</td> - <td class="tdr"><a href="#Label_14">44.</a></td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">Action of HCl on         ”</td> - <td class="tdr"><a href="#Label_15">45.</a></td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">Reduction of          ”</td> - <td class="tdr"><a href="#Label_16">46.</a></td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">Conclusion.</td> - <td class="tdr"><a href="#Label_17">47.</a></td> - </tr> - </tbody> -</table> - -<hr class="chap" /> -<p><span class="pagenum"><a name="Page_3" id="Page_3">[Pg 3]</a></span></p> - -<p class="f150"><b>On Sulphonfluoresceïn and some of its Derivatives.</b></p> - -<h2>Introduction.</h2> - -<p>The close analogy in composition and structure between phthalic acid -and ortho-sulpho-benzoic acid suggests the possibility of obtaining -from the latter, by its action on phenols, substances analogous to -the phthaleïns. If such compounds could be made they would afford -a favorable opportunity of studying the effects produced in the -properties of a compound by the replacement of CO by SO<sub>2</sub>. It was -with a view to such study that the following discussed work was -undertaken at the suggestion of Prof. Remsen and carried on under his -constant guidance.</p> - -<p>Some experiments previously performed by Remsen and Palmer (A.G.) -<span class="pagenum"><a name="Page_4" id="Page_4">[Pg 4]</a></span> -indicated the possibility of the formation of a fluorescent substance -by the action of ortho-sulpho-benzoic acid on resorcin but they did -not succeed in obtaining any definite crystallized compound from the -reaction.</p> - -<p>The chief obstacle to be overcome in the work is the difficulty in -obtaining the o-sulpho-benzoic acid and a large proportion of the -work here described was applied in that direction.</p> - -<h2><a name="Label_1" id="Label_1"></a>Ortho-sulpho-benzoic acid: Methods for its preparation.</h2> -<h3>1. From toluene and H<sub>2</sub>SO<sub>4</sub>.</h3> - -<p>A method employed by Remsen and Fahlberg (Am. Ch. Jour. Vol. 1. -p __ ) for getting the sulphonic acid group in the ortho position to -<span class="pagenum"><a name="Page_5" id="Page_5">[Pg 5]</a></span> -methyl was; (a) treat toluene with fuming H<sub>2</sub>SO<sub>4</sub> -forming thus ortho- and para- toluene sulphonic acids, (b) make -the calcium salt of the sulphonic acids thus formed and from this -the potassium salt. (c) treat this mixture of potassium toluene -sulphonates with phosphorous penta-chloride forming the corresponding -sulphonchlorides. One of these (para) being a solid and the other -(ortho) an oily liquid a nearly complete separation could be -effected. The difficulty with this method is however that the larger -part of the product is the para and only a comparatively small -proportion of the ortho compound is formed.</p> - -<h3><a name="Label_2" id="Label_2"></a>2. From p-nitro-toluene and H<sub>2</sub>SO<sub>4</sub>.</h3> - -<p>A second method employed consists in starting with -p-nitro-toluene. This when treated with H<sub>2</sub>SO<sub>4</sub> -forms toluene p-nitro o-sulphonic acid. If now a method could be -obtained for removing the nitro group the desired result would be attained. -<span class="pagenum"><a name="Page_6" id="Page_6">[Pg 6]</a></span></p> - -<p>The attempt was made by Remsen and Palmer (A.G.) to accomplish this -by (a) reducing the nitro compound to the amide, (b) making the diazo -compound and (c) boiling this with absolute alcohol. According to -generally accepted views this should effect the removal of the diazo -group and its replacement by hydrogen.</p> - -<p>Experiments however showed that the replacement was made not by -hydrogen but by the ethoxy group -OC<sub>2</sub>H<sub>5</sub>. This -method was therefore impracticable.</p> - -<p>A modification of this method was suggested by an observation of -Baeyer and Liebermann that if phenyl hydrazine be boiled with a -dilute solution of copper sulphate the hydrazine group is replaced -by hydrogen and benzene thus formed. Hence it was believed that if -the hydrazine compound should be made from diazo compound mentioned -above, the corresponding hydrocarbon, i.e. toluene o-sulphonic acid -<span class="pagenum"><a name="Page_7" id="Page_7">[Pg 7]</a></span> -could be obtained. The results of experiments showed that this -afforded a practicable method of preparing toluene ortho-sulphonic acid.</p> - -<p>After experimenting with various modifications of the method the -following was found to be the best adapted to the purpose.</p> - -<p>The potassium salt of toluene p-nitro-o-sulphonic acid is easily -obtained, as already stated, by heating p-nitro toluene on the -water bath with three times its weight of fuming H<sub>2</sub>SO<sub>4</sub>, -neutralizing with chalk and to the solution of calcium salt thus -obtained adding a slight excess of K<sub>2</sub>CO<sub>3</sub>. On filtering -from the precipitated CaCO<sub>3</sub> and evaporating slightly, -the salt is obtained in long needle shaped crystals of a pale straw -yellow color. This is</p> - -<table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdl"> </td> - <td class="tdc">⎧</td> - <td class="tdl"> CH<sub>3</sub></td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl">C<sub>6</sub>H<sub>3</sub></td> - <td class="tdc">⎨</td> - <td class="tdl"> SO<sub>2</sub>OH</td> - <td class="tdl"> (o)</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdc">⎩</td> - <td class="tdl"> NO<sub>2</sub></td> - <td class="tdl"> (p).</td> - </tr> - </tbody> -</table> - -<p>The reduction of the nitro group is best effected by means of tin and -HCl, in the proportion, salt 5 parts, tin 6 parts and concentrated HCl 30 parts. -<span class="pagenum"><a name="Page_8" id="Page_8">[Pg 8]</a></span></p> - -<p>The amido acid forms a compound with tin which crystallizes from the -HCl together with stannous chloride. This compound may be broken up -and the tin removed by continued boiling with water.</p> - -<p>A better method of removing the tin is by dissolving the compound -in Na<sub>2</sub>CO<sub>3</sub>. This forms a salt with the amido -acid and throws down the tin as Sn(OH)<sub>2</sub>, a white flocculent -precipitate. On filtering and adding to the solution conc. HCl, the -free amido acid is deposited in characteristic colorless, rhombic -crystals, having the formula</p> - -<table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdl"> </td> - <td class="tdc">⎧</td> - <td class="tdl"> CH<sub>3</sub></td> - </tr><tr> - <td class="tdl">C<sub>6</sub>H<sub>3</sub></td> - <td class="tdc">⎨</td> - <td class="tdl"> SO<sub>2</sub>OH</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdc">⎩</td> - <td class="tdl"> NH<sub>2</sub></td> - </tr> - </tbody> -</table> - -<p>The method at first employed for preparing the hydrazine compound -consisted in treating the amido acid, suspended in HCl, with -potassium nitrite and then with stannous chloride. The tin was then -removed from the solution by the addition of sodium carbonate and the -hydrazine compound thrown down with HCl. This method however gave -<span class="pagenum"><a name="Page_9" id="Page_9">[Pg 9]</a></span> -poor results the yield being only about 50% of the theoretical.</p> - -<p class="space-below1">Another method was accordingly substituted for the above, -namely that of Strecker and Römer (Ber. IV. s 784.) By this the diazo compound -is made first and isolated. This is done by suspending the finely -powdered acid in absolute alcohol, cooling and passing a current of -the oxides of nitrogen through in the ordinary way. The acid changes -in appearance, becoming more crystalline and slightly darker and -settles quickly on being shaken. The reaction here may be expressed -thus—</p> - -<table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdl"> </td> - <td class="tdl">⎧</td> - <td class="tdl"> CH<sub>3</sub></td> - <td class="tdl"> </td> - <td class="tdl">⎧</td> - <td class="tdl"> CH<sub>3</sub></td> - </tr><tr> - <td class="tdl">C<sub>6</sub>H<sub>3</sub></td> - <td class="tdl">⎨</td> - <td class="tdl"> SO<sub>2</sub>OH + HNO<sub>2</sub> = </td> - <td class="tdl">C<sub>6</sub>H<sub>3</sub></td> - <td class="tdl">⎨</td> - <td class="tdl"> SO<sub>3</sub> + 2H<sub>2</sub>O</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">⎩</td> - <td class="tdl"> NH<sub>2</sub></td> - <td class="tdl"> </td> - <td class="tdl"> <b>|</b></td> - <td class="tdl">   ╲</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">⎩</td> - <td class="tdl"> N=N</td> - </tr> - </tbody> -</table> - -<p class="space-above1">When the reaction is completed as shown by the appearance -of the suspended powder it is filtered and while still fresh is added to a -solution of acid sodium sulphite as long as it continues to dissolve readily. -<span class="pagenum"><a name="Page_10" id="Page_10">[Pg 10]</a></span></p> - -<p>To this solution there is added a quantity of solution of acid -sodium sulphite equivalent to that already used and the solution is -then boiled. It has at first a deep red color but in a few moments -becomes light reddish yellow. The reaction of HNaSO<sub>3</sub> on the diazo -compound may be represented in two stages, the first portion forming -an addition product and the second acting as a reducing agent. Thus,</p> - -<table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdl"> </td> - <td class="tdl">⎧ CH<sub>3</sub></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">⎧ CH<sub>3</sub></td> - </tr><tr> - <td class="tdl">1. C<sub>6</sub>H<sub>3</sub> </td> - <td class="tdl">⎨ SO<sub>3</sub> + HNaSO<sub>3</sub> = </td> - <td class="tdl"> </td> - <td class="tdl"> C<sub>6</sub>H<sub>3</sub></td> - <td class="tdl">⎨ SO<sub>2</sub>ONa</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b>  ╲</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">⎩ N=NSO<sub>3</sub>H</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">⎩ N=N</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl"> </td> - </tr> - </tbody> -</table> -<table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td colspan="4" class="tdc"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">⎧ CH<sub>3</sub></td> - <td class="tdl"> </td> - <td class="tdl">⎧ CH<sub>3</sub></td> - </tr><tr> - <td class="tdl">2. C<sub>6</sub>H<sub>3</sub></td> - <td class="tdl">⎨ SO<sub>2</sub>ONa + HNaSO<sub>3</sub> + H<sub>2</sub>O = </td> - <td class="tdl"> C<sub>6</sub>H<sub>3</sub></td> - <td class="tdl">⎨ SO<sub>2</sub>ONa</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">⎩ N=NSO<sub>3</sub>H</td> - <td class="tdl"> </td> - <td class="tdl">⎩ NH—NHSO<sub>3</sub></td> - </tr> - </tbody> -</table> - -<p class="space-above1">To the hot solution an excess of conc. HCl is added -when the hydrazine compound separates in a few moments in lustrous yellow -scales which completely fill the solution. On the addition of the HCl -<span class="pagenum"><a name="Page_11" id="Page_11">[Pg 11]</a></span> -a large amount of SO<sub>2</sub> is given off from the excess of HNaSO<sub>3</sub> -and the solution becomes deep red. When the hydrazine has separated the -mother liquor is again yellow.</p> - -<p class="space-below1">The reaction is represented as follows:</p> - -<table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdl"> </td> - <td class="tdl">⎧ CH<sub>3</sub></td> - <td class="tdl"> </td> - <td class="tdl">⎧ CH<sub>3</sub></td> - </tr><tr> - <td class="tdl">C<sub>6</sub>H<sub>3</sub> </td> - <td class="tdl">⎨ SO<sub>2</sub>ONa + HCl + H<sub>2</sub>O = </td> - <td class="tdl"> C<sub>6</sub>H<sub>3</sub> </td> - <td class="tdl">⎨ SO<sub>2</sub>OH + H<sub>2</sub>SO<sub>4</sub> + NaCl</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">⎩ NH—NHSO<sub>3</sub>H</td> - <td class="tdl"> </td> - <td class="tdl">⎩ NH—NH<sub>2</sub></td> - </tr> - </tbody> -</table> - -<p class="space-above1">The yield of hydrazine when both the diazo and the -NaHSO<sub>3</sub> are freshly prepared is practically quantitative.</p> - -<p class="space-below1">The hydrazine thus prepared was treated with a hot 10% -solution of copper sulphate till a permanent blue color was obtained in the -solution. Nitrogen is evolved and the copper sulphate is reduced to -cuprous oxide which is precipitated as a red powder. The reaction is -as follows.</p> - -<table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdl"> </td> - <td class="tdl">⎧ CH<sub>3</sub></td> - <td class="tdl"> </td> - <td class="tdl">⎧ </td> - </tr><tr> - <td class="tdl">C<sub>6</sub>H<sub>3</sub> </td> - <td class="tdl">⎨ SO<sub>2</sub>OH + 2CuSO<sub>4</sub> + H<sub>2</sub>O = </td> - <td class="tdl"> C<sub>6</sub>H<sub>4</sub> </td> - <td class="tdl">⎨ CH<sub>3</sub> + Cu<sub>2</sub>O + N<sub>2</sub> + 2H<sub>2</sub>SO<sub>4</sub></td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">⎩ NH—NH<sub>2</sub></td> - <td class="tdl"> </td> - <td class="tdl">⎩ SO<sub>2</sub>OH</td> - </tr> - </tbody> -</table> - -<p class="space-above1">Chalk was added to the solution to precipitate the -H<sub>2</sub>SO<sub>4</sub> and form a calcium salt of toluene-o-sulphonic acid. From this -the sodium salt was made by adding a slight excess of Na<sub>2</sub>SO<sub>3</sub> and -<span class="pagenum"><a name="Page_12" id="Page_12">[Pg 12]</a></span> -evaporating to dryness. The salt is very soluble being deliquescent -in the air while the corresponding potassium salt is not. From 1538 -gr. of para-nitro-toluene, 655 gr. of toluene ortho-sodium sulphonate -were obtained.</p> - -<p>Having thus obtained the toluene ortho-sulphonic acid the next -step in the problem was to find a convenient method for converting -this into ortho-sulph-benzoic acid. Two ways present themselves -for accomplishing this end. (1) direct oxidation of this salt and -(2) conversion into benzoic sulphinide from which the acid may be -obtained. Both of these methods were tried.</p> - -<h3><a name="Label_3" id="Label_3"></a>Oxidation of toluene-o-sodium sulphonate.</h3> - -<table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdl"> </td> - <td class="tdl">⎧</td> - <td class="tdl">CH<sub>3</sub></td> - </tr><tr> - <td class="tdl">C<sub>6</sub>H<sub>4</sub> </td> - <td class="tdl">⎨</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">⎩</td> - <td class="tdl">SO<sub>2</sub>ONa</td> - </tr> - </tbody> -</table> - -<p class="space-above1">The sodium salt of toluene-o-sulphonic acid is oxidized to -ortho-sulphobenzoic acid with considerable difficulty by KMnO<sub>4</sub> in neutral solution. -<span class="pagenum"><a name="Page_13" id="Page_13">[Pg 13]</a></span></p> - -<p>Thus two experiments showed that the oxidation was not complete after -24 hours boiling with excess of permanganate. If the solution be made -alkaline however, the oxidation is completed in a few hours, yet the -greatest difficulty still remains in the separation of the free acid -from the products of oxidation in the solution. If HCl be added to -the solution the acid salt</p> - -<table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">COOH</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">╱</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl">C<sub>6</sub>H<sub>4</sub> </td> - <td class="tdl"> </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">╲</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">SO<sub>2</sub>OK</td> - </tr> - </tbody> -</table> - -<p class="no-indent space-above1">is formed and this has nearly the -same solubility as the KCl also present. A better method therefore is -to add a slight excess of H<sub>2</sub>SO<sub>4</sub> and evaporate -nearly to dryness. In this way are formed sulphates and the free acid -presumably. The mixture is heated with alcohol (95%) which extracts -the acid leaving the greater part of the manganese salts. This -<span class="pagenum"><a name="Page_14" id="Page_14">[Pg 14]</a></span> -extract is evaporated and reextracted with alcohol. To -this solution BaCO<sub>3</sub> is added to precipitate the -H<sub>2</sub>SO<sub>4</sub> and form the Barium salt of the -o-sulphobenzoic acid. The solution is filtered from the -BaSO<sub>4</sub> and just enough H<sub>2</sub>SO<sub>4</sub> is added -to exactly precipitate the barium. The solution should thus contain -only the free acid sought, which crystallizes out on evaporating to a -small volume. While the method is theoretically possible it presents -so many difficulties that it is practically useless. The yield is -extremely small; only enough acid being obtained in this way to show -that it was possible.</p> - -<h3><a name="Label_4" id="Label_4"></a>Formation of Sulphinide from toluene-o-sodium sulphonate.</h3> - -<p>The second method for obtaining free o-sulphobenzoic acid from -toluene-ortho-sulphonic acid is by the conversion of the latter first -into benzoic sulphinide and then into the free acid. The sulphinide -was made essentially as described by Remsen (Am. Ch. Jour. Vol. I. -p. 428) with a few changes in the details as follows. -<span class="pagenum"><a name="Page_15" id="Page_15">[Pg 15]</a></span><br /><br />The salt</p> - -<table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdl"> </td> - <td class="tdl">⎧</td> - <td class="tdl">CH<sub>3</sub></td> - </tr><tr> - <td class="tdl">C<sub>6</sub>H<sub>4</sub> </td> - <td class="tdl">⎨</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">⎩</td> - <td class="tdl">SO<sub>2</sub>ONa</td> - </tr> - </tbody> -</table> - -<p class="no-indent">finely pulverized and in portions of from 10 -to 50 gr. was placed in a Florence flask; an equivalent quantity -of PCl<sub>5</sub> added; An inverted condenser was then attached -and the flask shaken. The action takes place at once and involves -sufficient heat to distill off the oxychloride formed in the -reaction. This being returned to the flask by the condenser furnishes -a liquid medium in which the reaction takes place more readily and -completely than when it is not present. It is best to cool the flask -at first and afterwards heat gently on the water bath. The reaction -which takes place may be represented as follows.</p> - -<table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdl"> </td> - <td class="tdl">⎧</td> - <td class="tdl">CH<sub>3</sub></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">⎧</td> - <td class="tdl">CH<sub>3</sub></td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl">C<sub>6</sub>H<sub>4</sub> </td> - <td class="tdl">⎨</td> - <td class="tdl"> </td> - <td class="tdl"> + PCl<sub>5</sub> = </td> - <td class="tdl"> C<sub>6</sub>H<sub>4</sub></td> - <td class="tdl">⎨</td> - <td class="tdl"> </td> - <td class="tdl"> + POCl<sub>3</sub> + NaCl.</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">⎩</td> - <td class="tdl">SO<sub>2</sub>ONa</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">⎩</td> - <td class="tdl">SO<sub>2</sub>Cl</td> - <td class="tdl"> </td> - </tr> - </tbody> -</table> - -<p class="space-above1 space-below1">On the addition of water the chloride -separates as a light yellow oil. This is washed with -water and concentrated aqueous ammonia added, which forms -toluene-o-sulphonamide thus. -<span class="pagenum"><a name="Page_16" id="Page_16">[Pg 16]</a></span></p> - -<table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">CH<sub>3</sub></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">CH<sub>3</sub></td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">╱</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">╱</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl">C<sub>6</sub>H<sub>4</sub> </td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl"> + NH<sub>3</sub> = </td> - <td class="tdl"> C<sub>6</sub>H<sub>4</sub></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">+ HCl.</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">╲</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">╲</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">SO<sub>2</sub>Cl</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">SO<sub>2</sub>NH<sub>2</sub></td> - <td class="tdl"> </td> - </tr> - </tbody> -</table> - -<p class="space-above1">The reaction is accompanied by a slight -evolution of heat and the formation, apparently, of an intermediate -product having a yellowish color, which passes over on longer -standing into the white amide. After standing several hours the -excess of ammonia was driven off by very gentle heating on the water -bath. If the heat is too high a large amount of a tarry product is -formed and the yield of amide is correspondingly small. In any case -some of this tarry product is formed. When nearly all the ammonia -had been driven off the mass was boiled with water which dissolves -everything except the tar. The hot solution was filtered through -charcoal and on cooling the amide separated in white feathery -crystals which melt at 155°-156°.</p> - -<p>The amide thus obtained was oxidized as described by Remsen (loc. cit.) -<span class="pagenum"><a name="Page_17" id="Page_17">[Pg 17]</a></span> -with potassium permanganate in neutral solution. The proportions are -10 gr amide. 40 gr KMnO<sub>4</sub> and 1 L. water. The oxidation was usually -effected in from four to six hours.</p> - -<p>To obtain the sulphinide from this solution after oxidation, the -latter, after filtration from the precipitated oxides of manganese, -was slightly acidified with HCl and evaporated to about one fourth -its original volume. On the addition of concentrated HCl to this -solution, the sulphinide separated out in white or slightly yellowish -feather shaped crystals melting at 212° and having the characteristic -intensely sweet taste.</p> - -<h3><a name="Label_5" id="Label_5"></a>Formation of Sulphinide -from Toluene by means of the chlorsulphonic acid reaction.</h3> - -<p>Before passing on to the methods used for converting the sulphinide -into free acid another method should be described by which -<span class="pagenum"><a name="Page_18" id="Page_18">[Pg 18]</a></span> -the former was obtained in larger quantities and much more easily -than by the one above described.</p> - -<p>Beckurts and Otto (Ber. XI. 2061) found that by treatment of toluene -with sulphuryl hydroxy-chloride or chlorsulphonic acid, ClSO<sub>2</sub>OH, -both o- and p- and as they supposed also m-toluene sulphonchlorides -were formed together with the corresponding sulphonic acid.</p> - -<p>Claesson and Wallin (Ber. XII. p. 1848) repeated the work reaching -practically the same results and finally Noyes (Am. Ch. Jour. Vol. -VIII. p. 176) employed the reaction as a convenient method for -obtaining toluene o-sulphon-chloride.</p> - -<p>Chlorsulphonic acid is made by passing dry HCl over solid sulphuric -acid so long as it continues to be absorbed. Since no solid sulphuric -acid was at hand, ordinary fuming Nordhausen acid was taken and from -<span class="pagenum"><a name="Page_19" id="Page_19">[Pg 19]</a></span> -one of two equal portions the SO<sub>3</sub> was driven over -into the other. HCl was passed into the latter and the resulting -chlorsulphonic acid distilled off at about 156°.</p> - -<p>This was placed in a flask, provided with a drop funnel and exit -tube, in portions of 150 gr. and to each portion 60 gr. of toluene -was added, very slowly, with constant shaking, the temperature -being kept near 10°. The action is violent and if any toluene is -allowed to collect on the surface of the liquid it is apt to produce -disastrous results. Large quantities of HCl are given off and the -liquid in the flask assumes a brown color. When all the toluene has -been added, it is poured into a large quantity of ice water, when -the sulphon-chlorides separate out, the ortho- as a heavy oil and -the para- as a white crystalline solid. After allowing to stand some -time in order that as much of the para-chloride might crystallize as -<span class="pagenum"><a name="Page_20" id="Page_20">[Pg 20]</a></span> -possible the ortho- was drawn off and subjected to a freezing -temperature for several hours. By this means more of the p-chloride -was removed and the operation was replicated as long as any crystals -continued to form, generally two or three times. In this way the -greater part of the para- may be removed, though some still remains -dissolved in the liquid chloride, which cannot be removed by repeated -freezings.</p> - -<p>The chloride thus obtained was treated with strong aqueous ammonia. -The conversion to the sulphamide does not take place so readily as -in case of the pure o-chloride obtained from the sulphonic acid and -phosphorus pentachloride.</p> - -<p>After standing about two days the whole of the oily chloride had -solidified to a yellowish brown mass. The excess of ammonia was -driven off by gentle heating on the water bath and the mass then -boiled with water. Not enough water was added at first for complete -<span class="pagenum"><a name="Page_21" id="Page_21">[Pg 21]</a></span> -solution but when the first portion was saturated it was poured -off through a filter and from it the amide separated in yellowish -feathery crystals which melted at 105°-125° and consisted therefore -as shown by Fahlberg (Am. Ch. Jour. Vol. I. p. 170) of a mixture -of o- and p-sulphonamides. It was recrystallized and from it was -obtained a portion melting at 153°-5° and one at 108°-20°.</p> - -<p class="space-below1">Since this mixture cannot be completely separated -by recrystallization another method was suggested. Remsen has shown that -K<sub>2</sub>Cr<sub>2</sub>O<sub>7</sub> in acid solution does not -oxidize the methyl group in</p> - -<table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">CH<sub>3</sub></td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">╱</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl">C<sub>6</sub>H<sub>4</sub> </td> - <td class="tdl"> </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">╲</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">SO<sub>2</sub>NH<sub>2</sub>  (o)</td> - </tr> - </tbody> -</table> - -<p class="no-indent">but does oxidize that in</p> - -<table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">CH<sub>3</sub></td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">╱</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl">C<sub>6</sub>H<sub>4</sub> </td> - <td class="tdl"> </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">╲</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">SO<sub>2</sub>NH<sub>2</sub>  (p).</td> - </tr> - </tbody> -</table> - -<p class="space-above1">It was thought that in a mixture of the two -the former might be left unchanged while the latter was oxidized to -p-sulphamine benzoic acid.</p> - -<p>To test this 15 gr of the mixture, melting at 105°-125°, was heated -<span class="pagenum"><a name="Page_22" id="Page_22">[Pg 22]</a></span> -with 40 gr K<sub>2</sub>Cr<sub>2</sub>O<sub>7</sub>, 55 gr H<sub>2</sub>SO<sub>4</sub> -and 2 vols. of water for about two hours. It was then tested and shown to -be still a mixture of p-& o-amides, since it was again heated for -several hours with half the original quantity of oxidizing mixture, then -diluted, filtered and washed. The white crystalline residue was -treated with sodium carbonate to dissolve the benzoic para-sulphamide -and the residue was found to be pure toluene o-sulphonamide melting -at 153°-155°. The small quantity remaining, 3 gr., indicated that -part of the o-amide had been completely broken down by the strong -oxidizing agent, though the proportion of o-& p-amides in the -original mixtures was known only approximately. The evolution of gas -during the oxidation would point to the same conclusion.</p> - -<p>Although this effects a complete separation it is hardly economical -<span class="pagenum"><a name="Page_23" id="Page_23">[Pg 23]</a></span> -since it will be shown later that a separation can be conveniently -effected after the oxidation with KMnO<sub>4</sub> so that the o-amide -contained in the mixture need not be lost.</p> - -<p>The original mass was treated with successive portions of water -till nothing remained but a black tarry substance. The amide which -separated from these extracts was perfectly white and melted at -153-5°. It was therefore regarded as practically pure o-amide. The -yield in amide melting above 153° was a little over one sixth the -weight of toluene used.</p> - -<p>The amide obtained in this way was oxidized in the manner already -described. It was found however that there was always some benzoic -p-sulphamide in the solution of the oxidation, due to the slight -admixture of p- with the o-amide used. This is thrown down with -the sulphinide on acidifying the solution and may be removed by -<span class="pagenum"><a name="Page_24" id="Page_24">[Pg 24]</a></span> -re-crystallization since it is somewhat less soluble in hot and cold -water than sulphinide.</p> - -<p>A better way to effect the separation, however, was found to be -the following. After having evaporated the solution containing the -products of oxidation, nearly neutralized with HCl, to about one -fifth its original volume, it is made very slightly acid and allowed -to cool. In this way very nearly all the benzoic p-sulphamide is -separated from the solution and none of the sulphinide. After -filtering, strong HCl is added and the sulphinide then separates -in its characteristic form. This indicates that sulphinide forms -an alkaline salt which is not decomposed by diluted HCl while the -p-sulphamide does not.</p> - -<p>The mixture of amides meeting at 105°-120° was oxidized -and the products separated in this way gave about equal -quantities of sulphinide and benzoic p-sulphamide. -<span class="pagenum"><a name="Page_25" id="Page_25">[Pg 25]</a></span></p> - -<p>When toluene is treated with chlorsulphonic acid there are formed -besides the ortho- and para- chlorides also ortho and para sulphonic -acids. These of course are in solution in the water from which the -chlorides separated. In order to recover the ortho-acid, the solution -was neutralized with chalk forming the calcium salt: this converted -into the potassium salt which by evaporating the solution to dryness -was obtained as a white crystalline powder. When treated with PCl<sub>5</sub> -in the manner already described this gave a mixture of ortho and para -sulphonchlorides consisting of about ⅓ ortho and ⅔ para.</p> - -<h3><a name="Label_6" id="Label_6"></a>Formation of -Orthosulphobenzoic acid from Sulphinide.</h3> - -<p>Benzoic sulphinide may be converted into a sulpho-benzoic -acid (1) by boiling with Ba(OH)<sub>2</sub>, (2) by heating in a closed -tube with conc. HCl or (3) by evaporating on the water bath with HCl. -<span class="pagenum"><a name="Page_26" id="Page_26">[Pg 26]</a></span></p> - -<p>1. Three gramms of sulphinide were boiled in a flask connected -with an inverted condenser for about two days with an excess of -Ba(OH)<sub>2</sub>. There was formed in the flask a hard mineral-like mass -which was insoluble in water and cold diluted HCl but dissolved in -hot HCl with effervesence. This was a Barium salt, probably basic (?) -of ortho sulphobenzoic acid. There was also formed an easily soluble -barium salt of that acid. The former was dissolved in H<sub>2</sub>SO<sub>4</sub> -and treated with BaCO<sub>3</sub>; the filtrate from the BaSO<sub>4</sub> which -contained a soluble barium salt was added to that above mentioned and -the barium exactly precipitated with H<sub>2</sub>SO<sub>4</sub> and the filtrate -evaporated to dryness giving the free acid but not in a perfectly -pure condition.</p> - -<p class="space-below1">2. 2.75 gr. of sulphinide was sealed up in a tube with -pure conc. HCl and heated two hours to 150°. On cooling nothing separated; the -<span class="pagenum"><a name="Page_27" id="Page_27">[Pg 27]</a></span> -liquid was evaporated to dryness giving 3.2 gr of acid and ammonium -chloride. The reaction taking place here may be represented thus:</p> - -<table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdl"> </td> <td class="tdl"> </td> - <td class="tdl">CO</td> - <td class="tdl"> </td> <td class="tdl"> </td> - <td class="tdl"> </td> <td class="tdl"> </td> - <td class="tdl">COOH</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">╱</td> - <td class="tdl"> </td> - <td class="tdl">╲</td> - <td class="tdl"> </td> <td class="tdl"> </td> - <td class="tdl">╱</td> - <td class="tdl"> </td> <td class="tdl"> </td> - </tr><tr> - <td class="tdl">C<sub>6</sub>H<sub>4</sub> </td> - <td class="tdl"> </td> <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">NH + 2H<sub>2</sub>O + HCl = </td> - <td class="tdl"> C<sub>6</sub>H<sub>4</sub> </td> - <td class="tdl"> </td> <td class="tdl"> </td> - <td class="tdl"> + NH<sub>4</sub>Cl.</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">╲</td> - <td class="tdl"> </td> - <td class="tdl">╱</td> - <td class="tdl"> </td> <td class="tdl"> </td> - <td class="tdl">╲</td> - <td class="tdl"> </td> <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> <td class="tdl"> </td> - <td class="tdl">SO<sub>2</sub></td> - <td class="tdl"> </td> <td class="tdl"> </td> - <td class="tdl"> </td> <td class="tdl"> </td> - <td class="tdl">SO<sub>2</sub>OH</td> - <td class="tdl"> </td> - </tr> - </tbody> -</table> - -<p class="space-above1">3. A more convenient method for obtaining the -acid than either of the above, is to heat the sulphinide with conc. -HCl on the water bath for two days. Then evaporate to dryness and -dissolve the residue in a small quantity of water. If the sulphinide -contained any para-sulphamide, as is usually the case, this will be -left undissolved and most of the NH<sub>4</sub>Cl will crystallize on -standing. This solution by slow evaporation deposits large colorless -crystals of the free acid.</p> - -<p>This acid is soluble in about two parts of cold water, very -difficultly soluble in absolute alcohol and almost completely -<span class="pagenum"><a name="Page_28" id="Page_28">[Pg 28]</a></span> -insoluble in ether. It does not melt under 250° but considerably -above that it melts, at first apparently without change and then with -slight sublimation of a very deliquescent substance, probably the anhydride.</p> - -<p class="space-below2">Two determinations of the S. made by Mr. A. F. Linn, gave the following results.</p> - -<table border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdr">I</td> - <td class="tdl"> ·1358</td> - <td class="tdl"> gr substance gave</td> - <td class="tdl"> ·1855</td> - <td class="tdl"> gr BaSO<sub>4</sub> representing</td> - <td class="tdl"> 15·72% S.</td> - </tr><tr> - <td class="tdr">II</td> - <td class="tdc"> ”</td> - <td class="tdc">”</td> - <td class="tdc"> ”</td> - <td class="tdc">”</td> - <td class="tdc">”</td> - </tr> - </tbody> -</table> - -<p class="space-above2">Calculated for the formula</p> -<table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">COOH</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">╱</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl">C<sub>6</sub>H<sub>4</sub> </td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl"> = 15·84% S.</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">╲</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">SO<sub>2</sub>OH</td> - <td class="tdl"> </td> - </tr> - </tbody> -</table> -<div> - <a name="Label_7" id="Label_7"></a> -</div> -<table border="0" cellspacing="0" summary="_" cellpadding="0" > - <tbody><tr> - <td class="tdl"><img src="images/i055.jpg" alt="_" width="250" height="373" /></td> - <td class="tdl">A crystallographic examination of the acid showed it to belong - to the orthorhombic system. Axial ratio: a: b: c = ·8507: 1: ·8121. - Planes. Ρ and α Ρ ὰ.<br /><br /> -<table border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">⎧</td> - <td class="tdl">Edge X = 131° 8'</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">⎧</td> - <td class="tdl">Ρ ^ Ρ</td> - <td class="tdl">⎨</td> - <td class="tdl">  ” Y = 82° 18'</td> - </tr><tr> - <td class="tdl">Angles measured  </td> - <td class="tdl">⎨</td> - <td class="tdl"> </td> - <td class="tdl">⎩</td> - <td class="tdl">  ” Z = 118° 40'</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">⎩</td> - <td class="tdr">Ρ ^</td> - <td class="tdl"> α Ρ ὰ</td> - <td class="tdl">    = 114° 38'</td> - </tr> - </tbody> -</table> - The crystals are up to 8 mm in length.<br />The pyramidal faces are - generally etched so that the image is poor.</td></tr> - </tbody> -</table> - -<p><span class="pagenum"><a name="Page_29" id="Page_29">[Pg 29]</a></span></p> -<hr class="chap" /> -<h2>Sulphonfluoresceïn.</h2> - -<p>Several attempts had already been made to obtain from the action -of o-sulphobenzoic acid and resorcin a substance analogous to the -fluoresceïn obtained by Baeyer<a name="FNanchor_1_1" id="FNanchor_1_1"></a><a href="#Footnote_1_1" class="fnanchor">[1]</a> -from phthalic anhydride and resorcin but while a strongly fluorescent -substance was easily obtained, no definite compound could be -separated from it. Thus Palmer obtained, by heating together the -above named substances to 160°(?) a solid mass, part soluble in water -and part insoluble as a dark brown amorphous powder. Both parts gave -a strong fluorescence with alkalis. He was unable however to obtain -the substance itself or any derivative in a crystalline form.</p> - -<p>The first experiments in this series gave the same negative results. -The mixture of acid and resorcin was heated in a sulphuric acid -<span class="pagenum"><a name="Page_30" id="Page_30">[Pg 30]</a></span> -both for several hours to 150°-170°, and as it showed no sign of -solidification the temperature was raised to 200° and then to 235° -where it was kept several hours longer. The black viscous mass -obtained in this way became vitreous on cooling, and in all respects -resembled that described by Palmer. This however is not the normal -course of the reaction as shown later but is probably due to a -decomposition of the normal product produced by too high heating.</p> - -<p>An experiment was made with the acid salt of ortho-sulphobenzoic acid.</p> - -<table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">COOH</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">╱</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl">C<sub>6</sub>H<sub>4</sub> </td> - <td class="tdl"> </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">╲</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">SO<sub>2</sub>OK</td> - </tr> - </tbody> -</table> - -<p class="no-indent">resorcin and H<sub>2</sub>SO<sub>4</sub> heating -the mixture to 150°-170°. A solid black mass was obtained strongly -fluorescent in alkaline solution and in all other respects like the -substance obtained above.</p> - -<h3><a name="Label_8" id="Label_8"></a>Preparation of Sulphonfluoresceïn.</h3> - -<p><span class="pagenum"><a name="Page_31" id="Page_31">[Pg 31]</a></span> -As the result of a number of experiments the following method of -preparing and purifying the sulphonfluoresceïn was found to give the -best results.</p> - -<p>The free acid is mixed with resorcin in the proportion of 1 part acid -to 1.2 parts resorcin, or a slight excess over two molecules of the -latter to one of the former. The mixture is placed in a deep vessel, -a test tube or beaker, which is placed in a sulphuric acid bath, a -thermometer being suspended in the mixture. The bath is heated and at -about 100° the resorcin melts and the acid slowly dissolves in the -liquid. No action appears to take place till the temperature reaches -175° where water begins to be given off and the liquid slowly assumes -a darker color. White crystals of resorcin collect on the sides of -the vessel. After the heating has been continued for about seven -hours at 178°-185° the liquid has a clear deep red color but shows no -<span class="pagenum"><a name="Page_32" id="Page_32">[Pg 32]</a></span> -signs of becoming viscous. At length lustrous yellow crystalline -plates appear in the liquid and soon the whole mass becomes a thick -nearly solid yellow paste. Continuous heating at the same temperature -causes no further apparent change. This mass, which on cooling is -made up of yellow crystals imbedded in a red vitreous matrix, is then -dissolved in hot water forming a clear red solution or at most one -containing but a small quantity of a brown flocculent precipitate. -This solution is filtered if necessary and evaporated to a small -volume from which the substance separates on cooling in reddish -yellow radial crystals. These are filtered and washed with ether -till the washings are perfectly colorless. The substance on repeated -crystallization from water has a pale straw yellow color and when -deposited slowly forms transparent crystal blocks from 2·6 mm long, -arranged in radial groups. -<span class="pagenum"><a name="Page_33" id="Page_33">[Pg 33]</a></span></p> - -<p>A considerable amount of resorcin is lost by sublimation during -the reaction especially if the operation is carried on in a beaker -so that some excess should be added. But even when the resorcin -is present in excess at the end of the reaction some free acid is -always left which may be obtained from the mother liquid in the -characteristic colorless orthorhombic crystals.</p> - -<p>The water of crystallization and sulphur were determined in the -new compound. In estimating the water, the substance was heated to -106°-123° for about ten hours till it attained a constant weight. -On standing in the air it quickly regains its original weight. When -heated to 130°-140° for some time it turns slightly reddish and loses -over 10% of its weight which is not regained by standing in the air. -<span class="pagenum"><a name="Page_34" id="Page_34">[Pg 34]</a></span></p> - -<p class="space-below1"><a name="Label_9" id="Label_9"></a>Estimation -No. I. was made by fusion with KOH and KNO<sub>3</sub>. Nos. II and -III were made by Mr. Mindileff by Morse’s method, oxidizing with -KMnO<sub>4</sub> in KOH solution.</p> - -<p>·3882 gr. heated to 106°-123° lost ·0302 gr. = 8·5%<br /> -Calculation for 2H<sub>2</sub>O - C<sub>19</sub>H<sub>12</sub>O<sub>6</sub>S + 2H<sub>2</sub>O  = 8·9% water.</p> - -<table class="lft" border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdr">I. </td> - <td class="tdl">·2007 </td> - <td class="tdl">gr sub. gave</td> - <td class="tdl">·1286</td> - <td class="tdl"> gr BaSO<sub>4</sub></td> - <td class="tdl"> = 8·77% S.</td> - </tr><tr> - <td class="tdr">II. </td> - <td class="tdl"> </td> - <td class="tdl">gr ” ”</td> - <td class="tdl"> ”</td> - <td class="tdl"> gr ”</td> - <td class="tdl"> = 7·91” ”</td> - </tr><tr> - <td class="tdr">III. </td> - <td class="tdl"> </td> - <td class="tdl">gr ” ”</td> - <td class="tdl"> ”</td> - <td class="tdl"> gr ”</td> - <td class="tdl"> = 7·89” ”</td> - </tr> - </tbody> -</table> -<p class="no-indent">Calculation for - C<sub>19</sub>H<sub>12</sub>O<sub>6</sub>S + 2H<sub>2</sub>O     = 7·92% S.</p> - -<p class="space-above1">These analyses show with but little doubt -that the substance has the composition indicated above i.e. -C<sub>19</sub>H<sub>12</sub>O<sub>6</sub>S + 2H<sub>2</sub>O. The -reaction therefore which takes place between ortho-sulpho benzoic -acid and resorcin from its analogy to that taking place between -phthalic anhydride and resorcin may be represented thus, as -shown by Baeyer in his second paper (Ann. 202. S. 43) -<span class="pagenum"><a name="Page_35" id="Page_35">[Pg 35]</a></span></p> - -<p>Representing the formation of the anhydride as the first action.</p> - -<table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">COOH</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">CO</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">╱</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">╱</td> - <td class="tdl"> </td> - <td class="tdl">╲</td> - </tr><tr> - <td class="tdl">C<sub>6</sub>H<sub>4</sub> </td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl"> = C<sub>6</sub>H<sub>4</sub></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">  O + H<sub>2</sub>O</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">╲</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">╲</td> - <td class="tdl"> </td> - <td class="tdl">╱</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">SO<sub>2</sub>OH (o)</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">SO<sub>2</sub></td> - <td class="tdl"> </td> - </tr> - </tbody> -</table> -<p class="no-indent">and the action of resorcin on this anhydride thus.</p> -<table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdl"> </td> <td class="tdl"> </td> <td class="tdl"> </td> - <td class="tdl"> </td> <td class="tdl"> </td> <td class="tdl"> </td> - <td class="tdl"> </td> <td class="tdl"> </td> <td class="tdc">O</td> - <td class="tdl"> </td> <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> <td class="tdl"> </td> <td class="tdl"> </td> - <td class="tdl"> </td> <td class="tdl"> </td> <td class="tdl"> </td> - <td class="tdl"> </td> <td class="tdl">╱</td> <td class="tdl"> </td> - <td class="tdl">╲</td> <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> <td class="tdl"> </td> <td class="tdl"> </td> - <td class="tdl"> </td> <td class="tdl"> </td> <td class="tdl"> </td> - <td class="tdl">  (HO)H<sub>4</sub>C<sub>6</sub></td> - <td class="tdl"> </td> <td class="tdl"> </td> - <td class="tdl">  C<sub>6</sub>H<sub>4</sub>(OH)</td> <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> <td class="tdl"> </td> <td class="tdl"> </td> - <td class="tdl"> </td> <td class="tdl"> </td> <td class="tdl"> </td> - <td class="tdl"> </td> <td class="tdl">╲</td> <td class="tdl"> </td> - <td class="tdl">╱</td> <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> <td class="tdl"> </td> <td class="tdl">CO</td> - <td class="tdl"> </td> <td class="tdl"> </td> <td class="tdl">OH</td> - <td class="tdl"> </td> <td class="tdl"> </td> <td class="tdc">C</td> - <td class="tdl"> </td> <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> <td class="tdl">╱</td> <td class="tdl"> </td> - <td class="tdl">╲</td> <td class="tdl">╱</td> <td class="tdl"> </td> - <td class="tdl"> </td> <td class="tdl">╱</td> <td class="tdl"> </td> - <td class="tdl">╲</td> <td class="tdl"> </td> - </tr><tr> - <td class="tdl">C<sub>6</sub>H<sub>4</sub></td> <td class="tdl"> </td> - <td class="tdl"> </td> <td class="tdl">  O + C<sub>6</sub>H<sub>4</sub></td> - <td class="tdl"> </td> <td class="tdl">   = </td> - <td class="tdl">   C<sub>6</sub>H<sub>4</sub></td> - <td class="tdl"> </td> <td class="tdl"> </td> - <td class="tdl">  O + 2H<sub>2</sub>O.</td> <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> <td class="tdl">╲</td> <td class="tdl"> </td> - <td class="tdl">╱</td> <td class="tdl">╲</td> <td class="tdl"> </td> - <td class="tdl"> </td> <td class="tdl">╲</td> <td class="tdl"> </td> - <td class="tdl">╱</td> <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> <td class="tdl"> </td> <td class="tdl">SO<sub>2</sub></td> - <td class="tdl"> </td> <td class="tdl"> </td> <td class="tdl">OH (m)</td> - <td class="tdl"> </td> <td class="tdl"> </td> <td class="tdl">SO<sub>2</sub></td> - <td class="tdl"> </td> <td class="tdl"> </td> - </tr> - </tbody> -</table> - -<p>The substance thus formed would naturally receive the name -Sulphonfluoresceïn from its analogy with Fluoresceïn.</p> - -<table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="30" rules="cols"> - <tbody><tr> - <td><table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdl"> </td> - <td class="tdl">⎧</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">OH</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╱</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> C<sub>6</sub>H<sub>3</sub></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╲</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">O</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╱</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl">C </td> - <td class="tdl">⎨</td> - <td class="tdl"> C<sub>6</sub>H<sub>3</sub></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╲</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">OH</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td colspan="3" class="tdl"> C<sub>6</sub>H<sub>4</sub>SO<sub>2</sub></td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl">  ╱</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">⎩</td> - <td class="tdl"> O</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - </tr> - </tbody> -</table></td> -<td><table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdl"> </td> - <td class="tdl">⎧</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">OH</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╱</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> C<sub>6</sub>H<sub>3</sub></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╲</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">O</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╱</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl">C </td> - <td class="tdl">⎨</td> - <td class="tdl"> C<sub>6</sub>H<sub>3</sub></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╲</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">OH</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td colspan="3" class="tdl">  C<sub>6</sub>H<sub>4</sub>CO</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl">   ╱</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">⎩</td> - <td class="tdl">  O</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - </tr> - </tbody> - </table></td> - </tr><tr> - <td class="tdc">Sulphonfluoresceïn.</td> - <td class="tdc">Fluoresceïn.</td> - </tr> - </tbody> -</table> -<h3><a name="Label_10" id="Label_10"></a>Properties of S.fluoresceïn.</h3> - -<p>This compound shows a marked similarity to the fluoresceïn described -by Baeyer as would naturally be expected from its great similarity of -composition and constitution, but it also shows decided differences -<span class="pagenum"><a name="Page_36" id="Page_36">[Pg 36]</a></span> -which may be attributed to the replacement of CO by SO<sub>2</sub>.</p> - -<p>Dissolved in water it shows a weak green fluorescence which in -alkaline solution becomes much deeper but not by any means so strong -as that of fluoresceïn. The dilute alkaline solution by transmitted -light is almost perfectly colorless and by reflected light a clear -green. Unlike fluoresceïn it is extremely soluble in water, about -one part in two or three of hot and five or six of cold water. It -is also soluble in absolute alcohol forming a yellow solution with -weak fluorescence. It is soluble with difficulty in ether but when in -solution is deposited only on evaporating to a small volume.</p> - -<p>It does not melt at 250° but if held at a lower temperature for a -long time becomes red undergoing some decomposition. If quickly -heated somewhat above 300° it melts to a deep red liquid and then -<span class="pagenum"><a name="Page_37" id="Page_37">[Pg 37]</a></span> -solidifies. If the mass is treated with water it partly dissolves -leaving a dark brown flocculent precipitate which dissolves on the -addition of an alkali, the solution having an intense fluorescence, -nearly if not quite equaling that of fluoresceïn. This change -produced by heating was not further studied.</p> - -<p>The crystals are very thin blades, apparently monoclinic, showing the -clinopinacoid αΡὰ and a very narrow prism αΡ and clinodome Ρὰ. The -angle β = 75° and the extinction angle against the ϲ axis = 20°. -The axial ratio could not be accurately determined.</p> - -<h3><a name="Label_11" id="Label_11"></a>Salts of sulphonfluoresceïn.</h3> - -<p>The influence of the SO<sub>2</sub> group is shown by the fact -that the substance acts as an acid decomposing carbonates and forming -salts which is not the case with fluoresceïn. -<span class="pagenum"><a name="Page_38" id="Page_38">[Pg 38]</a></span></p> - -<h4>Barium salt.</h4> - -<p>The substance was boiled with an excess of carefully purified -BaCO<sub>3</sub> for two hours. The filtrate from the BaCO<sub>3</sub> -evaporated to a small volume deposited yellow crystals resembling -the original substance but in shorter and thicker prisms. These were -twice recrystallized and had then a light straw yellow color.</p> - -<p class="space-below3">A determination of the Ba gave the -following results. The salt was dried in the air.</p> - -<div class="transnote bbox"> -<p class="f120 space-above1">Transcriber's Note:</p> -<hr class="r5" /> -<p>The following table was crossed out on the original. -A note on the previous page beside the table was:</p> -<p>   “<b>All these calculations are wrong.  J.R.</b>”</p> -</div> - -<table border="0" cellspacing="2" summary="Barium salts." cellpadding="0"> - <tbody><tr> - <td class="tdr">I </td> - <td class="tdl">·1078</td> - <td class="tdc"> gr salt gave </td> - <td class="tdl">·0304</td> - <td class="tdc"> gr BaSO<sub>4</sub> </td> - <td class="tdl"> = 15·73% Ba.</td> - </tr><tr> - <td class="tdr">II </td> - <td class="tdl">·1641</td> - <td class="tdc">” ”   ”</td> - <td class="tdl">·0457</td> - <td class="tdc">” ” ”</td> - <td class="tdl"> = 15·53” ”</td> - </tr><tr> - <td class="tdr">III </td> - <td class="tdl">·2425</td> - <td class="tdc">” ”   ”</td> - <td class="tdl">·0680</td> - <td class="tdc">” ” ”</td> - <td class="tdl"> = 15·65” ”</td> - </tr><tr> - <td class="tdr">IV </td> - <td class="tdl">·2860</td> - <td class="tdc">” ”   ”</td> - <td class="tdl">·0798</td> - <td class="tdc">” ” ”</td> - <td class="tdl"> = 15·54” ”</td> - </tr><tr> - <td class="tdr">V </td> - <td class="tdl">·1843</td> - <td class="tdc">” ”   ”</td> - <td class="tdl">·0498</td> - <td class="tdc">” ” ”</td> - <td class="tdl"> = 15·08” ”</td> - </tr><tr> - <td class="tdr">VI </td> - <td class="tdl">·2620</td> - <td class="tdc">” ”   ”</td> - <td class="tdl">·0708</td> - <td class="tdc">” ” ”</td> - <td class="tdl"> = 15·08” ”</td> - </tr><tr> - <td class="tdr">VII </td> - <td class="tdl">·3230</td> - <td class="tdc">” ”   ”</td> - <td class="tdl">·0906</td> - <td class="tdc">” ” ”</td> - <td class="tdl"> = 15·65” ”</td> - </tr><tr> - <td class="tdr">VIII </td> - <td class="tdl">·2875</td> - <td class="tdc">” ”   ”</td> - <td class="tdl">·0807</td> - <td class="tdc">” ” ”</td> - <td class="tdl"> = 15·66” ”</td> - </tr><tr> - <td colspan="5" class="tdl"><br />   Calculated for C<sub>19</sub>H<sub>13</sub>O<sub>7</sub>SBa</td> - <td class="tdl"><br /> = 15·10% Ba.</td> - </tr> - </tbody> -</table> - -<p class="space-above2"><span class="pagenum"><a name="Page_39" id="Page_39">[Pg 39]</a></span> -In the above determinations the salt analysed was taken from -specimens made at three different times and purified in slightly -different ways, Nos 1, 2, & 3 being washed with absolute alcohol. Nos -V and V were made by precipitating the Ba with H<sub>2</sub>SO<sub>4</sub> from a -solution of the salt.</p> - -<p class="space-below1">The water was determined by heating at 110° till constant weight was -reached. Part only of the weight lost was regained on standing in the air.</p> - -<p class="center">      ·3943 gr salt lost at 110° ·0286 gr = 7.25%<br /> -   Water calculated for C<sub>19</sub>H<sub>13</sub>O<sub>7</sub>SBa+2H<sub>2</sub>O = 7.35%</p> - -<p class="space-above1 space-below1">Although these analyses show a -per cent. of Ba somewhat above that required by a compound having -the formula C<sub>19</sub>H<sub>13</sub>O<sub>7</sub>SBa still -this appears to be the most probable formula which can be assigned -to the substance. If this is the true composition of the salt, then in -<span class="pagenum"><a name="Page_40" id="Page_40">[Pg 40]</a></span> -sulphonfluoresceïn the anhydride condition must be broken up by boiling -with BaCO<sub>3</sub> forming the salt thus.</p> - -<table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdl"> </td> - <td class="tdl">⎧</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">OH</td> - <td class="tdl"> </td> - <td class="tdl">⎧</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">OH</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╱</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╱</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> C<sub>6</sub>H<sub>3</sub></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> C<sub>6</sub>H<sub>3</sub></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╲</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╲</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">O</td> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">O</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╱</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╱</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl">C </td> - <td class="tdl">⎨</td> - <td class="tdl"> C<sub>6</sub>H<sub>3</sub></td> - <td class="tdl"> </td> - <td class="tdl">   + 2H<sub>2</sub>O = </td> - <td class="tdl"> C </td> - <td class="tdl">⎨</td> - <td class="tdl"> C<sub>6</sub>H<sub>3</sub></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╲</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╲</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">OH</td> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">OH</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td colspan="3" class="tdl"> C<sub>6</sub>H<sub>4</sub>SO<sub>2</sub></td> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td colspan="3" class="tdl"> C<sub>6</sub>H<sub>4</sub>SO<sub>2</sub>OH</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl">  ╱</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">⎩</td> - <td class="tdl"> O</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">⎩</td> - <td class="tdl"> OH</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - </tr> - </tbody> -</table> -<hr class="chap" /> -<table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdl"><br /></td> - <td class="tdl bb"><br /></td> - <td class="tdl"><br /></td> - <td class="tdl"><br /></td> - <td class="tdl"><br /></td> - <td class="tdl bb"><br /></td> - <td class="tdl"><br /></td> - - <td class="tdl bb"><br /></td> - <td class="tdl"><br /></td> - <td class="tdl"><br /></td> - <td class="tdl"><br /></td> - <td class="tdl"><br /></td> - <td class="tdl bb"><br /></td> - <td class="tdl"><br /></td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl bl"> </td> - <td class="tdl">⎧</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl br">OH</td> - <td class="tdl"> </td> - - <td class="tdl bl"> </td> - <td class="tdl"> </td> - <td class="tdl">⎧</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl br">OH</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl bl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╱</td> - <td class="tdl br"> </td> - <td class="tdl"> </td> - - <td class="tdl bl"> </td> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╱</td> - <td class="tdl br"> </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl bl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> C<sub>6</sub>H<sub>3</sub></td> - <td class="tdl"> </td> - <td class="tdl br"> </td> - <td class="tdl"> </td> - - <td class="tdl bl"> </td> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> C<sub>6</sub>H<sub>3</sub></td> - <td class="tdl"> </td> - <td class="tdl br"> </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl bl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╲</td> - <td class="tdl br"> </td> - <td class="tdl"> </td> - - <td class="tdl bl"> </td> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╲</td> - <td class="tdl br"> </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl bl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl br">O</td> - <td class="tdl"> </td> - - <td class="tdl bl"> </td> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl br">O</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl bl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╱</td> - <td class="tdl br"> </td> - <td class="tdl"> </td> - - <td class="tdl bl"> </td> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╱</td> - <td class="tdl br"> </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"><b>2</b> </td> - <td class="tdl bl"> C </td> - <td class="tdl">⎨</td> - <td class="tdl"> C<sub>6</sub>H<sub>3</sub></td> - <td class="tdl"> </td> - <td class="tdl br"> </td> - <td class="tdl"> + BaCO<sub>3</sub> = </td> - - <td class="tdl bl"> </td> - <td class="tdl">C </td> - <td class="tdl">⎨</td> - <td class="tdl"> C<sub>6</sub>H<sub>3</sub></td> - <td class="tdl"> </td> - <td class="tdl br"> </td> - <td class="tdl"> + Ba</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl bl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╲</td> - <td class="tdl br"> </td> - <td class="tdl"> </td> - - <td class="tdl bl"> </td> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╲</td> - <td class="tdl br"> </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl bl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl br">OH</td> - <td class="tdl"> </td> - - <td class="tdl bl"> </td> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl br">OH</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl bl"> </td> - <td class="tdl"><b>│</b></td> - <td colspan="3" class="tdl br"> C<sub>6</sub>H<sub>4</sub>SO<sub>2</sub>OH </td> - <td class="tdl"> </td> - - <td class="tdl bl"> </td> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td colspan="3" class="tdl br"> C<sub>6</sub>H<sub>4</sub>SO<sub>2</sub>OH </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl bl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl br"> </td> - <td class="tdl"> </td> - - <td class="tdl bl"> </td> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl br"> </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl bl"> </td> - <td class="tdl">⎩</td> - <td class="tdl"> OH</td> - <td class="tdl"> </td> - <td class="tdl br"> </td> - <td class="tdl"> </td> - - <td class="tdl bl"> </td> - <td class="tdl"> </td> - <td class="tdl">⎩</td> - <td class="tdl"> OH</td> - <td class="tdl"> </td> - <td class="tdl br"> </td> - <td class="tdl"> <b><sub>2</sub></b></td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl bt">  </td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl bt"> </td> - <td class="tdl"> </td> - - <td class="tdl bt">  </td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl bt"> </td> - <td class="tdl"> </td> - </tr> - </tbody> -</table> - -<p>By treating the salt with H<sub>2</sub>SO<sub>4</sub> the original -substance is reformed.</p> - -<h4>Calcium Salt.</h4> - -<p>Attempts were made to prepare the calcium salt but without success. -The S-fluoresceïn was boiled several hours with very finely powdered -calcite, and some salt was formed as shown by the CO<sub>2</sub> evolved -but on evaporating the solution and recrystallizing the substance -deposited it was found to be the unchanged S-fluoresceïn. Some Ca. salt was -in the mother liquors but its extreme solubility prevented a separation being made. -<span class="pagenum"><a name="Page_41" id="Page_41">[Pg 41]</a></span></p> - -<h3><a name="Label_12" id="Label_12"></a>Acetyl derivative of S.fluoresceïn.</h3> - -<p>S.fluoresceïn was boiled with an excess of acetic anhydride for about -three hours. The solution became quite dark and when evaporated on -the water bath left a black tarry residue. This was treated with -water which dissolved a part leaving a dark flocculent precipitate. -The solution was boiled with animal charcoal and evaporated nearly -to dryness. On cooling there separated a light yellow flocculent -precipitate very soluble in hot water and but slightly less so in -cold. This was dissolved in a small quantity of alcohol from which -it separated on evaporation in small radial crystals having a light -lavender color & satiny luster. They also have a peculiar odor -resembling slippery elm which is not removed by recrystallization. -<span class="pagenum"><a name="Page_42" id="Page_42">[Pg 42]</a></span> -They show a tendency to decompose, becoming yellow on exposure to -the air. The substance does not melt or change in appearance under -245°. With alkalis it gives a slight greenish fluorescence. From the -method of its formation this was taken to be an acetyl derivative -of S.fluoresceïn but whether the mono-or di-acetyl could not be -determined without analysis for which the substance did not suffice.</p> - -<h3><a name="Label_13" id="Label_13"></a>Bromine substitution products of S-fluoresceïn.</h3> - -<p>It was especially interesting to see what influence the SO<sub>2</sub> group -would exert upon the introduction of Bromine into the compound. In -the case of fluoresceïn four Bromine atoms enter easily and special -precautions are necessary to obtain a product containing a smaller -number. The case however is different with S.fluoresceïn.</p> - -<p class="space-below1">The latter was dissolved in glacial acetic acid in which -it is <span class="pagenum"><a name="Page_43" id="Page_43">[Pg 43]</a></span> -soluble with some difficulty and to the solution was added a 20% -solution of bromine in acetic acid, in sufficient quantity to make -eight atoms of bromine to one molecule of S.fluoresceïn. This -solution was evaporated on the water bath and while still having a -considerable volume, small, red, sharply defined crystals began to -separate. The solution was evaporated to a small volume and allowed -to cool but nothing further separated. These crystals are difficultly -soluble in water, alcohol and ether. The alkaline solution shows a -green fluorescence and slight red color by transmitted light. These -crystals were dissolved in a large quantity of alcohol which on -evaporation gradually deposited very small yellow crystals, which -were dried in the air and taken for analysis. The Br. was determined -by Carius method.</p> - -<table border="0" cellspacing="2" summary="Bromine salts." cellpadding="0"> - <tbody><tr> - <td class="tdr">I. </td> - <td class="tdl">·2345</td> - <td class="tdc"> gr sub. gave </td> - <td class="tdl">·1718</td> - <td class="tdc"> gr AgBr </td> - <td class="tdl"> = 31·17% Br.</td> - </tr><tr> - <td class="tdr">II. </td> - <td class="tdl">·2786</td> - <td class="tdc">” ”   ”</td> - <td class="tdl">·1815</td> - <td class="tdc">” ” ”</td> - <td class="tdl"> = 27·72% Br.</td> - </tr><tr> - <td colspan="5" class="tdl"><br />   Calculated for C<sub>19</sub>H<sub>10</sub>Br<sub>2</sub>O<sub>6</sub>S</td> - <td class="tdl"><br /> = 30·42% Br.</td> - </tr> - </tbody> -</table> - -<p class="space-above1"><span class="pagenum"><a name="Page_44" id="Page_44">[Pg 44]</a></span> -These results, though not conclusive, indicate that under the -given conditions it is the di-bromsulphonfluoresceïn which is -formed. Whether this is due to the presence in the compound of the -SO<sub>2</sub> group or simply to the greater insolubility of the di-than -of the tetra-brom product cannot be definitely stated. When the -original acetic acid mother liquor was evaporated to dryness, a red -non-crystalline substance remained which more closely resembled rosin -than the crystals. The concentrated alkaline solution had a deep red -color without fluorescence and acted as a red dye stuff. The dilute -alkaline solution showed the characteristic delicate pink of rosin.</p> - -<h3><a name="Label_14" id="Label_14"></a>Action of -H<sub>2</sub>SO<sub>4</sub> on S.fluoresceïn.</h3> - -<p>A test tube in which S.fluoresceïn was being made just at the end of -<span class="pagenum"><a name="Page_45" id="Page_45">[Pg 45]</a></span> -the reaction broke and allowed the contents to run out into the -sulphuric acid bath, which had a temperature of 175°. On standing -several days the solution deposited a heavy precipitate which was -separated by filtering through glass wool. When dry it formed a light -yellow powder extremely soluble in water, alcohol and ether.</p> - -<p>The alkaline solution had an intense green fluorescence with -delicate shades of pink by transmitted light. On account of its -great solubility it was impossible to purify it by crystallization, -hence the Ba salt was made. The substance decomposed BaCO<sub>3</sub> with -great ease forming an easily soluble salt. When it was attempted to -evaporate the solution of this salt to crystallization the latter -came out in a hard insoluble granular form and on continuous boiling -of the solution turned brown. To avoid this undesirable form it was -<span class="pagenum"><a name="Page_46" id="Page_46">[Pg 46]</a></span> -converted into the Ca. salt by treatment with H<sub>2</sub>SO<sub>4</sub> and then -CaCO<sub>3</sub>. This also formed a hard granular insoluble mass on boiling -but did not change in color. As there was no guarantee as to its -purity and only a small quantity was obtained it was not analyzed.</p> - -<h3><a name="Label_15" id="Label_15"></a>Action of HCl on S.fluoresceïn.</h3> - -<p>Hydrochloric acid does not dissolve S.fluoresceïn but converts it -into a light yellow granular powder. When recrystallized from water -in which it is quite easily soluble it melts partially at 130° -apparently with some decomposition. This compound was not further studied.</p> - -<h3><a name="Label_16" id="Label_16"></a>Reduction of S.fluoresceïn.</h3> - -<p>When treated with zinc dust in a strong alkaline solution -sulphonfluoresceïn is reduced to a colorless substance probably -<span class="pagenum"><a name="Page_47" id="Page_47">[Pg 47]</a></span> -analogous to fluoresceïn which is formed in the same manner. On -account of its great solubility it could not be obtained in the free -state. It is quickly oxidized to s.fluoresceïn by oxidizing agents -as KMnO<sub>4</sub> and HNO<sub>3</sub> and passes back spontaneously -on standing in the air. The latter action is however much slower than -in case of fluoresceïn.</p> - -<h2><a name="Label_17" id="Label_17"></a>Conclusion.</h2> - -<p>The principal results relating to s.fluoresceïn which have -been reached in this work may be briefly summarized as follows. -Orthosulphobenzoic acid acts on resorcin at a temperature of -about 180° giving off water and forming a substance analogous to -fluoresceïn but having the CO group replaced by SO<sub>2</sub>. -This substance sulphonfluoresceïn crystallizes from water -in light yellow monoclinic crystals having the composition -C<sub>19</sub>H<sub>12</sub>O<sub>6</sub>S + 2H<sub>2</sub>O. It is -very soluble in alcohol and water and with difficulty in ether. It -<span class="pagenum"><a name="Page_48" id="Page_48">[Pg 48]</a></span> -does not melt under 250° but above 300° melts with decomposition. -It shows in alkaline solution a clear green fluorescence. It acts -as an acid, decomposing carbonates and forming salts, the Ba salt -having the composition C<sub>19</sub>H<sub>13</sub>O<sub>7</sub>SBa. -It forms an acetyl compound when boiled with acetic anhydride. It -forms substitution products with Br, probably the dibrom-product -most easily. It forms a compound with H<sub>2</sub>SO<sub>4</sub>, -probably a substitution product, whose composition was not -determined. It is reduced by zinc dust and KOH to a colorless -substance analogous to fluoresceïn.</p> - -<p>Finally in terms of the prevalent theory the substance itself may -be represented thus—</p> - -<table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="30" > - <tbody><tr><td> -<table class="smtab" border="0" cellspacing="5" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">H</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">H</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - </tr><tr> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">C</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">O</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">C</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - </tr><tr> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">╱</td> - <td class="tdc">╲</td> - <td class="tdc"> </td> - <td class="tdc">╱</td> - <td class="tdc"> </td> - <td class="tdc">╲</td> - <td class="tdc"> </td> - <td class="tdc">╱</td> - <td class="tdc"> </td> - <td class="tdc">╲</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - </tr><tr> - <td class="tdc"> </td> - <td class="tdr">(HO</td> - <td class="tdl">)</td> - <td class="tdc">C</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">C</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">C</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">C</td> - <td class="tdc"> (OH)</td> - <td class="tdc"> </td> - </tr><tr> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">│</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">│</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">│</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">│</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - </tr><tr> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdr">H</td> - <td class="tdc">C</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">C</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">C</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">C</td> - <td class="tdl">H</td> - <td class="tdc"> </td> - </tr><tr> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">╲</td> - <td class="tdc"> </td> - <td class="tdc">╱</td> - <td class="tdc"> </td> - <td class="tdc">╲</td> - <td class="tdc"> </td> - <td class="tdc">╱</td> - <td class="tdc"> </td> - <td class="tdc">╲</td> - <td class="tdc"> </td> - <td class="tdc">╱</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - </tr><tr> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdl">C</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">C</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">C</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">= </td> - </tr><tr> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">H</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">H</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">╱</td> - <td class="tdc"> </td> - <td class="tdc">╲</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">H</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - </tr><tr> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">C</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> ╱</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">╲</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - </tr><tr> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">╱</td> - <td class="tdc"> </td> - <td class="tdr">╲</td> - <td class="tdc"> </td> - <td class="tdr">╱</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">O</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - </tr><tr> - <td class="tdr"> </td> - <td class="tdc">HC</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> C</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc">╱</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - </tr><tr> - <td class="tdc"> </td> - <td class="tdc">│</td> - <td class="tdc"> </td> - <td class="tdc"> </td> - <td class="tdc"> </td> - 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</tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╱</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl">C </td> - <td class="tdl">⎨</td> - <td class="tdl"> C<sub>6</sub>H<sub>3</sub></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl">╲</td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl"> </td> - <td class="tdl"> </td> - <td class="tdl">OH</td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td colspan="3" class="tdl"> C<sub>6</sub>H<sub>4</sub>SO<sub>2</sub></td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl"><b>│</b></td> - <td class="tdl">  ╱</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - </tr><tr> - <td class="tdl"> </td> - <td class="tdl">⎩</td> - <td class="tdl"> O</td> - <td class="tdl"> </td> - <td class="tdl"> </td> - </tr> - </tbody> -</table></td></tr> -</tbody> -</table> - -<hr class="full" /> -<div class="footnote"> -<a name="Footnote_1_1" id="Footnote_1_1"></a><a href="#FNanchor_1_1"> -<span class="label">[1]</span></a> -<table class="smtab" border="0" cellspacing="0" summary="_" cellpadding="0"> - <tbody><tr> - <td class="tdl">Annalin.</td> - <td class="tdl"> No.</td> - <td class="tdl"> 183.</td> - <td class="tdl"> S. 1. No. 202. S. 36 & S. 153.</td> - </tr><tr> - <td class="tdl">Berichte.</td> - <td class="tdl"> No.</td> - <td class="tdl"> IV.</td> - <td class="tdl"> S. 457. 555. 658. 662.</td> - </tr><tr> - <td class="tdc">”</td> - <td class="tdc">”</td> - <td class="tdl"> VIII.</td> - <td class="tdl"> S. 66. 146.</td> - </tr> - </tbody> -</table></div> - -<div class="transnote bbox space-above2"> -<p class="f120 space-above1">Transcriber's Notes:</p> -<hr class="r5" /> -<p class="indent">Illustration has been moved so it does not break up the paragraph.</p> -<p class="indent"> As this was a hand-written thesis, the spelling, punctuation and -hyphenation is very inconsistent.</p> -<p class="indent"> The original spelling, hyphenation and punctuation have been left unchanged.</p> -</div> - - - - - - - - -<pre> - - - - - -End of the Project Gutenberg EBook of On Sulphonfluoresceïn and some of it - Derivatives, by C. 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