EXCHANGE 8061 '12 NVP 'IVd 'A '& ' sojg j ami m Derivatives of Anthraquinone* J-Alkyl- Thio-Ether-S-Sulfpnic Acids and ^5-Dialkyl-Dithio-Ethers JUI24 A DISSERTATION SUBMITTED TO THE BOARD OF UNIVERSITY STUDIES OF THE JOHNS HOPKINS UNIVERSITY IN CONFORMITY WITH THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY BY COLIN MACKENZIE MACKALL June, 1920 EASTON, PA.: ESCHBNBACH PRINTING Co. 1922 Derivatives of Anthraquinone* J-Alkyl- Thio-Ether-5-Sulfonic Acids and J-5-Dialkyl-Dithio-Ethers A DISSERTATION SUBMITTED TO THE BOARD OF UNIVERSITY STUDIES OF THE JOHNS HOPKINS UNIVERSITY IN CONFORMITY WITH THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY BY COLIN MACKENZIE MACKALL June, 1920 EASTON, PA.: ESCHENBACH PRINTING Co. 1922 TABLE OP CONTENTS Acknowledgment 4 Introduction 5 Historical 5 Outline of Present Investigation 6 Materials 6 Analytical 7 The Compounds Obtained 7 I. Anthraquinone-l-alkyl-thio-ether-5-sulfonic acids 8 II. Anthraquinone-l-5-dialkyl-dithio-ethers 10 III. Anthraquinone-l-5-dialkyl-disulfones 12 Biography 13 ACKNOWLEDGMENT The author wishes to record his sense of grateful appreciation of the encouragement, kindly advice and helpful criticism of Professor E. Emmet Reid under whose direction this investigation was conducted. He also wishes to express his thanks for instruction received from Doctors Remsen, Frazer, Lovelace, Patrick, Lloyd and Swartz during his course at this University. He desires to thank Doctors Thornton and Milligan for advice and assistance. DERIVATIVES OF ANTHRAQUINONE. 1-ALKYL-THIO-ETHER- 5-SULFONIC ACIDS AND 1-5-DIALKYL-DITHIO -ETHERS. 1 Introduction. The original object in taking up the study of anthraquinone sulfonic acids was to obtain derivatives which could be used for their ready separa- tion and identification. This object was only partially attained but the reaction tried proved interesting and the products obtained appeared worthy of study, so the investigation was shifted from its original purpose and extended in other directions. On account of the instability of the esters of sulfonic acids the methods used for the identification of carboxy acids 2 were not promising and our efforts were directed to the replacement of the sulfonic groups. It was known that the sulfonic acid group of a-anthraquinone sulfonic acids can be replaced by methoxy 3 or phenoxy 4 groups, and that the result- ing compounds Ci4H7O2.OCH 3 and Ci4H 7 O2.OC6H 5 are crystalline and have definite, though rather high melting points. Hence it was thought that a compound of the type Ci 4 H7O 2 .SR would be of service. AT-butyl mercap- tan was used as being readily available, and it was thought probable that the compound Ci4H 7 O 2 .SC4H9 would have a low melting point, since sulfur compounds usually melt lower than the corresponding oxygen compounds, and since butyl derivatives are apt to melt considerably lower than methyl, and much lower than phenyl. The desired reaction was found to take place readily, although not quantitatively, when the sulfonic acid group is in the a-position. The resulting compounds were found to have convenient melting points suitable for the identification of anthra- quinone- a-sulfonic acid, and anthraquinone- 1,5- and -1,8-disulfonic acids. Our study has been extended to the derivatives of other mercaptans. Historical. Anthraquinone aliphatic thio-ether sulfonic acids and dithio-ethers may be prepared by the action of aliphatic mercaptans on anthraquinone sulfonic acids in alkaline solution. 6 In this way Bayer and Company pre- 1 Revised September 1922. 2 /. Am. Chem. Soc., 39, 124, 304, 701, 1727 (1917); 41, 75 (1919); 42, 1043 (1920); and 43, 629 (1921). 8 Bayer and Co., Ger. pat. 156,762. 4 Bayer and Co., Ger. pat. 158,531. s Bayer and Co., Ger. pat. 224,589. 6 pared anthraquinone-l-ethyl-thio-ether-5-sodium sulfonate and 1,5-di- ethyl-thio-ether. Gattermann 6 has shown that the nitro group is replaceable by the alkoxy group when treated with sodium alcoholate, thus, A.NO 2 + NaOC 2 H 6 > A.OC 2 H 6 + NaNO 2 representing the anthraquinone residue by A. He attempted to carry out the analogous reaction with aliphatic mercaptans in order to obtain anthraquinone thio-ethers, but was hindered by the reduction of the nitro group to the amino group. On the other hand, he found that treatment with alkali aromatic mercaptides readily caused a quantitative replace- ment of the nitro group with the formation of aromatic thio-ethers. A.NO 2 + NaSC 6 H 6 * A.SC 6 H 6 + NaNO 3 Gattermann 7 has also prepared anthraquinone aliphatic thio-ethers and thio-ether sulfonic acids indirectly by diazotizing amino-anthra- quinones, or amino-anthraquinone sulfonic acids in cone, sulfuric acid. Subsequent treatment of the diazo compound with potassium thiocyanate yielded anthraquinone thiocyanate which on boiling with alcoholic potash gave the mercaptan, which with alkyl halide yielded the thio-ether or thio-ether sulfonic acid. In this way he prepared anthraquinone- a: - methyl-thio-ether ; anthraquinone- a-ethyl-thio-ether ; anthraquinone- 1 - methyl- thio-ether-5-potassium sulfonate; and anthraquinone-1-methyl- thio-ether-8-potassium sulfonate, thus, A.NO 2 > A.NH 2 > A.N 2 C1 > A.SCN > A.SH A.SNa + BrCH, > A.SCH, + KBr Outline of Present Investigation. We have found that anthraquinone-l-5-disulfonic acid, on heating with alkyl mercaptans in alkaline solution, reacts readily to form anthraqui- none- 1-5-thio-ether-sulfonic acids and 1-5-dialkyl-dithio-ethers, the sul- fonic groups being replaced in turn. Materials The anthraquinone- 1-5-disodium sulfonate was obtained through the courtesy of E. I. du Pont de Nemours and Company. The methyl mer- captan was generated as required by dropping dimethyl sulfate into warm sodium hydrosulfide, which was prepared by warming crystallized sodium sulfide, Na 2 S.9H 2 O, to about 90 and saturating with hydrogen sulfide. The ethyl mercaptan was prepared in a similar manner using sodium ethyl sulfate. The propyl, butyl and iso-amyl mercaptans were prepared by the catalytic method of Kramer and Reid. 8 6 Bayer and Co., Ger. pat. 75,054. 7 Ann., 393, 113 (1912). 8 Kramer and Reid, J. Am. Chem. Soc., 43, 880 (1921). Analytical. 1. Water of Hydration. One-g. samples were exposed to an atmos- phere of 50% humidity 9 for 48 hours, then heated to constant weight in a vacuum at 110, 2 to 4 hours being generally sufficient to remove all the water. Analyses for sulfur and metals were made on the dry samples. 2. Sulfur. Sulfur was determined by means of the Parr bomb, 10 using a 0.2 g. sample and 5 g. of sodium peroxide, with subsequent pre- cipitation of barium sulfate. 3. Sodium, Barium, Strontium, Calcium. One-half g. samples were ignited in a platinum crucible until the carbon was burned off as com- pletely as possible. The residue was then evaporated with cone, sulfuric acid, and re-ignited with ammonium carbonate to constant weight. The metal was weighed as the sulfate. The Compounds Obtained. The anthraquinone-thio-ether sodium sulfonates are moderately soluble in water, the derivatives of the lower mercaptans being more soluble than those of the higher mercaptans. They crystallize from water in orange or orange-red needles containing one molecule of water of hydration. Salts of other bases are highly colored, ranging from yellow through through shades of orange to red and are mostly well crystallized. The anthraquinone dithio-ethers are insoluble in water, slightly soluble in alcohol and soluble in benzene, the solubility in benzene increasing with the size of the alkyl group. When crystallized from benzene they form lustrous crystals varying in color from light yellow to red. The corresponding sulfones are high melting, slightly yellow crystalline powders. 9 A dead air humidor containing 44% H 2 SO4 was used to obtain this humidity. 10 Parr, J. Ind. Eng. Ghent., 11, 230 (1919). I. Anthraquinone-l-alkyl-thio-ether-5-sulfonic Acid. O SR NaO 3 S O 1. Methyl or ethyl mercaptans were passed through a wide tube at the rate of one bubble per second into an alkaline suspension of anthraquinone-l-5-disodium sul- fonate. The mixture was gently boiled and vigorously stirred until the separation of yellow or orange crystals of anthraquinone-thio-ether-sodium sulfonate indicated that the reaction was complete. The reaction must be interrupted at the proper moment to prevent the formation of large amounts of the dithio-ether by the replacement of the second sulfonic acid group by the thio-alkyl group. The product was cooled, fil- tered, washed with a little water, dried and extracted with benzene to remove the dithio-ether which was always formed in small amounts. The crude anthraquinone- thio-ether-sodium sulfonates were recrystallized from water. 2. Anthraquinone-propyl-, butyl-, and iso-amyl-thio-ether-sulfonic acids were prepared by refluxing an alkaline suspension of anthraquinone-l-5-disodium sulfonate with slightly more than the calculated amount of mercaptan. The products were puri- fied as under I, 1 above. PREPARATION OP ANTHRAQUINONE-I-ALKYL-THIO-ETHER-S-SODIUM SULFONATES. l,5-RS.Ci 4 H 6 2 .SO 3 Na.H 2 O. Sulfonate. Water. NaOH. Alkyl. G. Cc. G. RSH. Methyl 50 400 13 gas Ethyl 100 600 26 gas Propyl 50 1000 10 12 Butyl 50 500 16 15 iso-Amyl 100 1000 32 34 Time. Hrs. Yield. G. %. 2 30 65 1 38 42 1 23 50 7 30 62 15 55 55 ANALYSES AND PROPERTIES OF SODIUM SALTS. l,5-RS.Ci4H 6 O 2 .SO 3 Na.H2O. Water. Calc. Found. Sodium. Calc. Found. Alkyl. % %. % %. Methyl 4.81 4.86 6.46 6.27 Ethyl 4.64 4.93 6.21 6.04 Propyl 4.48 4.42 5.98 5.92 Butyl 4.33 4.41 5.77 5.77 iso-Amyl 4.19 4.26 5.58 5.43 Color and form. orange-red needles dark orange-red needles rich orange-red needles orange-red needles orange-red needles Barium, Calcium and Strontium Salts. These were made by dissolving the sodium salts in hot water and adding the calculated amounts of the chlorides of the other metals. The resulting salts are extremely insoluble and are purified by boiling out with water. BARIUM SALTS. l,5-(RS.Ci 4 H 6 O 2 SO3)2Ba. Alkyl. Methyl Ethyl Propyl Butyl iso-Amyl Calc. %. 17.09 16.51 15.97 15.47 14.99 Barium. Found. %. 17.00 16.50 15.58 15.43 14.56 Color and form. red needles red crystal powder orange-red needles red crystals red crystals The strontium and calcium salts also were made of the butyl acid, the strontium salt being anhydrous, (Sr, calc. 10.45; found, 10.40). The calcium salt, unlike the others contains 4 molecules of water of crystallization, showing by analysis 8.12% of water and 5.09% of calcium compared to 8.35 and 5.07% respectively, by formula. The barium salt is a deep red and the calcium salt an orange-red, while the strontium salt is intermediate. Aniline, o- and p-Toluidine Salts. These salts were made by adding the corre- sponding hydrochlorides to the hot, saturated solutions of the sodium salts. All of them are very insoluble and precipitate. They were purified 'by extraction with hot water. They all separate as fine yellow needles which melt with decomposition at from 250 to 300. These temperatures are not sharp enough for characterization as had been hoped. The 0-toluidine salts decompose at lower temperatures than the aniline or p-toluidine. ANIUNE, 0-Toi,uiDiNE AND Alkyl. Methyl Ethyl Propyl Butyl iso-Amyl Base. SALTS. Decomp. temp. Calc. Sulfur. Aniline 290-299 o-Toluidine 285-290 -Toluidine 298-304 Aniline 276-285 0-Toluidine 264-274 -Toluidine 276-285 Aniline 270-277 o-Toluidine 255-257 ^-Toluidine 268-275 Aniline 257-259 o-Toluidine 234-237 -Toluidine 256-260 Aniline 263-265 0-Toluidine 250-254 p-Toluidine 267-277 15.00 14.53 14.53 14.53 14.08 14.08 14.08 13.66 13.66 13.66 13.26 13.26 13.26 12.89 12.89 Pound. %. 14.70 14.75 14.50 14.30 14.10 14.25 14.15 13.75 13.85 13.80 13.35 13.10 13.10 12.80 12.90 10 II. 1,5-Anthraquinone Dialkyl Dithio-ethers, O SR O SR and RS O R'S O When the two alkyl groups are the same, these may be obtained directly by heatinj the sodium 1,5-disulfonate with excess of alkali and mercaptan for a long time. The> are always formed to a greater or less extent in the preparation of the intermediate thio-ether sulfonates described above and are obtained by extraction of the crude products with benzene. The diethyl and dibutyl compounds were obtained in this way The intermediate monosulfonate may be isolated and purified and the second alky group, which may be the same as the first or different, introduced. Of course the mixec thio-ethers must be prepared in this way. The alkyl thio-ether sodium sulfonate is suspended in water, containing an exces; of caustic soda with the mercaptan, and the mixture boiled. The reaction is slow or account of the low solubility of the sodium salts, particularly of those containing th< higher alkyl groups. It is best to introduce the lower alkyl group first. The resulting di thio-ethers are extracted with hot benzene and recrystallized from benzene, or alcohol or mixtures of the two. The details of the various preparations are given in tabulai form. PREPARATION OF I.S-ANTHRAQUINONB DIALKYI, DITHIO-BTHBRS. First alkyl. Methyl Ethyl Propyl tso-Amyl Alkyl introduced. Wt. Vol. sulfonate. water. G. Cc. Caustic Wt. soda. RSH. G. G. Time. Hours. Yield. G. Methyl 5 500 2 gas 4 4 Ethyl 10 500 4 gas 4 1 Propyl 8 500 2 6 23 5 Butyl 8 500 2 4.6 22 5 iso-Amyl 8 500 2 4.4 6 6 Propyl 5 350 2 5 30 4 Butyl 5 350 2 5 30 4 iso-Amyl 5 300 2 5 12 4.5 Propyl 10 750 2 6 20 7 Butyl 8 750 2 6 7 3 Butyl 10 1000 2 5 41 6.5 iso-Amyl 10 300 2 5 11 2.5 11 PROPERTIES AND ANALYSES OP 1,5-ANTHRAQuiNONE DIALKYI, DITHIO-BTHERS. Ci 4 H 6 O 2 (SR)2 AND l,5-RS.CuH 6 O 2 .SR'. Alkyls. Sulfur. Methyl Ethyl Propyl Butyl iso-Amyl M. p. OU11I Calc. -ii . Found. d % %. Methyl Chars. 21.35 21.03 Ethyl 229 20.40 20.35 Propyl 209 19.53 19.45 Butyl 173.5 18.73 18.50 iso-Amyl 175 17.99 17.90 Ethyl 226.5 19.53 19.40 Propyl 188.5 18.73 18.65 Butyl 156 17.99 17.75 iso-Amyl 152 17.31 17.25 Propyl 227 17.99 18.30 Butyl 175 17.31 16.95 Butyl 159.5 16.68 16.65 iso-Amyl 134 16.09 15.80 iso-Amyl 158.5 15.55 15.59 Color and form. red needles yellow needles orange needles yellow needles orange-yel. leaflets orange grains orange grains red crystals gold-yellow plates orange cryst. powder orange prisms yellow needles orange needles yellow needles Comparing these, we see that the dimethyl compound has the highest melting point and that the melting point is progressively lowered as heavier alkyl groups are substituted for one of the methyls. Gattermann gives the diethyl thio-ether as melting at 230. 12 III. 1 ,5-Anthraquinone Dialkyl Disulf ones. O SO 2 R SO 2 R and O R'OaS These were prepared by oxidizing the dithio-ethers with fuming nitric acid. They separate as faintly yellow crystalline powders, when their nitric acid solutions are poured into hot water. They are very slightly soluble in most solvents. PROPERTIES AND ANALYSES OP I^-ANTHRAQUINONE DIALKYL DISULFONES, l,5-C u H 6 Oj- (SO 2 R) 2 AND l,5-R'SO 2 .Ci 4 H 6 O 2 .SO 2 R. Alkyls. M.p. Sulfur. Calc. Found. Form. Methyl Methyl chars. 17.60 17.53 powder Ethyl >300 16.95 16.90 fine needles Propyl 291 16.34 16.50 crystalline grains Butyl 264 15.78 15.75 crystalline grains iso-Amyl 266 15.25 15.00 crystalline grains Ethyl Ethyl 269.5 16.34 16.40 fine needles Propyl 243.5 15.78 15.65 fine needles Butyl 194 15.25 15.45 powder iso-Amyl 198 14.76 14.80 powder Propyl Propyl 265 15.25 15.15 fine needles Butyl 220 14.76 14.95 crystalline grains Butyl Butyl 184.5 14.30 14.10 crystalline powder iso-Amyl 203.5 13.87 14.00 crystalline powder iso-Amyl iso-Amyl 202 13.46 13.50 powder BIOGRAPHY Colin Mackenzie Mackall was born at Baltimore, Maryland on Decem- ber 26, 1884. He received his primary education in the public schools of that city, and graduated from the Baltimore City College in 1904. He then entered the University of Virginia, from which Institution he received the degrees of Bachelor of Arts in 1909 and Bachelor of Science in Chem- istry in 1910. The following year he was Assistant Chemist in the Bureau of Chemistry, U. S. Department of Agriculture, and in attendance upon courses at George Washington University. Upon the completion of a thesis in absentia, this University conferred the degree of Master of Science upon him in 1913. From 1911 to 1916 he was Professor of Chemistry in the University of the South, Sewanee, Tennessee. Resignining his position in order to continue his studies, he entered the Johns Hopkins University in the Fall of 1916 taking Chemistry, Physical Chemistry and Mineralogy. He entered the Officers' Training Camp in the Summer of 1917, and was commissioned Captain, Coast Artillery Corps, and went overseas. He was transferred to the Chemical Warfare Service, and served as Gas Officer of the Second Division, Assistant Gas Officer of the First Corps, and Assistant Chief, and later Chief, of Chemical Warfare Service, Second Army. He was promoted to Major C. W. S. in September 1918. After the armistice he attended the University of Paris for one semester, and re-entered the Johns Hopkins University as a University Fellow in the Fall of 1919. Mackall,C*I Derivatives an thr equine ne 544005 UNIVERSITY OF CAUFORNIA LIBRARY