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Northwestern University Manuscript Library Theses U n p u b l i s h e d t h e s e s s u b m i t t e d for the M a s t e r 's a nd D o c t o r ' s d e c r e e s a n d d e p o s i t e d in the N o r t h w e s t e r n U n i v e r s i t y L i b r a r y a r e o p e n f o r i n s p e c t i o n , but a re to be u s e d o n l y w i t h d ue r e g a r d to the r i g h t s of the a u t h o r s . Bibliographical r e f e r e n c e s m a y be n o t e d , but p a s s a g e s m a y be c o p i e d o n l y w i t h the p e r m i s s i o n of t he a u t h o r s , a n d p r o p e r c r e d i t m u s t be g i v e n in s u b s e q u e n t w r i t t e n or p u b l i s h e d w or k. Extensive c o p y i n g or p u b l i c a t i o n of the t h e s i s in w h o l e or in p a r t r e q u i r e s a l s o t h e c o n s e n t of the D e a n of the G r a d u a t e S c h o o l of N o r t h w e s t e r n U n i v e r s i t y . T h i s t h e s i s by..^h a s b e e n u s e d by the f o l ^ o ^ i n g a t t e s t t h e i r a c c e p t a n c e or the i ts persons, whose signatures above restrictions. A L i b r a r y 'which b o r r o w s p a t r o n s is e x p e c t e d to s e c u r e NAME AND ADDRESS t h i s t h e s i s f o r u s e by the s i g n a t u r e of e ach user . DATE NORTHWESTERN UNIVERSITY STUDIES ON THE SULFONATION OF OLEFINS A DISSERTATION SUBMITTED TO THE GRADUATE SCHOOL IN PARTIAL FULFILLMENT OF THE REQUIREMENTS for the degree DOCTOR OF PHILOSOPHY DEPARTMENT OF CHEMISTRY BY JAMES MARION HOLBERT EVANSTON, ILLINOIS AUGUST, 1940 ProQuest Number: 10101537 All rights reserved INFORMATION TO ALL USERS The qua lity o f this re p ro d u ctio n is d e p e n d e n t upon th e quality o f th e c o p y subm itted. In th e unlikely e v e n t th a t th e author did n o t send a c o m p le te m anuscript a n d th e re are missing pages, these will be no te d . Also, if m aterial had to be rem oved, a n o te will in d ica te th e deletion . uest. ProQuest 10101537 Published by ProQuest LLC (2016). C opyright o f th e Dissertation is held by th e Author. All rights reserved. This work is p ro te c te d against unauthorized co p yin g under Title 17, United States C o d e M icroform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106 - 1346 ACKNOWLEDGMENT The author wishes to express his sincere appreciation for the invaluable aid and encouragement of Dr. C. M. Suter, under whose supervision this work was carried out* TABLE OP CONTENTS page INTRODUCTION......................................... 1 HISTORICAL I* The Dioxane Sulf otrioxide Reagent • • • « • • • II • The Sulfonation of E t h y l e n e .............. • • • III* The Sulfonation of Propylene • IV* The Sulfonation of wAmylenesM • V* The Sulfonation of Cyclohexene. ........ VI* The Sulfonation of Styrene • VII* The Sulfonation of Higher Olefins • • • • • • • 2 4 7 8 8 8 10 DISCUSSION I* The Reaction of Dioxane Sulfotrioxide with Ethylene* • • . • • • • • » • * ............ • 12 II* The Reaction of Dioxane Sulf otrioxide with Propylene................................... 16 III* The Reaction of Dixoane Sulf otrioxide with l-Pentene . . . . .......................... 21 A* Possible Products from 2-Pentene * . • • • 24 IV* The Reaction of Dioxane Sulf otrioxide with Cyclohexene • • • • • • • • « • • • 25 V* The Reaction of Dioxane Sulf otrioxide with Styrene • • * • • • ' • • • • • • • • • • . • • 27 VI* The Reaction of Dioxane Sulfotrioxide with 1-Pentadecene . . . .......................... 30 VII* A Proposed Mechanism 3ov the Sulfonation of Olefins 32 EXPERIMENTAL I* Preparation of Dioxane Sulfotrioxide Reagent. » II* The Sulfonation of Ethylene • • • • • • , • • « III* The Sulfonation of Propylene. • • • • « • • • • IV. The Sulfonation of l-Pentene. . ............. A. The Sulfonation of 2-Pentene • • • • • • • V. The Sulfonation of Cyclohexene....... .......... VI. The Sulfonation of Styrene. VII. The Sulfonation of 1-Pentadecene. . . . . . . . A. The Preparation of 7 -Pentadecene . . . . . 34 34 39 49 52 53 55 60 65 SUMMARY............................... 67 B I B L I O G R A P H Y ..................................... 69 VITA............................................... 70 INTRODUCTION This investigation is a study of the reaction of dioxane sulfotrioxide with straight chain olefins with terminal unsaturation. The dioxane sulfotrioxide reagent was 1 developed in this laboratory by Evans, who found it to be an excellent sulfonating agent, reacting readily with olefins at room temperature to produce water soluble compounds, S,3 Kiefer, in a more detailed investigation, studied the action of this reagent on propylene and 1-nonene. Malkemus, in an investigation of the sulfonation of isobutylene, demonstrated that the reagent reacted b y substitution rather than addition, the products being unsaturated sulfonic acids. This thesis is concerned with the reaction of dioxane sulfotrioxide on ethylene, propylene, cyclohexene and 1 1 -pentene, styrene, -pentadecene, and the identification of the products formed. (1) (2) (3) (4) Evans, Ph.D. Thesis, Northwestern University, 1935* Kiefer, M.S.Thesis, Northwestern University, 1937. Suter, Evans and Kiefer, J.Am.Chem.Soc., 60, 538 (1938). Malkemus, Ph.D. Thesis, Northwestern University, 1939. 2. HISTORICAL I* The Dioxane Sulfotrioxide Reagent: It was found that when sulfur trioxide is added to a chilled solution of dioxane in some diluent such as ethylene dichloride or carbon tetrachloride a white, flakey addition product settles out which may have either of two structures 3 as indicated b y the following equations. 1. 0 ( 0 ^ 0 1 ^ ) 3 0 + S0a 2. 0(CH2CHs)3 0 + 2 S0 3 ---► 0 (OHgCHg )a 0S0 3 » 0aS 0 (CHaCHa )a OS 03 Both dioxane sulfotrioxide and dioxan«lisulfotrioxide are stable under anhydrous conditions at room temperature, hydrolyze instantly to dioxane and sulfuric acid, and exhibit similar sulfating and sulfonating action. The reaction of dioxane sulfotrioxide with alcohols is practically quantitative, resulting in alkyl hydrogen 6 sulfates. Reaction also occurs with a variety of aromatic compounds yielding sulfonic acids# By far the most important characteristic of dioxane sulfotrioxide is its reaction with simple olefins. The product of this reaction may be readily converted into hydroxysulfonates by hydrolysis as Indicated in the following equation. CHa -CH=GHa + 2 OfCHsCHgJOSOg -- > C H s - C H - C H s 1 I ? I 0aS-0-S0s (5) Suter, U.S.Patent 2,098,114. — 3. CH 3 -CHOH-CHsSGaH + E 3 SO 4 This reagent and reaction opened a new field of chemistry for investigation, as a convenient method of preparing pure hydroxysulfonates from olefins has not been available before. This reaction when extended to higher olefins, C 9 to C18, produces compounds of marked activity as detergents and 6 wetting agents# In addition to the hydroxysulfonates, unsaturated nature have also been obtained, compounds of an showing that reaction of the dioxane sulfotrioxide with an olefin may occur either by addition or substitution, depending upon the nature of the olefin and the conditions of the experiment# Malkemus found that the sulfonation of isobutylene at 0°, is not appreciably affected by the concentration of the reagents nor the manner in which they are added. Hydrolysis of the sulfonation mixture with barium hydroxide led to a mixture of three products, CH 3 CHS -C-CH 3 SO 3 Ba, OH CHS CHs=C-CHs -S0a Ba, and CH 3 CH»-C=CH-S0: Ba. These salts 2 could not be separated by fractional crystallization* It was also shown that when the sulfonation mixture, obtained by the interaction of dioxane sulfotrioxide and Isobutylene at 0°C, was heated to 70° a voluminous precipitate formed. This precipitate proved to be 2-methylpropene-l,3- (6) Suter, IT.S.Pat. 2135358 4 disulfonic acid coordinated with one mole of dioxane, ch 3 H 0 3 SCHs -C=GHS0 3 H #G 4 :H q0s . Hydrolysis of this intermediate with barium hydroxide led to the expected barium propene-1,3-disulfonate. 2 -methyl- It is interesting to note that the intermediate dioxane salt when refluxed with thionyl chloride is converted into its corresponding anhydride, CHg-C=CH , I I S0s -0-S0 3 the first example of a cyclic aliphatic sulfonic anhydride. II. The Sulfonation of Ethylene: 7 Regnault, in 1837, was the first to study the action of sulfur trioxide on ethylene. Ke found that when the two anhydrous gases were mixed carbyl sulfate, 1 1 OgS-CHg-CEg-OSOg, 0 crystallized on the walls of the container. This compound when treated with water was converted to a mixture of ethionic acid, H0sS-CEg-CEg0S0 3 H, and isethionic acid, I E0GHsGHsS0 3 H. Huber , 8 in an investigation of isethionic acid, found ! that when sulfur trioxide reacted with anhydrous ethyl ether, i several products were formed. In the two phase system ] resulting from the aqueous hydrolysis of the reaction mixture, Huber found that the major product, remained in the ether layer. ethyl, sulfate, This was identified by con version to a barium salt. (7) Regnault, A h n ., 25, 32 (1837). (8 ) Huber, A n n . , 2 2 3 , 1S8 (1884). Prom the water layer, he isolated additional ethyl sulfate, methionic acid, and a mixture containing 15% ethionic acid and 85% isethionic acid* This latter mixture, he converted completely to barium isethionate by treatment with barium hydroxide. Prom his results, Huber concluded that the initial product of the reaction was ethyl sulfate, and that the additional products arose from the further reaction of sulfur trioxide with this substance* To support his theory, he prepared a quantity of ethyl sulfate and found that on treatment with sulfur trioxide it was converted to a mixture of methionic acid and isethionic acid* This led him to propose the following steps for the reaction 1 * CgHgOCgHg + SQg ——+ SOg (OCgHg)g 2. SOg (OCsH s )s + 3 S0 3 » CHoSOgH l,H os ls CHS 0S03H 3. qjj gQ H -- * + 2 S°s 3x + OgS-CEg-CEg- I 0----- CHS CSOsH)3 + 2 S 0 s + C 0 S + Hs 0 9 Plant and Sidgwick showed that carbyl sulfate and ethyl hydrogen sulfate were formed when ethylene is absorbed in fuming sulfuric acid* As a result of his work on the action of nitric acid io on olefins Wieland concluded that fuming sulfuric acid added to ethylene as HO- and SOGH, thereby forming isethionic acid directly. This theory is not only in contradiction to (9) Plant and Sidgwick, J.Soc.Chem.Ind., 40, 14 (1921). 10) Wieland and Sakellarios, B e r . , 5 5 , 205 (1920)* 6 the work of Plant and Sidgwick, but also has been shown 1 1 to be incorrect by Michael and Weiner. These investi gators pointed out that carby^sulfate is due to the action of sulfur trioxide, acting in the bitnolecular form, on ethylene while ethionic acid results from the reaction of pyrosulfuric acid with the olefin. It was also found that isethionic acid was converted into carbyl sulfate by the action of two moles of S0 3 [Ss OsJ , while with only one mole of sulfuric acid or S03 , ethionic acid was formed* is Kohler prepared 1, 2 -ethane^disulfonic acid by the reaction of sodium sulfite with 1,2-dibromoethane. Hydrolysis of sodium- 2 -bromoethane- 1 -sulfonate produced sodium isethionate in a 9h% yield. sulfonic acid, 13 In a later investigation of unsaturated Kohler prepared ethylenesulfonic acid by three methods; namely, 1 . hydrolysis of ethanedlsulfonyl chloride 2 . distillation of l-broxno -2 -ethane sulf onyl chloride 3. from isethionic acid The last method is of interest in that all attempts to dehydrate isethionic acid led to the formation of di-isethionic acid, H 0 3 SCHsCHs -0-CEs -CH 2 SG 3 H; however, is first converted to the acetate, it loses acetic acid readily to give the unsaturated acid. (11) (12) (13) if the isethionate Ethylenesulfonic Michael and Weiner, J.Am.Chem.Soc., Kohler, Am.Chem.J., 19., 728 (1897). Kohler, ibidem, 20, 680 (1898). 58, 294 (1936). acid reacts readily with bromine water and neutral permanganate, and may be hydrated to isethionic acid by heating with water in a sealed tube at 150°. 14 Koiker and Lapworth, various double bonds, in a study of the activity of reported that an acid sulfite reacts readily with ethylene to produce ethaneSsulfonic acid as the major product. A more recent investigation by Kharasch, 15 May and Mayo confirmed this result and in addition showed that the presence of some oxidizing agent is essential for the success of the reaction. III. The Sulfonation of Propylene: The reaction of propylene with the dioxane sulfotrioxide s,s reagent was investigated In 1937 by Suter and Kiefer who found that at room temperature the reaction occurred readily according to the following equation: 2 C 4 H s0-3«S0s + CH 3 -CH=CHs -- > CHa -CH-CHs + C 44 H 8 0 j X18^J8 homologue was not isolated but the solution hydrolyzed with barium hydroxide to produce, product, barium-2-hydroxypropane-1-sulfonate. as the final The structure of this compound was proven by its oxidation to barium acetonesulfonate and subsequent hydrolysis to acetic acid. (14) Kolker and Lapworth, J.Chem.Soc., 127. 313 (1925). (15) Kharasch, May and Mayo, J.Org.Chem., 3, 175 (1938). 8. 15 Kharasch found that propylene reacts with ammonium bisulfite only in the presence of oxidizing agents to produce propane-l-sulfonic acid* The best yield was obtained in the presence of nitrates* IV* The Sulfonation of Amylenes; 1 Evans demonstrated that wamylenen reacts readily with dioxane sulfotrioxide forming a reddish oil readily / soluble in water to produce an acidic solution. That crude amylene reacts readily with ammonium hydrogen sulfite was 14 shown b y Koiker and Lapworth, who found that this olefin, unlike many others, was converted completely to saturated sulfonic acids. Since the olefin was a mixture of isomers, the structure of the product was not further investigated. V. The Sulfonation of Cyclohexene: Cyclohexene is sulfonated readily, although not rapidly, by the action of M/4 ammonium bisulfite solution In the presence of kieselguhr as an emulsifying agent. The product Is composed of approximately 90% of ammonium cyclo id hexanesulfonate and 10% of an organic compound which yields sulfurous acid or sulfites on hydrolysis. j The major product |was Identified by its conversion to the corresponding sulfonanilide. i VI. The Sulfonation of Styrene: 1 6 j Quilico and Pleischner first prepared 1 -phenyli iethylene-2 -sulfonic acid by the action of sulfamic acid, I} (16) Quilico and F l e i s d m e r , Atti.accad.Lincei, 6 , 7 1 0 5 0 (1929); G.A., 23, 1628 9« KHe SOaH, on styrene* Their assignment of structure was made on the basis of the fact that the compound was oxidized to benzoic acid by permanganate and that fusion with sodium formate resulted in cinnamic acid* Derivatives prepared were the sulfonyl chloride melting at 85° and the sulfonamide melting at 140°* 17 In 1929 it was reported by Ashworth and Burkhardt that the sulfonation of styrene with ammonium hydrogen sulfite resulted in 1-phenylethane-l-sulfonate. assigned since the reaction of This structure was ^-bromoethylbenzene with ammonium sulfite resulted in an identical product, both being converted to the same sulfonamide* The reaction product from ^ - b r o moethy l b e n z e n e and ammonium sulfite produced a sulfonamide differing from the above* These results are not in accord with those reported by 15 Kharasch and co-workers, who found that the action of bisulfite on styrene produced a compound identical with |Quilicofs l-phenylethylene-2-sulfonic acid* |discrepancy was explained by the fact that This seeming «x-bromoethyl- benzene, under the conditions imposed b y Ashworth and Burkhardt, is dissociated into styrene and hydrogen bromide. The halogen acid is then absorbed in the aqueous layer with the evolution of sulfur dioxide* Thus, under such conditions, the reactive agents were styrene and bisulfite, the same reagents that were used in the production of the compound (17) Ashworth and Burkhardt, J.Chem.Soc., 1791 (1928) 10. in question. J The reaction of c*-bromoe thy lb enzene with bi- sulfite was later carried out in a strongly ammoniacal solution to prevent the formation of styrene. The resulting compound could not be converted to the sulfonyl chloride, all attempts leading to the formation of secondary phenylethyl chloride. A mechanism for the sulfonation of styrene has | been proposed by Kharasch, but this will be presented in a J later section of this thesis. | VII. | | The Sulfonation of Higher Olefins: The reaction of the dioxane sulfotrioxide reagent with higher molecular weight olefins, 9 to 18 carbon atoms, j occurs readily at 20-25° without more than slight darkening, jI The 10 sodium hydroxysulfonates, prepared by the hydrolysis of j | the sulfonating mixture with sodium hydroxide or sodium 1 i carbonate, show, in many cases, decided soaplike properties. | The straight chain products seem to exhibit this property to j \ a greater degree than do the branched chain olefins, or I | olefins of the type R-CH=CH-R. The fact that these hydroxy!i j sulfonates possess detergent properties will make this method j I of sulfonation extremely interesting commercially should a ! ! convenient source of these higher olefins be found. | ! A brief resume of compounds investigated Is given below: Sulfonation of 1-Nonene. - 1-Uonene, prepared by the !j action of n-hexylmagnesium bromide on allyl bromide, was (18) Suter, Unpublished Review, northwestern University, 1937. 11 sulfonated at room temperature by adding the olefin to the dioxane sulfotrioxide reagent in ethylene dichloride• Refluxing the mixture with aqueous barium hydroxide resulted in the formation of the insoluble barium- 2 -hydroxynonane sulfonate* 1 - This salt was converted to the corresponding sodium salt in a practically quantitative yield by treatment with sodium sulfate# The sodium sulfate-sulfonate was pr e pared by exactly neutralizing the sulfonation mixture with sodium hydroxide and removing the solvents at room temp erature under reduced pressure. Sulfonation of Tridecene. - 1-Tridecene, prepared from n-decylmagnesium bromide and allyl bromide, was sulfonated as described and the product converted to a sodium salt by hydrolysis with sodium hydroxide. A sample of this salt re- crystallized from water analyzed correctly for sodium- 2 hydroxytridecane-1 -sulfonate. Sulfonation of Cetene. - Getene (du Pont product) was sulfonated by the same method as described above and c on verted to a sodium salt by hydrolysis with sodium hydroxide. A water solution of this salt is soap-like in behavior, foaming when heated to boiling. Sulfonation of 1-Pentadecene and 1-Heptadecene. - These olefins, prepared by the Grignard reaction, were sulfonated in the usual manner at room temperature. were prepared by alkaline hydrolysis, amorphous rather than crystalline. cussion of 1 The sodium salts the product being A more detailed di s -pentadecene is given later in this thesis. 12. DISCUSSION Reaction of Dioxane Sulfotrioxide with E t h y l e n e : It was found that no reaction occurred when ethylene was passed into the dioxane sulfotrioxide reagent at room temperature, 2 2 ° , although all other olefins investigated reacted readily even at lower temperatures. This, however, is not surprising when one recalls that the absorption of ethylene by sulfuric acid is much slower than that of higher olefins. For example, in the separation of gaseous olefins, 63-64 % sulfuric acid is used for the absorption of Iso 83-84 % sulfuric acid for the absorption of butylene, ie propylene, and 1 0 0 -1 0 2 % acid for the absorption of ethylene. 2 0 Mutuszak reports that the 63-64% acid absorbs Isobutylene 500 times as fast as propylene, and propylene, in turn, absorbed 500 times as fast as ethylene In 83-84% acid. Is With this In mind, the temperature of the sulfonating solution was raised to 50° and ethylene again passed In. Reaction occurred readily producing a light straw colored solution. It was later demonstrated that the reaction occurred slowly at 35-40°. Since the reaction of ethylene with sulfur trioxide is 7 11 known to produce carbyl sulfate, , the reaction mixture was examined closely for any indication of its formation; however, the formation of a new solid was not observed, nor (19) Dobryanskii, Neftyanoe Khozyalstvo, 9, 565 (1925); C.A., 20, 1576 (1926). (20) Mutuszak, Ind.Eng.Chem.,Anal.Ed., 10, 354 (1938). could carbyl sulfate, products. as such, be Isolated from the reaction The products isolated were methionic acid, as Its slightly soluble barium salt, and an unsaturated salt of uncertain structure* The formation of methionic acid from the sulfonation of ethylene was surprising but not without parallel, for 8 Huber has shown that one of the products obtained by the action of sulfur trioxide on ethyl ether is methionic acid, GII3 (S03 E)s * Huber concluded that methionic acid was formed by the action of sulfur trioxide on ethionic acid and suggested the following equation to represent the reaction. CE s 0S03H I CHa SOsH That this, + 2 S0a > CES (S03 H)s + 2 S0 2 + C0S + Hs 0 or some very similar method of formation, is quite plausible Is indicated by the fact that the sulfonation carried out at 50° produced appreciable quantities of methionic acid while at 35-40° little or no methionic acid was detected. This also eliminates the suggested possibility that the methionic acid might have arisen by the reaction of sulfuric acid and acetylene, ethylene, a possible Impurity in the since similar results should have been obtained at both temperatures• Strength is also given to this argument by the fact that sulfur trioxide often leads to the oxidation ai of hydrocarbons, itself being reduced to sulfur dioxide. The methionic acid was isolated as Its sparingly (21) Brooks, The Hon-Benzenoid Hydrocarbons, 1922, p. 143. 14. soluble barium, salt which crystallizes from aqueous solution with two moles of water. An anhydrous sample of this salt analyzed correctly for barium. These results, other checking physical properties, combined with leave little doubt as to its correct identification. The major product obtained from the sulfonation of ethylene with dioxane sulfotrioxide has so far not been properly identified. Analysis of the dry salt showed it contained approximately 32$ barium. expected ethane derivatives, barium content, A list of the normally together with their corresponding is given below. % barium C omp ound 1 . (CH3 OECHeS03 )sB a ........... . 2 . fOaSCH*CHa OSOg ) B a ......... . 3. (CHS =CHS03 )sB a ............. . 4. OfGH 3 CH 2 SOs )sB a ........... . That it is plausible to expect these compounds is shown by the fact that the sulfonation of propylene by this process resulted in homologues of 1 and 2. It will presently be shown in this thesis that compounds of type 3 are also is produced by this same process* Kohler reports that diisethionates, 4, are produced when isethionates, 1, are dehydrated, by heat. The formation of large amounts of barium sulfate, when the sulfonation mixture was hydrolyzed with barium hydroxide, is evidence that some type of sulfate ester linkage must have been formed in the sulfonation process. Reasoning would then lead one to suspect that carbyl sulfate was first formed by the action of sulfur trioxide on ethylene, and that it, in turn, was hydrolyzed to barium isethionate and barium sulfate. Barium analysis, however, not the case. indicated that this was It is possible that the barium sulfate might have arisen by the hydrolysis of excess dioxane sulfotrioxide, but the copious quantity of barium sulfate obtained, coupled with the fact that all solid dioxane sulfotrioxide had disappeared when only two-thirds of the theoretical amount of ethylene had b e e n passed In, makes this possibility extremely doubtful. The fact that the product reacted rapidly with neutral permanganate and bromine water points strongly to ethylene1S sulfonic acid, 3, as the probable answer, but here also the barium analysis was far too low. Since the barium salt was very difficult to work with, being extremely hygroscopic, it was converted to the sodium salt, but this was of little value since the sodium salt was also hygroscopic. A portion of the sodium salt was recrystallized from alcohol and gave on analysis a value corresponding closely to that of sodium ethylenesulfonate; however, since no other proof could be brought to bear, the Identification is considered incomplete. Since the barium analysis was consistently low, the possibility of a polymerized sulfonated product immediately presents itself. Isobutylene when sulfonated by the dioxane sulfotrioxide reagent has been shown to produce not only sulfonated dimers but also some sulfonated dodecene 16. ££ derivatives# However it must be remembered that while isobutylene is easily polymerized, ethylene is polymerized only with great difficulty b y the action of acids# Fr o m the results, it seems that the principle product obtained by the sulfonation of ethylene with dioxane sulfotrioxide is either a complex mixtuhe of some or all of the suggested compounds together with a rather high molecular weight polymer, or that another compound, unexpected and heretofore unobtained, is formed by the reaction. The Reaction of Dioxane Sulfotrioxide with Propylene# One of the chief disadvantages in the type of work described in this thesis is the lack of rapid identification of the compounds by melting point, been proven by analysis# once their structure has For example, any attempted reaction involving the salts must be followed by a time consuming analysis before it is known whether or not reaction has actually occurred# Consequently, an attempt was made to find a simple solid derivative by which the compounds involved could be rapidly identified# For this investigation barium- 2 -hydroxypropane-l-sulfonate, obtained b y the action of dioxane sulfotrioxide on propylene, was chosen, as its structure had been proven by the work of Kiefer. Contrary to the report of Kiefer, it was found that (22) Malkemus, This Laboratory, Private Communication. (23) Whitmore, Organic Chemistry, 1S37, p. 35# 17. the reaction of propylene with dioxane sulfotrioxide occurred "below room temperature, 12-15°, to produce a solid similar in color and texture to the original dioxane sulfotrioxide* The compound proved too unstable to identify directly, as it liquefied rapidly forming a brown oil even when kept in a vacuum desiccator over phosphorus pentoxide* The structure seeming most likely for this solid is that of the next higher homologue of carbyl sulfate, CHSC H — CHs -SOs * OSO-s agreement with this structure, In 0 It was found that the oil reacted vigorously with barium hydroxide to produce barium sulfate and barium- 2 -hydroxypropane- 1 -sulfonate in approxithe mately the correct ratio required by/following equation 2 CHSC H — lsoB CEg-SOg + 3 Ba(OH)g ► (CH3 CH0KCHs S0 3 )sBa + 2 BaS0 4 CH Hydrolysis of an unweighed sample of the oil with barium hydroxide resulted in the formation of 16*42 g. of barium sulfate* After removal of excess barium hydroxide, evap oration to dryness led to 15*08 g. of barium-2-hydroxypropane-1-sulfonate. According to the above equation 15*08 g* of the hydroxysulfonate should be accompanied by 16.95 g. of barium sulfate if the original product is the pure homologue of carbyl sulfate* However, since the final product obtained ! J 1 gives the -usual tests for slight unsaturation, it must be assumed that the hydroxysulf onate Is contaminated with some sodium propylenesulfonate. If this arose by the dehydration of the hydroxy compound, the barium sulfate would run high when calculated on the basis of the sodlum- 2 -hydroxypropane-lsulfonate obtained. If, on the other hand, the unsaturated product arose from a substitution rather than an addition product of the reaction of propylene and dioxane sulfotrioxide, the amount of barium sulfate would be less than calculated. This latter suggestion is in accord with other results. The persistent odor of ethylene chloride, which remains with the oil even after several months, suggests that the solid may be carbyl sulfate or some similar structure co ordinated with one or more moles of ethylene chloride. On this basis, the gradual loss of ethylene chloride would account for the decomposition of the solid. Normally propylene was sulfonated at room temperature, the temperature rising to about 30° as the reaction progressed. This produced a compound which consistently analyzed high for barium content. The fact that an aqueous solution of the salt rapidly reduced cold, neutral permanganate and decolorized bromine water indicated that some barium propylenesulfonate had been formed either by dehydration of barium- 2 -hydroxy- j propane- 1 -sulfonate or that the dioxane sulfotrioxide had jj reacted by substitution rather than addition. Although in || the normal reaction of dioxane sulf otrioxide with olefins j| it has been assumed that reaction occurs by addition across i! j the double bond, it has been demonstrated by Malkemus and j will be shown later (see styrene) that reaction may proceed i j almost entirely to yield unsaturated products. Analysis of 19 the acetyl derivative also indicated the presence of the unsaturated derivative in the same amounts as calculated from the original analysis. Since it has been shovjn the sodium -2-hydroxy-propane-l2 sulfonate is readily oxidized to barium acetonesulfonate, the question was raised as to whether or not the reaction with cold, neutral permanganate actually indicates unsat uration. This objection was answered by the preparation of a pure sample of sodium- 2 -hydroxypropane- 1 -sulfonate, which was shown to give no reaction with either permanganate or bromine water. The pure sample was also converted to sodium- 2 -acetoxypropane-l-sulfonate and found to analyze correctly for sodium content. Attempts to prepare the benzoyl derivative resulted in failure, apparently due to the insolubility of the salt in benzoyl chloride. As the conversion of sodium 3 -hydroxypropane- 1 -sulfonate' to the sharply melting 3-chloropropane-l-sulfonamide has 15 been successfully carried out, an attempt was made to prepare similar derivatives for the compound in question, j Following the directions given by Kharasch, the product j obtained from the sulfonation of propylene was first converted to the corresponding chlorosulfonyl chloride. Subsequent reaction with ammonia produced an oil from which crystals could not be obtained. Similar results were obtained by reacting the chlorosulfonyl chloride with ! xenylamine and p-toluidine. I ! A possible explanation of the failure to obtain solid I derivatives by the above procedure lies in the fact that the 20 starting material is a mixture of sodium propylenesulfonate and sodiuni'-2-hydroxypropane-l-sulf onate. Since these could not he separated hy fractional crystallization, the obvious procedure was to separate their sulfonyl chlorides by distillation. This procedure resulted in two fractions boiling about 9 degrees apart. Analysis indicated the low fraction to be a propylenesulfonyl chloride and the higher fraction to be 2 -chioropropane-1-sulfonyl chloride. So far no attempt has been made to react these compounds with amines. Considerable doubt as to the value of the above sep aration arose when it was found that 2 -chloropropane-l- sulfonyl chloride, prepared from the pure sample of s o d i u m 2 - hydroxypropane- 1 -sulfonate, also produced two fractions when distilled. These fractions were identical with those obtained in the above distillation. The suggestion that occurrence of sodium propylenesulfonate, from the sulfonation of propylene, explained by the dehydration of sodium 2 could be -hydroxypropane- 1 - sulfonate is not without basis when one recalls the instability of a^?-hydroxy carboxylic acid. A similar situation exists j in the above case, since the hydroxy group is to the |negative sulfonic acid group and should, as a result of its position, be extremely active. While this does not seem to be the case in the sodium salts, as indicated by the i| apparent stability of the pure sample, it is not unlikely ! |that the conditions imposed by the preparation and subsequent distillation of the sulfonyl chloride were severe enough to cause a splitting out of hydrogen chloride thus producing propylenesulfonyl chloride. separation, As a more probable method of it is suggested that the acetyl derivative first be prepared and the mixture then converted to the sulfonyl chloride. Such a procedure v;ould eliminate the formation of propylenesulfonyl chloride by the splitting out of hydrogen chloride from the chiorosulfonyl chloride. Of general interest is the pyrolysis of a pure sample of sodium~2-acetoxypropane-l-sulfonate. This compound on heating was found to completely liquify at 235° and exude an acidic gas. The product recovered after this treatment reduced cold, neutral permanganate rapidly and absorbed copious quantities of bromine water, indicating the presence of sodium propylenesulfonate. action is reported for sodium 2 An analogous r e -acetoxyethane-l-sulfonate, in which acetic acid was lost by heating at 2 0 0 ° to produce 1 2 sodium ethylenesulfonate, III. The Reaction of Dioxane Sulfotrioxide with 1-Pentene. The olefin, 1-pentene, was found to be readily sulfonated by dioxane sulfotrioxide at room temperature, but at ice temperature no reaction was observed* recent investigations, In the light of more it might well be that the last observation is erroneous as It has been shown that new solids, similar In color and texture to dioxane sulfotrioxide, are produced by low temperature sulfonation. The product of this reaction, isolated as its barium salt, was found to reduce neutral permanganate in the cold 22. and to react rapidly with bromine water. A high barium analysis of 31.50 % as compared to a theoretical value of 29.08?& also pointed to the presence of unsaturated material in the expected barium-2 -hydroxypentane-1-sulf onate. This unsaturated material probably originated from a substitution reaction of dioxane sulfotrioxide with bility already discussed. 1 -pentene, a possi It is logical to suppose that substitution occurred on the carbon atom ,,allyl,f to the double bond, as this should be the position of greatest reactivity. On this basis, the structure proposed for the unsaturated material is fCH3 CHs -CHS0 3 CH=CHs )sBa. Since the barium salts of these isomers are not as extremely soluble in water as the lower homologues, a fractional crystallization was undertaken in order to effect a separation. The following diagram represents the course of the crystallizations. filtrate residue a 10 11 12 13 14 Analysis of samples 8 and 14 gave 30.18 and 29.30/£ barium, respectively, indicating that qualitative separation had occurred as expected; i.e., the unsaturated product should the be/less soluble of the two, while the hydroxysulfonate would b© concentrated in the filtrates. While the value of 14 checks within experimental limits the calculated barium content of barium- 2 ~hydroxypentane- 1 -sulfonate, the fact that it still reacts with dilute permanganate points to its contamination with barium pentenesulfonate. Fraction 4, which was very small, gave the surprisingly high analysis of 39.42% barium and in addition reacted with neither permanganate nor bromine water. At first these results were regarded as meaningless, but in view of the i results obtained from the sulfonation of ethylene, it is now believed that this compound was, in all probability, barium methionate. It will be recalled that barium methionate crystallizes from water as a dihydrate which contains | 39.40%' barium. If one accepts the work of Huber, the formation | of methionic acid from the sulfonation of 1 -pentene could | be explained by a similar process; that is, the action of j| sulfur trioxide upon the intermediate anhydride. Since the i ! (! carbon atom which is attached directly to the sulfur is I !j the one broken off in the formation of methionic acid, it | would not be surprising if methionic acid were formed as a | by-product when any simple olefin with terminal unsaturation l i ! | is sulfonated at elevated temperatures. ; l It has been shown that sodium 2 -hydroxypropane-1 i ; j! sulfonate is oxidized by chromic acid to sodium acetoneSj I sulfonate, which in turn is hydrolyzed by concentrated 2 i| alkali to acetic acid and methanesulf onic acid. An ! I attempt to apply the same procedure to barium 2 -hydroxy- 24. pentane- 1 -sulfonate resulted In the formation of a mixture of propionic and acetic acid as indicated "by Duclaux constants* This result does not mean that the proposed structure of the original compound is incorrect; for it was doubted at the outset if the oxidation would stop at the expected butyric acid* 2-Pentene was also sulfonated by means of the dioxane sulf otrioxide reagent, but a preliminary survey of the resulting material indicated such a complex mixture that further work was discontinued. It is of interest, however, to note the number of possible compounds theoretically obtainable from such a reaction. Primarily, the 2-pentene, as prepared by the dehydration of diethylcarbinol, consists of a mixture of cis and trans isomers. The refractive index of the constant boiling fraction used in the sulfonation, indicated the olefin to be composed largely of the trans compound. Sulfonation to give 3-hydroxypentane-2-sulfonic acid would lead to the formation of two asymmetric centers and result in the production of two racemates or four optically active diasterioisomers. Similarly, if the sulfonation resulted in the formation of 2-hydroxypentane-3-sulfonic acid four additional isomers would be formed, of eight isomers giving a possible total (four racemates) if the reaction occurred by addition across the double bond. If, however, reaction occurred by substitution, as is entirely plausible, would be expected that the 2 it -pentene would react either at positions 1 or 4. Substitution at the 4 position would lead to the production of a new asymmetric center and therefore result in a d- and 1- modification. 1 Substitution at the position would result in the formation of only one compound, 2-pentene-l-sulfonic acid* Therefore the trans compound would result in three isomers as would the cis, 1 producing a possible total of six isomers. Thus the maxi- I mum number of products obtainable from such a reaction is fourteen* type of 2 Prom this it is apparent that olefins of the -pentene would lead to exceedingly complex mixtures | which would require special methods for separation. IV. I J The Reaction of Dioxane Sulfotrioxide with Cyclohexene. The chief interest associated with the sulfonation of cyclohexene is that it was the first compound investigated | in which a solid formed during the actual sulfonating process. I The fact that this solid formed when the sulfonation was i | carried out at low temperatures (below 1 0 °) while its | appearance was not noted at room temperature and above, led j | to the discovery of the formation of a similar solid from ! j the sulfonation of propylene. i j This fluffy white solid was immediately suspected of ! being the sulfuric-sulfonic anhydride, postulated as an '5 jj |! intermediate In this sulfonation process but never Isolated. jj ij In order to avoid its immediate decomposition, i! j the solid was removed by filtration at ice temperature under anhydrous 5 conditions. This was of little value for the solid dei j ]j composed rapidly even in a vacupm desiccator over Ps 0 5 to 26. form a deep purple oil. Due to the fact that the odor of I ethylene chloride remained with the solid and resulting oil even after prolonged washing with dry air, and that under reduced pressure the oil bubbled vigorously indicating the presence of some extremely volatile component, the solid was suspected of being in some way coordinated with one or more moles of ethylene chloride. To test this theory, cyclohexene was sulfonated at the same temperature in a solvent of dry carbon tetrachloride. In this case no solid formed but an oil very similar in appearance to that ob tained by the decomposition of the solid separated from solution. Both oils on hydrolysis with barium hydroxide i | produced barium sulfate and barium 2 -hydroxycyclohexane-l- ! sulfonate along with a trace of unsaturated material. The | significance of the production of these products was dis! ) cussed under the sulfonation of propylene* | Hydrolysis of the filtrate from the sulfonation of | cyclohexene produced as the major product barium 2 -hydroxy- | cyclohexane-1-sulfonate. That this material was contaminated i ; with some unsaturated product was indicated by its slightly j high barium content, 28.40/c as compared to a calculated ! value of 27.82^, and the fact that the product reacted I readily with neutral permanganate and decolorized small i quantities of bromine water. It was found that the product ' i tj | could be purified slightly by recrystallization from alcohol. 27 V* The Reaction of Dioxane Sulfotrioxide with Styrene. The reaction of styrene with dioxane sulfotrioxide produced one of the most interesting and unexpected results studied in this investigation. Styrene was slowly added to the dioxane sulfotrioxide reagent in ethylene chloride at 5° with the idea of obtaining a solid similar to that obtained in the sulfonation of propylene and cyclohexene. At first the solution seemed to be clearing of solid, but toward the end of the styrene addition a white solid began to separate. On standing in the ice box for several days, the amount of this solid increased. It should be noted at this point that the formation of a solid during the sulfonation process seems to depend upon several factors, the principle ones being the rate of addition of styrene and the temp erature of the sulfonation mixture. In some cases, where these precautions were not observed, no solid was formed during the addition of the styrene; however, when any of the final solutions were allowed to stand for five to six days at ice temperature, the formation of some solid material was always observed. This solid, naturally being assumed to be similar to that obtained from propylene and cyclohexene, was removed under anhydrous conditions. On standing it showed very little tendency to liquify as did the previous examples. It was found that most of this material was insoluble in water and when put into solution by prolonged boiling, produced no barium sulfate when hydrolyzed with barium hydroxide. 28 This indicated that here was a new type of intermediate, differing radically from those previously obtained. The solid reacted readily with permanganate but showed very little tendency to decolorize bromine water. Hydrolysis of the compound with barium hydroxide led to the formation of barium 2-phenylethylene-l-sulfonate. A portion of the solid, recrystallized from a mixture of acetone and high boiling petroleum ether, melted with decomposition at 134136 °. This indicated that the compound was not 2 -phenyl^ 16 ethylene- 1 -sulf onic acid which is known to melt around 70°. A sulfur analysis of 17*49$, together with a molecular weight determination of 176-177, limited the composition of the compound to one mole of styrene combined with one mole of sulfur trioxide. That the compound was not some type of benzothiophene derivative was shown by its oxidation to benzoic acid and the sulfate ion. As the above mentioned method of recrystallization led to the recovery of only small amounts of purified product, an attempt was made to recrystallize the product from methyl alcohol. enough, the recovered compound melted at 66-67°. Surprisingly Prom ethyl alcohol a compound melting at 46-48° was obtained. This immediately suggested that reaction of the compound with alcohols led to the formation of esters. Since the compound has been shorn not to be 2-phenylethylene- 1 -sulfonic acid, a possible though heretofore unreported structure was suggested, that of the suit one of 2 -hydroxy-2-phenylethane-1-sulfonic acid, G 6 H 5 GH-CE 3 -S0s • i— — 0— I 29. Reinvestigation showed that the sulfnr analysis and molecular weight checked this compound within experimental error* Reaction of the compound with methyl alcohol was shown, by sulfur analysis, to result in methyl ethylene-l-sulfonate, C 6 H 5 CH=CES0 3 CHa . to the formation of barium 2 2 -phenyl- This is analogous -phenylethylene-l-sulfonate by the action of barium hydroxide on the suit one. The insta bility o f hydroxy acids has been discussed, and it has been shown that in general the salts of acids exhibit no tendency to dehydrate. -hydroxy sulfonic It will be noted j that the hydrolysis of the sultone should result in 2 2 -hydroxy- -phenylethylene- 1 -sulfonic acid, but here the hydroxy group In addition to b e i n g t o a sulfonic acid group Is on a carbon atom attached to the benzene ring. Such a position should result in the enhanced activity of the | hydroxy group. This seems to be the case, for in no instance did any reaction of the sultone, however mild, result in the formation of a $ hydroxy derivative. The filtrate from the sultone was hydrolyzed with barium hydroxide to produce barium sulfate and barium 2 -phenylethylene-l-sulfonate. This indicates that the I expected intermediate, phenyl carbyl sulfate, was also i formed b y the reaction. ! of barium sulfate and barium | sulfonate, | compound. jt Its hydrolysis led to the production 2 -hydroxy- 2 -phenylethane which Immediately dehydrated to the isolated Oxidation of barium 2-phenylethylene-l-sulf onate with 30. neutral permanganate resulted In, first, the formation of benzaldehyde, Identified by its phenylhydrazone, final production of benzoic acid. and the Reaction of the barium, salt with phosphorus pentachloride produced 2 -phenyl- ethylene- 1 -sulfonyl chloride; this on reaction with ammonia resulted in the isolation of 2 phenylethylene- 1 -sulfonamide. The melting point of both these derivatives check the 15,16 accepted values given in the literature, and serve to Identify the compound. VI. The Reaction of Dioxane Sulfotrioxide with 1-Pentadecene. As it has been shown that the sodium. 2 -hydroxyalky1-1- sulfonates, obtained by the sulfonation of high molecular weight olefins, possess detergent properties, this investi gation was undertaken to prepare a representative higher hydroxysulfonate for purposes of investigating Its chemical and physical properties in more detail. The sulfonation of 1-pentadecene occurred smoothly at 5° to produce as the final product sodium 2-hydroxypentadecane-l-sulfonate. Its solubility in water was such that it could be removed from the sodium sulfate, also formed by the hydrolysis, by several crystallizations. The fact that it reacted with neither permanganate nor bromine water plus a satisfactory sodium analysis indicated the compound to be pure sodium 2-hydroxypentadecane-l-sulfonate. version of this compound to sodium 2 The con -acetoxypentadecane-I- sulfonate was accomplished by the action of acetic anhydride. Il ( Reaction of the hydroxysulfonate with benzoyl chloride did j not produce the benzoyl derivative* ! ] j Several attempts were made to oxidize the hydroxysulfonate to sodium 2 -pentadecanone-l-sulfonate, but attempts to isolate this compound as its 2,4-dinitrophenylhydrazone led to inconclusive results. Attempts to hydrolyze the oxidation mixture as indicated on page 23 resulted In failure for no myristic was isolated. The problem of preparing derivatives of the hydroxy sulf onates that could be Identified by their melting points, j originated at this stage of the investigation. j in this direction, a solution of sodium 2 As a step -hydroxypenta- decane-l-sulfonate was mixed with p-toluidine hydrochloride, i Salt formation should occur according to the following equation i ( j Cl a HS7CH0HCHsS03 Na + p -C H 3 CQH4 MH3 C l I ! j -----> CHaCQH 4 NHaS0 3 CHsCHQHClaH S 7 + NaCl. Unfortunately the salt obtained from the reaction did not I melt sharply. ! j 2 -Chloropentadecane- 1 -sulfonyl chloride was prepared ! by the action of phosphorus pentachloride on sodium 2 -hydroxy- ' pentadecane-l-sulfonate. The sulfonyl chloride was treated l ! with ammonia, aniline, p-toluidine, and 0 * -naphthylamine j respectively but all products were oils which showed no jj tendency whatever to crystallize. ; | ij j| '! 34 It had been found earlier that sodium 2 -hydroxy- (24) McAllister, Private Communication, The Procter and Gamble Company, Ivorydale, Ohio. pentadecane- 1 -sulfonate possessed marked detergent properties comparing favorably with the commercial products containing sodium lauryl sulfate. VII. A Proposed Mechanism to Explain the Products Formed "by the Action of Dioxane Sulf otrioxide on Olefins. 35, According to the suggestion of several investigators, any addition to the olefin linkage must be preceded by a polarization of the double bond. The adding positive ion then attaches itself to the carbon atom possessing a negative charge. Assuming that the addition of sulfur 3 trioxide occurs by a similar mechanism, Suter has suggested the following mechanism to explain the formation of the hydr oxy sulf ona t e s . H H H R : 0 :: 0 : H t ; R H : 0 : C : H 0(CHsCHs )3 0*S0 3 II I H H R : C : C : H «« :0 : :0 : .. :0: S :0: S :0: III IV jj This final compound on hydrolysis produces the normal hydroxy i j !' sulfonate. A logical explanation of the formation of unsaturated products such as phenylethylenesulfonic acid would be as ij !i (25) Lowry, J.Chem.Soc., 822 (1923) (26) Kharasch and Reinmuth, J.Chem.Ed.,8 , 17 03 (1931) 53 follows: Compound III is first formed as indicated above, but instead of adding another mole of sulfur trIoxide to satisfy its unbalanced structure, a proton is lost followed by the regeneration of the double bond. H H H R : C : C : H :---- * R : C : C : H :p0•:S :# 0 : « :0 :S:0 : :0 : :0 : III V H V ----* H :0 : R:C : :C :S :0: :S:"* The formation of the y S sultone of 2-hydroxy-2-phenylethane-l-sulfonic acid by the sulfonation of styrene is explained by a slight variation of the above mechanism. It must again be assumed that an intermediate of type III is first formed. This time the unbalanced electron structure Is not satisfied by either the addition of another mole of sulfur trioxide or by the loss of a proton, but rather by the sharing of a pair of electrons of one of the already present oxygen atoms with the carbon atom possessing the ,Jopen sextet*1. H R This may be represented as follows: H : C : C : H :b :S :0 : :0 : (R = C6H 5 ) --- > H H R : C : C : H :0 : S : :0 : 0 : EXPERIMENTAL I. Preparation of Dioxane Sulfotrioxide Reagent, The dioxane sulfotrioxide reagent (hereafter referred to as the D, S. reagent) used in all sulfonating reactions described in this thesis was prepared according to the s method given by Kiefer, Briefly this consists of distilling liquid sulfur trioxide, from 6 0 % oleum, into a chilled solution of dioxane dissolved in several times its own volume of ethylene chloride. It is desirable to keep the j temperature as low as possible during the addition of the j sulfur trIoxide as considerable heat is evolved by the ! | reaction and charring may occur if the temperature rises j much above 20°. As the liquid sulfur trioxide drops into j the cold solution., the formation of the B.S. reagent is I evinced by the immediate appearance of a white solid. The | first few grams of this material dissolves in the ethylene | chloride solution. The amount of sulfur trioxide added j | was determined by weighing the reaction flask before and I I after the addition of the sulfur trioxide, j II. The Sulfonation of Ethylene. Commercial ethylene was bubbled into a solution of the i ; D.S. reagent in amounts necessary to conform to the equation I o L I The amount of ethylene required was measured volumetrically 55. by passage through a wet flow meter. The emerging gas was dried by conducting it through two drying towers and then led into the sulfonating reagent. Experiment A. To a solution of 520 cc. of ethylene chloride and 100 cc. (1.19 moles) of dioxane was added 50 g. (.625 moles) of liquid sulfur trioxide under the condition described above. At a temperature of 22° and a pressure of 761.7 mm., .2885 cu. ft. (.54 moles) of ethylene was bubbled slowly into the solution of the D.S. reagent which was kept at 15°. There was no apparent change in composition or amount of the D.S. reagent. With no ethylene entering, the temperature of the sulfonating solution was raised to 50° by heating on a water bath. The solid present did not dissolve confirming the original assumption that no reaction had occurred at 15°. It should be noted here that in cases where a solid was obtained by low temperature sulfonation propylene) to 40°. (see cyclohexene or it dissolved readily when the solution was heated The D.S. reagent seems to be perfectly stable up to about 80°. Ethylene was again passed in until an additional .2318 cu. ft. (.32 moles) had been added. Sulfonation had occurred to give a light yellow, clear solution. This solution on standing produced a small amount of an oil which settled to the bottom of the reaction flask. A portion of this oil was removed but showed no tendency to crystallize either on cooling or from solution. This sarnie oil was precipitated when the clear ethylene chloride solvent jwas diluted with carbon tetrachloride. | All samples were combined and the mixture hydrolyzed J by refluxing it with 1.5 1 . of distilled water. The aqueous i I layer was separated and after another extraction of the I ethylene chloride layer, the combined aqueous layers were made basic by the addition of a slight excess of barium hydroxide. This neutralization process evolved considerable heat, making it necessary to cool the solution in a water bath during the addition of the solid barium hydroxide. The solution was boiled for an hour and then digested.on a steam bath for two hours in order to avoid the coprecipij tation of the desired product along with the barium sulfate. S The barium sulfate was filtered and excess barium hydroxide |removed from the filtrate by treatment with carbon dioxide until neutrality was obtained. The clear solution, after removal of the barium carbonate, was evaporated to approxiImately 600 cc. On cooling, the solution produced 6.95 g. ! of shiny v/hite crystals. I j These crystals were very slightly, if at all, soluble | in cold water but dissolved rather readily in hot water. i ITheir water solution failed to react with either bromine |water or neutral permanganate. i! 8 ''Huber, By analogy to the work of these crystals were suspected of being barium jmethionate, which crystallizes from water as the dihydrate. ' i Analysis: Calcd. for CHsSs 06 B a » 2 H ^ 0 : Ba, 39.40; IFound: Ba, 39.28, 39.17; 0,10.3 H s 0, 10.27. ,1A sample of the crystals were recrystallized from water and j dried to a constant weight at 1 11 0 and 15 mm. pressure. I Analysis: Galcd. for CHsSs OsBa: Ba, 44.05. Found: IBa, 44.07, 43.83. J The filtrate from the barium methionate .was evaporated to dryness, the last 50 cc. of water being removed at reduced pressure by heating on a steam bath. 93 g. of a white, crystalline, product was obtained. A yield of extremely hygroscopic This product was soluble in water and reacted readily with neutral permanganate and bromine water; thereby indicating unsaturation. As no satisfactory method of crystallization was fou"nd for this salt, an i ij jjanalysis was run on a sample of the product obtained by j evaporation to dryness. This product contained 30.34 and i |-30.32$ barium and analyzed for 4.68$ water; thereby making i j the barium analysis on the dry basis run about 31.80$. j Experiment B. I To 70 cc. (.84 moles) of dioxane in 250 cc. of ethylene chloride was added 64 g.f.SO moles) of liquid sulfur trioxide. The sulfonating reagent was heated to l i|35° on a water bath, and .3050 cu. ft. (.35 moles) of I j|ethylene at 24° and 748 mm. was bubbled slowly into the D.S. reagent. Reaction occurred very slowly at this temp- ierature and for the reaction of the last one-third of the il jolefin, the temperature was raised to 40°. On standing, an i il ; !oil similar to that formed in experiment A settled from '!so lution. ij ■j The entire mixture was hydrolyzed with water and the 38 final product obtained exactly as described for the previous experiment. It is interesting to note that the formation of barium methionate was not observed in this experiment. The product obtained, after being thoroughly dried, gave a barium analysis of 32.12 and 31.80/o. Conversion of the Barium Salt to the Sodium S a l t . Fifteen grams of the barium salt obtained above was dissolved in 500 cc. of distilled water and heated to boiling. A sortition of 5.63 g. of sodium sulfate was added dropwise to the boiling solution with vigorous stirring. precipitate of barium sulfate formed. was removed, An immediate After digestion, this and the filtrate evaporated to dryness, pro ducing a waxy solid of hygroscopic nature. A portion of the sodium salt was boiled with 9b% alcohol but complete solution could not be effected. was removed, and on cooling, a small amount of white solid separated from solution. pressure, Excess solid This was dried at 100° and 15 mm* and on analysis found to contain 18.07^ sodium. The fact that the product reacted with neutral permanganate suggested the product to be sodium ethylenesulfonate, but the analysis is not within experimnntal error. Attempt to Acetylate the Barium S a i t . ;! Five grams of the barium salt was moistened with acetic j, ianhydride and heated on a steam bath for two hours. Some decomposition occurred. The solid was washed free of acetic i j anhydride with boiling ether and dried. Analysis indicated ' I ii:ino acetylation had occurred. 39. I i i i f | III. The Sulfonation of Propylene. | Experiment A. i To 8 8 g. (1 mole) of dioxane dissolved in several times I its own volume of ethylene chloride was added 6 8 g. (.85 I j moles) of sulfur trioxide. The temperature of the solution i j was allowed to rise to that of the room and commercial j propylene passed In until the D.S. reagent h a d disappeared and a clear yellow solution resulted. The temperature rose to about 30° during the sulfonation process. The solution was hydrolysed with an excess of barium hydroxide and j ethylene chloride and dioxane distilled from the emulsified i jmixture. The excessive foaming, often encountered in j removing the volatile components of a sulfonation mixture, i ! ; may be avoided by directing a small stream of air upon the ! surface of the boiling liquid. | The barfum sulfate formed by the hydrolysis was removed, J and the filtrate brought to neutrality Ytfith carbon dioxide. i After removal of the barium carbonate, the s olution was ji | evaporated to dryness yielding 39 g. of dry material. This | corresponds to a 22 %g yield of barium jjsulfonate. 2 -hydroxypropane- 1 - In the light of present knowledge, this low i yield is explained by coprecipitation of the hydroxy sulf onate ji iwith the barium sulfate, and also by the fact that disap! ) !pearance of the D.S. reagent does not mean the reaction is ■ i ; i complete. The D.S. reagent is appreciably soluble in ij \\ !jethylene chloride. i ! I ! 40. Preparation of 2 -Chi or opr opane - 1 - s ulf onyl Chloride. A mixture of 10 g. of barium 2 -hy dr oxypr op an e -1 sulfonate and g. of phosphorus pentachloride in 2 0 1 0 0 cc. of dry carbon tetrachloride was refluxed for eight hours. The remaining solid was filtered, at 40° b y vacuum distillation. and the solvent removed A yellowish oil remained which was dissolved in ether, filtered, calcium chloride. and dried over The oil has a pungent, irritating odor and is a lachrymator. Reactions of 2 -Chior opr opane-1-sulf onyl Chloride. 1. With p-toluidine. A sample of .40 g. of p-toluidine was dissolved in ether and to this was added an ether solution containing .35 g. of the sulfonyl chloride. Reaction was instantaneous resulting in the formation of a precipitate of p-toluidine hydrochloride. After removal of this solid, evaporation of the ether resulted in a light yellow oil soluble in b% sodium hydroxide. This oil could not be made to crystallize from any of the common solvents. 2. With ammonia. To a benzene solution containing one gram of the ; sulfonyl chloride was added gaseous ammonia, until the !| ' jinitial violent reaction had subsided. After removal of the ammonium chloride, the benzene was distilled at low j !pressure. The resulting oil refused to crystallize. il3. With xenylamine* Five-tenths gram of the oily sulfonyl chloride in ether was added to an ether solution of 0*95 g. of xenylj I amine. j A precipitate of xenylamine hydrochloride formed slowly and was later removed. A small amount of solid j remaining after the removal of the ether could not be r e crystallized. Experiment B • Liquid sulfur trioxide was added to a solution of dioxane and ethylene chloride until the gain in weight was 60 g. f.75 moles). To this was added 23 g. ( # 5 5 moles) of propylene, the temperature of the reaction being kept j around 12°. A heavy white solid, similar in appearance to dioxane sulfotrioxide, formed during the addition of the olefin. I After standing in the ice box for two days, the solid i |was filtered at ice temperature under anhydrous conditions. ||This was accomplished by means of a sintered glass funnel [fitted with a tight metal top into which had been soldered ) I two tubes, a large one for introducing the solution and a I i| smaller one for dry air. The stem of the funnel was placed in a large rubber stopper which fitted tightly into a hole ;cut in the bottom of a granite pot. The pot could then be Ifilled with ice-salt mixture and the filtration carried out j! |iwith suction if desired. The solid remaining after filtration was washed several f Utimes with cold ethylene chloride. Dry air was sucked 1 through the solid to remove any ethylene chloride adsorbed 42. | i i ] on the surface* The solid was rapidly transferred to a vacuum desiccator containing PS 0 5J| The pressure was reduced to 18 mm* and dry air then allowed to flow slowly into the desiccator* This process was repeated several j times in an attempt to remove any remaining solvent* In spite of all precautions the solid completely liquefied within four hours to for m a rather thick brown oil* An unweighed portion of this oil was hydrolyzed with j excess barium hydroxide* The barium sulfate formed was | washed with dilute hydrochloric acid to remove any barium | carbonate, dried, and found to weigh- 16*42 g. The filtrate, after removal of excess barium hydroxide, was evaporated ! to dryness to yield 15*08 g. of barium 2 -hydroxypropane-l- J sulfonate mixed with some unsaturated material* i I |Experiment C. i ! Sulfur trioxide, to the extent of 70 g* (.87 moles), I was distilled into a flask containing 105 g. (1*19 moles) j dioxane and 300 cc. of ethylene chloride* I of 21° and 746 mm. pressure, .39 cu. ft. of At a temperature (.44 moles) of |jpropylene was bubbled into the sulfonating mixture kept at ji j! 5°. The formation of a thick white solid occurred. The >i 'solid was filtered under cold, anhydrous conditions, washed i j with cold ethylene chloride and sucked dry. : ! The solid was placed in a vacuum desiccator containing Iphosphorus pentoxide and a block of paraffin. The pressure 'i 'was reduced to 15 mm. and then dry air was admitted to j "raise the pressure to normal. The desiccator was placed in 43 | an ice box ■where it stood for two days, forming a semiI solid. On standing at room temperature, liquefaction occurred within a few hours. Experiment I). To 80 cc. (#95 moles) chloride was added 56 g. of dioxane in 350 cc. of ethylene (.70 moles) of sulfur trioxide. The sulfonating mixture was heated to 50° on a water bath and 14.7 g. (.35 moles) the solution. of propylene bubbled slowly into Reaction occurred readily to produce a clear yellow solution. This solution was hydrolyzed with distilled jwater and the final product, barium 2 -hydroxypropane-l- sulf onate, obtained in a 45%' yield. Analysis: Calcd. for C 6 H 1 4 Ss 0 aBa: Ba, 33.01. Found: |Ba, 32.81. J Experiment I E. A solution containing 500 cc. ethylene chloride and I 125 cc. (1.49 moles) was chilled to 0 ° in an ice-salt bath. J To this solution was added 130 g. (1.62 moles) of liquid sulfur trioxide. The solution was kept at 20° and .72 cu. j ft. (.81 moles) of propylene was added at 23° and 736 mm. I jAt the end of the addition a clear yellow solution was formed. i *This was refluxed with an equal volume of distilled water I |for an hour and the aqueous layer removed. The ethylene !|chloride layer was again extracted with an equal volume of Jwater and the aqueous layers combined. To the aqueous 5 f \, ]jsorution was added 176 g. of barium hydroxide (a slight excess) to give a dense precipitate of barium sulfate* The solution was boiled for an hour and then digested on a steam bath for two hours* The barium sulfate was filtered and excess barium hydroxide removed by treatment with carbon dioxide. Evaporation of the clear solution to dryness resulted in 108 g. of material. Analysis: Ba, 36.15. This is a 6dfo yield. Calcd. for G 6 H 1 Found: 4 Ss O eBa: Ba, 33.01; C6 H 1 0 S 2 OsBa: Ba, 33.60. The analysis, plus the fact that the compound reacts readily with permanganate and decolorizes small amounts of bromine water, indicates the presence of some barium propylene- 1 - sulfonate in the barium 2 -hydroxypropane- 1 -sulfonate. Preparation of Sodium-2-Eydroxypropane-1-sulfonate. To a solution of 100 g. of the barium salt dissolved in 1500 cc. of boiling water was added 34.8 g. of sodium sulfate dissolved in approximately ICO cc. of water. The mixture was boiled for one hour, digested for three hours, and the barium sulfate filtered. The barium sulfate was extracted with boiling water and the combined aqueous solutions evaporated to dryness, producing 77 g. of the sodium salt or practically a quantitative yield. A portion of this salt was recrystallized from 95^ ethyl alcohol. i ! Analysis: Calcd. for CsIi7 S 0 4 ha; Ba, 14.20. Found: ha, |j14.62. ji The high analysis is explained by the presence of seme !unsaturated material also present in the barium salt. Preparation and Distillation of 2-Chloropropane-l-sulfonyl Chloride. In a solution of carbon tetrachloride, 50 g. (.31 moles) of the dry sodium salt was mixed with 125 g. (.60 Imoles) of ground phosphorus pentachloride. Reaction occurred vigorously for an hour even at ice temperature. After the initial reaction had subsided, the mixture was |refluxed for three hours on a steam bath and allowed to ji | stand over night. The remaining solid was removed and j extracted with carbon tetrachloride. The solvent was J removed from the combined solutions by vacuum distillation i |leaving a light yellow oil in the flask. This was taken up Iin ether, washed with ice cold water to remove any |remaining phosphorus oxychloride, and dried over CaCls . The ether was removed at reduced pressure and the oil 1 i j distilled through a short Vigreaux at 8 mm. pressure with ! I:the following results. i i | 1 j 1 fraction 1 2 3 4 5 b.p. 48-71 71-73 73-75 75-76 80-95 weight •61 3.59 3.68 6.07 6.44 refractive ........ 1.4802 1.4808 1.4818 1.4655 Fraction 5 was collected while vigorous pyrolysis of the !residue was occurring and was later discarded. The total I ; ii weight of all fractions is 20.39 g. or a 37% yield. ■i Redistillation of the first four fractions through a i; more efficient column at 5 mm. resulted in the following !separation. 46 fraction 6 7 8 9 10 b*p. 48-49° 49-51° 51-53° 53-55° 55-56.5° weight refractive 1.4782 1.4797 1.4808 1.4819 1.4828 1.00 2.35 5*62 1.65 1.45 Experiment P. A sample of sodium 2-hydroxypropane-l-sulf onate was ,, is prepared by a similar method used by Khar as eh for the preparation of sodium -l-hydroxypropane-3-sulfonate. To a solution of 126 g. (1 mole) of sodium sulfite in distilled water was added 175 g. of a 54*6$ propylene chlorohydrin (1 mole)* The mixture was refluxed for two hours* As the solution was evaporated to dryness, the sodium chloride which separated was removed from time to time* On evap- j oration to dryness 118 g* of the product contaminated with j a little sodium chloride was obtained* | a 73$ yield* j This corresponds to A portion of the solid recrystallized from alcohol failed to react with either permanganate or bromine water* Analysis: Calcd* for C3H7S04Ua; Na, 14*20. Pound; Ha, 16*56, 16*65. A determination of the sodium chloride content revealed | that the sodium 2-hydroxypropane-1-sulfonate was contaminated jwith the equivalent of 2.60^ sodium. Thus a corrected 1 analysis revealed 13*96 and 14*05^ sodium. I !Preparation of sodium 2-acetoxypropane-l-sulf onatS. | Seven grams of the sodium salt was treated with acetic 47 . anhydride and refluxed for two hours* The mixture was cooled and the excess anhydride and acetic acid extracted with boiling ether. from alcohol. The resulting solid was recrystallized A solution of the salt gave a faint cloudiness with silver nitrate. Analysis: Calcd. for C6HoS05Ha; Na, 11.28. Pound; Ha, 11.50. Pyrolysis of Sodium 2"Acetoxypropane-1-sulfonate. A portion of the acetate, which gave no reaction with permanganate or bromine water, was placed in a test tube and heated on an oil bath. At 220° the compound began to soften and at 235° it completely liquefied giving off an acid gas. On cooling, a portion of the remaining substance iBhen dissolved in water reacted readily with permanganate and decolorized copious quantities of bromine water. Preparation and Distillation of 2 -Chi or opr opane "1 -sulf onyl Chloride. Sodium 2-hydroxypropane-l-sulf onate (50 g., .31 moles) was mixed with 125 g. (.70 moles) of phosphorus pentachloride in carbon tetrachloride. The sulfonyl chloride was isolated as a yellowish oil by exactly the same procedure as described under Experiment E. The crude oil was fractionated at 9 mm. pressure with the following results. .ction b.p. 75-79 79-82 84-85 changing l1 2f 3f 4f weight 1.67 5.93 5.94 3.04 refractive index 1.4795 1.4808 1.4830 1.4828 j Fractions l 1 and 2 1 -were combined and distilled at 6 mm. ! 1 pressure* fraction b*p* weight refractive index 5* 61 7* 81 50-51° 51-55° 53-56° 58-59° *61 3.37 .48 1.06 1.4785 1.4789 1.4810 1.4826 Samples 3 1, 4 f and 8 1 were combined and fractionated at i 8 mm. pressure. fraction b.p. 91 101 ll1 12* 72-75° 75-76.5° 76.5-78° 78° weight refractive index .89 1.44 4.48 1.40 1.4800 1.4813 1.4828 1.4829 Fraction 6 1 (A) was taken as representative of the low boiling component and fractions 111 and 12* (B) combined to represent ! the high boiling component. Analysis: (A)Cl, 27.34. Calcd. for CsHgSOgCl; Cl* 25.27; Calcd. for CsHeSOaClg; Cl, 40.11. Found, Found; (B) Cl, 58.52#. ) 27,28 j The analysis for chlorine as usually carried out failed ■ : i to give satisfactory results due apparently to the formation •■i Iof some sulfide. results. The following modification gave good Approximately 1 g. of sodium was dissolved in (27) Drogin and Rosanoff, J.Am.Chem.Soc., 38, 711 (1916). ! (28) Cook and Cook, Ind.Eng. Chem. (Anal.Ed.775* 1S6 (1933). 15 cc# of alcohol and to this was added the sample of j "unknown# After refluxing the mixture for 15 minutes, the ! usual procedure of analysis was continued# For example, j 1*08 g# of sodium was dissolved in 16 cc# of absolute | alcohol# To this was added #1324 g. of sample B# After j refluxing for 15 minutes, alcohol was added to bring the total to 21 cc#, and an additional 1#77 g# of sodium added gradually over a period of one hour. The final steps in the analysis were by the usual method# In the absence of commercial propylene, an attempt to prepare propylene from both n-propyl alcohol and isopropyl alcohol by dehydration with varying concentrations of sulfuric acid led to unsatisfactory re stilts# The dehydration of n^propyl alcohol with sulfuric acid and aluminum sulfate is reported to proceed readily, resulting in an 80$ yield 39 of crude product# IV. The Sulf onation of 1-Pentene. The Preparation of 1-Pentene. The preparation of 1-pentene was carried out according 30 to the directions given by Hurd. Ethyl bromide (275 g., 2.52 moles) in 800 cc. of dry butyl ether was added to 65 g. ij (2.70 moles) of magnesium turnings. The formation of the ! Grignard reagent occurred readily. The Grignard solution ili ■ I (29) Klstiakowsky, Ruhoff, Smith and Vaughan, J.Am.Chem.Soc., ; ■ 57 , 877 (1935). ? (30) Hurd, Goodyear and Golasby, J.Am.Chem.Soc., 58, 235 (1936). was filtered through glass wool, by means of a filter stick, Into a large separatory funnel and added slowly to a cold i solution of 215 g# (1.76 moles) of allyl bromide in 300 cc# of butyl ether. When the reaction was complete, the solution was decanted into a 3 1. r.b. flask# The remaining solid, magnesium bromide, was washed thoroughly with dry butyl ether. The flask containing the ether solution of 1-pentene was connected to a long, efficient condenser cooled by a brine solution. The ether solution was heated on an oil bath at 140-160° until all 1-pentene had distilled. Re- distillation of the product gave 76.5 g. (62$ yield) of 26 j 1-pentene, b.p. 29-30°, n^ 31 1.3705. (Hurd reported Up | 1.3717). Experiment A# j Dioxane (175 cc., 2#.l moles) was dissolved in 500 cc# | of ethylene chloride and 154 g# (1.93 moles) of sulfur trioxide distilled into the ice cold solution. On the basis i j | of sulfur trioxide added, 57#6 g. (.83 moles) of 1-pentene ! was added dropwise to the sulfonating mixture# At first there was no apparent reaction so the solution was allowed to come to room temperature# Reaction occurred readily at ; this temperature to produce a clear, yellow solution. ! The sulfonated 1-pentene was treated with an aqueous i ifI; solution ! basic. of barium hydroxide until the upper layer remained After removal of the ethylene chloride and dioxane |iby distillation, the heavy precipitate of barium sulfate i; ijwas filtered. Carbon dioxide was passed In to remove excess 51. J I ! "barium hydroxide as barium carbonate. t The solution was | evaporated to 150 cc. and allowed to stand in the ice box ! over night. A heavy precipitate of white crystals formed, which when filtered out and dried, weighed 54 g. An additional 78 g* of a white solid was obtained by evaporating the filtrate to dryness. or a 65$ yield. from |j Total material obtained was 132 g. A portion of the solid was recrystallized water, but still gave a positive test with permanganate. Analysis: Calcd. for CloHasS808Ba; Ba, 29.08. Founds ji j 31.72, 31.34. | A 25 g. sample of the salt was fractionally recrystal- 1 Iliged from water. The course of the crystallization is jj j given on page 22. Fraction 14 analyzed for 29.30$ barium, j indicating a partial separation of barium-2-hydroxypentane-lj sulfonate from the unsaturated material. i j i SOxidation of barium 2-hydroxypentane-1*sulfonate♦ | Ten grams f.022 moles) of the crude salt was dissolved i jin water to which was added 1.4 g. (.010 moles) of sulfuric i jacid. The barium sulfate was coagulated by boiling and I ''filtered. To the filtrate was added 2.84 g. f.028 moles) j ] of chromium trioxide and 3 cc. of sulfuric acid. The solution | l !jwas heated on a steam bath for several days producing a green colored solution. The solution was hydrolyzed with 40$ sodium hydroxide and after prolonged heating was decanted 'from the chromium hydroxide. After acidification with sulfuric acid, the organic acid was removed by distillation. ;The distillate was redistilled to obtain a 110 cc. sample of j the acid, a 10 cc# sample of which was found to contain the equivalent of #025 g# of butyric acid. A solution of 110 cc. containing#275 g. butyric acid gave the following Duclaux constants: 20.5, 16.9, 14.7 (Shriner and Fuson give 17.9, 15.9, 14.6). The Duclaux I constants of the oxidation product were found to be 8.94, 8.27 , 8.03. This indicates a mixture of propionic and jacetic acid. j ! j The Sulf onation of 2-Pentene. si ! Preparation of 2-Pentene. I | To a cooled mixture of 200 cc. of water and 200 cc. of I J j |concentrated sulfuric acid was added 214 cc. j l i f technical 3-pentanol. (2 moles) of The flask containing these was !i jl j attached to a long condenser cooled by brine. The flask j ; |was surrounded by a boiling water bath. Distillation j l I started at 34° but rose rapidly to 51° as the reaction ! j|became more vigorous. On completion of the distillation, 1 j the hydrocarbon was washed with 25 cc. of 5$ sodium hydroxide | Ij and dried over calcium chloride. A total of 110 g. (79$ |i j!yield) of crude product was obtained. I The crude 2-pentene was fractionated through a long, !i iefficient column at a pressure of 753 mm. with the following results. i (31) "Organic Synthesis", John Wiley and Sons, Inc., New York, N.Y., Coll. Vol. 1, 1932, p.421* 53 fraction X 2 3 approx* vol* 20 b.p. 5 cc. 20 cc. 100 cc. n^ 32-35.4° 35.4-35.9° 35.9-36.3° 1.3783 1.3793 1.3805 About 10 cc. of a high boiling material remained 'which was probably polymerized pentene. The reflux ratio of the distillation varied from 50 -1 to 30 - 1. Cis-2-pentene bolls at 36.5° at 755 mm. so (np 1.3825): SO trans-2-pentene boils at 36.0° at 755 (n-Q 33 Lucas and Prater S report 3S 1.3798). O 1.3817 for cis-2-pentene. Prom the results, it seems that fraction 3 contains a predominance of trans material. Experiment A. | Following exactly the same procedure used in the i |sulfonation of 1-pentene, 53.38 g. (.76 moles) of 2-pentene Ifrom fraction 3 was sulfonated and converted to the barium ; salt. A sample of the salt, twice crystallized from water, reacted rapidly with cold permanganate and bromine water. Analysis: Calcd. for CioHsaSsOeBa; Ba, 29.08. Found; Ba, 33.94, 33.88. V. The Sulf onat ion of Cyclohexene. Preparation of Cyclohexene. A mixture of 250 g. (2.5 moles) of cyclohexene and 8 cc. (.15 moles) of concentrated sulfuric acid was placed (32) Kharasch, Walling, and Mayo, J.Am.Chem.Soc., 61. 1559 (1939). (33) Lucas and Prater, J.Am.Chem.Soc., 59, 1683 (1937). 54. i! jin a Claisen flask attached, through a condenser, to a | i |receiving flask packed in ice. | ;oil hath to 150-160°• | !The The flask was heated on an The distillation required four hours, distillate was saturated with sodium chloride, the |cyclohexene separated and dried over calcium chloride, |Fractionation through an efficient column gave 125 cc, boiling at 82-82,2°, > Experiment A. Thirty nine grams (,49 moles) of liquid sulfur trioxide jwas added to dioxane dissolved in ethylene chloride. j| the D,S, reagent was added dropwise 20 g, jicyclohexene. j10°, ; ! To (,244 moles) of The temperature of the reaction was kept at As the cyclohexene was added, the amount of solid in J jj [the flask increased until at the end of the addition more j ! [ethylene chloride was necessary to permit stirring. An attempt to filter the solid under anhydrous conditions jresulted in failure as the solid liquified before the \ |filtration was complete. The entire solution was hydrolyzed |!wlth barium hydroxide. After removal of the barium sulfate I . ft jiand barium carbonate, the filtrate was evaporated to 150 cc, jj jOn standing, the solution solidified, A portion of the solid was crystallized from alcohol-water mixture and found to react readily with permanganate and bromine water, indicating the presence of some unsaturated material. Analysis: Calcd. for CeHnSO^Ba; Ba, 23.50, 23.40. Ba, 27.32. ^ Found; jExperiment B. Sulfur trioxide (55 g., *69 moles) was reacted with j29 g. (.35 moles) of cyclohexene by means of the D.S. ij i j jreagent. The temperature was kept at 5°, and again the i jjformation of a heavy white solid was noted. The solid was filtered at ice temperature under anhydrous conditions and placed In a desiccator containing a block of paraffin, jThe desiccator was exhausted from time to time and kept in ian ice box. In spite of all precautions, the material 1liquified to give a purple oil. Experiment C. j Dioxane (75 cc., .90 moles) was dissolved in 300 cc. jof carbon tetrachloride and to this was added 40 g. (.50 Imoles) of sulfur trioxide. At a temperature of 5°, 21 g. | i !j (.25 moles) of cyclohexene was added dropwise. Instead ji i of the expected solid, a thick yellowish oil separated from the solution. This was separated, but crystallization |could not be induced. j On hydrolysis, barium 2-hydroxy- cyclohexane-1-sulfonate was produced along with unsaturated |material, j IjVI. i! The Sulf onat ion of Styrene. jExperiment A. Dioxane (80 cc** #95 moles) was dissolved in 300 cc. i ^ of ethylene chloride and treated with 64 g. (.30 moles) of liquid sulfur trioxide. Styrene (42 g., *40 moles) was ,added dropwise to the D.S. reagent at 5°. In the initial stages of the reaction the mixture seemed to be clearing of solid, but when one-half to two-thirds of the olefin had been added, a solid began to separate from solution. Following the complete addition of the olefin, the mixture was placed in the ice box for several days, during which time the amount of solid seemed to increase. j The solid was filtered under anhydrous conditions at ice temperature and jplaced in a desiccator over phosphorus pentoxide. i Since the solid showed very little tendency to liquify, it was treated with cold water. The portion failing to dissolve j i ■ was filtered, yielding 5.5 g. of a white, pellet-like material which melted at 90-91? A sample of the solid when j | suspended in water reacted readily with permanganate, but f! i ) Its benzene solution failed to give a positive test with i! I !bromine* i Five-tenths gram of the substance was boiled with water and found to dissolve slowly, producing an acidic 1 solution, which reacted readily with permanganate and ibromine water. i i The filtrate of ethylene chloride was extracted twice iwith its own volume of water. The aqueous extracts were i | combined and made basic with barium hydroxide. After the | solution had been boiled, the barium sulfate was removed by r filtration. Following removal of excess barium hydroxide !as barium carbonate, the solution was evaporated to a small volume. On standing in the ice box, a solid, proving to be barium 2-phenylethylene-l-sulfonate, separated in white crystals. A sample of the solid was brought to constant weight at 100° and 15 mm* pressure* jl ! Analysis: Calcd* for C16H 18Ss0eBa; Ba, 27*28* ] | Pound; Ba, 27,58, 27.69. ) IOxidation of Barium 2-Phenylethylene-1-sulf onate * ! J Five-tenths of a gram of the barium salt was dissolved Iin water and neutral permanganate added slowly from a i burette* time* The manganese dioxide was removed from time to At one stage of the oxidation, the odor of benzaldehyde ijwas noted; therefore, a small sample of solution was j removed, made acidic with acetic acid, and treated j phenylhydrazine. The precipitate which formed was j crystallized with re- from a water-alcohol solution, m*p* 157-8°* ji j!Melting point of phenylhydrazone of benzaldehyde Is given ! as 158° (Shriner and Fuson; * | The addition of permanganate was continued until a faint pink color remained* |refluxed for two hours* The solution was made basic and After the manganese dioxide was J removed, a portion of the solution was found to give a precipitate with barium chloride, thereby indicating the Ipresence of the sulfate ion* ij The solution was made acidic and excess permanganate Iremoved with bisulfite* The aqueous solution was extracted 'twice with ether and the ether in turn extracted with a i:dilute solution of sodium bicarbonate* The basic solution ■was acidified and on cooling gave a precipitate of benzoic acid; m*p* 122°* 58 Preparation of 2-Phenylethy1ene -1 -sulfonyl Chloride* Dry barium 2-phenylethylene-l-sulf onate (12 g., *015 j moles) was ground with 8 g# (*038 moles) of phosphorus |pentachloride# The mixture was heated on a steam bath for h | 8 hours, and after cooling, poured into ice water# The I solid was filtered, taken up in ether, and dried over I calcium chloride# 1 The ether was removed leaving a 60^ yield " ^ I of 2-phenylethylene-l-sulf onylchl or ide; m#p# 82-85# 15,16 | 2 -Pheny 1ethylene-1 -sulfonamlde was prepared by adding a few j | drops of liquid ammonia to a portion of the sulf onyl chloride dissolved in ether# iI the solid was twice recrystallized from water; m#p# 142-3°# jExperiment i After removal of the ether, 15 B * Liquid sulfurtrioxide (75 g#, #94 moles) was added to j a solution of 80 cc# ! | (#95 moles) of dioxane in 300 cc# of i ! ethylene chloride. Styrene (49 g#, #47 moles) was added ■ dropwise to the D#S# reagent at 5°. The solution, containing | considerable solid, was placed in an ice box for six days# i iThe solid was filtered at 0° under anhydrous conditions, washed with cold ethylene chloride, and sucked dry# The ■j l |material weighed 35 g# The solid was treated with cold |water to remove any water soluble portion, filtered, and i !dried# A small sample, crystallized from acetone-petroleum ether mixture, melted at 134-136°. ij A portion of the crude material was analyzed for i isulfur by the Parr bomb method# J Analysis: i 17.28, 17.29. Calcd# for C 8H QS03; S, 17#44# Pound; S, 59. S jAcid, of y?-Suit one of 2-Hydroxy-2-phenylethane-l-sulf ofilc / A portion of the above crude material was dissolved in boiling water. The solution was cooled to room temperature and permanganate added until a faint pink color remained. The solution was made alkaline and refluxed for an hour. i j The manganese dioxide was removed; the filtrate made acidic and extracted with ether. On evaporation, the ether solution deposited benzoic acid; m.p. 122-3°. Titration of Suit one with Sodium Hydroxide. i j Weighed samples of the crude ^x^sultone of 2-hydroxy-2- !phenylethane-l-sulfonic acid were dissolved in boiling water I j | and cooled to room temperature. Titration with standard j sodium hydroxide gave the following neutral equivalents. | Calcd. for C QH QSOs; m.w., 184. Pound; m.w., 176,177. l | !Hydrolysis of^-Sul tone to Bar lum-2 -Phenyl ethylene -1 -sulf onate ♦ j A portion of the crude sultone was dissolved in boiling j t |water and cooled to room temperature. The solution was i1 treated with excess barium hydroxide. * (it is important to note that no barium sulfate was formed by this reaction.) jj The excess barium hydroxide was removed as the carbonate, jj i ;and crystals formed from the concentrated aqueous solution. j j !These were recrystallized from water and found to react ^readily with permanganate and bromine water. Analysis: Ba, 27.34. H" Calcd. for C16H laSsOQBa; Ba, 27.28. Pound; 60. j j I Ji j I of Methyl 2 -Phenylethylene-1-sulfonate. One gram of the sultone was dissolved in 15 cc. of ji jboiling methyl alcohol. j hot. The solution was filtered while Distilled water was added to the boiling solution until a faint cloudiness was observed. j The solution was |jallowed to cool and produced .4 g. of a white crystalline precipitate; m.p. 66-67°. jj The product reacted readily i! Iwith neutral permanganate and bromine water. S i j! Analysis: Calcd. for C0HloSO3 ; S, 16.11. j i Pound; Is, 16.15. ! | S' !Ethyl 2-phenylethylene-l-sulf onate (m.p. 46-48°) may be i j prepared by an analogous reaction. i 'i i :VII. The Sulfonation of 1-Pentadecene* 3 |Preparation of 1-Pentadecene. ij j! The 1-pentadecene was prepared by the action of lauryl- j! magnesium bromide on allyl bromide according to the method j • jgiven by Wilkinson. ! 3* Lauryl bromide (250 g., 1 mole) in 500 cc. of dry ether was added to 24 g. (1 mole) of magnesium turnings. j Gentle j heating and a small crystal of iodine were necessary to |start the reaction. After the preparation of the Grignard reagent was complete, 130 g. (1.07 moles) of allyl bromide i j in an equal volume of dry ether was added at such a rate as ^to produce vigorous refluxing. After the addition of allyl ! ,(34) Wilkinson, J.Chem.Soc., 3057 (1931). * bromide was complete, the mixture was refluxed for approxi mately 30 minutes, and then hydrolyzed by pouring into a mixture of ice and water. The ether layer was separated |and dried over calcium chloride# The ether was removed by distillation on a water bath and the olefin distilled at reduced pressure# j fraction j 1 2 3 pressure 12-13 am. 12 mm. 14-15 mm# b#p# 120-127° 127-132 132-137 weight 14 g. 140 g. 18 g# IThis gives a total yield of 172 g# (82$) of crude product# jThe boiling point of 1-pentadecene is given as 127 •595 ! !128*5 at 10 mm# j A solid residue remained after removal of the olefin# IThis was recrystallized from alcohol and identified as I |tetracosane (m.p* 51)* l i I Preparation of Sodium 2-Hvdroxypentadeoane-1-sulfonate# | Sulfur trioxide (76 g#, #95 moles) was added to 50 cc# j (.59 moles) of dioxane dissolved in 300 cc* of ethylene | |chloride# To this sulf onating solution was added 100 g# ! (.48 moles) of 1-pentadecene (fraction 2), the temperature (being maintained at less than 10°. After the addition of I |the olefin, the solution was hydrolyzed by pouring it into jan aqueous solution of 57 g* (1*42 moles) of sodium i; ^hydroxide# An emulsion formed which showed no tendency to j: j; f35) Kozacik and Reid, J.Am.Chem.Soc., 60, 2436 (1938). 62. separate even after standing several days; therefore, the ethylene chloride and dioxane were removed by distillation, j a stream of' air being blown on the surface of the liquid to li prevent excessive foaming* j| The aqueous residue was con- j! centrated and upon standing produced a eopious precipitate i| jiof sodium 2-hydroxypentadecane-l-sulfonate contaminated with j sodium sulfate* A portion of the solid was crystallized j twice from water* j Analysis: It gave no reaction with permanganate* Calcd* for CleE31S04Na; Na, 6*96* Found; | Ha, 7*01, 6*94* Preparation of Sodium 2-Ac et oxypentade cane-1-sulfonate* j I Five-tenths gram of the above pure sodium salt was i| jrefluxed with 5 cc* of acetic anhydride* ji jhours, solution was practically complete* After about 4 The solution was jfiltered while hot and upon cooling deposited a dense prej j cipltate of a white solid* This was filtered and washed 1 j free of anhydride with ether* Yield obtained *61 g* ji j Analysis: Calcd* for ClgH S3S06Ha; Ha, 6*18* Found; j Na, 6*54, 6*14* j Oxidation of Sodium 2-Eydroxypentadeoane -1 -sulf onate * jj An attempt was made to oxidize the above salt to s odium-2- ■pentadecanone-1-sulfonate according to the following equation* 3 C j.3H s 7CHOECHg S03 Na + 2 KMn04 + NaOH i -- ► 3 C13HS7C00KCNa) + 3 CH3S03K(Na) + 2 MnOs + 3 Es 0. On this basis, 5 g* (*015 moles) of the hydroxy sulfonate was dissolved In a b% solution of sodium hydroxide and heated j to boiling* Potassium permanganate Cl#6 g., .101 moles) was dissolved In w%ter and added gradually to the hot solution* ! Reaction was evinced by the immediate formation of manganese jj j !dioxide* After addition of the permanganate, the solution . was refluxed for an hour and then filtered free of manganese J dioxide* Enough sodium hydroxide to make a 20$ solution was j added to the filtrate, which was then boiled in an attempt i j to split the bond between Gx and Cs * The solution was j filtered, made acidic, and extracted twice with its own j | volume of ether* The ether layers were combined and the j solvent removed on a steam bath, leaving a small amount of !| a low melting solid resembling lard* f | An attempt to prepare ■j the p-bromophenacyl bromide produced a solid, which, on jj crystallization from alcohol, melted at 110-112°* (The j imelting point of p-bromophenacyl Tester derivative of i| myristic acid is given as 81°) j i ji jj Preparation of 2-Chloropentadeoane-l-sulfonyl Chloride* i j Sodium 2-hydroxypentadecane-l-sulfonate (3*3 g*, *01 | mole) was finely ground and mixed with 2*4 g* (*011 moles) jl i! of phosphorus pentachloride* That reaction occurred was ] j 1evinced by the evolution of hydrogen chloride* The mixture was heated on a steam bath, but as considerable decomposition v occurred, the product was discarded, and the preparation 15 carried out by a method given by Khar as ch. Twelve grams (*036 moles) of sodium 2-hydroxypentaji decane-l-sulfonate was added to 16 g* (#077 moles) of 64* i y phosphorus pentachlorlde suspended in 50 cc# of carbon i | tetrachloride# The mixture was warmed on a steam bath, | initiating a vigorous reaction that lasted for 30 minutes# j! | After the initial reaction had subsided, the mixture was refluxed gently for eight hours and allowed to stand over |night# j After filtration,the solvent was removed at reduced pressure, leaving a light yellow oil# This oil was dis solved in ether, washed twice with ice water, and dried over calcium chloride# i The oil could not be indhced to form | crystals# j |Reactions of 2 -Chioropentadecane-1-sulf onyl Chloride# i ! An ether solution of the sulf onyl chloride was added |dropwise to an ether solution of 6 g# (#056 moles) of jp-toluidine until no further reaction was observed. The p- j 'toluidine hydrochloride was filtered and the filtrate washed several times with a dilute solution of hydrochloric acid# After the ether solution had been dried over calcium chloride, |the solvent was removed at reduced pressure leaving a reddish |j brown oil which could not be crystallised j| or from its solution of various solvents# either on cooling 1With PC naphthylamine . Sodium 2 -hydroxypentadecane-1-sulfonate (6 g#, #018 moles) was converted to 2-chloropentadecane-l-sulfonyl chloride as has been described# To an ether solution of the sulf onyl chloride was added 5 g# (#035 moles) of oC naphthylamine also dissolved in ether# rr Formation of oc naphthylamine i jhydrochloride occurred rapidly. | !with charcoal. The filtrate was decolorized After removal of the solvent, there remained j! ||a yellowish oil. j with failure. All attempts to crystallize this oil met Both this oil and the one obtained from the reaction of the sulf onyl chloride with p-toluidine were kept for several months, but no evidence of crystal formation was observed. Preparation of 7 -Pentadecene. J Heptyl bromide (180 g., 1 mole) in approximately 500 cc. | of dry ether was added to 24 g. (1 mole) of magnesium I Iturnings. To the Grignard reagent was added 35 g. (.47 moles) of ethyl formate (b.p. 53-54°) at such a rate as to i |j produce refluxing. The reaction product was filtered and |hydrolyzed by pouring it into a mixture of ice and water ! i containing a little sulfuric acid. The ether layer was it Iseparated, washed with a dilute solution of sodium bicarbonate, I I'and dried over anhydrous potassium carbonate. jj j After removal of the ether, the residue was distilled at 12 mm. pressure j lto give 75 g. (Q6% yield) of di-n-heptylcarbinol boiling at 149-151°. A portion of the alcohol was crystallized from I 36 jjpetroleum ether and found to melt at 46-48°. Kipping |49.5-50° for the melting point. The stearate of di-n-heptylcarbinol was prepared by the following series of reactions. (36) Kipping, J.Chem.Soc., 455 (1893) gives j (A) CE3 (CHsi)l6COOE + SOCls J (B) (C7H 15)aOHOE + CH3 (CHS )10COC1 ji I -- > CE3 (CHg )10COC1 + SOs + EC1 -- » CE3 CCEs )lsCOOCE(C7Els)£ + EG1 | To 30 g* (*25 moles) of thionyl chloride was added in small portions 62 g. (*23 moles) of stearic acid* After the reaction was complete, air was drawn through the liquid | to remove any excess thionyl chloride* Finely ground | di-n-heptylcarbinol (50 g., *22 moles) was added to the J stearyl chloride* i The reaction mixture was heated on a steam bath until no more hydrogen chloride was evolved* The total amount of material obtained from the above ! reaction was placed in a Claisen flask and heated on a salt !bath in order to decompose the ester into stearic acid and ji I the olefin, 7 -pentadecene* With a bath temperature of 300°, jmost of the olefin distilled at 210°• jj Redistillation of the olefin gave two fractions. ! i j fraction | 1 2 n pressure 8 mm* 8 mm* weight 120-122° 123-125 13 g. 22 g* ! This gives a total amount of 35 g* or a 75# yield of the olefin* | A sample of 7-pentadecene was found to react readily with the D*S. reagent and a white barium salt was isolated* Eowever, due to the complexity of the product (See Sulfonation of 2-Pentene) the investigation was abandoned* SUMMARY SI i l || i ji A study has been made of the reaction of dioxane ;!sulfotrioxide with ethylene, propylene, 1-pentene, cyclo- | J hexene, styrene, and 1-pentadecene. j It was found that reaction may occur either by addition or substitution, the former leading to the j formation of hydr oxy sulf onat es, the latter to unsaturated j sulfonic acids. ! j The reaction of ethylene with dioxane sulfotrioxide occurs readily at 50° to yield methionic acid and a major product of uncertain structure. Propylene reacts with dioxane sulfotrioxide readily at ||5-10° to produce an unstable solid which is thought to be a jjhomolog of carbyl sulfate coordinated with one or more |moles of ethylene chloride. Both the solid and filtrate on jhydrolysis with barium hydroxide produce barium 2-hydroxyl | propane-1-sulfonate contaminated with an unsaturated product | thought to be a barium propene-1-sulf onate. i 2-Chloropropane-l- sulf onyl chloride and a propene-1-sulf onyl chloride have jbeen prepared. 1-Pentene sulfonates normally to give on hydrolysis 2-hydroxypentane-l-sulfonic acid contaminated with an unsaturated salt. Cyclohexene reacts with dioxane sulfotrioxide at low |temperatures, 5-10°, to produce a white unstable solid jsimilar to that obtained from propylene. The solid is |suspected of being the sulfuric-sulfonic anhydride co ilordlnated with ethylene chloride. ii Both the solid and filtrate ij Ion hydrolysis with barium hydroxide give barium 2-hydroxycyclohexane-1-sulf onate contaminated with some unsaturated material. I | j has The sulf onat ion of styrene at 5° produced a solidwhich been Identified as the !phenylethane-l-sulfonlc acid. sultone of 2-hydroxy-2The filtrate on hydrolysis I !yielded barium 2 -phenylethylene-1-sulfonate. This was !converted to 2-phenylethylene-1-sulfonyl chloride and 2 -phenyle thylene-1-sulf onamide . j| 1-Pentadecene is sulfonated readily by the dioxane , 1 jsulfotrioxide reagent at 10° to give on hydrolysis with Isodium hydroxide, sodium 2-hydroxypentadecane-l-sulf onate. | !This is reported to possess very good detergent properties. I | Sodium 2-acetoxypentadecane-1-sulf onate was prepared by ijthe action of acetic anhydride on the hydroxysulf onate. m*>rthw#etern **tv*rst*y 69 « Library BIBLIOGRAPHY 1* 2. 3. 4. 5* 6. 7. 8. 9. 10. 11. 12. 13. 14. 15* 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 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Brooks, The Non-Benzenoid Hydrocarbons, 1922, p. 143. Malkemus, This Laboratory, Private Communication. Whitmore, Organic Chemistry, 1937, p.35. McAllister, Private Communication, The Procter and Gamble Company, Ivorydale, Ohio. Lowry, J.Chem.Soc., 822 (1923). Kharasch and Reinmuth, J.Chem.Ed., 8^ 1703 (1931). Drogin and Rosanoff, J.Am.Chem.Soc., 38, 711 (1916). Cook and Cook, Ind.Eng.Dhemi* (Anal.Ed.T/ 5, 186 (1933). Kistiakowsky, Ruhoff, Smith and Vaughan, J.Am.Chem.Soc., 57. 877 (1935). Hurd, Goodyear and Goldsby, J.Am.Chem.Soc., 58, 235 (1936). w0rganic Synthesis w, Coll. Vol., 1, 1932, p.421. Kharasch, Walling and Mayo, J.Am.Chem.Soc., 61, 1559 (1939) . Lucas and Prater, J.Am.Chem.Soc., 59, 1683 (1937). Wilkinson, J.Chem.Soc., 3057 (193l7V Kozaclk and Reid, J.Am.Chem.Soc., 60, 2436 (1938). Kipping, J.Chem.Soc., 455 (1893). 70. VITA James Marion Holbert Born: November 17, 1914 at Chattanooga, Tennessee Education: B.S., University of Chattanooga, Chattanooga, Tennessee, 1932-1936. M.S., University of Tennessee, Knoxville, Tennessee, 1936-1937. Positions Held: Assistant in Chemistry, University of Chattanooga, 1934-1936. Assistant in Chemistry, University of Tennessee, 1936-1937. Assistant in Chemistry, Northwestern University, 1937-1940. Affiliations: Sigma Xi Phi Lambda Ups lion Gamma Sigma Epsilon American Chemical Society