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The synthesis of certain alpha nitro sulfides

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The synthesis of certain alpha nitro sulfides

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Content THE SYNTHESIS OF CERTAIN ALPHA NITRO SULFIDES A THESIS P re se n te d to th e F a c u lty o f the Graduate School U n iv e rs ity o f Southern C a lif o rn ia In P a r t i a l F u lfillm e n t of th e Requirements fo r th e Degree M aster o f Science i n Chemistry by James Lorne Cameron. June 1949 U M I Number: EP41568 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. Dissertation Publishing UMI EP41568 Published by ProQuest LLC (2014). Copyright in the Dissertation held by the Author. Microform Edition © ProQuest LLC. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 4 81 0 6 -1 3 4 6 fi! ✓ m y c l ' V*! ( L f This thesis, written by ..... under the guidance of h.iat,.. Faculty Committee, and approved by all its members, has been presented to and accepted by the Council on / T ° * } I I ^ Graduate Study and Research in partial fulfill- [ ment of the requirements for the degree of M S.m ...Q F....SC.IEM ....................................... ~~ -Emor-y-S^-Bogardus- Dean H. W . P a t mpr e Secretary Date June..l942 ........ Faculty Committee Chairman ACKNOWLEDGMENT The au th o r w ishes to express h is a p p re c ia tio n to Dr. Norman Kharaseh f o r h is in v a lu a b le d i r e c t i o n and encourage ment during this, i n v e s t i g a t i o n . CONTENTS I I . I I I . In tro d u c tio n / A. Statem ent of P r o b l e m ..............................................................1 B. C e rta in P ro p e rtie s o f N itro alk an es . . . . 4 C. H ydrolytic Decomposition of S u lfe n y l C h lo rid e s. 9 D. Alpha N itro S u lfid e s ................................................... 11 D iscussion of Experim ental S tu d ies ............................. 14 Experim ental A. S ta r tin g M a te ria ls .. .. ... .. 26 1. N itro alk a n es 2. Reagents 3. P re p a ra tio n of Other Required Compounds B. 2 , 4 -D in itro p h en y l 1 f-N itro p ro p y l S u lfid e . . 27 1 . P re p a ra tio n by R eaction of 2 ,4 - D in itr o - b en zen esu lfen y l Chloride w ith the Sodium ' S a lt of 1-N itropropane in Ether 2. Behavior in Sodium Hydroxide S o lu tio n . 29 C. 2 ,4 -D in itro p h en y l ( 1 , - N i t r o - l t -M ethylethyl) S u lfid e 1. P re p a ra tio n by R e a c tio n .o f 2 ,4 - D in itr o - ben zen esu lfen y l C hloride w ith the Sodium. S a lt of 2-N itropropane in Ether 2. Behavior in Sodium Hydroxide S o lu tio n . 30 D. 2 ,4 -D in itro p h e n y l 1 '- N it r o e th y l S u lfid e . 1. P re p a ra tio n by R eaction of 2 , 4 - D in itr o - ben zen esu lfen y l C hloride w ith th e Sodium S a lt of N itro eth a n e in E ther . . . . 3 1 2.. Attempted P re p a ra tio n by Treatment of 2 ,4 -D in itro b e n z e n e su lfe n y l Chloride a) With th e Sodium S a lt of N itro eth an e in Absolute A lcohol; the Formation of 2 ,4 -D in itro p h e n y l 2 1 ,4 * -D in itro - b e n z e n e th io lsu lfo n a te R eaction of 2 ,4 -D in itro b e n z e n e su l fe n y l C hloride w ith Absolute A lc o h o l.33 b) With Excess N itro e th a n e , Without Solvent 3. Attempted P re p a ra tio n by Treatment of 1-Brom onitroethane a) With Sodium 2.,4 - D in itr o th io - phenoxide in Absolute Alcohol b) With 2 ,4 -D in itro th io p h e n o l in Benzene and T o l u e n e ..........................................................34 c) By Fusion w ith 2 ,4 -D in itr o th io p h e n o l.35 i. E. £ ,4 -D in itro p h en y l N itrom ethyl S u lfid e 1 . P re p a ra tio n by Reaction o f 2 ,4 - D in itr o - b en zen esu lfen y l Chloride w ith the Sodium S a lt of N itrom ethane in E th er 2. Attempted P re p a ra tio n by Treatment of 2 ,4 - D in itro b e n z e n e su lfe n y l Chloride w ith N itr o - methane in Carbon T e tra c h lo rid e ............................. 36 F. 2-N itrophenyl 1 '-N itro p ro p y l S u lfid e 1. P re p a ra tio n by R eaction o f th e Sodium S a lt . of 1-N itropropane i n E ther a) With 2-N itrobenzenes.ulfenyl Chloride . . 37 b) With 2 -N itro b e n ae n esu lfen y l Bromide e) With 2 -N itro b e n ze n esu lfen y l Thiocyanate . 38 2. M olecular Weight D eterm ination 3. O xidation to 2-Ni.trophenyl 1 *-N itropropyl Sulfone G. 2-N itrophenyl (1 *-N itro-M ethylethyl) S u lfid e 1. P re p a ra tio n by R eaction of 2-N itrobenzene s u lf e n y l Chloride w ith the Sodium S a lt of 2-N it r opr o p a n e ................................................. 39 H. 2-N itrophenyl 1 r- N itro e th y l S u lfid e 1. P re p a ra tio n by R eaction of 2-N itrobenzene- s u lf e n y l C hloride w ith the Sodium S a lt o f N itro eth a n e in E ther 2, Attempted P re p a ra tio n by Treatment of 2 -N itro b e n z e n esu lfe n y l C hloride a) With th e Sodium S a lt o f N itro eth a n e - in A bsolute A lcohol; th e Formation of 2-N itrophenyl 2 '-N itro b e n zen e- t h i o l s u l f o n a t e . . . . . . . . . 40 b) With N itro e th a n e in Carbon T etruchlori.de . 41 c) With N itro eth a n e in G la c ia l.A c e tic Acid . 42 X. 2-N itrophenyl N itrom ethyl S u lfid e 1. P re p a ra tio n by R eaction of 2-N itro b en zen e s u lf e n y l Chloride w ith the Sodium S a lt of Nitromethane J . 1-A nthraquinonyl 1 f -Ni.tropropyl S u lfid e 1* P re p a ra tio n from 1 -A n thraquinonesulfenyl Chloride and the Sodium S a l t of 1 -N itro - propane . . . . . . . . . . . . . 43 ii K. Attempted R eaction of Triphenylm.ethanesu.lfenyl C hloride and the Sodium S a lt o f l-N itro p ro p an e L. R eaction of P ara-T o lu en esu lfe n y l C hloride w ith the Sodium S a lt o f N itro eth a n e . . . . . . . . 44. I T . S u m m a r y .............................................................................................................................4 6 V. B ib lio g rap h y ...............................................................................48 i i i LIST OE TABLES L. Some R eactions o f S u lfe n y l Chlorides w ith N u eleo p h ilic Reagents . . . . . . . . . . Z I I . P h y sica l P ro p e r tie s o f C e rta in N itroalkanes. . . . 4 I I P . Attempted Syntheses of- Alpha N itro S u lfid e s hy Reactions of S u lfe n y l C hlorides w ith N itro a lk a n e s . 15 I¥ . P re p a ra tio n of Alpha N itro S u lfid e s . . . . . . 19 I . INTRODUCTION A. STATEMENT OF PROBLEM Although 1 -a n th ra q u in o n e su lfe n ic a c id i s th e only a c id o f i t s c la s s to have been is o l a te d ^ , a very co n sid erab le number of d e r i v a t i v e s o f s u lf e n ic acid s i s now known. Of th e s e , th e s u lfe n y l c h lo rid e s (RSC1), the s u lfe n y l bromides (RSBr), and th e s u lfe n y l th io c y a n a te s (RSSCN) a re of p a r t i c u l a r i n t e r e s t in the p re s e n t study. The re a c tio n s of the d e r iv a tiv e s of s u lf e n ic a c id s have been 2 summarized in d e t a i l in a re ce n t review . I f one compares th e se known r e a c tio n s o f th e s u lfe n y l h a lid e s and s u lfe n y l th io c y a n a te s w ith th o se o f th e a lk y l h a lid e s , some very d i s t i n c t s i m i l a r i t i e s are to be noted. Because of th ese s i m i l a r i t i e s , and also because many r e a c tio n s of a lk y l h a lid e s a re b e st i n te r p r e t e d as n u c le o - p h i l i c a tta c k s by the reag e n ts at th e alpha carbon atoms o f th e h a l id e , R*X , i t appears reasonable to suggest t h a t th e c o rre sponding r e a c tio n s o f s u lfe n y l h a lid e s and s u lfe n y l th io c y a n a t e s also occur through n u e le o p h ilic a tta c k o f th e e l e c t r o n - r i c h re a g e n ts ( e . g . , SON- , Br", CN~, 0R~, o le f in s e t e .) o n th e p o s i t i v e l y charged s u l f u r atom o f RS^X**. Table I l i s t s some t y p i c a l r e a c tio n s o f s u lfe n y l c h lo rid e s which may be re p re se n te d as o c c u rrin g in t h i s manner. In many cases th e analogy to a lk y l h a lid e s i s q u ite c le a r . >1- Table I . Some R eactions o f S u lfen y l Ghlorid.es w ith N u e le o p h ilic R eagents, React ant s P roducts Ref. (1 o r 2) RS^Cl" r e a c tin g w ith K* + Br" RSBr + K * + Cl" 3 K* > SON" RSSCN + K* + Cl" 4 K* + ON" RSGN + K+ + 01“ 5 K* + 21” sjjasi] + 3K+ + 301“ RSSR + I 2 6 HgS RSSSR + 2H+ + 20l" 7 + 2SH” 2 [RSSH] + 2K+ + 201” RSSR * Hgs + S 8 r ' s h • > . RSSR* + H* + 01 9 M* + RS" RSSR* + M* + Cl” 10 Ag* + RSOg" t RSSOgR + • AgOl 11 MgBr+ + R- RSR* + Mg* + Br" + Cl" 12 M 1 * «. OR” RSOR1 + M * + '0 l “ 13, 14 2NHs RSNHg + NH^ + 01” 15 3R*8h2 RSNHR* + RNHg^ h . 01“ 16 3R2§H rsnr' •* r2nh2% 01" 17 h2° - ch3 rsoh2ch2oi 18 ch3coch3 RSCH2C0CH3 + H++ 01" 19, 20 m+ -t- (gh3ooohcoc2h53 ” 0H3COCH(-SR)OO02H5 01" $ 15 -2- P rev io u s s tu d ie s of the r e a c t i o n s of the d e r iv a tiv e s of s u lf e n ic ac id s w ith n itr o a lk a n e s have n o t been re p o r te d . In view of the g e n e ra l c o n s id e ra tio n s p re se n te d above, i t was p r e d ic te d th a t n itro a lk a n e anions (RCHNOg) would r e a c t w ith s u lfe n y l c h lo rid e s and brom ides, and w ith s u lf e n y l th io c y a n a te s , to y ie ld alpha n i t r o s u l f i d e s . H RS*C1~ + [r *CHNOg] Ha+ ---- * R S-C-N02 -f- Na+ C l” ... } Rf I n t e r e s t in the c o rre c tn e ss of t h i s p r e d ic tio n was enhanced by the r e s u l t of a l i t e r a t u r e survey which, confirmed th a t alpha n i t r o s u lf id e s have n o t been p re v io u sly re p o rte d . M. study of the r e a c tio n s o f c e r t a in s u lfe n y l c h lo rid e s and bromides and s u lf e n y l th io c y a n a te s w ith com mercially a v a ila b le n itr o a lk a n e s was acco rd in g ly made, and the r e s u l t s have been recorded in t h i s d i s s e r t a t i o n . The rem ainder of t h i s in tro d u c to ry s e c tio n i s devoted to such f u r th e r n o ta tio n s concerning th e n i t r o alkanes and s u lf e n y l h a lid e s as seem e s p e c ia lly p e r tin e n t to the purpose of th e p rese n t study. S ectio n IT d isc u sse s the experim ental r e s u l t s . The experim ental d e t a i l s , p resen ted i n S ectio n I I I , are follow ed by a summary and b ib lio g ra p h y . -3- B. CERTAIU PROPERTIES o f NITROALKANES. The s u c c e s s fu l development o f methods fo r th e vapor-phase n i t r a t i o n o f alk an es has made th e n itr o a l k a n e s r e a d i ly a v a i l ab le and has promoted a v ery w idespread i n t e r e s t in th e p r o p e r t i e s and p r a c t i c a l u t i l i t i e s o f th e low er members o f t h i s s e r i e s o f compounds. Table I I l i s t s c e r t a i n p h y s ic a l p r o p e r t i e s o f th e n i t r o a lk a n e s . U nless o th e rw ise s t a t e d , th e v a lu e s are th o s e r e p o rte d pi by Scheer . TABLE I I PHYSICAL PROPERTIES o f CERTAIN NITROALKANES. Mol. , Wt. S.G. 20/20 M.P. °C. B .P . °C. k20 D S o lu b i l i t y * *# * > Ka N itrom ethane 61.04 1.139 -29 101.2 1.3818 9 .5 10.2 N itro e th a n e 75.07 1.052 -90 114.0 1.3916 4 .5 8 .5 1-N itro p ro p an e 89.09 1.003 -108 131.6 1.4015 1.4 2 -N itropropane 89.09 0.992 -93 120.3 1.3941 1 .7 7.7 * g/100 ml* H20 a t 20PC. ** R eference 22 The magnitude o f th e d i s s o c i a t i o n c o n s ta n ts shows t h a t n i t r o a lk a n e s a re weak a c id s . The a c id s tr e n g th o f n itro m e th a n e , fo r example, i s approxim ately eq u a l to th a t o f phenol o r o f a c e to - 23 a c e t i c e s t e r . I t may be n o te d t h a t th e v a lu e s fo r a c i d i c d is s o - -4- e l a t i o n In w ater in crease p ro g re s s iv e ly from n itro e th a n e to 2 -n itro p ro p a n e . The re v e rse order would have been p re d ic te d from a comparison of the in d u c tiv e e f f e c t s of hydrogen and methyl groups. This in v e rs io n of the expected order of acid s tre n g th s has been r a tio n a liz e d by the su g g estio n th a t an isom e r i z a t i o n of the n itro a lk a n e to an a c i form precedes io n iz a tio n , This is o m e riz a tio n , which i s a ls o suggested by o th e r p r o p e r tie s of n itr o a lk a n e s , may be form ulated as follow s: /OH RCHoN0o*=* RCH=N 4 C N Q . 0 RCH=N N 0 + H 22 T urnbull and Maron suggested t h a t replacem ent of an alpha hydrogen by a methyl group (which has a sm a lle r in d u c tiv e e f f e c t ) c o n trib u te s to the s t a b i l i t y of th e a c i form, th e re b y in c re a s in g i t s e q u ilib riu m c o n c e n tra tio n and fa v o rin g an in c re a se in the d is s o c ia tio n c o n s ta n t. I t is i n t e r e s t i n g to n o te , however, th a t the r a t e of iso m e riz a tio n to the ac i form, has been shown to 24 in c re a se in p assin g from 2 -n itro p ro p a n e to nitrom ethane By r e a c tio n of n itr o a lk a n e s co n ta in in g alpha hydrogen atoms, 25 w ith s u f f i c i e n t l y stro n g b a ses, h ig h ly conducting s a l t s r e s u l t 26 Various n itro a lk a n e s a l t s have been re p e a te d ly is o la te d as, such 2 7 In 1872, Meyer and Stuber re p o rte d th a t sodium n itro e th a n e may be obtained by h e a tin g a s o lu tio n of the n itro a lk a n e in anhydrous benzene w ith sodium, or by i n t e r a c t i o n of an a lc o h o lic s o lu tio n of sodium hydroxide w ith n itr o e th a n e . By e i th e r procedure the n e a rly -in s o lu b le s a l t i s p r e c i p ita t e d and can be c o l le c te d , but i t explodes i f heated above 100°. S a lt form ation does no t occur -5- when i n t e r a c t i o n s o f a lc o h o lic potassium hydroxide o r a lc o h o lic ammonia with n itro e th a n e are attem pted. In th e case o f n i t r o e th a n e , th e sodium s a l t i s p r e c i p i t a t e d when th e n i t r o p a r a f f i n 28 i s t r e a t e d w ith a lc o h o lic sodium hydroxide. Meyer a lso d is covered th a t sodium nitrom ethane can he p r e c i p i t a t e d by adding an a lc o h o lic s o lu tio n o f sodium ethoxide to an a lc o h o lic solu t i o n o f the n itr o a lk a n e . He re p o rte d th a t th e r e s u l t i n g s a l t i s v i o le n tly e x p lo siv e. Other workers have recorded t h a t th e dry sodium n itro e th a n e i s r e l a t i v e l y s ta b le bu t th a t i t ex- 29,30,31.32 p lo d e s i f m oistened . * S a lts of 2 -n itro p ro p an e and of a n itro p e n ta n e o f u n d esig n ate d s tr u c tu re are re p o rte d to be ob- 33 34 ta i n a b l e by procedures s im ila r to those d e s c rib e d above. * Considerable e f f o r t has been d ir e c te d towards e s ta b li s h - 33 35 36 37 38 in g th e s tr u c t u r e of the n itr o a lk a n e s a l t s . » > > » ^he b e s t 39,40 su p p o rted view point, suggested by Kornblum , involves a r e s o n a tin g anion which may be d e p ic te d as shown below. As would be p r e d ic te d on the b a s is o f t h i s p ro p o s a l, th e o p tic a l a c t i v i t i e s o f 2 -n itro o c ta n e and 2 -n itro b u ta n e are d estro y e d when th e n itr o a lk a n e s are n e u t r a liz e d w itn sodium eth o x id e o r sodium hydroxide. One might expect th e fre e n itro a lk a n e s to be re g e n e ra te d on tre a tm e n t o f the s a l t s w ith a c id s . This i s not always found to be th e case. When attem p ts were made to reg en e ra te the fre e n i t r o a lk a n e s by a c i d i f i c a t i o n w ith stro n g m ineral a c id s , v a rio u s de- -6- composition products were observed. For example, treatm ent of an aqueous solution of sodium n itroethane with hydrochloric acid 33 41 r e s u lt s in the formation of nitrogen oxid,es and acetaldehyde .* Weaker acids, such as carbonic or a c e tic acids, or d ilu te aqueous so lu tio n s of mineral acids at low temperatures do, however, re- * n - p « 14- 34,35,36,37,38,41,42,43,44 generate the nitroalkanes from th e ir s a l t s . * * * * * * * * The n itro alk an e s a l t s are much more re a c tiv e nueleophilic reagents than are the free n itro alk an es. Reactions of the free n itro alk an es with chlorine or bromine are reported to occur only under 45 very forced conditions, whereas the reaction of sodium n itr o - ethrane with bromine, for example, is reported to occur in sta n - 46 taneously . Of special in te r e s t to th is study are the known cases wherein the s a lts of c e rta in su b stitu te d n itro alk an es enter in to m etathetic exchanges with alkyl halides. Certain examples, 47 summarized by Thurston and S hriner, are shown below. O N -C-NO, Ag* + BxCH(C6H5) 2 Cl I “ ° ~m 2 ch(c6h5) 2 Ag Br C H A O^' 5 2 ! 1 o 1 Ag+ + OHjI A Br* s A Br A C N f •C=/ och3 Ag A -0-NOg Ha* + CH3I 0°o - . -9 A A ■ A CN -c-r OCH, Na I CB3-C(N02) 2 Ag ch3i Both C -alkylation and 0- and 0* alk y latio n s are reported. Contact of th e n itro a lk a n e s w ith aqueous or a lc o h o lic solutions; of b a sic re a g e n ts promotes in te rm o le c u la r condensation 48 r e a c tio n s . I t was re p o rte d th a t these r e a c tio n s are more ra p id 27 at e le v a te d tem p eratu res. Dry potassium, carbonate was d e c la re d to have no e f f e c t upon n itr o e th a n e , but prolonged co n tact w ith a stro n g aqueous s o lu tio n of the carbonate produced sodium n i t r i t e ammonia, a c e t o n i t r i l e and tr im e th y lis o x a z o le . Aqueous potassium hydroxide or sodium hydroxide induce s im ila r co n v ersio n s, w hile s o lu tio n s of ammonia and ethylam ine a c t le s s e n e r g e tic a ll y . De com position of the ni.tr opr opane s to s im ila r products a lso occurs, 49 50 although h e a tin g i s r e q u ir e d . : ’ In r e c e n t years L ip p in c o tt 51 has extended such i n v e s tig a tio n s . He r e p o rte d th a t prim ary n itr o a lk a n e s , ex c ep tin g n itro m e th a n e , condense in the presence of b a sic re a g e n ts to y ie ld t r i a l k y l i s o x a z o l e s ., By u sin g pro p y l- v amine as th e base he was able to i s o l a t e jS-dioxIme interm ediates.. His s tu d ie s le d him to p o s tu la te th e follow ing mechanism for the form ation of th e is o x a z o le s . Compared to o th e r n itr o a lk a n e s , n'itromethane has been found 49 50 53 53 to be un iq u ely s e n s itiv e to a l k a l i . > > » Thus tre a tm e n t o f nitrom ethane w ith a l k a l i hydroxides r e s u l t s i n conversion to th e s a l t s of methazonic a c id (I) 0H 2 * 9 H 2 I 0 2 f CH2 - C H 2 H0 J C H -C H = NO gK + HgO H0 ?K H L N -O K HOH ' I OH A C. H y d ro ly tic Decomposition o f S ulfenyl C hlorides. In c e r t a in o f th e experim ents d escrib e d in t h i s d i s s e r t a t i o n i t was found th a t th e s u lfe n y l c h lo rid e s employed were converted to th e th io l s u l f o n a t e e s te r s (RSOgSR). A b r i e f resume' o f s im ila r o b se rv a tio n s by o th e r au th o rs th e r e fo r e seems a p p ro p ria te a t t h i s tim e. L im iting t h e i r s tu d ie s to 3 -n itro b e n z e n e su lfe n y l c h lo rid e , 5 4 Zincke and Farr found t h a t trea tm en t w ith w ater r e s u l t s i n the form ation of 3 -n itro b e n z e n e s u lfe n ic anhydride. In cold methanol or e th a n o l, m ixtures o f 3 -n itro p h e n y l d i s u l f i d e and the t h i o l s u lfo n a te are o b ta in ed . In hot alco h o l 3 - n itr o b e n z e n e s u lfin ic a c id and th e d is u l f id e are produced. When b o ili n g , d i l u t e methanol i s th e s o lv e n t, the d i s u l f i d e , s u l f i n i c a c id , t h i o l s u l f o n a t e e s t e r and a 30 $ y i e l d of o-am inobenzenesulfonic a c id are the p ro d u c ts. Analogous o b se rv a tio n s have been made by o th e r w orkers, who 55 s tu d ie d the b ehavior of ben zen esu lfen y l c h lo rid e , 3 ,5 - d ic h lo r o - 56 b en z en e su lfen y l c h lo rid e , 1 -a n th ra q u in o n e su lfen y l ch lo - 1 18 57 58 59 r i d e , * * * jD -nitrobenzenesulfenyl c h lo rid e , 3 - n i t r o - 60 4-m eth y lb en zen esu lfen y l c h lo rid e , and 2 -n itro -4 -c h lo ro b e n z e n e - fil s u lf e n y l c h lo rid e . -9- To ex p la in th e form ation o f th e se v a rio u s p ro d u c ts, i t has been g e n e ra lly assumed th a t s u lf e n ic ac id s are formed as the prim ary p ro d u cts in th e h y d ro ly sis o f the s u lfe n y l c h lo rid e s , and t h a t th e s e u n s ta b le a c id s th en undergo d ism u tatio n r e a c tio n s , y ie ld in g pro d u cts which can i n t e r a c t f u r th e r to form those 3 ? a c t u a l l y is o l a te d . R S C 1 — » • [R S O H ] RSO„H «- [RSOH] * o T — » RSH * RSOgH R S 0 1 ] [RSOH] * (RSOH] RSOgSR R S SR D. Alpha N itro S u lfid e s A l i t e r a t u r e s u r v e jr has f a i l e d to r e v e a l an example of a s u lf id e having a n i t r o or an amino group on the alp h a carbon atom. Form ation of alp h a n i t r o s u lf id e s as in te rm e d ia te s were, however, p o s tu la te d by Melnikov to ex p la in the form ation of d i s u l f i d e s , carbon monoxide, n itr o g e n , and water in r e a c tio n s of th io p h e n o l and t h io c r e s o l with, bromonitromethane or 1-bromo- n itr o e th a n e . He suggested th a t alpha n i t r o s u lf id e s (ArSCHHNOg) are formed as in te rm e d ia te s and then undergo decom positions to the A O observed p ro d u c ts. Although the u su a l p re p a ra tio n of organic s u lf id e s i s by m e ta th e tic r e a c tio n of a h a lid e and a m e ta l lic m ercap tid e, the only o th e r re fe re n c e to the use of h a l o n i t r o - 63 " p a r a f f in s was made by Connor. He reco rd s th a t in s te a d of undergoing m e ta th e s is , compounds co n ta in in g p o s itiv e halogen may ox id ize the m ercaptide to d i s u l f i d e . . . m e tath esis may sometimes be made the main r e a c tio n by o p e ra tin g a t room tem perature or ft lower . Besides b ro m o n itro eth an e, compounds which he c i t e d as d is p la y in g p o s itiv e halogen c h a ra c te r in such r e a c tio n s are e th y l alpha c h lo r o a c e to a c e ta te , phenacyl c h lo rid e , alpha bromoamides, alpha s u lfo n y l alpha haloam ides and a lp h a brom osulfones. A few s p e c if ic examples are l i s t e d below. Simple m e ta th e tic exchange was not observed in any ease. * B e i l s t e i n (issu e s 1918,1928,1942), Chemical A b stra c ts (1906-1948), B r i t i s h A b stra c ts (1870-1906) were se arch ed , under the g e n e ra l head in g " s u lf id e s " and under the l i s t s of s p e c if ic s u l f i d e s . Et S02 C - CONHg + C4H9SNa Br alcohpl 0° -11- Br °4H9S02 "?"00HH2 E t h 3o / V - S I a \ s -OOCSHgOl \ y h 3 o /X - \ s SNa h3o r ' X - S - S - H MeOH & - S - / X + . O.H SO - G-OOHH, L a » s V ^ CH3 (64) -C O CHr v / (65) 66 D 'O uville and Connor re p o rte d th e g eo m e tric a lly expected meta t h e s i s in th e case of chloroacetam ide. They recorded th a t th e y i e l d i s b e s t when th e r e a c tio n i s e f f e c te d a t 0 °, whereas h igher tempera t u r e s promote c o n sid erab le o x id a tio n o f the m ercaptide to d i s u l f i d e . H T Na + C 4H9S- ClCHgCONHg -> • C4Hg SCH2C0NH2 In th e form ation o f c e r t a i n s u l f i d e s , fu sio n o f the r e a c ta n ts t o permit- b e t t e r co n tact has proved p r a c t i c a b l e . Thus, although th e re i s no r e a c tio n when th e re a g e n ts are h eated in s o lu tio n , Hoggarth N found th a t when 2-acetam ino -5-brom othiazole i s fused w ith g_-nitro- th io p h e n o l, th e re r e s u l t s th e in sta n ta n e o u s form ation of th e d e s ire d s u l f i d e . - S H HC N II I I H B rC v C- H S 0 W -0 - CH 3 0 / X - s ^ hc— n ^ ; ; I' h 0 ; ‘On.^C-N-0-CH, C e rta in in v e s tig a to r s have re p o rte d th e p re p a ra tio n o f s u lf id e s having n i t r o groups on b e t a carbon atoms, by a d d itio n o f m ercaptans 68,69 to alp h a n i t r o b l c f i n s . -1 2- The corresponding b e ta amino s u lf id e s can be o b ta in ed by re d u c tio n . These b e ta amino s u lf id e s are claim ed to be e x c e lle n t v u lc a n iz a tio n , 70,71 a c c e le r a to r s . * -13- II. DISCUSSION OF EXPERIMENTAL STUDIES The o b je c t of t h i s stu d y was to e f f e c t the sy n th e sis of alpha n i t r o s u l f i d e s by i n t e r a c t i o n of the s u lf e n y l h a lid e s or s u lfe n y l th io c y a n a te s w ith n itr o a lk a n e s . The f i r s t experim ents attem pted involved th e r e a c tio n s of 2 -n itro b e n z e n e su lfe n y l c h lo rid e and 2 ,4 -d in itro b e n z e n e s u lfe n y l c h lo rid e and of the n itro a lk a n e s as such. As shown in Table I I I , t h i s approach did not y ie ld the d e s ire d p ro d u c ts. In s te a d , the u n reac ted s u lfe n y l c h lo rid e s , and varying p ro p o rtio n s of the d i s u l f i d e s (RSSR) and the th io l s u lf o n a te e s te r s (RSO^SR) were o b ta in e d . The propor tio n s of the l a t t e r products v a rie d , as shown, w ith the d u ra tio n and tem perature of h e a tin g , w ith the so lv e n t employed, and w ith the r a t i o of n itro a lk a n e used. As was d iscu sse d in the preceding s e c tio n , the d i s u l f i d e s and th io l s u lf o n a te e s t e r s have re p e a te d ly been observed by o th e r in v e s tig a to r s as products of the therm al or h y d ro ly tic decom positions of s u lfe n y l h a l i d e s . The p o ssib le use of b asic re a g e n ts (such as amines or sodium a c e ta te ) as c a t a l y s t s in the r e a c tio n of n itro a lk a n e s w ith s u lfe n y l h a lid e s was co n sid ered , but was not in v e s tig a te d , sin c e th ese b a sic compounds them selves r e a c t w ith s u lfe n y l h a l id e s . -14- Table III Attempted Synthesis of © 4 -Nitro Sulfides by Reactions o f Sulfenyl Chlorides with Nitroalkanes Sulfenyl Halide Nitroalkane Conditions Results 2-nitrobenzene- sulfenyl chloride 1 eq. nitroethane C C 1 4 at reflux for 3 hrs. 2 eq. nitroethane CCI4 at reflu x for 30 hrs. 2 eq. nitroethane g la cia l acetic acid at 80° for 3 hrs. 2,4-dinitrobenzene- 1 eq. nitroethane CCl* at reflu x for 3 hrs. su lfen yl chloride 20 eq. nitroethane no solvent, at reflu x for 3 hrs. Recovery o f 97$ o f the sulfenyl chloride Crude sulfenyl chloride 2-Nitrophenyl d isu lfid e 2-Nitrophenyl 2-nitrobenzene- th iolsu lfon ate ( 3$) Crude sulfenyl chloride 2-nitrophenyl d isu lfid e 0 5 $ ) 2-Nitrophenyl 2-nitrobenzene- th iolsu lfon ate ( 5$) Sulfenyl chloride (95$) Sulfenyl chloride (47$) plus unidentified ta r -lik e product — possibly containing some d isu lfid e / The n o n - r e a c t iv ity of th e s u lfe n y l c h lo rid e s with n i t r o a lk a n e s , as such, stren g th en ed our o r ig in a l f e e lin g th a t th e p rep a r a tio n o f th e alpha n i t r o s u lf id e s would probably re q u ire the use o f a p p ro p ria te s a l t s o f the n itr o a lk a n e s . This p r e d ic tio n had been made on th e b a s is t h a t many o th e r re a c tio n s o f su lfe n y l h a lid e s a re known to proceed by n u e le o p h ilic a tta c k o f anions on th e p o s i- t i v e s u lf u r atom of RS 01 . A ccordingly, a study was made o f the r e a c tio n s of 2 -n itro b e n z e n e su lfe n y l c h lo rid e and 2 ,4 - d i n i t r o - b en z en e su lfen y l c h lo rid e w ith th e sodium s a l t o f n itro e th a n e . The sodium s a l t was p re p a red in ab so lu te e th y l alco h o l s o lu tio n , and th e n brought in to r e a c tio n w ith th e s u lfe n y l c h lo rid e s in t h i s same so lv en t a t low te m p eratu re. I t was, o f co u rse, r e a l iz e d th a t s u lfe n y l c h lo rid e s may re a c t w ith b o ilin g a lc o h o ls to y i e l d th e i 54 s u lf e n a te s (RSOR ) , and th a t Zincke re p o rte d th a t 2 - n i t r o - b e n z en e su lfen y l ch lo rid e was converted in th e presence o f cold a b s o lu te alco h o l in to th e corresponding th io l s u lf o n a te and d is u l f i d e ; but th e above procedure was n e v e rth e le s s in v e s tig a te d , in view o f the p o s s i b i l i t y th a t th e r e a c tio n o f th e su lfe n y l h a lid e w ith th e n itr o a lk a n e anion might be s u f f i c i e n t l y ra p id to tak e precedence over the a l t e r n a t e re a c tio n s . As i s d isc u sse d below, t h i s was not found to be th e case. The p ro d u cts o b tain ed in the case o f 2 ,4 -d in itro b e n z e n e s u lfe n y l c h lo rid e ( re a c te d w ith sodium n itro e th a n e in a b so lu te alco h o l a t 5° 0. for t h i r t y minutes) were 40 fo 3 ,4 -d in itro p h e n y l d i s u l f i d e and 34 $ 2 ,4 -d in itro p h e n y l 2 ,4 - d in itr o b e n z e n e th io ls u lfo n a te . -16- The l a t t e r compound has not been p re v io u sly re p o rte d . In a sim i l a r experiment in volving 3 -n itro b e n z e n e su lfe n y l c h lo rid e , the p ro d u c ts were 10 $ 2 -n itro p h en y l d is u l f id e and 57 fo 2 -n itro p h e n y l 3 - n itr o b e n z e n e th io ls u lf o n a te . The form ation o f the th io l s u lf o n a te e s te r s under th e s e condi t i o n s i s o f s p e c ia l i n t e r e s t , and would seem to w arrant f u r th e r in v e s tig a tio n . That th e n itro a lk a n e i s involved in th e o x id a tio n i s suggested by the o b se rv a tio n t h a t w ith in t h i r t y m inutes of s t i r r i n g a t room tem perature i n th e absence of sodium n itr o e th a n e ( i . e . w ith ab so lu te alco h o l alone) 2 ,4 -d in itro b e n z e n e s u lfe n y l c h lo rid e g iv es a q u a n titiv e y i e l d o f e th y l 2 ,4 -d in itro b e n z e n e - s u lf e n a te . I f w ater, or oxygxn in th e a i r , or alco h o l were re sp o n sib le fo r th e conversion to t h i o l s u l f o n a t e , th e form ation o f th e l a t t e r should have occurred in t h i s experim ent, w ith n i t r o alkane ab sen t. In c o n tra s t to th e above a tte m p ts, which d id not y i e l d th e d e s ir e d p ro d u c ts , p relim in ary experim ents soon e s ta b lis h e d th a t s u lf e n y l c h lo rid e s can re a c t smoothly w ith sodium n itr o a lk a n e s , in a b so lu te e th e r , to form alpha n i t r o s u l f i d e s . An in v e s tig a tio n o f th e most s u ita b le c o n d itio n s fo r conducting th e r e a c tio n s shown in Table I ? r e s u l t e d in the development o f a r e l a t i v e l y sim ple g e n e ra l . procedure. This procedure in v o lv es th e p r e p a r a tio n o f th e sodium s a l t o f th e s e le c te d n itr o a lk a n e by a r e a c tio n of t h e l a t t e r w ith sodium methoxide in ab so lu te e th y l a lc o h o l, and i s o l a t i o n o f th e s a l t by su c tio n f i l t r a t i o n . Subsequent s t i r r i n g o f t h i s s a l t w ith an approxim ately e q u iv a le n t amount of th e s u lfe n y l -17- d e r iv a tiv e in anhydrous e th e r , f i r s t a t -5 ° c. and f i n a l l y a t r e f l u x te m p eratu re, y ie ld s p ro d u cts which are r e a d ily p u r i f i e d . Table IV Sulfenyl Chloride 2 ,4-Dinitroben- zenesulfenyl chloride 2-Nitrobenzene- sulfenyl chloride 1-Anthraquinone- sulfenyl chloride Sodium Product M.P. °C. % Yield % Carbon % Hydrogen Salt o f Crude Pure Calcd. Found Calcd. Found Nitromethane 2, 4-Dinitrophenyl 129- 10a 32.44 32.63 1.95 2.05 nitromethyl su l- 129.5 fid e , C 7H 506N 3S Nitroethane 2 ,4-Dinitrophenyl 117-118 74^ 50 35.18 35.26 2.58 2.76 1 '-nitroeth yl su l fid e , C 8H 706N3S 2-Nitropropane 2,4-Dinitrophenyl 1O 1- 1OI.5 40 25 37.62 27.82 3.16 3.53 ( l ’-n itr o -1 ’-methyl- ethyl) su lfid e, C 9H 906N 3S 1-Nitropropane 2,4-Dinitrophenyl 81,5-82.5 85 56 37.62 37*78 3.16 3.09 1 '-nitropropyl su lfid e, C9H 906N 3S Nitromethane 2-nitrophenyl 70-71 12 39.25 39.52 2.82 3.06 nitromethyl sul fid e , C 7H 80^N3S Nitroethane 2-Nitrophenyl 57-58 56 41 42.11 42.36 3.53 3.53 1 1-n itroeth yl su lfid e, C aH gO ^N gS 1-Nitropropane 2-Nitrophenyl 72.5-73.0 84 56° 44.62 45.16 4.16 4.41 (1 ’-nitropropyl) su lfid e, G 9Hfq O ^N ^S 2-Nitropropane 2-Nitrophenyl 81-82 36 25 44.62 44.81 4 .1 6 4.10 ( l ’-nitro-1 '-raethyl- ethyl) su lfid e, C9H j oO^NgS 1 -Nitropropan©;/,- ?-Anthraquinonyl 158 dec. 64 43 62.37 62.11 4.00 4.07 ■ f 1 ’-nitropropyl su lfid e, C , 7H , ^ O ^ IIS ( Hotes to Table IV ) All m eltin g p o in ts re p o r te d in t h i s paper are u n c o rre c te d . b 2 - Iitro p h e n y l and 2 ,4 -d in itro p h e n y l d i s u l f i d e s were a lso is o l a te d . c * in 10-20 fa y ie ld s in th e s e ru n s. 2 - Iitro p h e n y l 1 - n itr o p r o p y l s u l f id e was also o b tain ed in 70 fa crude (56 fa pure) y ie ld u sin g 2 -n itro b e n z e n e su lfe n y l bromide; and in 77 fo_ crude (72 fa pure) y ie ld u s in g 2 -n itro b e n z e n e su lfe n y l th io c y a n a te . 3 -Iitro p h e n y l d i s u l f i d e . d was also i s o l a t e d in 10-15 fo y ie ld s in th e se ru n s. The micro an a ly se s were perform ed by th e l a t e Dr. G ertrud Oppenheimer and by Dr. G.A. Swinehart o f the C a lif o rn ia I n s t i t u t e of Technology. -20- As shown below, i t i s p o s s ib le th a t a n i t r o n i c e s te r may b e formed as an in te rm e d ia te in th e form ation o f the t h i o l s u l - fo n a te . Bender and Haas have suggested a s im ila r in te rm e d ia te t o ex p lain th e form ation of s u b s t i t u t e d benzaldehydes in th e r e a c tio n of s u b s t i t u t e d benzyl h a lid e s w ith sodium s a l t s of 72 n itr o a lk a n e s . SCI O g N / 'V H 0 JTOg N02 StOH SOH I H ^ CH3-C = ■ > d i s u l f i d e and t h io l s u lf o n a te e s t e r OEt \ H O 2 -21- Although th e a p p ro p ria te s u lf e n y l c h lo rid e s were used in the m a jo rity of th e r e a c tio n s , th e s u lfe n y l bromides and th io c y a n a te s may a ls o be used. This i s in d ic a te d by th e fin d in g th a t th e same pro d u ct (1 - n itr o p r o p y l s '- n itr o p h e n y l) s u lfid e ) was o b tain ed by a l t e r n a t e l y r e a c tin g 3 -n itro b e n z e n e su lfe n y l c h lo rid e , bromide or th io c y a n a te w ith sodium 1-n itro p ro p a n e . As a m a tte r o f fa c t the b e s t y ie ld of th e pure alpha n i t r o s u lf id e (73 f o ) was obtained i n th e p r e p a r a tio n u s in g th e s u lfe n y l th io c y a n a te . I t i s q u ite l i k e l y t h a t th e r e l a t i v e l y low y i e l d (35 $) of , i i 2 ,4 - d in itr o p h e n y l (1 - n i t r o - 1 -m eth y leth y l) s u lf id e o b tain ed i n th e r e a c tio n in v o lv in g 2-n itro p ro p a n e and 2 , 4 -d in itro b e n z e n e - s u lf e n y l c h lo rid e could be in c re a s e d by f u r th e r study. However, th e low y ie ld (10 fs) of 2 ,4 -d in itro p h e n y l n itro m e th y l s u l f i d e , o b ta in e d in th e r e a c tio n o f nitrom ethane w ith 2 ,4 - d i n i t r o benzene s u lfe n y l c h lo rid e , was achieved only a f t e r co n sid erab le e f f o r t . The f a c t t h a t t h i s was th e only r e a c tio n in which th e r e was recovery o f s u lf e n y l c h lo rid e in d ic a te s th a t th e la c k o f r e a c tio n must be due e i t h e r to th e in e rtn e s s o f sodium n i t r o methane or to i t s tendency to undergo condensation r e a c tio n s w ith i t s e l f . Other workers have re p o rte d a b n o rm a litie s w ith n i t r o methane which were not g e n e ra lly observed w ith th e higher n i t r o - a lk a n e s . I t was found th a t trip h e n y lm e th a n e su lfe n y l c h lo rid e does not r e a c t w ith sodium 1-n itro p ro p a n e in e th er or benzene a t r e f lu x tem p eratu re of th e s o lv e n ts . In both cases th e s u lfe n y l c h lo rid e was reco v e red , although in benzene th e re was a lso i s o l a t e d a -23- t r a c e o f product corresponding to one d esig n a te d as tr ip h e n y l - methyl p eroxide by R.H. McMenamy. The in e r tn e s s o f t r ip h e n y l - m ethanesulfenyl c h lo rid e to n u c le o p h ilic a tta c k by th e n i t r o a l - kane anion is probably to be a s c rib e d to the absence o f a s u f f i c i e n t l y stro n g p o s it iv e charge on th e s u lf u r atom o f PhgOSOl ( a r e s u l t o f the e le c tro n r e le a s in g p ro p e rty o f th e t r i - phenylm ethyl r a d i c a l ) . B asis f o r D esignation of th e P roducts as Alpha N itro S u lfid e s . In view o f th e f a c t th a t t h i s study i s th e f i r s t to re p o rt th e p r e p a r a tio n o f alpha n i t r o s u l f i d e s , every p re c a u tio n must be ta k e n to assu re t h a t th e p ro d u cts o b tain ed do a c tu a lly have th e proposed s t r u c t u r e s . In th e p re s e n t study th e follow ing co n sid era t i o n s have been made to a s c e r ta in th e c o rre c t s tr u c t u r e o f th e p ro d u c ts. 1) The a n a l y t i c a l r e s u l t s suggest s tr u c t u r e s A, B, or polymers of th e s e . H R .0 i RO ■ = JT \ OSR A. Alpha N itro S u lfid e S tru c tu re B. N itro n ic E s te r S tru c tu re 2) Oryoscopic m olecular weight measurements have dem onstrated th a t th e polymer p o s s i b i l i t y may be e lim in a te d . 3) The b eh a v io r o f th e p ro d u cts towards ac id s and bases i s s tr o n g ly i n favor of the alpha, n i t r o s u lf id e s t r u c t u r e , fo r th e re i s a marked resemblance to th a t o f normal n itr o a lk a n e s . The t p ro d u c t, 2 ,4 -d in itro p h e n y l 1 - n itr o p ro p y l s u l f i d e , in which th e n i t r o group i s a tta c h e d to a secondary carbon atom i s so lu b le in sodium hydroxide s o lu tio n , whereas 2 ,4 -d in itro p h e n y l ( l * - n i t r o - i 1 -m eth y leth y l) s u lf id e , having a t e r t i a r y n i t r o group, i s in s o lu b l e . In a d d itio n , th e former i s reg en e ra ted by treatm en t of the b a s ic s o lu tio n o f the s u lf id e w ith d i l u t e a c e t i c ac id . These r e s u l t s in d ic a te tha/t the p ro d u cts p o ssess f re e n i t r o groups. The n i t r o n i c e s t e r s tr u c t u r e B, (corresponding to c e r t a in of the compounds re p o rte d as p ro d u cts o f a r e a c tio n o f a lk y l io d id e s w ith 47 s a l t s o f n itro a lk a n e s ) would c e r t a in ly not be expected to be rec o v e ra b le a f t e r a l k a l i tre a tm e n t, sin ce i t should be e s p e c ia lly prone ( l i k e S c h iff bases) to a c id h y d ro ly sis. . i 4) One of th e p ro d u c ts, 3 -n itro p h e n y l 1 - n itr o p r o p y l s u l f i d e , has been o x id iz e d by hydrogen p ero x id e in g l a c i a l a c e t i c a c id to th e s u lfo n e . On th e whole, th e n , th e re i s l i t t l e doubt o f th e c o rre c tn e ss o f d e s ig n a tin g th e p ro d u cts in Table IV as alp h a n i t r o s u lf id e s , s in c e th e p o s s i b i l i t y o f th e c o rre c tn e ss of the n i t r o n i c e s t e r is q u ite com pletely ru le d o u t. As alread y noted, however, th e n itr o n i c e s t e r s tr u c t u r e may occur as an u n s ta b le in te rm e d ia te in the r e a c tio n . -24- 62 I t was suggested by Melnikov th a t a lp h a n i t r o s u lf id e s were u n s ta b le in te rm e d ia te s in th e r e a c tio n s o f th io p h e n o l and nt h i o c r e s o l ” w ith alpha brom onitroalkanes, and th a t th ese were th e p re c u rs o rs of th e p ro d u cts a c tu a lly observed: d i s u l f i d e s , 62 carbon monoxide, n itr o g e n , n i t r i c oxide and w ate r. In view o f th e c o n sid e ra b le s t a b i l i t i e s of th e alpha n itr o s u lf id e s l i s t ed in Table IV, t h i s suggestion was q u estio n ed by u s , and we have undertaken th e sy n th e sis of the alp h a n i t r o s u lf id e s suggest ed by Melnikov. The n ecessary experim ents are s t i l l in p ro g re s s . In view o f our f a i l u r e , on th e one hand, to o b ta in the alp h a n i t r o s u l f i d e s from r e a c tio n s of 1-brom onitroethane w ith 2 , 4 - d i n i t r o - th io p h en o l or 2 ,4 -d in itro th io p h e n o x id e ( i n which cases th e r e was i s o l a t e d in s te a d 2 ,4 -d in itro p h e n y l d is u lf id e ) and our su c c ess, on th e o th e r hand, in o b ta in in g th e d e s ire d alpha n i t r o s u lf id e s v i a th e s u lfe n y l c h lo rid e s , the p o s tu l a ti o n of Melnikov r e q u ir e s c o n s id e ra b le s c ru tin y . Our p re lim in a ry s tu d ie s , re p o rte d in th e experim ental s e c tio n , have given r e s u l t s which are not i n accord w ith th o se to be expected on th e b a s i s of M elnikov’ s i n t e r p r e t a t i o n s . -25- I l l Expe r im ental A. S ta r tin g M a te ria ls 1. H itro a lk a n e s . The n itr o a lk a n e s were d r ie d over ttD r i e r i t e H f o r tw elve hours and were c a r e f u l ly f ra c tio n a te d . Source Range °C. Hitromethane Eastman Kodak, White Label 101.5-102.0 H itro eth an e Eastman Kodak, White Label 113.5-114.0 2-H it rop ropane Monsanto * 120.0-120.5 1-H i t ropropane Eastman Kodak, P r a c t i c a l 130-131 2. Reagents. ,, o 2-H itrochlorobenzene : Eastman Kodak # 184; m.p. 25-30 C. 2 .4 -D in itro ch lo ro b en z en e : Paragon T estin g L a b o ra to rie s # 5204; m.p. 51-53°C. Sodium Methoxide F ish er S c i e n t i f i c Go. Reagent Grade. Solvents ; The O.P. re a g e n ts were employed throughout; e th e r and benzene were d rie d over sodium. 1-A nth raq u in o n esu lfen y l c h lo rid e : p re p a ra tio n s o f A. Fowler, and R. R osenthal, Univ. of So. G al., m.p. 219-231°G. T riphenylm ethanesulfenyl c h lo rid e : p r e p a r a tio n of G. Lindberg, m.p. 131-134°0. 3. P re p a ra tio n s w ith th e Methods Employed. 2 .4 -D in itro b e n z e n e su lfe n y l c h lo rid e : Kharasch, Wehrmeister and Tigerman19, m.p. 95-96.5°^ 2-.H itrobenzenesulfenyl c h lo rid e ; H ubacker?^ m.p. 74-75°. 2 -H itro b en zen esu lfen y l bromide ; S trash u n ^, m.p. 81-83°. 2-H itro b en zen esu lfen y l th io c y an ate : S trashun , m.p. 91-93° 1-Brom onitroethane : Tscherniak , b .p . 146-147.5°. Para T o lu en esu lfen y l c h lo rid e : Lecher and H olschneider . 74 2 ,4 -D in itro th io p h e n o l : W illgerodt . B. 2 .4 -D in itro n h en v l 1 -N itro p ro p y l S u l f i d e . 1. P re p a ra tio n by R eaction of 2 ,4 -D in itro b e n z e n e su lfe n y l Chloride w ith the Sodium S a lt of 1-N itropropane in E th e r. The g e n e ra l procedure which was found most s u it a b le fo r th e p r e p a ra tio n o f the a lp h a n i t r o s u lf id e s has been in d ic a te d on page 17. The sta n d a rd equipment f o r the p re p a ra tio n s d e sc rib e d be low was an Erlenmeyer f l a s k fo r the p re p a ra tio n o f the dosium n i t r o - alk an e, w h ile , fo r th e r e a c t i o n w ith the s u lfe n y l d e r i v a t i v e , th e re was used a th ree -n e ck ed f l a s k of s u it a b le s i z e , f i t t e d w ith a mechanical s t i r r e r , an e x te r n a l te m p e ra tu re -c o n tro l v e s s e l, and a r e f lu x condenser which could be l a t e r rep la c e d by a curved tube fo r the d i s t i l l a t i o n of th e e t h e r . The g e n e ra l c o n d itio n s were developed in g r e a te s t d e t a i l in the s y n th e s is of 2 , 4 - d i n i t r o phenyl 1 f- n itr o p r o p y l s u l f i d e , and i t is fo r t h i s reason th a t i t s p re p a ra tio n i s d escrib ed below, f i r s t , and most com pletely. To a s t i r r e d s o lu tio n of 1.35 g . (0.025 mole) o f sodium methoxide in 25 ml. o f absolute, alc o h o l was added dropwise 4.45 ml. (0.050 mole) of 1 -n itro p ro p a n e over a one minute p e rio d . A white p r e c i p i t a t e of sodium 1 -n itro p ro p a n e was im m ediately produced. A fte r th re e minutes of a g i t a t i o n , 25 ml. of e th e r was added. The f in e ly - d iv id e d p r e c i p i t a t e was c o lle c te d by su c tio n f i l t r a t i o n and was washed w ith 25 ml. o f e t h e r . This product was -27- added to a suspension o f 5.86 g. (0.035 mole) o f 2 ,4 - d i n i t r o - b en z en e su lfen y l c h lo rid e i n 75 ml. of e th e r a t -5 °0 . The mix tu r e was s t i r r e d fo r t h i r t y m inutes, w ithout co o lin g , and then fo r t h i r t y m inutes at r e f lu x tem perature. The e th e r was r e moved by d i s t i l l a t i o n , 5 ml. o f w ater being added toward th e com pletion o f i t s removal. The orange re sid u e was washed w ith 150 ml. o f w ater and was c o lle c te d by su c tio n f i l t r a t i o n . ,The y i e l d o f p ro d u c t, m elting a t 75-77°, was 6.61 g. This was t r e a t ed w ith 22 ml. o f b o ili n g methanol, le av in g an undissol.ved r e s idue o f 0.50 g. which d id not melt below 250° and was presumed t o be 2 ,4 -d in itro p h e n y l d i s u l f i d e . On c o o lin g , th e r e p r e c i p i t a t e d from th e methanol s o lu tio n 4.99 g. of a yellow pro d u ct m elting a t 79-81°. R e c r y s t a l l i z a t i o n from 25 ml, o f carbon t e t r a c h l o r i d e r e s u l t e d in a y i e l d o f 4.00 g. of 2 ,4 - d in itr o p h e n y l 1 *-n itro p ro p y l s u l f i d e , m.p. 8 1 .5 -8 2 .5 °o . The y ie ld o f crude product was c a l c u la te d to be 85 jo and the y ie ld o f pure compound was 56 $>. A nalysis Humber JLC- 6 ; Cal-Tech Humber 4755 Sample : 3.733 mg. ; C02 : 5.168 mg. ; H2Q ; 1.030 mg. Oalcd. fo r 09H90 6H3S : C, 37.62 jo ; H, 3.16 jo Found :;C , 37.78 jo ; H, 3.09 jo Conditions which were v a r ie d in the development of th e above procedure in c lu d ed the p r e p a ra tio n o f th e sodium n i t r o - propane in la r g e r amounts of alco h o l and e t h e r , and th e a d d itio n o f a warm e th e r e a l s o lu tio n o f the s u lfe n y l c h lo rid e to an eth e r e a l suspension o f the sodium s a l t . A higher molar r a t i o of sodium methoxide was used in c e r ta in cases b u t t h i s was found to be advantageous only with c e r t a in of th e o th er n itr o a lk a n e s . E vaporation of th e e th e r solvent and treatm en t of th e re s id u e w ith hot carbon t e t r a c h l o r i d e was found to be le s s e f f i c i e n t th a n the procedure adopted. 3. Behavior in Sodium Hydroxide S o lu tio n . A m ixture o f 1.00 g. of yellow 2 ,4 -d in itro p h e n y l l ' - n i t r o p ro p y l s u l f i d e and 10 ml. of 10 ^ sodium hydroxide s o lu tio n was a g i t a t e d fo r two hours on a m echanical shaker. The r e s u l t i n g orange m ixture was f i l t e r e d and th e orange f i l t r a t e was c o lle c te d . The yellow re s id u e was t r e a t e d tw ice ag ain by the same procedure except t h a t th e m ixtures were a g i t a t e d fox t h i r t y m inutes. The f i n a l r e s id u e of 0.32 g. m elted a t 80-81° and th e re was no i d e p re s sio n w ith 2 ,4 -d in itro p h e n y l 1 - n itr o p r o p y l s u lf id e . The mixed f i l t r a t e s were a c i d i f i e d w ith 20 $ a c e tic a c id a t 5°0. The r e s u l t i n g yellow p r e c i p i t a t e weighed 0.43 g. and m elted at 80-84°c. A r e c r y s t a l l i z a t i o n from carbon t e t r a c h l o r i d e r e s u lt e d i n th e recovery o f 0.30 g. o f p ro d u ct, m.p. 80.5-81.5°0.-. There was-no d e p ressio n w ith 2 ,4 -d in itro p h e n y l 1 '- n i tr o p r o p y l s u l f i d e . 0. 3 ,4 -p jn itro p h e n y l ( l -IIitro -1 '-M eth y leth y l) S u lfid e . 1. P re p a ra tio n by R eaction o f 2 .4 -D in itro b e n z e n e su lfe n y l C hloride w ith Sodium S a lt o f 2-K itropropane i n E th er. In a s o lu tio n o f 15 ml. o f ab so lu te alco h o l and 15 ml. of e th e r was d iss o lv e d 1.35 g. (0.025 mole) o f sodium methoxide. To \ t h i s was added dropwise a s o lu tio n o f 4.50 ml. (0.050 mole) o f 2 -n itro p ro p a n e i n 15 ml. o f e th e r. A g e la tin o u s white p r e c i p i t a t e was imm ediately produced. A fter four m inutes of a g i t a t i o n , 50 ml. -29- o f e th e r was added, and th e sodium 2-n itro p ro p a n e was c o lle c te d by f i l t r a t i o n and washed w ith 50 ml. o f e t h e r . The product was t r a n s f e r r e d to 100 ml. o f e th e r a t -5 ° . The m ixture when s t i r r e d was very th ic k and g e la tin o u s . A fter th e a d d itio n o f 5.86 g. (0.025 mole) of 2 ,4 -d in itro b e n z e n e s u lfe n y l c h lo rid e , t h i s p ro p e rty became l e s s apparent and the. m ixture became yellow in c o lo r. S t i r r i n g was continued fo r t h i r t y m inutes, w ithout cool in g , and fo r t h i r t y m inutes a t r e f lu x te m p eratu re. The eth e r was removed by d i s t i l l a t i o n , 10 ml. o f carbon t e t r a c h l o r i d e b ein g added toward th e end o f t h i s o p e ra tio n . The re s id u e was r e flu x e d w ith 50 ml. o f carbon t e t r a c h l o r i d e and th e hot m ixture was f i l t e r e d . On co o lin g , 2.05 g. o f yellow product m eltin g a t 90-95° p r e c i p i t a t e d from th e carbon t e t r a c g l o r i d e f i l t r a t e . C o n cen tratio n o f th e mother liq u o r y ie ld e d 0.78 g. of a d d itio n a l p ro d u c t. Two r e c r y s t a l l i z a t i o n s o f the p ro d u c ts y ie ld e d 1.75 g. , i » o f 2 ,4 -d in itro p h e n y l (1 - n i t r o - 1 -m eth y leth y l) s u l f i d e , m.p. 101- O i 101.5 . The y i e l d o f crude product was 40 and th e y ie ld of pure compound was 25 A nalysis Humber JLC-5 : Cal-Tech Humber 4728 Sample : 4.629 mg. ; C02 j 6.415 mg. ; HgO ; 1.461 mg. Calcd. fo r CgHg0 6N3S : C, 37.62 $ ; H, 3.16 jo Found : C, 37.82 $ ; H, 3.53 $ 2. Behavior i n Sodium Hydroxide S o lu tio n . When 1.00 g, o f yellow 2 ,4 - d in itr o p h e n y l (1 - n itr o - 1 '- m e t h y l e th y l) s u lf id e was t r e a t e d by the same procedure as in S ection B -2 -, no c o lo ra tio n of th e sodium hydroxide s o lu tio n was observed. -30- There was no p r e c i p i t a t e when th e f i l t r a t e s were a c i d i f i e d . The u n d isso lv e d re s id u e , 0.94 g. , m elted at 100-101°. There was no / ' 1 V d ep re ssio n w ith 2 ,4 -d in itro p h e n y l (1 - n i t r o - 1 -m eth y leth y l) s u l f id e . D. 2 .4 -D in itro p h en y l 1*- N itro e th y l S u lfid e . 1. P re p a r a tio n by R eaction o f 3 .4 -D in itro b e n z e n e su lfe n y l C hloride w ith Sodium S a lt o f N itro eth an e i n E ther. The procedure d e sc rib e d in B -i was follow ed, u sin g 3.60 ml. (0.050 mole) o f n itr o e th a n e , 1.55 g. (0.029 mole) of sodium methoxide and 5.86 g. (0.025 mole) o f 3 ,4 -d in itro b e n z e n e s u lfe n y l c h lo rid e . B esides a 15 fo y i e l d o f a product decomposing above 250° (probably 2 ,4 -d in itro p h e n y l d i s u l f i d e ) , th e re was o b tain ed a 74 fj y i e l d o f a yellow s o l i d . Two r e c r y s t a l l i z a t i o n s o f t h i s p ro d u ct r e s u l t e d in a 50 fo y i e l d of a compound, m.p. 117-118°, which was presumed to be 2 ,4 -d in itro p h e n y l 1 '- n i t r o e t h y l s u lf id e . A nalysis Number JLC-4 : Cal-Tech Number 4527 Sample : 4.437 m g*. ; C02 ; 5.733 mg. ; HgO : 1.093 mg. Calcd. fo r C8H70 6N3S : 0, 35.18 fo ; H, 2.58 fo Found : C* 35.26 fo ; H, 2.76 fo 3a. Attempted P re p a ra tio n by Treatment o f 3 .4 -D in itro b en ze n e- s u lfe n y l C hloride w ith th e Sodium S a lt of N itro eth a n e in Absolute Alcohol; th e Formation o f 2 ,4 -D jn itro p h en y l 3 . 4 ,- p j - n itr o b e n z e n e th io ls u lfo n a te . A s o lu tio n o f 0.025 moles o f sodium ethoxide was p rep ared by d is s o lv in g 0.57 g. (0.025 mole) o f sodium in 100 ml. o f ab so lu te a lc o h o l, in a 500 ml. th ree -n e ck ed f la s k , equipped w ith a rubber- s e a le d s t i r r e r and dropping fu n n el. While th e s o lu tio n was s t i r r e d in an ic e b a th , 1.65 ml. (0.027 mole) o f n itro e th a n e was added -31- dropwise over a p e rio d o f two m inutes. A w hite p r e c i p i t a t e of sodium n itr o e th a n e was produced. A fter te n m inutes o f s t i r r i n g , th e ic e - b a th was removed and 5.86 g. (0.025 mole) o f 2 ,4 - d i n i t r o - b en z en e su lfen y l c h lo rid e was added to th e s t i r r e d r e a c tio n mix tu r e over a twenty-m inute p e rio d . The m ix tu re, which became deep re d at th e beginning o f th e a d d itio n , was f i n a l l y orange i n c o lo r. A fter te n m inutes o f s t i r r i n g , th e m ixture was f i l t e r e d by su c tio n ( f i l t r a t e A) and th e re sid u e was d r ie d at 45°C. This o m a te r ia l (2.61 g . ) , m elting a t 110-200 , was washed w ith b o i l in g benzene ( f i l t r a t e B) and w ith w ater, le a v in g a product m e ltin g above 250°. F i l t r a t e s A and B were c o n c en tra te d by evap o r a tio n , u s in g a d r y - a i r stream , and the p r e c i p i t a t e s which formed were p e r io d ic a ll y c o lle c te d . When c o n c e n tra tio n f i n a l l y y ie ld e d o i l s , a d d itio n a l product was ob tain ed by e th e r d i l u t i o n . The p ro d u cts were t r e a t e d by f r a c t i o n a l r e c r y s t a l l i z a t i o n , using m ethanol and chloroform p o r tio n s . The t o t a l y ie ld o f m a te ria l m e ltin g above 250° (probably 2 ,4 -d in itro p h e n y l d is u l f id e ) was 2.16 g. (40 i o ) and the y ie ld of yellow product m e ltin g a t 100- 130° was 1.18 g. (24 $>). Repeated r e c r y s t a l l i z a t i o n o f the l a t t e r r a is e d th e m elting p o in t to 126-126.5°. This product is » i b e lie v e d to be 2 ,4 -d in itro p h e n y l 2 ,4 - d in itr o b e n z e n e t n io ls u l fo n a te . A nalysis Number JLC-3 : Gal-Tech Number 5426 Sample : 5.234 mg. ; COg : 6.446 mg. ; HgO : 0.803 mg. ; ash 0.014 mg. Calcd. fo r C 13H60 10N 4 Sg : C, 33.49 $ ; H, 1.41 fo -32- Found ; 0, 33.60 # ; H, 1.73 $ R eaction of 2 .4 -D in itro b e n z e n e su lfe n y l C hloride w ith A bsolute A lcohol. Over a twenty-mi mite p e rio d 5.86 g. (0.025 mole) of 2 ,4 - d i - n itro b e n z e n e s u lfe n y l c h lo rid e was added p o rtio n w ise w ith s t i r r i n g to 100 ml. of ab so lu te e th y l a lco h o l. A fte r te n minutes addi tio n al.' s t i r r i n g , 5.23 g. of yellow product m elting at 115-120° was c o lle c te d by f i l t r a t i o n . Two r e c r y s t a l l i z a t i o n s from carbon t e t r a c h l o r i d e r a is e d th e m eltin g p o in t to 120- 122° and th e r e was no d ep re ssio n w ith an a u th e n tic sample of e th y l 2 ,4 - d i n i t r o - b e n z e n e su lfe n a te . 2b. Attempted P re p a ra tio n by Treatment of 3 .4 -P in itro b e n z e n e - s u lf e n v l Chloride w ith Excess N itro eth an e Without S o lv e n t. A s o lu tio n o f 5.86 g. (0.025 mole) o f 2 ,4 -d in itro b e n z e n e - s u lf e n y l c h lo rid e i n 36 ml. (0.50 mole) of n itro e th a n e was re flu x e d fo r th r e e hours. The yellow co lo r g ra d u a lly darkened and was f i n a l l y b la ck . A small amount of b la ck p r e c i p i t a t e was r e moved from th e cooled s o lu tio n by su c tio n f i l t r a t i o n and the f i l t r a t e was c o n c en tra te d , le a v in g a dark re s id u e . Treatment w ith 25 ml. of b o ilin g carbon t e t r a c h l o r i d e l e f t a t a r - l i k e m a te ria l from which no pure compound could be i s o l a t e d . On co o lin g , 2.73 g. o f yellow p ro d u c t, m e ltin g a t 90-95°, p r e c i p i t a t e d from th e carbon t e t r a c h l o r i d e ; th e m elting range was not depressed w ith 2 ,4 -d in itr o b e n z e n e s u lfe n y l c h lo rid e . 3a. Attempted P re p a ra tio n by Treatment o f 1-Brom onitroethane w ith Sodium 2 .4 -D jn itro th io p h e n o x id e in Absolute A lcohol. At 0°, 1.50 g. (0.0075 mole) o f 2 ,4 -d in itr o th io p h e n o l was d is s o lv e d in a s o lu tio n o f 0.30 g. (0.0075 mole) ,of sodium hydrox id e in 60 ml. o f ab so lu te a lc o h o l. The red s o lu tio n o f sodium -33- 2 .4 -d in itr o p h e n y l m ercaptide was cooled to -10° and a s o lu tio n of 1.15 g. (0.0075 mole) of 1-brom onitroethane in 30 ml. of a b so lu te o alco h o l a t -10 was added p o rtio n w ise . Immediately th e re was formed o a voluminous yellow p r e c i p i t a t e m elting above 250 , probably 2 .4 -d in itro p h e n y l d i s u l f i d e . A fter sta n d in g fo r te n hours the m ixture was heated to b o ilin g and was f i l t e r e d . C o n cen tratio n of th e f i l t r a t e l e f t a sm all amount of product which was so lu b le in w ate r. b. Attempted P re p a ra tio n by Treatm ent of 1-Brom onitroethane w ith 2 ,4 -D in itro th io p h e n o l in Benzene and T oluene. (1) A s o lu tio n of 2. g. (0.01 mole) of 2 ,4 - d in itr o th io p h e n o l and 1.55 g. (0.011 mole) of 1-brom onitroethane in 65 ml. of benzene was l e f t fo r f iv e days a t room te m p eratu re, A sm all amount of yellow m a te ria l was removed by f i l t r a t i o n and on c o n c e n tra tio n , the f i l t r a t e l e f t a yellow product m.p. 130-132°» w ith no d epression w ith 2 ,4 - d in itr o th io p h e n o l. (2) A s o lu tio n i d e n t i c a l w ith t h a t . i n (a) was re flu x e d fo r t h i r t y - s i x hours and 0.20 g. of brown m a te ria l was removed by f i l t r a t i o n . The f i l t r a t e on ev ap o ratio n l e f t 1 .8 g., of yellow product m e ltin g a t 115-125°. This was t r e a t e d w ith 10 m l. of b o ilin g carbon t e t r a c h l o r i d e , th e g r e a te r p a rt rem aining u n d isso lv e d . On co o lin g , a yellow p ro d u ct, m eltin g a t 123-130° p r e c i p ita t e d from the carbon t e t r a c h l o r i d e . Only a n e g l ig ib le amount of product was recovered by ev a p o ra tio n of the carbon te t r a c h l o r i d e mother liq u o r . (3) A s o lu tio n of 1 g. (0.005 mole) of 2 ,4 - d in itr o th io p h e n o l and 1.5 g. (0.01 mole) of brom onitroethane in 60 ml. of toluene was heated at 110-120° fo r f o r t y h o u rs. An a p p re c ia b le q u a n tity of d ark re sid u e was removed by f i l t r a t i o n and th e f i l t r a t e was c o n c e n tra te d , le a v in g 0.3 g. of brown p ro d u ct. This was tr e a te d -34- w ith 6 ml, o f b o ili n g chloroform , th e u n d isso lv ed p o r tio n of o 0.24 g, m elting above 250 , The chloroform was co n c e n tra te d , le a v in g a very small amount o f dark o ily s o li d , c. Attempted P re p a ra tio n by Fusion o f 1-Brom onitroethane w ith 3 ,4 -D in itro th io p h e n o l. A m ixture o f 0.50 g. (0,0025 mole) o f 2 ,4 -d in itr o th io p h e n o l and 2 ml, (0.015 mole) o f 1-brom onitroethane was h eated a t 140° f o r fiv e m inutes, under an atmosphere o f n itro g e n . A brown p r e c i p i t a t e which was c o lle c te d and washed w ith carbon t e t r a c h l o r i d e weighed 0.4 g. and decomposed above 250°. lone o f the d e s ire d a lp h a n i t r o s u lf id e was observed. E. 3 .4 -D in itro p h e n y l N itrom ethyl S u lfid e . 1. P re p a r a tio n bv R eaction o f 3 .4 -D in itro b e n ze n e su lfe n v l C hloride w ith Sodium S a lt o f Hitrom ethane in E th er. To a s t i r r e d s o lu tio n o f 0.050 moles of sodium ethoxide in 100 ml. o f a b so lu te a lc o h o l, p re p are d by th e a d d itio n o f 1.14 g. (0.050 mole) of sodium to the a lc o h o l, was added dropwise 4.05 ml. (0.075 mole) o f nitrom ethane. A fte r one minute a w hite p r e c i p i t a t e o f sodium nitrom ethane was c o lle c te d by f i l t r a t i o n and was wash ed w ith 50 ml. o f e th e r. This product was added p o rtio n w ise to a s t i r r e d s o lu tio n of 5.86 g. (0.025 mole) o f 2 ,4 -d in itro b e n z e n e - s u lf e n y l c h lo rid e in 300 ml. o f e th e r during a tw enty-m inute p e rio d . A fter f u r t h e r s t i r r i n g fo r one hour an orange p r e c i p i t a t e (A) was c o lle c te d by f i l t r a t i o n . This was washed w ith 40 ml. o f b o ili n g carbon t e t r a c h l o r i d e and 40 ml. o f b o ilin g m ethanol, le a v in g a dark re s id u e which was so lu b le i n w ater. By ev a p o ratio n -35- 0.09 g. o f yellow product (B ), m eltin g at 121-135°, was recov ered from th e carbon t e t r a c h l o r i d e ; s im ila r trea tm en t of the methanol y ie ld e d no re s id u e . The e th e r f i l t r a t e from (A) was c o n c e n tra te d , le a v in g 3.34 g. of yellow p ro d u ct. This was tr e a te d w ith 20 ml. o f b o ili n g carbon t e t r a c h l o r i d e ( f i l t r a t e C) leav in g an u n d iss o lv e d re s id u e , (D). On co o lin g , 2.28 g. o f yellow product (E ), m elting at 83-90° p r e c i p i t a t e d from f i l t r e , t e 0. A fte r r e c r y s t a l l i z a t i o n s from a c e ti c acid and carbon t e t r a c h l o r id e , th e m.p. was 96.5-97° and a mixed m eltin g p o in t w ith 3 ,4 - d i n i t rob enzene s u lfe n y l c h lo rid e was not d ep ressed . Product D almost com pletely d iss o lv e d in 30 ml. of b o ilin g m ethanol, end t h i s s o lu tio n when c o n c en trated y ie ld e d 0.79 g. o f yellow (F ), m elt in g a t 79-110°. A m ixture o f (B) and (e) was r e c r y s t a l l i z e d from methanol and chloroform four tim es, y ie ld in g 0 .1 2 g. having a m e ltin g p o in t 128-129°. From th e 0.88 g. o f t o t a l crude prod u c t i t i s estim a ted t h a t about 0 .6 g. (10 fo) o f t h e o r e t i c a l y i e l d was 2 ,4 -d in itro p h e n y l n itro m e th y l s u lf id e . The y i e l d in t h i s case was decidedly much lower th an i n th e case o f th e o th er n itr o a lk a n e s . A nalysis Humber JLC-7 : Cal-Tech Number 4798 Sample : 4.956 mg. ; OOg : 5.925 mg. ; HgO : 0.907 mg. Calcd. f o r CyH gO ^S : C, 32.44 <f, ; H, 1.95 fo Found : C, 32.63 f o ; H, 2.05 f o 2. Attempted P re p a ra tio n by Treatment of 3 .4 -D ln itro b en ze n e- s u lf e n y l Chloride w ith Nitromethane in Carbon T e tr a c h lo r id e . A s o lu tio n of 5.86 g. (0.025 mole) o f 2 ,4 -d in itro b e n z e n e - s u lf e n y l c h lo rid e and 1.35 ml. (0.035 mole) o f n itro m eth an e in —36— 50 ml. of carbon t e t r a c h l o r i d e was re flu x e d fo r th re e h o u rs. A tr a c e of brown m a te r ia l was removed from the ho t s o lu tio n by- f i l t r a t i o n . The f i l t r a t e was co n cen trated by e v a p o ra tio n , u sin g a d r y - a ir stream , and the yellow re sid u e was d rie d a t 45°, y ie ld in g 5.58 g. of p ro d u ct, m e ltin g a t 93-96°• A mixed m e lt in g p o in t w ith 3 ,4 -d in itro b e n z e n e s u lfe n y l c h lo rid e was not de p re sse d . F. 2-N itrophenyl 1 ’-N itro p ro p y l S u l f i d e . 1 . P re p a ra tio n by ffeaction of the Sodium S a lt o f 1-N itropropane in E th e r. a) With 2-N itro b e n ze n esu lfen y l C h lo rid e . The procedure d escrib ed in Expt. B -l was re p e a te d , u sin g 4.45 ml. (0.050 mole) of 1 -n itro p ro p a n e , 1.55 g. (0.029 mole) of sodium m ethoxide, and 4.74 g. (0.025 mole) of 2 -n itro b e n z e n e su lfe n y l c h lo rid e . There was an 84 fo y ie ld of a porduct m elting a t 66-71°* Re c r y s t a l l i z a tio n s from methanol and carbon t e t r a c h l o r i d e y ie ld e d 56 fo yellow p ro d u ct, m.p. 7 2 .5 -7 3 .0 °. This was presumed to be 2 -n itro p h e n y l 1 '- n itr o p r o p y l s u l f i d e . A nalysis Number JLC- 8 : Cal-Tech Number 5040 Sample : 3.473 mg. ; C0g ; 5.739 mg. ; HgO : 1.348 mg. Calcd. f o r C9H1()04NgS : C, 44.62 fo ; H, 4.16 fo Found : C, 45.09 fo ; H, 4.34 fo b) With 2 -N itro b e n ze n esu lfen y l Bromide. By a s im ila r p ro ce d u re , using 5.85 g. (0.025 mole) of 2 -n itro b e n z e n e su lfe n y l bromide, a product was ob tain ed which did not dep ress the m elting p o in t , , o o f th a t in ( a ) . The y ie ld of crude product m e ltin g a t 71-72 was 70 fo and the y ie ld of pure compound m elting a t 72-73° was -37- 56 f o . There was a ls o a 20 fo y ie ld of a compound m eltin g a t 191-192°. There was no d e p re ssio n observed in a mixed m e lt ing p o in t d eterm in atio n of t h i s product w ith a known sample of 2-n itro p h e n y l d i s u l f i d e . c) With 2 -N itro b e n ze n esu lfen y l T hio cy an ate. When 5.30 g. (0.025 mole) of 2 -n itro b e n z e n e su lfe n y l th io c y a n a te was used, the y ie ld s were 72 fo . pure 2 -n itro p h e n y l 1 '- n itr o p r o p y l s u lf id e (77 fo crude) and 10 fo 2 -n itro p h e n y l d i s u l f i d e . 2. M olecular Weight D eterm ination of 2-H itrophenyl l '- N i t r o - propyi S u l f i d e . The d eterm in a tio n was made by the cryoscopic method, in 75 benzene, by the u su a l method. Beckmann thermometer read in g : At F reezing po in t of C.P. benzene .................................... 4.185 At F reezing p o in t of s o lu tio n c o n tain in g 1.4510 g. substance in 23.0760 g. benzene ................. 2.866 Mol. Wt. Calcd. fo r C9H1004W gS : 242 Mol. Wt. Found 5 *12 1-4510 1000 244 23.0760 1.319 3. O xidation to 2-N itrophenyl 1 '-N itro p ro p y l S u lfo n e . To a s o lu tio n of 2 .4 g. (0.01 mole) of 2 -n itro p h e n y l l ’- n i t r o - propyl s u lf id e in 50 ml. of b o ilin g g l a c i a l a c e tic acid was add ed 15 ml. of 30 fo hydrogen p ero x id e . A fter r e f lu x in g fo r four hours the s o lu tio n was co n cen trated and the r e s u l t i n g o i l c ry s t a l l i z e d p a r t i a l l y a f t e r s c ra tc h in g . The product was washed w ith a lc o h o l y ie ld in g 1.05 g. of w hite c r y s t a l s which, when r e c r y s t a l l i z e d from aqueous e th an o l melted a t 7 4 .5 -7 5 .5 °. -38- A nalysis Number JLG-12 : Oal-Tech Number 5163 Sample i 3.093 mg. , J 4.505 mg. j ^ 3® * 1.046 mg. Calcd. fo r CgH1006N2S : -G, 39.41 fo ; H, 3.67 fo Found ; C, 39.75 fo ; H, 3.73 fo G. 2-N itrophenyl ( 1 '- N itro - 1 ^ M e th y le th y l) S u lfid e . 1. P re p a ra tio n by R eaction o f 2 -N itro b e n ze n esu lfen y l C hloride w ith th e Sodium S a lt of 2-N itropropane. 'The procedure d escrib ed in s e c tio n B -l was re p e a te d , u sin g 4 .7 4 g. (0.025 mole) o f 2 -n itro b e n z e n e su lfe n y l c h lo rid e , and sodium 2 -n itro p ro p a n e p repared from 1.80 g. (0.033 mole) of sodium methoxide and 4.50 ml. (0.050 mole) of 2 -n itro p ro p a n e by th e method o f s e c tio n C -l. There was, in a d d itio n to high m elt in g b ip ro d u c ts , a y i e l d of 2.18 g. impure product m elting at 79-81° and, on r e c r y s t a l l i z a t i o n from carbon t e t r a c h l o r i d e a t 81-82°. The y ie ld s were c a lc u la te d to be 36 fo impure and 25 fo o f pure p ro d u c t. i H. 3-N itrophenyl 1 - N itr o e th y l S u lf id e . 1 . p r e p a r a tio n by R eaction of 2 -N itro b en zen esu lfen y l Chloride w ith th e Sodium S a lt of N itro e th a n e in E th e r. The procedure d e sc rib e d in s e c tio n B-l was re p e a te d , u sin g 3.60 ml. (0.050 mole) of n itr o e th a n e , 1.55 g. (0.029 mole) of sodium methoxide, and 4.74 g. (0.025 mole) o f 2 -n itro b e n z e n e - s u lfe n y l c h lo rid e . A fte r removal o f th e e th e r , th e orange re s id u e was s t i r r e d f o r four hours w ith 150 ml. o f w ater and th e m ixture was cooled a t 5° fo r te n hours. The product was c o lle c te d by s u c tio n f i l t r a t i o n and was washed w ith th re e -5 ml. p o r tio n s of co ld methanol ( a) , which -removed;the orange c o lo r. The yellow re s id u e was d rie d a t 40°, y ie ld in g 1*008 g. o f product m e ltin g a t 58-130°. This was tr e a te d w ith 15 ml. o f methanol (B) a t 45°, le a v in g 0.30 g. o f un d isso lv ed m a te r ia l , m.p. 192-194°, The methanol (B) was c o n c e n tra te d , u s in g a d r y - a i r stream , to 5 m l., y ie ld in g 0 .5 4 g. m e ltin g a t 51-57°, and f i n a l l y to a yellow re s id u e o f 0.17 g. m e ltin g a t 51-56°. Methanol s o lu tio n (A) was l e f t o v e rn ig h t a t - 5 ° , y ie ld in g 2.476 g. o f p r e c i p i t a t e m e ltin g a t 52-56°, By rep eated ev ap o ratio n o f th e mother liq u o r and d i l u t i o n o f the o i l re s id u e w ith cold m ethanol, a d d i tio n a l m a t e r i a l , 0.20 g . , m e ltin g a t 140-190°, was c o l le c te d . The t o t a l y ie ld o f crude product was 3.19 g, (56$), and by two r e c r y s t a l l i z a t i o n s from m ethanol, 2.3 g* (41$) o f 2 -n itro p h e n y l 1*- n i t r o e t h y l s u l f i d e , m.p. 57-58°, was o b ta in ed . A n aly sis Number JX C-ll : Gal-Tech Number 5164 Sample : 3.139 mg. ; C0g:4.873 mg. ; HgO :0,991 mg. Calcd. f o r CgHQ0 N S : C, 42.11$ ; H, 3.53 $ Found : C, 42.36 $ ; H, 3.53 $ 2a. Attempted P re p a ra tio n by Treatment o f 2 -N itro b en zen esu lfen y l C hloride w ith th e Sodium S a l t o f N itro e th a n e in A bsolute A lcohol: th e Formation o f 2-N itrophenyl 2 ^ N itro b en z en e^ t h i o l s u l f o n a t e . The procedure d escrib ed in s e c tio n D-2-a was follow ed, u s in g 4.74 g. (0.025 mole) o f 2 -n itro b e n z e n e s u lfe n y l c h lo rid e . The p ro d u cts were a 10$ y ie ld o f 2r-nitrophenyl d i s u l f i d e , m.p. 192-193°, and a 57$ y ie ld o f 2 -n itro p h e n y l 2 * -n itro b en zen e- —40— t h i o l s u l f o n a t e , m.p. 147-147.5°. ^ A nalysis Number JLC-2 : Oal-Tech Number 4398 Sample : 6.000 mg. ; BaSO^ j 8.358 mg, Calcd. fo r C13Hq06N2S2 : S, 18.84 fo Found : S, 19.14 fo 3b. Attempted P re p a ra tio n by Treatment o f 2 -N itro b en zen esu lfen y l C hloride w ith N itro eth an e in Carbon T e tr a c h lo r id e . A s o lu tio n of 4.74 g. (0.025 mole) o f 3 -n itro b e n z e n e su lfe n y l c h lo rid e and 1.80 ml. (0,035 mole) o f n itro e th a n e in 50 ml. o f carbon t e t r a c h l o r i d e was re flu x e d fo r th r e e h o u rs. The cooled red s o lu tio n was c o n c e n tra te d , u s in g a d r y - a i r stream , and th e brown re sid u e was d rie d a t 50° for one hour. The weight was 4 .6 g . , m.p. 72-73°. There was no d ep ressio n w ith 2-n itro b en zen e s u lfe n y l c h lo rid e . 54 n # The m e ltin g p o in t re p o rte d by Zincke and F a rr is 142-143 . A p r e p a r a tio n o f t h i s compound by O.F. M arkles, o f t h i s la b o ra to ry , decomposed a t 142-143°, and d id not give an observable de p r e s s io n w ith th e product prep ared six months b e fo re by the w r i t e r , and o r i g i n a l l y m eltin g as recorded above. R edeterm ination o f th e m eltin g behavior o f th e conpound s ix months a f t e r prepa r a tio n showed d i s t i n c t d if fe re n c e . O rig in a lly th e compound m elt ed to a c le a r l i q u i d a t 147-147.5°; but now, l i k e th e compound o f M arkles, i t decomposed to a dark re s id u e a t 142-143°. No e x p lan atio n o f t h i s beh av io r i s suggested by th e w r ite r at t h i s tim e, but sin ce th e o r i g i n a l o b se rv a tio n s were made w ith co n sid erab le c a re , i t i s f e l t th a t a rec o rd o f th e s e should be made a t t h i s tim e. -41- 2c. Attempted P re p a r a tio n by Treatment o f 2-H itrobenzene- s u lf e n y l C hloride w ith H itro e th a n e in G la c ia l A c e tic A cid. A s o lu tio n o f 4.74 g. (0.025 mole) of 2 -n itro b en zen e s u lf e n y l c h lo rid e and 3.60 ml. (0.050 mole) o f n itr o e th a n e in 50 ml. o f g l a c i a l a c e t i c a c id was h eated at 80° fo r th re e hours i n an Erlenmeyer f la s k f i t t e d w ith a re f lu x condenser and drying tu b e . A s im ila r s o lu tio n when h eated to r e f lu x tem p eratu re dark ened to such an ex ten t th a t th e r e a c tio n was d isc o n tin u e d . A t r a c e o f brown m a te r ia l was removed by f i l t r a t i o n and th e f i l t r a t e was c o n c e n tra te d by a d r y - a i r stream , le a v in g a brown re s id u e . F ra c tio n a l r e c r y s t a l l i z a t i o n , u s in g methanol and carbon t e t r a c h lo rid e su c c e s s iv e ly as s o lv e n ts , r e s u l t e d in y ie ld s o f 65 f> 2 -n itro b e n z e n e s u lfe n y l c h lo rid e , 15 f> 2 -n itro p h e n y l d i s u l f i d e , and 5 crude 2 -n itro p h e n y l 2 - n itro b e n z e n e th io ls u lfo n a te . The i d e n t i t y o f th e p ro d u c ts was confirm ed by mixed m eltin g p o in t d e te rm in a tio n s w ith p ro d u cts of s e c tio n G-2-a. 3-N itrophenyl H itrom ethyl S u lfid e . 1. P re p a r a tio n by R eaction o f 2 -F itro b e n z e n e su lfe n y l C hloride w ith th e Sodium S a lt o f N itrom ethane. The p ro ced u re d e s c rib e d in s e c tio n E -l was re p e a te d , u s in g 5.40 g. (0.10 mole) o f sodium m ethoxide, 8 .1 ml. (0.15 mole) o f n itro m e th an e , and 9.48 g, (0.050 mole) of 2 -n itro b e n z e n e s u lfe n y l c h lo rid e . By f r a c t i o n a l r e c r y s t a l l i z a t i o n , u sin g methanol and carbon t e t r a c h l o r i d e , 1.30 g. o f product m elting a t 57-70° was i s o l a t e d from th e h ig h e r-m e ltin g b y -p ro d u c ts. F urther r e c r y s t a l l i z a t i o n r a is e d th e m elting p o in t to 70-71°. The y ie ld of crude p ro d u c t was 12 f o . -43- J . 1-Anthraquinonyl 1 r-N ltro p ro p y l S u l f i d e , 1. P re p a ra tio n from. 1-A nthraquinonesulfenyl C hloride and th e Sodium S a lt of 1 -N itro p ro p a n e . Sodium 1 -n itro p ro p a n e was prepared by the method o f s e c tio n B - l, u sin g 0.432 g. (0*008 mole) of sodium m ethoxide. To a s t i r red suspension of h a l f of t h i s product in 50 ml. of benzene was added p o rtio n w ise 0.534 g. (0.002 mole) of 1 -an th raq u in o n e- s u lfe n y l c h lo rid e . A fte r tw enty minutes the rem aining sodium 1 - n i t r o propane, which had been p ro te c te d under benzene, was added and the m ixture was s t i r r e d a t r e f lu x tem perature fo r f o r t y m inutes. The cooled m ixture was f i l t e r e d and the f i l t r a t e was co n c e n tra te d , le a v in g 0.433 g. o f orange product m e ltin g at 137-143° (d e c .) . This was e x tra c te d w ith 5 ml. of hot benzene le a v in g 0.08 g. of yellow re sid u e m e ltin g above 250°. A yellow p ro d u ct, decomposing a t 145°, p r e c i p i t a t e d from the benzene s o lu tio n on co o lin g . R e c r y s ta lliz a tio n s from carbon te t r a c h l o r i d e r a is e d th e decompo s i t i o n p o in t to 158°. The y ie ld s were c a lc u la te d to be 64 $ impure and 43 % of pure p ro d u c t. A nalysis Number JLC-10 : Gal-Tech Number 5143 Sample : 3.054 mg. ; C0g : 6.951 mg. ; Hg0 : 1.112 mg. Calcd. f o r C17H1304NS : C, 62.37 % ; H, 4.00 % Found : C, 62.11 fo ; H, 4.07 $ K. Attempted R eaction of T riphenylm ethanesulfenyl C hloride and th e Sodium S a lt of 1 -N itro p ro p an e. Sodium 1 -n itro p ro p a n e was prepared as in B-l but from 1.55 g. (0.029 mole) o f sodium methoxide and corresp o n d in g ly la r g e r amounts -43- o f o th e r re a g e n ts . This product was added to a s o lu tio n of 3.48 g. (0.008 mole) of trip h e n y lm e th an e su lfe n y l ch lo rid e in 50 ml. o f benzene a t r e f lu x te m p eratu re. A fte r t h i r t y m inutes s t i r r i n g and r e f lu x in g , 3 ml. of th e m ixture was removed and f i l t e r e d . The f i l t r a t e was c o n cen trated to a w hite re sid u e m e ltin g a t 130-130°. The r e a c tio n was continued fo r f iv e hours w ith s t i r r i n g and re f lu x in g . The m ixture was cooled to room tem perature and f i l t e r e d . The re s id u e was so lu b le in w ater except f o r a co n sid e ra b le q u a n tity o f w ax-like w hite m a te r ia l. The benzene f i l t r a t e was co n c e n tra ted , le a v in g an orange s o li d . This was washed w ith 10 ml. o f hexane, le a v in g 1.074 g. of orange product m e ltin g at 100-135°. Two r e c r y s t a l l i z a t i o n s from hexane l e f t 0.13 g. of u n d isso lv ed re s id u e (A) m eltin g a t 163-165°.The hexane, on co o lin g , y ie ld e d a product m elting a t 133-139°. The mixed m eltin g p o in t w ith tx ip h e n y lm eth an esu lfen y l c h lo rid e was 125-132°. Product (A) was r e c r y s t a l l i z e d tw ice from chloroform to a w hite compound m eltin g a t 174-175°. Q u a lita tiv e t e s t s in d ic a te d t h a t £ t d id not co n tain n itro g e n or s u lf u r . This product seems to correspond to one d esig n a te d as trip h e n y lm e t’ nyl p e ro x id e by R.H* McMenamy (Univ. of Southern C a lif o rn ia D is s e r t a t i o n , 1947). L. p-T o ly l 1 -H itro e th y l S u lf id e . The sodium s a l t o f n itr o e th a n e , p rep ared by th e method d e s c tlb ed in s e c tio n ,D-1,using 3.78 g. (0.070 mole) o f sodium m ethoxide, was added p o rtio n w ise over a tw enty-m inute p e rio d to a s t i r r e d -44- s o lu tio n o f 8.4 g. (0.053 mole) o f p .to lu e n e s u lf e n y l c h lo rid e in 250 ml. o f e th e r kept a t -10 to 0° 0. The e th e r was removed by- d i s t i l l a t i o n , le a v in g 7.5 g. of yellow o i l . The product was in s o lu b le in w ater bu t so lu b le in 25 $ sodium hydroxide s o lu tio n . An o i l se p a ra te d when th e b a s ic s o lu tio n was a c i d i f i e d by 35 fo a c e t i c ac id . -45- SUMMARY 111 e th e r or benzene, th e sodium s a l t s of the n itr o a lk a n e s r e a c t r e a d i l y w ith s u lf e n y l c h lo rid e s , s u lf e n y l bromides or s u lf e n y l th io c y a n a te s to y ie ld alpha n i t r o s u l f i d e s , a ty p e of compound which has not been p re v io u s ly repor te d . ArS+X“ + [rgHN0£J“ ♦ Ma* — » ArSCRHNOg ♦ Na+ • * Cl~ The r e a c tio n s in v o lv e n u c le o p h ilic a t t a c k on the p o s it iv e s u l f u r atom of th e s u lfe n y l h a lid e by th e a lk a n e n itro n a te an io n . The s u lfe n y l c h lo rid e s which were found to r e a c t in t h i s manner were 2 -n itro b e n z e n e su lfe n y l c h lo rid e , 2 , 4 -d in itro b e n z e n e - s u lfe n y l c h lo rid e , and l-a n th ra q u in o n e s u lfe n y l c h lo rid e . I t was found, however, th a t trip h e n y lm e th a n e s u lfe n y l ch lo rid e f a i l e d to re a c t under s im ila r c o n d itio n s . Except in the r e a c tio n s w ith n itro m e th a n e , th e y ie ld s of products o b tain ed were s a t i s f a c t o r y . The follow ing new compounds have been prepared: M.P. °C. 2 .4 -d in itro p h e n y l n itro m e th y l s u l f i d e 129-129.5 2 .4 -d in itro p h e n y l 1 ’- n i t r o e t h y l s u lf id e 117-118: 2 .4 -d in itro p h e n y l ( 1 * - n i t r o - i ’-m e th y le th y l) s u lf id e 101-101.5 2 .4 - d in itro p h e n y l 1 ’- n itro p ro p y l s u lf id e 8 1 .5 -8 2 .5 2-n itro p h e n y l n itro m e th y l s u lf id e 70-71 2 -n itro p h e n y l 1 ’- n i t r o e t h y l s u l f i d e 57-58 2-n itro p h e n y l (1 * - n i t r o - l ’-m e th y le th y l) s u lf id e 81-82 2-n itro p h e n y l 1 ’- n itr o p ro p y l s u lf id e 7 2 .5 -7 3 .0 1-an th ra q u in o n y l 1 ’- n itr o p ro p y l s u lf id e 158° (d e c .) 2-n itro p h e n y l 1 ’- n itr o p r o p y l su lfo n e 74.5-75.5 2 .4 - d in itro p h e n y l 2 ,4 - d in itr o b e n z e n e th io l s u lf o n a te 126-126.5 - 46 - Evidence i s p rese n ted i n support of th e d e s ig n a tio n o f the products as alpha n i t r o s u l f i d e s . The p ro d u cts are monomeric, as shown hy m olecular weight measurements. T heir behavior .in sodium hydroxide s o lu tio n is i d e n t i c a l w ith th a t of n itr o a lk a n e s . They may be oxidized to corresponding alpha n i t r o s u lf o n e s . Previous workers have re p o rte d th a t 4-m ethylphenyl l * - n i t r o - e th y l s u lf id e cannot be i s o l a t e d because of i t s i n s t a b i l i t y . P re lim in ary experim ents have y ie ld ed r e s u l t s which do n o t confirm t h i s . I n te r a c tio n of s u lfe n y l c h lo rid e (BSCl) w ith n itr o a lk a n e s , as such, r e s u l t s in the reco v e ry of the major p o r tio n of the s u lfe n y l c h lo rid e , and th e form ation of sm all amounts of d i s u lf id e s (RSSR) and t h io l s u lf o n a te s (RSOgSR). The p ro p o rtio n s of the products vary w ith th e so lv e n t employed (carbon t e t r a c h lo rid e , g l a c i a l a c e tic a c id , or no s o lv e n t) , w ith the d u ra tio n and tem perature of h e a tin g , and w ith th e molar r a t i o of n i t r o - alkane and s u lfe n y l c h lo rid e used. When ab so lu te alco h o l i s used as th e s o lv e n t, 2-n itro b e n z e n e - s u lfe n y l c h lo rid e and 2 ,.4-dinitrobenzene s u lfe n y l ch lo rid e are converted, in th e presence of th e sodium s a l t of n itr o e th a n e , to the corresponding d i s u l f i d e s and t h i o l s u l f q n a t e . One of the products th u s o b ta in e d , 2 ,4 -d in itro p h e n y l 2 ,4 -d in itro b e n z e n e - t h i o l s u l f onate , has n o t been p re v io u s ly re p o rte d . 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Creator Cameron, James Lorne (author)

Core Title The synthesis of certain alpha nitro sulfides

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