THIETANE DIOXIDEDERIVATIVES
Oct. 20, 1963
was then decanted into a mixture of pentane and water and the nickel rinsed twice with pentane. The rinses and the aqueous mixture were combined and the pentane phase washed with water and dried over calcium chloride. The pentane was then evaporated and the residue crystallized from ethanol to give 70 mg. of trans-4-tert-butyl-1-phenylcyclohexane(111), m.p. 42". X more convenient route t o I11 was achieved by shaking 6.0 g. of l-tert-butyl-l-phenylcyclohexene,21 200 mg. of 10% .palladium-on-carbon, and 25 ml. of acetic acid under 40 p.s.1. of hydrogen at room temperature until the reaction was complete. The resulting mixture of stereoisomeric 4-tert-butyl-1-phenylcyclohexanes consisted of 45Yc of I11 and 55s.; of IV (by g.1.c.). The hl-drogenation mixture was transferred to a boiling flask and refluxed for 1.5 hr. The mixture was then filtered into 30 ml. of water and the solid collected by filtration. Kecrystallization from ethanol gave 3.9 g. of 111, m.p. 41-42". Further recrystallization raised the melting point t o 42'. Anal. Calcd. for C1fiH24: C , 88.82; H, 11.18. Found: C, 88.i0; H, 10.94. The preparation of I V was effected'O by refluxing a mixture of 1.64 g. of 11, 5.0 g. of Raney nickel,2o70 mg. of sodium methoxide, and 25 ml. of ethanol for 30 min. The mixture was filtered and the filtrate was cooled in methanol-Dry Ice. The material which crystallized was collected by filtration and recrystallized twice from methanol to give 0.75 g. of II', m.p. 24.5'. Anal. Calcd. for C~fiH24:C, 88.82; H , 11.18. Found: 89.03; H , 11.18. General Equilibration Procedure (Table I).-Equilibrations of I11 and I\' were carried out by sealing in Pyrex tubes under nitrogen mixtures of 100 mg. of a mixture of 457, of I11 and of IV,4G50 mg. of potassium tert-butoxide,22and 1.0 g. dimethyl sulfoxide. The tubes were then placed in refluxing reagent grade acetone (for 56.5'), benzene (for 80"), acetic acid (for 118"), or bromobenzene (for 155.5'); or in a thermostated water bath at 39". Tubes were withdrawn periodically and the contents poured into water. The hydrocarbon mixture was extracted with pentane and the pentane extract washed and dried over calcium chloride. The pentane was evaporated and the residue analyzed at 200' by g.1.c. using a 14i t . column packed with QF-1 on firebrick. Equilibrations were continued until steady state compositions of 111 and I V were reached. The equilibrium data in Table I represent averages of a total of a t least ten analyses (planimeter integration) of a t least two mixtures a t equilibrium a t each temperature. At 155.5", appreciable decomposition of dimethyl sulfoxide oc(21) E , W . Garbisch, Jr., J Org. Chem., 26, 4165 (1961). ( 2 2 ) A sample of this material was provided by t h e MS.4 Research Corporation, Callery, P a .
[CONTRIBUTIOX FROM
THE
323 1
curred during the 15 inin. required to reach equilibrium. Extending the equilibration time to 30 min. did not effect the equilibrium composition. The cRromatographic column was calibrated with known mixtures of pure (>99.9%) I11 and IV. cis- and trans-4-Methyl-1-phenylcyclohexanes( V and VI).trans- and cis-4-methyl-1-phenylcyclohexanols were prepared through the reaction between phenylmagnesium bromide and 4methylcyclohexanone. The resulting mixture (10 g.) of stereoisomeric carbinols was separated by chromatography as described for I and 11. The trans-carbinol, 4.70 g. melting a t 63.5" after recrystallization from pentane, was eluted first. Anal. Calcd. for ClSH180: C, 82.06; H, 9.53. Found: C, 81.87; H,9.53. The cis-carbinol, 4.22 g . melting a t 68-69.5" after recrystallization from pentane, was eluted last. Anal. Calcd. for ClaHIRO: C, 82.06; H, 9.53. Found: C, 82.15; H, 9.63. h mixture of 1.05 g. of czs-4-rnethyI-l-phenylcyclohexanol, 6.0 g. of Raney nickel,t0 and 20 ml. of ethanol was stirred at room temperaturelo for 20 min. The mixture was then worked up as described for the preparation of I11 using Ni (Raney), except the pentane extract was treated with 5 g. of silica gel to remove the unreacted carbinol. Distillation of the product gave 0.6 g. of V boilingat 104' ( 6 m m . ) , 1 ~ 1.5190. 2 ~ ~ Anal. Calcd. for C13H18: C, 89.59; H , 10.41. Found: C, 89.70; H , 10.60. The preparation of VI was carried out in the same manner as for the c i s stereoisomer V except that the reaction mixture was refluxed for 13 min. Distillation afforded 0.8 g. of VI ~ boilingat 90" (3 mm.), n 2 f i1.5123. Anal. Calcd. for C13H,8: C, 89.59; H , 10.41. Found: C, 89.26; H , 10.91. Both the n.m.r. (Fig. 4 and 5 ) and the infrared spectra of V and V I (obtained by the above procedure) show that these products are probably greater than 9OU&configurationally homogeneous. When the hydrogenolysis of cis-4-methyl-1-phenylcyclohexanol was carried out by refluxing for 15 min. a mixture of 300 mg. of the carbinol, 3.0 g. of Ni (Raney), and 10 ml. of ethanol, it was apparent from the infrared spectrum of the product that equilibration had progressed to a significant extent leading to a contamination of V by roughly 20-407, of V I .
Acknowledgment.-Support of this work from the Louis Block Fund of the University of Chicago and from the Petroleum Research Fund (Grant No. 1536) of the ilmerican Chemical Society is gratefully acknowledged.
DEPARTMENT O F CHEMISTRY,
PURDUE
UNIVERSITY, LAFAYETTE, IND.]
Thietane Dioxide Derivatives dia the Interaction of Sulfonyl Chlorides with Ketene Diethylacetal BY M;ILLIAM E. TRUCE AND
JOHN
R. NORELL
RECEIVED JUXE 3, 1963 The formation of nine new thietane 1,l-dioxide derivatives, from the interaction of sulfonyl chlorides (RCH2cy to the sulfonyl group, with ketene diethylacetal in the presence of triethylamine, is described. Cyclization products are obtained when R is an acidifying group such as phenyl but not if R is an alkyl group. The possible intermediacy of sulfenes (RCHSO2) is discussed.
S02CI),containing a hydrogen atom
I n aqueous media, as in the well-known Hinsberg test, generally no reaction occurs between sulfonyl chlorides and tertiary amines. However, sulfonyl chlorides react with tertiary amines in nonprotic solvents to form unstable addition compounds,3 or by the over-all disproportionation reaction4 ( 1 ) Abstracted from t h e P h . D . Thesis ot John R . Norell, Purdue University, 1903. (2) R. L Shriner, R . C. F u s o n , and 1). Y . C u r t i n , "The Systematic Identification of Organic Compounds,' 4th Ed., John Wiley and Sons, Inc., New York. N . Y . , 19.56, p . 103. (3) ( a ) M . Kauffmann a n d n.Vorlander, Ber., 43, 2741 (1910). ( b ) G . L. Schwartz and W. M . D e h n , J. A m . Chem. S O L . ,39, 2144 (1917); (4 I*. Horner a n d H . Nickel, A n n . , 697, 20 (1955); (d) H . iMajda-Grabowska a n d K. Okon, Rorzniki C h e w . , 37, 379 ( l Y 6 3 ) , isolated pyridiniurn salts from benzenesiilfonyl chlorides. (4) L. UT.Jones and H. F. Whalen, . I , A m . Chem. Soc., 47, 1343 (1925).
CsHjSO2CI
+ 2ICH3)3S --+ CsHjS02N(CH3)2 + (CHs)aS+CIC6H6
If the sulfonyl chloride contains a hydrogen atom to the sulfonyl group, then a different reaction occurs. With benzylsulfonyl chloride in the presence of triethylamine in benzene, Wedekind and Schenkj found that trans-stilbene was formed in an unspecified yield. CsHa
~ C ~ H ~ C H Z S+O2~( CCzIH j ) a N ~ C s H j C H = C H C s H j - t 2( C2H,)aS.HCI
AS a reaction path these workers postulated initial abstraction of the proton by the base and loss of &lo( 5 ) E . Wedekind and D. Schenk, Rer., 44, 198 (1911); recently J F King and T . Durst, Telrahedvon Letters, 585 ( 1 9 6 3 ) , obtained CdHsCCISO when t h e reaction was carried o u t in cyclohexane.
3232
WILLIAME. TRUCE AND
JOHN
R. NORELL
Vol. 85
TABLE I 3,3-DIETHOXYTHIETANE DIOXIDES (111) Yield,
M . p . , OC.
%
, -
C
H
49-50 43.30 65 7 22 89-90 57 75 70 6 72 113-114 49 51 54 5 44 72-73 5 59 12 55 7 10 51 22 82-83 Good 5 62 72-74 36 i 6 31 5 i3 103-105 36 64 61 5 00 49.0; 46--48 7 32 46 118-120 6.5 49 0 i i 32 49-50 51 118-120 7 6 a Recrystallized from n-pentane. Recrystallized from hexane and abssolute ethanol. J From 2-propenesulfonyl
Calcd., -% S
16 11 10 11 10 14 12 14 14
49 86 17 28 52 02 23 56 56
7
Other
C
194 pi,.4.44 ...
CI, 1 1 . 6 3 CI, 15.51 F, 2 1 . 7 4 . . .
...
Found, %
-
Mol. w t .
43 57 49 59 51 36 36 49 49
315 284 305 229 262 220 220
S
H
59 96 79 34 18 82 59 05 36
7 10 6.70 5 i0 7 13 5 76 5 74 5 03 7 32 7 40
16 11 9 11 10 14 12 14 14
7
Mol. wt.
Other
74 90 86 39 25 07 50 34 27
n-hexane Recrystallized from absolute ethanol. chloride. u From 1-propenesulfonyl chloride.
202 S , 4 18
CI, 11 67 C1, 15 31 F, 22 00
328 286 305 232 269 220 220
Recrystallized from n-
ride ion to form an unstable intermediate, C6H6CH- such as benzene or ether and added to an equimolar SOz ( I ) , for which they coined the term "sulfene," mixture of ketene d i e t h y l a ~ e t a l ' and ~ triethylamine a sulfur analog to ketene. According to these authors, dissolved in the solvent, a white flocculent precipitate the "sulfene" lost sulfur dioxide to form a divalent of triethylamine hydrochloride is formed immediately. species (C6HbCH),which dimerized to stilbene. Later After stirring, usually overnight, the salt is filtered and e ~ i d e n c e , ~however, ,' cast some doubt on the interthe solvent is removed in vacuo. A yellow oil or mediacy of carbene-like species in the formation of the crystalline solid remains, which can be purified by resubstituted ethylenes. An alternate path suggested crystallization from n-pentane, n-hexane, ethanol, involved dimerization of the sulfene followed by loss of or mixtures of these solvents. two molecules of sulfur dioxide to form the olefin. SulThese white crystalline compounds have been identifenes have also been postulated as intermediates refied as thietane derivatives (111) as shown in the equasulting from the interaction of diazoalkanes with sulfur tion 250 dioxide.x The present status concerning the chemisty (CZHj)3N --+ of "sulfene" intermediates has recently been s ~ r v e y e d . ~ RCHzSOlCl CHz=C(OC2Hs)z ether Few attempts have been made to trap sulfenes for CHz-C(OC2Hj)g useful synthetic purposes.*bb10Almost simultaneously, I 1 SOl--CHK 111 two brief communications" appeared concerning the interaction of certain sulfonyl chlorides with enamines Table I lists the thietanes obtained, the yields of rein the presence of triethylamine to form aminosulfones crystallized material, melting points, and elemental analyses. The sulfonyl chlorides employed were either (11). The possibility of the intermediate formation of a sulfene followed by cycloaddition was presented. commercially available or synthesized according to known methods (see Experimental). \ ---c-x \ / \ \ / -c The structures assigned are supported by n.m.r. RCHzSO2Cl + k-k=C +- ' 1 \ and infrared spectroscopy. Table I1 illustrates the / \ SOz-CHK I1 n.m.r. data,I4 which were obtained for the various These results prompted us to publish a preliminary TABLE I1 report" briefly describing the interaction between N.M.R.I'ALUES ( 6 ) FOR THE ADDUCTS OBTAINED' ketene diethylacetal and methanesulfonyl chloride in Relative the presence of triethylamine to yield 3,3-diethoxyareas thietane 1,l-dioxide. I t is the purpose of the present R a b C d e a:b:c:d:e communication to expand on this reaction and in parH 1.253 3 4 8 4 4.191 . . .... 3:2:2 ticular to report our observations where various sulC6Ha 1.10 3 3 45 4 4 . 1 2 I 5 . 3 7 I 7 . 3 4 c 6:4:2:1:5 fonyl chlorides and olefins were employed. 6:4:2:1:4 p-NOsC6Ha 1 . 1 8 3d 3 . 4 2 4 4 . 3 1 I 5 . 5 5 I 7.98 c
+
Results and Discussion Description of the General Reaction.-When certain sulfonyl chlorides are dissolved in a nonprotic solvent (8) H. Kloosterziel a n d H . J . Backer, R e t . lrav. c h i m . 71, 1235 (1952). (7) In a n a t t e m p t t o t r a p the carbene, derived from p-nitrobenzylsulfonyl chloride, with acenaphthylene [used t o demonstrate carbene formation from sulfur ylides by H . Hruby a n d A. W Johnson, J . A m Chem Soc., 84, 3588 (1982) I, only the stilbene derivative (44%) was obtained along with unreacted acenaphthylene (unpublished results from this Laboratory) (8) (a) H . Staudinger a n d F. Pfenninger, B e y . , 49, 1941 (1918); (b) L von Vargha and E . Kovacs, i b i d . , 76, 791 (1942); (c) H . Kloosterziel and H . J. Backer, Re
