J . Org. Chem., Val. 44, No. 7, 1979 1177
Notes Anal. Calcd for C ~ ~ H I ~ N S F . H C,~75.55; O : H, 5.07; N, 10.57. Found: C, 75.89; H, 4.83; N, 10.64. From 1 and Diphenylketene-N-p-iodophenylimine. The adduct was obtained in 5090 yield: mp 249-251 "C; IR 3010 (w), 1625 (s), 1560 (m), 1540 (s), 1490 (m), 1435 (m), 1300 (m), 1140 (s), lo00 (w), 950 (w), 840 (m), 760 (m). 750 (s), 735 (w), 710 (w), 700 (m) cm-I; NMR 6
C,H,CCI
CH,CCI
II so
so
II
1 2 o n t h e synthesis of alkyl-substituted thiirene oxide^:^^^ we h a d 6.8-8.5 (m). occasion t o examine t h e synthesis of t h e acetyl analogue 2. Anal. Calcd for C25H18N3IJ/2H20:C, 60.49; H, 3.79; N, 8.47. Found: Although 2 could be generated in ether solution at -30 O C by (2, 60.49; H, 3.86; N, 8.47. dehydrochlorination of sulfinyl chloride 4 according t o t h e Reaction of 2-Bromopyridine-N-imine with 3. From these rem e t h o d devised by Strating, Thijs, and Zwanenburg5 for agents using similar quantities and conditions for the other reactions, only diphenyl N - p -tolylacetamide (the amide corresponding to 3) was c o m p o u n d 1 (see S c h e m e I), isolation of the p u r e s u b s t a n c e isolated. proved t o be impossible.6 The s t r u c t u r e of 2 was established by its reaction with Acknowledgment. T h e high-resolution mass spectrum was chlorine t o give ap'-dichloroethanesulfinyl chloride ( 5 ) which furnished by Dr. Catherine Costello of t h e National Institutes itself was identified by oxidation to t h e corresponding sulfonyl of H e a l t h facility of t h e D e p a r t m e n t of C h e m i s t r y at t h e chloride 6. T h e latter was unambiguously synthesized by oxM a s s a c h u s e t t s Institute of Technology t h r o u g h NIH g r a n t idation of cup'-dichloroethanesulfenyl chloride (7), t h e chloNo. RR00317 with K. B i e m a n n as t h e principal investirinolysis p r o d u c t of ethyl dithioacetate (8).Sulfinyl chloride gator. (4) was identified by comparison with spectral d a t a kindly Registry No.--1, 25275-41-6; 3, 5110-45-2; 4, 69027-81-2; 7, provided by King' who o b t a i n e d i t by t r e a t m e n t of t h e cor69027-82-3;8 (Y= OMe), 40012-82-6:8 (Y= H), 14181-84-1;8 (Y = responding sulfinic acid with thionyl chloride. Oxythioacetyl F), 41563-37-5; 8 (Y = I), 69027-83-4;N-aminopyridinium iodide, chloride (2) did n o t react with d i a z o m e t h a n e a t low t e m p e r 6295-87-0;diphenylketene-N-(2,6-dimethylphenyl)imine, 42549-11-1; a t u r e s and above room t e m p e r a t u r e u n d e r w e n t s p o n t a n e o u s pyridine-ds-N-imine, 69027-84-5; 2-picoline-N-imine,51135-75-2; decomposition. With 1 phenyldiazomethane gave n o t t h e 12,3-dihydro-3,3-diphenyl-2-(2,6-dimethylphenyli1nino) -lH-pyrroLo[3,2-b]pyridine.69027-85-6: 2,3-dihydro-3,3-diphenyl-2-(p-tolyli-expected episulfoxide b u t instead 2,5-diphenyl-1,3,4-thiadiminoi-lH-pyrrolo[3,2-b]-d3-pyridine, 69027-86-7; 2J-dihydroazole.418 :3,3-diphenyl-5-methyl-2(p-tolylimino)-lH-pyrrolo[3,2-b]pyridine, 69027-87-8; 2.:3-dihydro-3,3-diphenyl-2-(p-anisylimino)-lHE x p e r i m e n t a l Section!' pyrrolo[3,2-b]pyridine, 69027-88-9; 2,3-dihydro-3,3-diphenyl-21-Chloroethanesulfenyl Chloride ( 3 ) . 1-Chloroethanesulfenyl iphenylimino)-lH-pyrrolo[3,2-b]pyridine, 69027-89-0:2,3-dihydro:3,3-diphenyl-2-(p-flu~~rophenylimino)-lH-pyrrolo[3,2-~]pyridine,chloride can be obtained in yields of :3-30% by chlorination of a so69027-90-3; 2,3-dihydro-3,3-diphenyl-2-(p-iodophenylimino)-lH-lution of trithioacetaldehyde in CHZCl:! at -10 oC.li) A superior preparation was adapted from a more recent general method of pyrrolo[3,2-b]pyridine, 69027-91-4; 2-bromopyridine-N-imine, Douglass and co-workers." A solution of 30 g (0.25 mol) of ethyl di69027-92-5. sulfide in 400 mL of pentane was placed in a 1 -L, three-neck flask References a n d Notes equipped with a mechanical stirrer, gas in- and outlet tubes, and a low-temperature thermometer. After cooling to -60 " C in a dry iceI 1) For part XI, see M. W. Barker and Hsiu-Sun Sung, J. Heterocycl. Chem., 14, acetone bath a gentle stream of C12 was flashed over the surface of the 693 (1977). vigorously stirred solution by evaporation of' 5:1 g (0.76 mol) of pre(2) Hans-Joachim Timpe, Adv. Heterocyl. Chem., 17, 213 (1974). condensed chlorine. After t h e addition of Clz was completed. the thick (3) J. Epsztajn, E. Lunt, and A. R. Katritsky, Tetrahedron, 26, 1665 (1970). (4) One reviewer suggested that structures 4a and 4b were consistent with the slurry of white crystals was slowly warmed to room temperature. data and should have been observed. We did not observe these comVigorous stirring was essential due t o the evolution of H('1 at the pounds. decomposition temperature of' the sulfur trichloride (ca. 13 " C ) . Following decomposition the solvent was removed with a water aspirator from a water bath and the residual yellow-orange oil distilled t o give 50.9 g (78%)of the sulfenyl chloride as a vellou-orange liquid: h p 49 O C (40 mm) (lit.10hbp 47-50 "C ( 4 0 m m ) ) :N M R (('DCl,
