J . Org. Chem., Vol. 43, No. 2, 1978 337
Notes
(14) M. Libert, C. Caullet, and S. Longchamp, Bull. SOC. Chim. h.,2376 When compound 2b was electrolyzed in methanol, the electrolyzed (1971). solution became dark brown. The solution showed several spots on (15) T. Shono and A. Ikeda, J. Am. Chem. SOC.,94, 7802 (1972). TLC. The main products were isolated by silica gel chromatography (16) T. Shono, A. lkeda and Y. Kimura, Tetrahedron Left., 3599 (1971). using chloroform-ethyl acetate (91)as eluate. These were compounds (17) S. H. Pines, J. Org. Chem., 38,3854(1974). 3b (41%) and 6 (4.5%).The physical constants of compound 3b ob(18) L. Eberson and H. Schafer, Fortscr. Chem. forsch., 21, Chapters 7 and 9 (1971). tained here were in complete agreement with those described above. (19) S. Umino, K. Kariyone, K. Tanaka, and Noguchi, Chem. Abstr., 70, 57622 Compound 6 (syrup) was a mixture of cis and trans isomers: NMR (1969); Japan Patent 244 17 (1968). (CDC13) 6 2.14and 2.24(s and s, 3 H),3.55and 3.52(s and s, 3 H), (20) P. A. Bovey, "HigMesolution NMR of Macromolecules." Academic Press, 3.8-4.0and4.0-4.2 (mand m, 1 H), 5.1-5.5(m, 2 H),6.6-7.6 (m,6H). New York, N.Y., 1972, Chapter XIII. The ratio of these isomers is 7:6(cishans). Compound 3c. Electrolysis of compound 2c gave the titled compound: bp 99-100"C (1mm); IR (film) 3150,1740-1710(broad) cm-'; NMR (CDC13)6 1.34(t,3 H), 2.22(s, 3 H),2.48(s, 3 H), 4.33(q,2H), Thiocarbonyl Transfer Reagents] 6.05(d, 1 H), 7, 12 (d. 1 H); MS (intensity) 185 (M+,411, 143 (base peak), 115 (36),43 (23).Anal. Calcd for C10H1303N:C, 61.52;H, 6.71; Charles Larsen,2 Kosta Steliou, and David N. Harpp' N, 7.18.Found: C, 61.33;H, 6.43;N, 7.01. Compound 3d. Anodic oxidation of compound 2d afforded the tiDepartment of Chemistry, McGill Uniuersity, tled compound: bp 41-42 "C ( 2 mm); IR (film) 3050,1715cm-'; NMR Montreal, Quebec, Canada (CDC1~)62.07(s,3H),2.46(s,3H),6.0-6.2(m,1H),6.9-7.1(m,1H), 7.1-7.3(m, 1 H);MS (intensity) 123 (M+,26),97(lo),81 (43),80 (base Receioed June 28,1977 H, 7.37;N, peak), 53 (18),43 (48).Anal. Calcd for C7H90N: C, 68.27; 11.37.Found: C, 68.31;H,7.32;N, 11.31. Heterocyclic thiocarbonyl transfer reagents, first prepared Preparation of cis-4.N-Acetyl-2,2-diethoxycarbonyl-3-phenylby Staab and c o - ~ o r k e r shave , ~ in the recent years found pyrrolidine12 was saponified with potassium hydroxide under the several important applications in the synthesis of new comsame conditions as described above to afford the title compound in 49% yield; this was recrystallized from ethyl acetate-n-hexane: mp p o u n d ~ . Among ~,~ these reagents mainly 1,l'-thiocarbonyl97-99 "C; IR (Nujul) 1740,1720,1620,1560 cm-'; NMR (CDC13) 6 diimidazole (1) has been used, though reactions involving the 1.01(t, 3 H), 2.22(s, 3 H), 2.0-2.9(m, 2 H), 3.5-4.5(m, 3 H), 3.88(4, 2 H),7.35(s,5 H). Anal. Calcd for CIcH1905N: C, 62.94;H,6.27; N, 4.59.Found: C,62.94; H, 6.23;N, 4.56. Electrolysis of (tis-4.After compound 4 (910mg) was electrolyzed under the conditions as shown in Table I, the electrolyzed solution \ / was neutralized by the addition of acetic acid, and the solvent was 1 CH CH, evaporated to dryness in vacuo. The resulting residue was extracted with ethyl acetate, and the solution was washed with water, dried over L magnesium sulfate, and then evaporated to dryness in vacuo. The use of l,l'-thiocarbonylbis(3,5-dimethylpyrazole) (2) also have residue was treated with silica gel chromatography using chlorobeen reported.6 form-ethyl acetate (54)as eluate to afford 460mg of cis-5a and 420 Very little attention has been paid to the other members mg of trans-5b. ComDound 5a: mu 130-131"C: NMR (CDCln) 6 1.25(t,3 H), 2.10 of this series, including 1,l'-thiocarbonyldibenzimidazole (3), (s.3 H):2.0-3.0 (m,i H),3.35(s, 3 H),3.5-3.8 (m, 3 H),4.22and 4.24 1,l'-thiocarbonyldibenzotriazole (4), and thiocarbonyldi( q , 2 H), 7.25(s. 5 13). Anal. Calcd for C16H2104N:C, 65.95;H, 7.27; indazole ( 5 ) . Compounds 1 and 2 have been prepared in exN, 4.81.Found: C, 65.74;€I, 7.14;N,4.76. Compound 5b (syrup): NMR (CDCl?)6 0.81and 0.89(t and t, 3 H), cellent yield3v6according to the following reaction. Compounds 1.98and2.15(sands,3H),2.0-3.0(m,2H),3.46(s,3H),3.72and3.79 S S (q and q, 2 H), 3.4-4.5(m, 3 H), 7.1-7.4(m, 5 H).Anal. Calcd for II II CieH2104N: C, 65.95; H, 7.27;N.4.81.Found: C,65.89;H,7.31;N, 4>N-H ClCCl --+ > N C - N < .".?;+< CI4.93. The separation of the NMR signals of each group observed above 3 and 5 have been synthesized by this reaction, but yields were is attributed to the rotational barrier about the C-N bond.20 ~ n c e r t a i n For . ~ 4 the use of the free base is reported to be precluded, as this method results in the formation of 1-(2Acknowledgment. We thank Drs. I. Chibata and M. benzothiazolyl)benzotriazole.8However, using the sodium salt Matsuoka for their encouragement. of the heterocycle, compound 4 is formed, though no yield is Registry No.-2a, 64163-63-9; 2b, 51212-32-9; 2c, 64163-64-0; 2d, rep~rted.~,~ 64163-65-1; 4, 64163-66-'1: 3a, 64163-67-3; 3b, 64163-68-4; 3c, A more general approach to the preparation of these com64163-69-5; 3d, 823-75-6; l a , 51212-30-7; lb, 64163-70-8; IC, 584604-8Id, 64163-71-9; 5a, 64175-43-5; 5b, 64163-72-0; cis-6,64163-73-1; pounds requiring only 2 mol of the heterocycle involves the trans- 6, 64163-74-2; 2-ethoxycarbonyl-5-phenylpyrrole, 13355-43-6; reaction between its silylated derivative and thiophosgene. N-acetyl-2,2-diethoxycarbonyl-3-phenylpyrrolidine, 51212-36-3. In this way we have synthesized not only 1,3, and 4 but also 0
+
+
R e f e r e n c e s a n d Notes Synthetic Electroorganic IChemistry. VII. Part VI: T. Iwasaki. H. Horikawa, K. Matsurnoto, and M. Miyoshi, J. Org. Chem., 42, 2419 (1977). K. Tanaka, K. Kariyone, and S.Umino. Chem. Pharm. Bull., 17, 611 (1969), and references cited therein. E. Baltazzi and L. I. Krirnen, Chern. Rev., 63,51 1 (1963). and references cited therein. J. M. Patterson, Synthesis, 281 (1976), and references cited therein. V. A. Treibs and R . Derra, Justus Liebigs Ann. Chem., 589, 176 (1954). L. Everson, in "The Chemistry of Carboxylic Acids and Esters", S.Patai, Ed., lnterscience New York. N.Y., 1969, p 53. J. T. Keating and P. S. Skell, Carbonium lons, 2, 573 (1976). S. D. Ross, M. Finkelstein, and E. J. Rudd, "Anodic Oxidation", Academic Press, New York, N.Y., 1975, p 134. H. Horikawa, T. iwasaki, K. Matsumoto. and M. Miyoshi. Tetrahedron Left., 191 (1976). D. A. Cox, A. W. Johnson, and A. 8. Mauger, J. Chem. SOC., 5024 (1964). A. E. Mauger, F. Irreverre, and B. Witkop, J. Am. Chem. Soc., 88,2019 (1966). R. Sarges and J. R. Trettei,, J. Org. Chem., 39, 1710 (1974). N. L. Weinberg ard H. R. Weinberg, Chem. Rev., 68,449 (1968).
S DN-SiMe
+
S
I1
ClCCl
I1
-+
>N-C-N
