Sheikh Chanmiya

吉村 敏章

Article富山大学地域連携推進機構産学連携部門ベンチャー・ビジネス・ラボラトリー年報, 平成21年度, 2009, Page 99-100departmental bulletin pape

Sheikh, Chanmiya

吉村, 敏章

University of Toyama Repository

Alkylation of Super Acid from Alkoxy-A. 6-Sulfanenitriles 研究代表者理工学研究部（工学）吉村敏章VBL研究員Md.Chanmiya Sheikh (PhD) 1. Introduction λ6-Sulfanenitriles (thiazynes）紅e relatively unusual compounds bearing a kind of sulfur-nitrogen triple bond. Only a few inorganic入札sulfanenitrilessuch as F3SN, have been known and their chemistry has been developed by Glernser et al.1 in the field of fluorine and inorganic chemistry, while there are few examples of organic compounds, e.g., S,S' -diphenyl-S-fluorothiazyne Ph2SF(N) was claimed to be prepared by A. F. clifford et al.2 in 1978 though it was not purified. In recent ye訂SYoshimura et al.3 prepared a series of organicλ6”sulfanenitriles and repo抗edthe X-ray stmctural analysis of some 入6-sulfanenitriles and also reported that alkoxy－入札sul faneni triles exceptionally undergo a facile Ei reaction, although入6”sulfanenitrilesare tetracoordinated hexavalent sulfur compounds like sulphones and sulfoximides. Under these backgrounds, for the purpose of modification of versatile compounds it is very interesting and challenging to develop new type of organicλ6-sulfanenitriles and our interest for organic入6”sulfanenit1ilesis how the SN triple bond activates other sulfur bond. 2. Results and Discussion The alkoxy入6-sulfanenitriles(1) was synthesized by the reaction of S-fluoro－入6-sulfanenitriles with sodium alkoxide in the corresponding alcohol. Initially, I studied the reaction of alkoxy-λ6司sulfanenitrileswith various nucleophiles to afford the corresponding alkylation products in high yields. Interesting sequence involving in the reaction of 1 with strong acid (trifluoroacetic acid) and also even super acid (trifluoromethanesulfonic acid) to afforded the co汀espondingtrifluoroacetic acid alkyl ester and alkyl triflate in moderate to high yields. The results are shown in Table 1. Table 1. Reaction of alkoxy－λ6-sulfanenitriles (1} with trifluoroacetic acid or trifluorometltanesulfonic acid OR 0 0 OR I CF3C02H (1.0 eqJ I I 1 CF3S03H (2.0 eq.) Ph-S-Ph -- F3C-Cー OR+Ph-S-Ph Ph-S-Ph 1 CDCl3, rt., 5 min I 1 CDCl3, rt., 5 min N NH N 0 I F<!C－目S園田OR+3 - I 0 la-e 2a-e 3 Entry Compound R Product 2 (yield%/ 3 (yield %t la Me 2a 80 .10 』ヲ lb Et 2b 86 99 3 le n縄Pr 2c 98 JOO 4 ld i-Pr 2d 92 99 5 le n-Bu 2e 99 99 a Yield was cletemined by 1H NMR analysis. la・eEntry Compound 6 la 7 lb 8 le 9 ld 10 le 4a-e R Product 4 (yield %)a 3 (yield %)a Me 4a Et 4b 86 95 99 97 n-Pr 4c i-Pr 4d ???????? 98 98 100 n-Bu 4e a Yield was detemined by 1H N》fRanalysis. 99 These finding will provide the utilization in the new synthetic application of alkyl triflates‘which訂 Cusually hard to prepare, starting from super acid. The most probable mechanism for this reaction is illustrated in Scheme 1. R 0 Ph-S-Ph 1 N 、 、 ， ? 、 ??? 。 ??????、??????????『? ? ???，???????．?? ??????? ???「???? ??????? ??????? ?? ?。I Ph-S聞 PhI NH Sa-e 4 Scheme 1. Possible reaction mechanism for the formation of Sa-e 3. Conclusions Alkoxy－λ6-sulfanenitriles were found to be versatile alkylating reagents toward various nucleophiles, bearing at least one proton. The reaction of strong acids such as trifluroacetic acid, even super acid (trifluroamethane sulfonic acid) with alkoxy－λ乞sulfanenitrilesallows the isolation of the corresponding trifluoroacetic acid alkyl ester and alkyl triflates in good yields. We are now succeedingly studying the reactivity of alkylating reagents, alkyl triflates and alkoxy－入6-sulfane-nitriles with a variety of nucleophile derivatives such as alcohol，出凶ne，出iol,phenol組 dso on. Also we are going to prepare optically active alkoxy－入6-sulfanenitriles. If we can prepare this optically active alkoxy－入6-sulfanenitrilesthen we can easily obtain the corresponding inverted alkyl tritlates unlike usual method. 4. References (l) Glemser, 0冒； Schroder,H.; Haeseler, H. Z Anorg. Allg. Chem., 1955, 279, 28 (2) Clifford, A. F.; Howell, J. L；但1dWooton, D. LJ. Flumine Chem., 1978, 11, 433 (3) Yoshimura, T; Ki旬、 H.;Takeuchi, K.; Takata, E.; Hasegawa, K.; Shimasaki, C.; Tsukurimichi, E Chem Lett 1992, 1433. 100 

Alkylation of Super Acid from Alkoxy-λ6-Sulfanenitriles

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Alkylation of Super Acid from Alkoxy-λ6-Sulfanenitriles

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