수용액에서 술포닐 우레아 유도체들의 합성

이천수; 윤무홍; 최석범; 노승백

Journal of the Korean Industrial and Engineering Chemistry, Vol.3, No.1, 100-110, March, 1992

Export Citation

수용액에서 술포닐 우레아 유도체들의 합성

A Synthesis of Sulfonyl Urea Derivatives in Aqueous Media

이천수, 윤무홍, 최석범, 노승백

초록

수용액에서 amlne류와 arylsulfonyl carbamate류를 반응시켜 다음과 같은 arylsulfonyl urea유도체들을 좋은 수율로 쉽게 합성할 수 있다 : 1) N-Arylsulfonyl-N'-arylurea유도체, 2) N-Arylsulfonyl-N'-alkyl urea 유도체, 3) N-Arylsulfonyl-N'-heterocyclic urea 유도체. Arylsulfonyl urea의 합성에 관한 반응메카니즘은, 먼저 산-염기 반응에 의해 ion-pair형태가 만들어지고, 그 다음 사면체형 중간체를 형성하는 친핵성첨가반응, 그리고 산촉매에 의한 alkoxide ion과 양성자의 제거반응에 따라 일어난다.

Arylsulfonyl urea derivatives can be easily prepared in good yield by treating amines with arylsulfonyl carbamates in aqueous solution : 1) N-Arylsulfonyl-N'-aryl urea derivatives, 2) N-Arylsulfony-N'-alkyl urea derivatives, 3) N-Arylsulfonyl-N'- heterocyclic urea derivatives. The proposed reaction mechanisms for preparing arylsulfonyl ureas involve formation of an ion-pair conformation by initial acid-base reaction, then formation of a so-called tetrahedral intermediate by nucleophilic addition, followed by an acid-catalyzed elimination of an alkoxide ion and loss of a proton.

[References]

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Rusching, U.S. Patent, 2,968,158, Upjohn (1961)
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McLamore WM, U.S. Patent, 3,349,124, Pfizer (1967)
Brit. Patent, 912,789, Lilly (1962)
Wright JB, Willette RE, J. Med. Pharm. Chem., 5, 815 (1962)
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Aumuller W, Bander A, Heedt R, Muth K, Pfaff W, Schmidt FH, Weber H, Weyer R, ArzneimItter-Forsch, 16, 1640 (1966)
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Sauers RF, E.I. Du Pont de Nemours and Company, U.S. Patent, 4,420,325 (1983)
Tseng CP, U.S. Patent, 4,484,939 (1983)
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Amrein J, Gerber HR, Proc. BCPC, 55 (1985)
Yamamoto S, Sato T, Oguti T, Nawamaki T, U.S. Patent, 4,668,277 (1987)
Sykes P, "A Guidebook to Mechanism in Organic Chemistry," 6th Ed., Longman Scientific and Technical, p. 238-240 (1990)
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[1] Franke H, Fuchs J, Dtsch. Med. Wochenschr., 80, 1449 (1955)

[2] Brit. Patent, 808,071, Aumuller, Herr. (1961)

[3] Ger. Patent, 1,066,575, Hoecht (1959)

[4] Rusching, U.S. Patent, 2,968,158, Upjohn (1961)

[5] Marshall FJ, Sigal MV, J. Org. Chem., 23, 927 (1958)

[6] Marshall FJ, Sigal MV, J. Med. Chem., 6, 60 (1963)

[7] Marshall FJ, Sigal MV, Brit. Patent, 853,555, Corresp. (1960)

[8] McLamore WM, U.S. Patent, 3,349,124, Pfizer (1967)

[9] Brit. Patent, 912,789, Lilly (1962)

[10] Wright JB, Willette RE, J. Med. Pharm. Chem., 5, 815 (1962)

[11] Wright JB, Brit. Patent, 887,886, Upjohn (1962)

[12] Logemann, Artini, Ber., 90, 2527 (1957)

[13] Aumuller W, Bander A, Heedt R, Muth K, Pfaff W, Schmidt FH, Weber H, Weyer R, ArzneimItter-Forsch, 16, 1640 (1966)

[14] Aumuller W, Bander A, Heedt R, Muth K, Pfaff W, Schmidt FH, Weber H, Weyer R, Neth. Patent, Appl., 6,603,398, Boehringer, Mann. (1966)

[15] Aumuller W, Bander A, Heedt R, Muth K, Pfaff W, Schmidt FH, Weber H, Weyer R, C.A. 66, 65289 h (1967)

[16] Weber H, Neth. Patent, Appl., 6,610,580 Corresp. (1967)

[17] Weber H, U.S. Patent, 3,454,635, Hoechst (1969)

[18] Levitt G, Ger. Patent, 2,715,786, C.A., 88,6935x (1978)

[19] Levitt G, U.S. Patent, 4,127,405, Du Pont (1977)

[20] Levitt G, Ploeg HL, Weigel RC, Fitzgerald DJ, J. Agric. Food Chem., 29, 416 (1981)

[21] Levitt G, European Patent, Appl., 7867, Du Pont (1980)

[22] Levitt G, U.S. Patent, 4,383,113, Du Pont (1983)

[23] Wolf AD, Austrian Patent, 8,316,181 (1984)

[24] Wolf AD, U.S. Patent, 4,547,215, Du Pont (1985)

[25] Wolf AD, U.S. Patent, 4,602,940, Du Pont (1986)

[26] Sauers RF, E.I. Du Pont de Nemours and Company, U.S. Patent, 4,420,325 (1983)

[27] Tseng CP, U.S. Patent, 4,484,939 (1983)

[28] Tseng CP, U.S. Patent, 4,604,133 (1986)

[29] Amrein J, Gerber HR, Proc. BCPC, 55 (1985)

[30] Yamamoto S, Sato T, Oguti T, Nawamaki T, U.S. Patent, 4,668,277 (1987)

[31] Sykes P, "A Guidebook to Mechanism in Organic Chemistry," 6th Ed., Longman Scientific and Technical, p. 238-240 (1990)

[32] Norman ROC, "Principles of Organic Systhesis," 2nd Ed., John Wiley & Sons, Inc., p. 336 (1978)