MFB를 이용한 PABA One-Pot 합성법

김경덕; 류영; 김석찬; Kyung-Duck Kim; Young Ryu; Seok-Chan Kim

Applied Chemistry for Engineering, Vol.25, No.3, 337-339, June, 2014

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MFB를 이용한 PABA One-Pot 합성법

Facile One-Pot Synthesis of PABA from MFB

김경덕, 류영, 김석찬^†

국민대학교 생명나노화학과

Kyung-Duck Kim, Young Ryu, and Seok-Chan Kim^†

Department of Bio & Nano Chemistry, Kookmin University, Seoul 136-702, Republic of Korea

E-mail:

초록

본 연구의 내용은 Dimethyl terephthalate의 생성 과정 중 필연적으로 생성되는 부산물인 Methyl 4-formylbenzoate를 이용해 one-pot reaction을 통한 p-Aminobenzoic acid를 얻는 방법이다. 이 방법은 Methyl 4-formylbenzoate에 chlorine gas와 methylene chloride를 이용해 acid chloride를 형성하고 ammonia gas를 통해 amide를 중간체로 가진다. 생성된 amide는 Hofmann degradation을 통해 p-Aminobenzoic acid로 전환된다. 이 방법은 폐기물인 Methyl 4-formylbenzoate를 재활용하여 기존의 p-Aminobenzoic acid를 수율 90%로 합성하였으며 이는 기존의 p-Aminobenzoic acid 생산과정을 대체할 수 있을 것으로 예상된다.

A facile one-pot synthesis of p-aminobenzoic acid from methyl 4-formylbenzoate which is a main by product in dimethyl terephthalate production process has been developed. This process involves the formation of amide intermediate obtained from the reaction of an aldehyde in methyl 4-formylbenzoate with chlorine in methylene chloride and the subsequent treatment of acid chloride with ammonia. The resulting amide was converted into amine using Hofmann degradation to afford a p-aminobenzoic acid. This facile one-pot process does not involve any expensive materials and should offer an attractive alternative to p-aminobenzoic acid production.

Keywords:Methyl 4-formylbenzoate;p-Aminobenzoic acid;Hofmann degradation;Industrial waste;Second pollution

[References]

Mitchell AR, Pagoria PF, Schmidt RD, 27th Int. Ann. Conf. ICT; Karlsruhe : Germany, 29 (1996)
Mitchell AR, Pagoria PF, Schmidt RD, 29th Int. Ann. Conf. ICT; Karlsruhe : Germany, 49 (1998)
Kim KD, Yu Y, Jeong HJ, Ham MJ, Kim KL, Kim AN, Davgajantsan O, Park GS, Kim SC, Bull. Korean Chem. Soc., 33, 4275 (2012)
Suzuki K, Kuroda H, Nabeta S, Process for the purification of trans-4-aminomethyl-cyclohexane carboxylic acid, US Patent, 3,875,217 (1975)
Richard H, Wang S, Process for the preparation of bis (2-benzoxazolyl) stilbenes, US Patent, 5,332,828 (1994)
Gasparro FP, Mitchnick M, Nash JF, A review of sunscreen safety and efficacy, Photochemistry and Photobiology., 68, 243-256 (1998) and references cited therein.
Mallonee JE, Process for preparing p-aminobenzoic acid, US Patent, 3,324,175 (1967)
Finger GC, Starr LD, Roe A, Link WJ, J. Org. Chem., 27, 3965 (1962)
Imamoto T, Tsuno Y, Yukawa Y, Bull. Jpn. Chem. Soc., 44, 1632 (1971)
Fushimi, Norio, Nakamura, Kenichi, Takagawa, Makoto, Process for producing alkylbenzoyl chloride, EP Patent, 0,723,950 (1996)
Weast RC, Grasselli JG, Handbook of Data on Organic Compounds, 2nd ed., 1348, CRC Press, Boca Raton, FL (1994)

[Referenced By]

[1] Mitchell AR, Pagoria PF, Schmidt RD, 27th Int. Ann. Conf. ICT; Karlsruhe : Germany, 29 (1996)

[2] Mitchell AR, Pagoria PF, Schmidt RD, 29th Int. Ann. Conf. ICT; Karlsruhe : Germany, 49 (1998)

[3] Kim KD, Yu Y, Jeong HJ, Ham MJ, Kim KL, Kim AN, Davgajantsan O, Park GS, Kim SC, Bull. Korean Chem. Soc., 33, 4275 (2012)

[4] Suzuki K, Kuroda H, Nabeta S, Process for the purification of trans-4-aminomethyl-cyclohexane carboxylic acid, US Patent, 3,875,217 (1975)

[5] Richard H, Wang S, Process for the preparation of bis (2-benzoxazolyl) stilbenes, US Patent, 5,332,828 (1994)

[6] Gasparro FP, Mitchnick M, Nash JF, A review of sunscreen safety and efficacy, Photochemistry and Photobiology., 68, 243-256 (1998) and references cited therein.

[7] Mallonee JE, Process for preparing p-aminobenzoic acid, US Patent, 3,324,175 (1967)

[8] Finger GC, Starr LD, Roe A, Link WJ, J. Org. Chem., 27, 3965 (1962)

[9] Imamoto T, Tsuno Y, Yukawa Y, Bull. Jpn. Chem. Soc., 44, 1632 (1971)

[10] Fushimi, Norio, Nakamura, Kenichi, Takagawa, Makoto, Process for producing alkylbenzoyl chloride, EP Patent, 0,723,950 (1996)

[11] Weast RC, Grasselli JG, Handbook of Data on Organic Compounds, 2nd ed., 1348, CRC Press, Boca Raton, FL (1994)