재사용이 가능한 MFB로부터 4,4’-Bis(2-benzoxazolyl)stilbene의 합성 공정 개발

류영; 김종천; 함미정; 김석찬; Young Ryu; Jong Cheon Kim; Mi Jeong Ham; Seok Chan Kim

Applied Chemistry for Engineering, Vol.27, No.2, 195-198, April, 2016

DOI10.14478/ace.2016.1012 Export Citation

재사용이 가능한 MFB로부터 4,4’-Bis(2-benzoxazolyl)stilbene의 합성 공정 개발

Process Development of 4,4’-Bis(2-benzoxazolyl)stilbene from Recyclable Source MFB

류영, 김종천, 함미정, 김석찬^†

국민대학교 생명나노화학과

Young Ryu, Jong Cheon Kim, Mi Jeong Ham, and Seok Chan Kim^†

Department of Bio & Nano Chemistry, Kookmin University, 77 Jeongneung-ro, Seongbuk-gu, Seoul 02707, Republic of Korea

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초록

DMT 생산과정의 부산물로서 폐기 처리되어 왔던 MFB를 출발 물질로 하여 고급 형광증백제 중의 하나인 4,4’-bis(2-benzoxazolyl)stilbene (BBS) 합성을 4단계를 거쳐 총 수율 73%의 경쟁력 있는 공정개발을 수행하였다. 제시된 합성법은 MFB와 ethyl 4-((diethoxyphosphoryl)methyl)benzoate (1)과 반응시킨 후, coupling 생성물 4,4’-stilbenedicarboxylate (2)를 얻고 이를 4,4’-stilbenedicarbonyl chloride (3)으로 변환 후 BBS 합성의 핵심 단계인 benzoxazole 형성 단계에서 상용화가 가능한 용매와 촉매를 탐구하여 용매로는 1,2,4-trichlorbenzene 촉매로는 boric acid의 사용이 가능한 것을 확인하였다.

A total four-step synthetic process of high quality optical brightening agent 4,4’-bis(2-benzoxazolyl)stilbene (BBS) from methyl 4-formylbenzoate (MFB) was developed with 73% total yield. MFB is one of the main by-products in dimethyl terephthalate (DMT) production process. Our process involves the formation of 4,4’-stilbenedicarboxylate (2) obtained from the reaction of an aldehyde in MFB with ethyl 4-((diethoxyphosphoryl)methyl)benzoate (1) and the subsequent transformation to 4,4’-stilbenedicarbonyl chloride (3). In order to prepare benzoxazole ring in BBS, various solvents and catalysts were studied. The best solvent and catalyst were found to be 1,2,4-trichlorobenzene and boric acid, respectively suitable for mass production of BBS.

Keywords:methyl 4-formylbenzoate;recyclable source;DMT;optical brightening agent;4,4’-bis(2-benzoxazolyl)stilbene

[References]

(a) Mitchell AR, Pagoria PF, Schmidt RD, A new synthesis of TATB using inexpensive starting materials and mild re action conditions, 27th International Annual Conference ICT on Energetic Materials, June 25-28, Karlsruhe, Germany (1996). (b) Mitchell AR, Pagoria PF, Schmidt RD, New synthesis of TATB process development studies, 29th International Annual Conference ICT on Energetic Materials, June 30-July 3, Karlsruhe, Germany (1998).
(a) 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)
Kim SH, Ryu Y, Kim JC, Kim SC, Appl. Chem. Eng., 26(5), 621 (2015)
Kim KD, Ryu Y, Kim SC, Appl. Chem. Eng., 25(3), 337 (2014)
Richard H, Wang S, Process for the preparation of bis(2-benzoxazolyl) stilbenes, US Patent 5,332,828 (1994).
Bowers JS, Mayberry GL, Process for the preparation of stilbene derivatives, US Patent 4,921,964 (1989).
Brown HC, Ash AB, J. Am. Chem. Soc., 77, 4019 (1955)
Ford-Moore AH, Perry BJ, Org. Synth. Coll. Vol. IV, 325 (1963)
Richard HS, Wang K, Process fot The Preparation of Bis(2-benzoxazolyl)stilbenes, EP Patent 0,684,946 (1995).
Sundberg RJ, Buckowork PA, Holcombe FO, J. Org. Chem., 32, 2938 (1967)

[Referenced By]

[1] (a) Mitchell AR, Pagoria PF, Schmidt RD, A new synthesis of TATB using inexpensive starting materials and mild re action conditions, 27th International Annual Conference ICT on Energetic Materials, June 25-28, Karlsruhe, Germany (1996). (b) Mitchell AR, Pagoria PF, Schmidt RD, New synthesis of TATB process development studies, 29th International Annual Conference ICT on Energetic Materials, June 30-July 3, Karlsruhe, Germany (1998).

[2] (a) 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)

[3] Kim SH, Ryu Y, Kim JC, Kim SC, Appl. Chem. Eng., 26(5), 621 (2015)

[4] Kim KD, Ryu Y, Kim SC, Appl. Chem. Eng., 25(3), 337 (2014)

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

[6] Bowers JS, Mayberry GL, Process for the preparation of stilbene derivatives, US Patent 4,921,964 (1989).

[7] Brown HC, Ash AB, J. Am. Chem. Soc., 77, 4019 (1955)

[8] Ford-Moore AH, Perry BJ, Org. Synth. Coll. Vol. IV, 325 (1963)

[9] Richard HS, Wang K, Process fot The Preparation of Bis(2-benzoxazolyl)stilbenes, EP Patent 0,684,946 (1995).

[10] Sundberg RJ, Buckowork PA, Holcombe FO, J. Org. Chem., 32, 2938 (1967)