KR0139486B1 - Precess for the preparation of n-metan sulfoniloxyimide - Google Patents

Precess for the preparation of n-metan sulfoniloxyimide

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KR0139486B1
KR0139486B1 KR1019940020037A KR19940020037A KR0139486B1 KR 0139486 B1 KR0139486 B1 KR 0139486B1 KR 1019940020037 A KR1019940020037 A KR 1019940020037A KR 19940020037 A KR19940020037 A KR 19940020037A KR 0139486 B1 KR0139486 B1 KR 0139486B1
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formula
msomi
structural formula
tfomi
epoxy
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KR960007559A (en
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안광덕
정찬문
구덕일
조형숙
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김은영
한국과학기술원
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/08—Bridged systems

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyrrole Compounds (AREA)
  • Epoxy Compounds (AREA)

Abstract

다음 구조식(I)의 N-메탄술폰옥시말레이미드(MsOMI)및 다음 구조식(II)의 N-트리플로로메탄술폰일옥시말레이미드(TfOMI)및 그의 제조방법.N-methanesulfonoxymaleimide (MsOMI) of the following structural formula (I), and N-trifluoromethanesulfonyloxymaleimide (TfOMI) of the following structural formula (II) and a preparation method thereof.

Description

N-메탄술폰일옥시말레이미드, N-트리플로로메탄 술폰일옥시말레이미드 및 그의 제조방법N-methanesulfonyloxymaleimide, N-trifluoromethane sulfonyloxymaleimide and its preparation method

본 발명은 광조사시 각각 메탄술폰산(CH3SO3H)과 트리플로로메탄술폰사(CF3SO3H)을 발생하는 새로운 광산발생형 고분자의 단량체인 N-메탄술폰일옥시말레이미드(N-methansesulfonyloxymaleimide : 이하 Msomi로 표시함)와 N-트리플로로메탄술폰일옥시말레이미드; 이하 Tfomi로 표기함) 및 그의 제조방법에 관한 것이다.The present invention is N-methanesulfonyloxymaleimide (N-methanesulfonyloxymaleimide, which is a monomer of a new photoacid generator polymer that generates methanesulfonic acid (CH 3 SO 3 H) and trichloromethanesulfone (CF 3 SO 3 H), respectively) when irradiated with light. N-methansesulfonyloxymaleimide (hereinafter referred to as Msomi) and N-trifluoromethanesulfonyloxymaleimide; Hereinafter referred to as Tfomi) and a method for producing the same.

말레이미드 화합물 특징으로서, 말레이미드의 N-위치에 기능성 관능기(functional group)를 용이하게 도입할 수 있으며 이 N-치환 말레이미드 단량체를 사용하여 여러가지 기능성 말레이미드 고분자를 합성할 수 있다. 전자 결핍성인 말레이미드 단량체는 스티렌 유도체 등 전자 풍부성 단량체와 라디칼 공중합 반응시 매우 반응성이 높아 고분자 전환율이 매우 높고, 생성된 중합체의 우수한 내열성 때문에 여러분야에서 응용된다. 특히, 말레이미드 고분자 구조는 이러한 내열성 이외에도 짧은 파장의 자외선 영역에서의 낮은 광흡수율, 필름 재막성 등의 특성을 가지므로 미세화상형성용 포토래지스트 재료로서의 적용성이 매우 크다. 예를 들어 본 발명자들은 각각 터셔리부톡시카보닐(t-BOC) 및 터셔리부톡시 보호기로 N-치환된 N-터셔리부툭시카보닐말레이미드(t-BOCMI) 및 N-터셔리부톡시말레이미드(t-BuOMI)를 신규 합성하여, 그 레지스트 특성을 조사하였으며 현재 특허 출원중에 있다. [대한민국 특허 제94-70225호, 특허출원번호91-10272, 92-3539, 92-3540호]As a characteristic of the maleimide compound, a functional group can be easily introduced at the N-position of the maleimide, and various functional maleimide polymers can be synthesized using this N-substituted maleimide monomer. Electron deficient maleimide monomers are highly reactive in radical copolymerization reactions with electron-rich monomers such as styrene derivatives, resulting in very high polymer conversion and excellent heat resistance of the resulting polymers. In particular, since the maleimide polymer structure has characteristics such as low light absorption in a short wavelength ultraviolet ray and film refilming property in addition to such heat resistance, it is highly applicable as a photoresist material for microimage forming. For example, the present inventors have described N-tertibutoxycarbonylmaleimide (t-BOCMI) and N-tertiary moiety N-substituted with tert-butoxycarbonyl (t-BOC) and tert-butoxy protecting groups, respectively. Toxymaleimide (t-BuOMI) was newly synthesized and its resist properties were investigated and are currently pending. [Korean Patent No. 94-70225, Patent Application No. 91-10272, 92-3539, 92-3540]

광조사시 한개의 광자에 의해 생성된 산이 1000회 정도의 연쇄반응을 일으키는 화학증폭성 레지스트계에서 광반응에 의해 산을 발생하는 중요한 성분은 광산발생제(photoacid generator)이다. 그간 많이 사용된 광상발생재로는 양이온 광중합 개시재로 알려진 오니움염 등이 있다. 광산발생제의 대표적인 오니움염은 암모늄염, 아이오도니움염, 술포늄염 등이 있는데 이들이 함유하고 있는 금속성분이 미세회로 가공 공정에서 반도체 소자를 오염시킬 우려가 있을 뿐만 아니라 열적 불안정성과 낮은 용해서 등의 단점을 가지고 있으므로 이를 대체하기 위하여 비이온성의 유기 광산발생제인 유기 술폰산 애스터가 연구되고 있다. 반도체 미세가공용 화학증폭성 레지스트는 이와같은 고아산발생제를 첨가하여 이성분계 또는 삼성분계의 혼합물로 대부분 제고되고 있다.The photoacid generator is an important component that generates acid by photoreaction in a chemically amplified resist system in which an acid generated by one photon causes a chain reaction of about 1000 times. The photo-generators used in the past include onium salts known as cationic photopolymerization initiators. Representative onium salts of photoacid generators include ammonium salts, iodonium salts, and sulfonium salts. The metal components contained therein may not only contaminate semiconductor devices in the microcircuit processing process but also have disadvantages such as thermal instability and low melting. Organic sulfonic acid aster, a nonionic organic photoacid generator, has been studied to replace it. Chemically amplified resists for semiconductor micromachining have been mostly upgraded as a mixture of two-component or ternary systems by adding such a high acid generator.

여러가지 술폰기로 치환도니 히드록시이미드나 히드록시프탈이미드를 광개시제로 사용한 예는 이미 문헌에서 보고된 바 있다. 예를들면 미국특허 4,111,926과 4,066,636에서는 N-아릴과 N-알킬술폰일옥시이미드에 대해, 미국특허 4,371,366에는 N-토실옥시테트라클로로프탈이미드, N-메탄술폰일옥시테트라클로로프탈이미드, N-토실옥시프탈이미드, N-트리플로로메탄술폰일옥시숙신이미드에 대해 기재되어 있다. 그리고 미국특허 5,002,853와 문헌 Bull. Chem. Soc. Jpn., 1971, 44, 1084에는 N-벤젠술폰일옥시말레이미드를 광개시제로서 이용가능성이 기재되어 있다.Examples of using substituted donor hydroxyimide or hydroxyphthalimide as photoinitiators have already been reported in the literature. For example, in US Pat. Nos. 4,111,926 and 4,066,636 for N-aryl and N-alkylsulfonyloxyimides, US Pat. No. 4,371,366 discloses N-tosyloxytetrachlorophthalimide, N-methanesulfonyloxytetrachlorophthalimide , N-tosyloxyphthalimide, N-trifluoromethanesulfonyloxysuccinimide. And US Patent 5,002,853 and Bull. Chem. Soc. Jpn., 1971, 44, 1084 discloses the availability of N-benzenesulfonyloxymaleimide as photoinitiator.

본 발명은 저럼한 일반 원료를 사용하여 효과적인 산발생능과 열안정성을 갖춘 광산발행형 말레이미드 단량체를 용이하게 합성하는 데 관한 것이다.The present invention relates to easily synthesizing a photo-issued maleimide monomer having an effective acid generating ability and thermal stability using low cost raw materials.

다음의 화학반응식에 나타낸 바와 같이 딜스-알더(Diels-Alder) 반응과 레트로 딜스-알더 반응을 이용하여 메탄술폰일ㅇ옥시말레이미드(I)와 트리플로로메탄술폰일옥시말레이미드(II)의 두가지 단량체를 합성하였다.As shown in the following chemical reaction scheme, methanesulfonyloxymaleimide (I) and trichloromethanesulfonyloxymaleimide (II) were prepared using Diels-Alder reaction and retro Diels-Alder reaction. Two monomers were synthesized.

본 발명에 의하면 구조식(IV)의 N-히드록시기애메탄술폰일클로라이드(CH3SO2C1) 또는 트리플로로메탄술폰일클로라이드(CF3SO2C1)를 반응시켜 메타술폰일기가 도입된 구조식(V) 또는 트리플로로메탄술폰일기가 도입된 구조식(VI)의 화합물을 합성한다.According to the present invention, by reacting N-hydroxy group ethanesulfonyl chloride of formula (IV) (CH 3 SO 2 C1) or trichloromethanesulfonyl chloride (CF 3 SO 2 C1) to the structural formula introduced metasulfonyl group ( V) or a compound of formula (VI) having a trichloromethanesulfonyl group introduced therein.

최종단계에서 각각 150℃와 110℃ 부근의 열해분해반응에 의해 MsOMI와 TfOMI가 고순도로 용이하게 제조된다. 전체적인 합성방법에 있어서 조작이 간편하고 경제적으로 대량생산이 가능할 뿐 아니라, 제조된 MsOMI와 TfOMI 단량제는 라디칼 중합에 의해 감도와 내열성이 우수한 광산발생형 고분자의 합성이 가능하여 레지스트 재료의 제조에 적합하다.In the final step, MsOMI and TfOMI are easily produced in high purity by thermal decomposition reactions around 150 ° C and 110 ° C, respectively. It is easy to operate and economically mass-produced in the overall synthesis method, and the prepared MsOMI and TfOMI monomers are suitable for the production of resist materials because it is possible to synthesize photoacid polymers with excellent sensitivity and heat resistance by radical polymerization. Do.

상기 화학반응식에서와 같이(한국특허출원번호 92-3539호의 N-터셔리부톡시말레이미드 제조법에 명시됨) 무수말레인산과 퓨란을 반응시키면 딜스-알더 반응에 의하여 구조식(III)의 3,6-에폭시-1,2,3,6-테트라히드로프탈릭안히드리드가 정량적으로 생성되고, 구조식(III)화합물과 히드록실아민을 반응시키면 구조식(IV)의 N-히드록시-3,6-에폭시-1,2,3,6-테트라히드로프탈이미드가 생성된다. 피리딘을 촉매로 하여 구조식(IV)의 화합물과 메탄술폰일클로라이드를 반응시키면 구조식(V)의 N-(메탄술폰일옥시)-3,6-애폭시-1,2,3,6-테트라히드로프탈이미드가 생성되고 이 화합물을 열분해하면 목적물인 구조식(I)의 MsOMI가 60%이상의 수율로 생성된다.As in the chemical reaction scheme (as specified in the preparation method of N-tertiarybutoxymaleimide in Korean Patent Application No. 92-3539), when maleic anhydride is reacted with furan, a Diels-Alder reaction gives 3,6- Epoxy-1,2,3,6-tetrahydrophthalic anhydride was produced quantitatively, and the reaction of the compound of formula (III) with hydroxylamine resulted in N-hydroxy-3,6-epoxy of formula (IV). -1,2,3,6-tetrahydrophthalimide is produced. Reaction of the compound of formula (IV) with methanesulfonyl chloride using pyridine as a catalyst results in N- (methanesulfonyloxy) -3,6-epoxy-1,2,3,6-tetrahydro of formula (V). Phthalimide is produced and pyrolyzing the compound produces MsOMI of the desired structure (I) in a yield of 60% or more.

이와 유사한 방법으로 구조식(II)의 TfOMI를 90%이상의 고수율로 합상할 수 있다. 생성된 MsOMI와 TfOMI 단량체의 녹는점은 각각 113℃,56℃이고 적외선분광분석, 탄소-13 및 양성자 핵자기공명분석, 질량분석, 가스크로마토그라피부탁 질량분석, 원소분석에 의하여 그 화학구조가 확인되었다.In a similar manner, the TfOMI of formula (II) can be summed up to a high yield of 90% or more. The melting points of the produced MsOMI and TfOMI monomers are 113 ℃ and 56 ℃, respectively, and their chemical structure is confirmed by infrared spectroscopy, carbon-13 and proton nuclear magnetic resonance analysis, mass spectrometry, gas chromatography-charged mass spectrometry and elemental analysis. It became.

본 발명으로 제조한 MsOMI와 TfOMI의 단량체는 상업적으로 생산되는 스티렌 등의 일반단량체와 용이하게 라디칼 중합되고 이로서 얻어진 중합체는 술폰일옥시숙신이미드 구조를 갖고 있어서 광조사시 용이하게 술폰산을 생성한다. 그러므로 MsOMI 또는 TfOMI 단량체와 산에 의하여 탈보호가능한 보호기로 치환된 단량체와의 공중합체는 광조사시 술폰산을 생성하고 노광후 가열과정에서 이 산에 의해 고분자의 탈보호반응이 일어나게 되므로 광산발생제를 따로 혼합할 필요가 없는 일성분계 광산발생형 고분자로 된다. 또한 MsOMI, TfOMI의 공중합체는 숙신이미드 구조를 갖고있어 200℃이상의 높은 유리전이온도를 가지므로 미세화상의 중요한 요구물성인 200℃이상의 내열성을 만족시킨다. 또한 미세화상형성시에 0.5㎛이하의 고해상도 달성을 위하여 조사파장이 단파장인 원자외선 영역(deep UV, 200㎚-300㎚파장)에서 레지스트의 광흡수율이 크지 않아야 하는데, 본 발명으로 제조한 단량체를 함유하는 고분자, 예를들면 MsOMI와 t-BOC-스티렌과의 공중합체는 250㎚에서 0.1/㎛정도의 광흡수율을 갖는 등 원자외선 영역에서의 광흡수율이 낮아서 원자외선 및 감방사선 레지스트 응용에 매우 적절한 고분자로 기대된다.The monomers of MsOMI and TfOMI prepared by the present invention are easily radically polymerized with commercial monomers such as styrene produced commercially, and the resulting polymer has a sulfonyloxysuccinimide structure to easily produce sulfonic acid upon light irradiation. Therefore, copolymer of MsOMI or TfOMI monomer and monomer substituted with protecting group deprotectable by acid generates sulfonic acid during light irradiation and deprotection reaction of polymer by this acid during post-exposure heating process. It is a one-component photoacid generator polymer that does not need to be mixed separately. In addition, the copolymer of MsOMI and TfOMI has a succinimide structure, which has a high glass transition temperature of 200 ° C. or higher, thereby satisfying heat resistance of 200 ° C. or more, which is an important property of microscopic images. In addition, in order to achieve a high resolution of 0.5 μm or less when forming microscopic images, the light absorption of the resist should not be large in the far ultraviolet region (deep UV, 200 nm to 300 nm wavelength) in which the irradiation wavelength is short. Polymers containing, for example, copolymers of MsOMI and t-BOC-styrene have a low light absorption in the far ultraviolet region, such as light absorption of about 0.1 / μm at 250 nm, which is very suitable for applications in ultraviolet and radiation-sensitive resists. It is expected to be a suitable polymer.

이하 MsOMI와 TfOMI단량체를 제조하는 본 발명이 실시예를 들어 자세히 설명한다. 그러나 이들 실시예가 본 발명의 범위를 한정하는 것은 아니다.Hereinafter, the present invention for preparing MsOMI and TfOMI monomers will be described in detail with reference to Examples. However, these examples do not limit the scope of the present invention.

실시예 1 : 구조식(V) 화합물의 제조Example 1 Preparation of Structural Formula (V) Compound

2ℓ반응용기에 무수말레인산 150.03g(1.53mol)과 퓨란 104.16g(1.53mol), 톨투엔 200mol를 넣고 24시간 환류시켰다. 반응물을 실온으로 식히고 여과 및 건조하여 구조식(III)의 화합물 220.26g(수율87%)을 얻었다. 히드록실아민-메탄올 용액 1ℓ(2M)를 만들어 반응용기에 넣고 구조식(III)의 화합물 220.70g(1.33mol)을 천천히 부가하면서 실온에서 24시간 교반하였다. 반응물을 여과하고 건조하여 N-히드록실기로 치환된 흰색분말의 구조식(IV)의 화합물 166.24g(수율69%)을 얻었다. 구조식(IV)의 화합물 9.05g(0.05mol)과 피리딘 15㎖를 100㎖ 반응용기에 넣고 10분간 교반한 후 메탄술폰일클로라이드 3.87㎖(0.05mol)을 가하고 실온에서 5분간 반응시켰다. 반응물을 증류수에 부어 침전시키고 여과후 건조하여 구조식(V)의 흰색분말 11.87g(수율92%)을 얻었다.150.03 g (1.53 mol) of maleic anhydride, 104.16 g (1.53 mol) of furan, and 200 mol of toluene were added to a 2 L reaction vessel and refluxed for 24 hours. The reaction was cooled to room temperature, filtered and dried to afford 220.26 g (87% yield) of compound of formula III. 1 L (2 M) of hydroxylamine-methanol solution was prepared and placed in a reaction vessel, and 220.70 g (1.33 mol) of Compound (III) was slowly added thereto and stirred at room temperature for 24 hours. The reaction product was filtered and dried to obtain 166.24 g of a compound of formula (IV) as a white powder substituted with an N-hydroxy group (yield 69%). 9.05 g (0.05 mol) of the compound of formula (IV) and 15 ml of pyridine were placed in a 100 ml reaction vessel, stirred for 10 minutes, and then 3.87 ml (0.05 mol) of methanesulfonyl chloride was added and reacted at room temperature for 5 minutes. The reaction product was poured into distilled water, precipitated, filtered and dried to obtain 11.87 g (yield 92%) of white powder of the formula (V).

실시예 2 : 구조식(I)의 MsOMI단량체 제조Example 2 Preparation of MsOMI Monomer of Structural Formula (I)

구조식(V)의 화합물 5.18g(0.02mol)을 플라스크에 취하여 165℃의 기름 중탕에서 감압하에 2시간 동안 열분해시켰다. 얻어진 고체를 클로로포름으로 재결정하여 MsOMI를 2.48g(수율65%) 얻었다. 얻어진 MsOMI는 녹는점이 113℃이고, 양성자 핵자기공명 분석에서 이중결합의 2개의 프로톤(7.12ppm)과 매틸기의 3개 프로톤(3.50ppm)을 각각 단일 피크로 확인하였다. 적외선 분광분석에서 탄소-탄소 이중결합에 해당하는 1580㎝-1, 카르보닐에 해당하는 1750㎝-1와 술폰일기에 해당하는 1386㎝-1, 1188㎝-1의 흡수띠가 확인되었다. 가스크로마토그라피 부착 질량분광분석으로 부터 MsOMI의 분자이온 피크가 190.95에서, 메탄술폰일기가 이탈된 이온피크가 112.95에서, 메탄술폰일옥시기가 이탈된 이온 피크가 112.95에서, 메탄술폰옥시기가 이탈된 이온 피크가 97.00에서 각각 확인되엇다. 원소분석으로부터 탄소가 32.14%, 수소가 2.79%, 질소가 7.09%, 황이 16.86% 존재하는 것으로 나타났고 계산결과 C5H5NO3S의 분자식과 일치하였다.5.18 g (0.02 mol) of the compound of formula (V) were taken into a flask and pyrolyzed for 2 hours under reduced pressure in an oil bath at 165 ° C. The obtained solid was recrystallized from chloroform to give 2.48 g (yield 65%) of MsOMI. The obtained MsOMI had a melting point of 113 ° C., and proton nuclear magnetic resonance analysis confirmed two protons (7.12 ppm) of double bonds and three protons (3.50 ppm) of a methyl group as single peaks, respectively. The 1386㎝ -1, the 1188㎝ -1 absorption band was observed for the 1580㎝ -1, 1750㎝ -1 and sulfone group for the carbonyl, which corresponds to the carbon-carbon double bond in the infrared spectroscopic analysis of carbon. MsOMI has a molecular ion peak of 190.95, an methane sulfonyl group deviated ion peak from 112.95, a methane sulfonyloxy group deviated from an ion peak of 112.95, and a methane sulfonoxy group released ion Peaks were identified at 97.00 respectively. Carbon 32.14% from elemental analysis, hydrogen 2.79%, showed that the presence of nitrogen 7.09%, sulfur 16.86% calculated result was consistent with the molecular formula C 5 H 5 NO 3 S.

실시예 3 : 구조식(II)의 TfOMI단량체 제조Example 3 Preparation of TfOMI Monomer of Structural Formula (II)

구조식(IV)의 화합물 9.44g0.05mol)과 피리딘 10㎖, 트리플로로메탄슬폰일클로라이드 5.55㎖(0.05mol)를 실온에서 1시간 반응시켜 트리플로로메탄술폰일기가 치환된 구조식(VI)의 화합물을 14.75g(수율91%)얻었고, 9,69g(0,09mol)을 취하여 110℃의 온도에서 갑압하에 1시간동안 열분해시켰다. 얻어진 고체를 벤젠과 헥산으로 재결정하여 TfOMI를 7.01g(수율93%) 얻었다. 얻어진 TfOMI는 녹는점이 56℃이고, 양성자 분광분석에서 이중결합의 2개 프로톤(6.90ppm)을 단일 피크로 확인하였다. 적외선 분광분석에서 카르보닐에 해당하는 1770㎝-1와 술폰일기에 해당하는 1320㎝-1, 1210㎝-1의 흡수띠가 확인되었다. 탄소-13 헥자기공명분석에서 트리프ㅍ로로메틸기의 탄소가 125.6, 121.3, 117.0, 112.7ppm에서, 말레이미드의 이중결합이 133.7ppm, 캐론탄소가 162.0ppm에서 확인되었다.9.44 g 0.05 mol) of the compound of formula (IV), 10 ml of pyridine and 5.55 ml (0.05 mol) of trichloromethanesulfonyl chloride were reacted at room temperature for 1 hour to convert the trichloromethanesulfonyl group of the formula (VI). 14.75 g (91%) of a compound were obtained, and 9,69 g (0,09 mol) was taken and pyrolyzed for 1 hour under reduced pressure at a temperature of 110 ° C. The obtained solid was recrystallized from benzene and hexane to obtain 7.01 g (yield 93%) of TfOMI. The obtained TfOMI had a melting point of 56 ° C. and identified two protons (6.90 ppm) of double bonds as single peaks in proton spectroscopy. The 1320㎝ -1, the 1210㎝ -1 absorption band was found in the infrared spectroscopic analysis for the 1770㎝ -1 and sulfone group for the carbonyl group. In carbon-13 hex resonance analysis, the trifluoromethyl group had carbon of 125.6, 121.3, 117.0, and 112.7 ppm, and the double bond of maleimide was 133.7 ppm and the caron carbon was 162.0 ppm.

Claims (3)

다음 구조식(I)의 N-메탄술폰일옥시말레이미드(MsOMI) 및 다음 구조식(II)의 N-트리플로로메탄술폰일옥시말레이미드(TfOMI).N-methanesulfonyloxymaleimide (MsOMI) of the following structural formula (I) and N-trifluoromethanesulfonyloxymaleimide (TfOMI) of the following structural formula (II). 다음 구조식(IV)의 N-히드록시-3,6-에폭시-1,2,3,6-태트라히드로프탈이미드와 메탄술폰일클로라이드를 반응시켜 다음 구조식(V)의 N-(메탄술폰일)-3,6-에폭시-1,2,3,6-테트라히드로프탈이미드를 제조하고 구조식(V)의 화합물을 150-200℃로 가열분해하는 다음 구조식(I)의 N-메탄술폰일옥시말레이미드(MsOMI) 제조방법.N-hydroxy-3,6-epoxy-1,2,3,6-tatrahydrophthalimide of methanesulfonyl chloride of the following structural formula (IV) is reacted with N- (methanesulfuric acid of the following structural formula (V) N-methane sulfide of the following formula (I) to prepare ponyl) -3,6-epoxy-1,2,3,6-tetrahydrophthalimide and thermally decompose the compound of formula (V) to 150-200 ° C. Method of preparing ponyloxymaleimide (MsOMI). 구조식(IV)의 N-히드록시-3,6-에폭시-1,2,3,6-테트라히드로프탈이미드와 트리플로로메탄술폰일클로라이드를 반응시켜 다음 구조식(VI)의 N-(트리플로로메탄술폰일)-3,6-에폭시-1,2,3,6-테트라히드로프탈이미드를 제조하고 구조식(VI)화합물을 105-110℃로 가열분해하는 구조식(II)의 N-트리플로로메탄술폰일옥시말레이미드(TfOMI) 제조방법.N-hydroxy-3,6-epoxy-1,2,3,6-tetrahydrophthalimide of formula (IV) is reacted with trichloromethanesulfonyl chloride to form N- (triple) of the following formula (VI): N- of Structural Formula (II) to prepare chloromethanesulfonyl) -3,6-epoxy-1,2,3,6-tetrahydrophthalimide and thermally decompose the structural formula (VI) at 105-110 ° C. Method for preparing trichloromethanesulfonyloxymaleimide (TfOMI).
KR1019940020037A 1994-08-13 1994-08-13 Precess for the preparation of n-metan sulfoniloxyimide KR0139486B1 (en)

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