KR950002550B1

KR950002550B1 - N-tert-butoxymaleimide and its preparation

Info

Publication number: KR950002550B1
Application number: KR1019920003539A
Authority: KR
Inventors: 안광덕; 구덕일
Original assignee: 한국과학기술연구원; 박원희
Priority date: 1992-03-04
Filing date: 1992-03-04
Publication date: 1995-03-21
Also published as: KR930019624A

Abstract

N-tertiary butoxy maleimide of formula (1) is prepd. by: reacting maleic anhydride and furan to prepare 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride of formula (2); reacting the cpd. (2) with hydroxyl amine to prepare N-hydroxy-3,6-epoxy-1,2,3,6-tetrahydrophthal imide of formula (3); reacting the cpd. (3) with isobutylene at 110 deg.C in the presence of acid catalyst to prepare N-(t-butoxy)-3,6-epoxy-1,2,3,6-tetrahydrophthal amide of formula (4); then pyrolysis of the cpd. (4) at 145 deg.C. The obtd. maleimide derv. is useful for germicide or insecticide, and good heat resistance.

Description

N-tertiary-butoxymaleimide and its preparation method

본 발명은 산이나 열에 의한 분해가 용이하여 N-히드록실기의 보호 및 탈보호반응에 유리한 터셔리-부틸(tert-butyl)기를 N-히드록시말레이미드(N-hydroxymaleimide : 이하 HOMI로 표기함)에 도입한 구조식(I)의 새로운 단량체인 N-터셔리-부톡시말레이미드(N-tert-butoxymaleimide : 이하 t-BuOMI로표기함.) 및 그의 제조방법에 관한 것이다.In the present invention, a tert-butyl group, which is easily decomposed by an acid or heat and is advantageous for protecting and deprotecting N-hydroxyl groups, is referred to as N-hydroxymaleimide (hereinafter referred to as HOMI). N-tert-butoxymaleimide (hereinafter referred to as t-BuOMI), which is a new monomer of the structural formula (I) introduced in the present invention, and a preparation method thereof.

일반적으로 말레이미드와 그 유도체는 살균제, 살충제등의 유기화합물로 유용하게 쓰이고 염료, 가소제의 합성시 중간체로 이용된다. 말레이미드 화합물은 라디칼 중합반응시 매우 반응성이 좋은 단량체로 쓰이며, 그 중합체는 내열성이 우수하므로 여러 분야에서 이용된다. 말레이미드 구조의 독특한 내열성과 히드록실기의 큰 극성때문에 탈보호전후에 있어서 용해도의 현저한 차이가 있어 미세형상용 레지스트재료로 적용성이 매우 크다.In general, maleimide and its derivatives are useful as organic compounds such as fungicides and insecticides, and are used as intermediates in the synthesis of dyes and plasticizers. Maleimide compounds are used as monomers that are very reactive during radical polymerization, and the polymers are used in various fields because of their excellent heat resistance. Due to the unique heat resistance of the maleimide structure and the large polarity of the hydroxyl group, there is a remarkable difference in solubility before and after deprotection, so that it is very applicable as a microscopic resist material.

앞서 본 연구진은 터셔리-부톡시카르보닐(t-BOC) 보호기로 N-치환된 N-터셔리 부톡시카르보닐 말레이미드(t-BOCMI)를 신규 합성하여, 그 레지스트 특성을 조사하였으며, 현재 특허 출원중에 있다(1991년 특허출원 제10273호). 계속적인 연구결과 반도체의 초미세 가공기술에서 고감도와 내열성의 미세화상 형성이 가능한 N-히드록시말레이미드구조에 기초를 둔 새로운 레지스트 고분자를 발명하였다.Previously, the researchers synthesized N-terminated butoxycarbonyl maleimide (t-BOCMI) N-substituted with a tert-butoxycarbonyl (t-BOC) protecting group and investigated its resist properties. Patent is pending (Patent Application No. 10273, 1991). Continuing research has resulted in the invention of a new resist polymer based on N-hydroxymaleimide structure capable of forming microscopic images with high sensitivity and heat resistance in the ultra-fine processing technology of semiconductors.

앞서 발표된 t-BOC보호된 말레이미드 고분자는 약 150℃의 다소 낮은 탈보호온도를 갖고 있으나 200℃이상의 높은 분해온도를 갖는 말레이미드 단량체가 요구되어 본 발명에서는 이러한 열적 특성을 갖는 t-BuOMI를 발명하게 되었다.The t-BOC protected maleimide polymer disclosed above has a slightly lower deprotection temperature of about 150 ° C., but a maleimide monomer having a high decomposition temperature of 200 ° C. or higher is required. Thus, t-BuOMI having such a thermal characteristic is used in the present invention. Invented.

D.A.Laufer등은(JACS., 1968, 90, 2696) 에틸렌/HOMI 공중합체가 펩티드 합성에 중요한 시약으로 이용됨을 보고한 바 있으며, 이같은 고분자는 펩티드의 단계적인 합성에서 시약이나 지지물질로 이용되기도 한다. 종래 공지된 문헌(Bulletin of the Chemical Society of Japan., 1971, 44, 1084)에 의하면 본 발명과 유사한 여러가지 N-히드록시말레이미드유도체(O-벤질, O-아세틸, O-벤젠술폰일, O-메틸말레이미드)의 제조에 관하여 개시되었지만, 이들 기존의 HOMI 유도체는 안정한 화합물로 보호/탈보호반응이 가능한 화합물이 아니다. 따라서 본 발명자들은 공지의 제조기술을 기본원리로 하여 딜스-알더반응시킨 후 t-부틸기를 도입하고 다시 레트로딜스-알더반응을 통해 퓨란을 열분해 제거하여 보호기를 갖는 원하는 t-BuOMI 단량체를 제조하였다.DALaufer et al. (JACS., 1968, 90, 2696) reported the use of ethylene / HOMI copolymers as important reagents in peptide synthesis. Such polymers may be used as reagents or supporting materials in the phased synthesis of peptides. . According to the previously known Bulletin of the Chemical Society of Japan., 1971, 44, 1084, various N-hydroxymaleimide derivatives similar to the present invention (O-benzyl, O-acetyl, O-benzenesulfonyl, O -Methylmaleimide), but these existing HOMI derivatives are stable compounds and are not compounds capable of protection / deprotection. Therefore, the present inventors prepared a desired t-BuOMI monomer having a protecting group by introducing a di-alder reaction based on a known production technique and then introducing a t-butyl group and pyrolyzing and removing furan via a retrodils-alder reaction.

본 발명의 t-BuOMI 단량체는 신규한 화합물로서 공중합체의 제조에 유리하고 t-부틸기는 열이나 산반응에 의하여 용이하게 탈보호되어 HOMI구조로 변하므로 극성이 크게 변하여 미세화상 형성용 레지스트재료로 응용성이 크다.The t-BuOMI monomer of the present invention is a novel compound, which is advantageous for the production of copolymers, and since the t-butyl group is easily deprotected by heat or acid reaction to change into a HOMI structure, the polarity is greatly changed and thus as a resist image forming material. Applicability is great.

본 발명에 의하면, 구조식(Ⅲ) 화합물의 N-히드록실기에 산 촉매 조건하에서 이소부틸렌을 반응시켜 t-부틸기가 도입된 구조식(IV) 화합물을 생성하는데 이 생성물은 분리하기가 쉽고, 최종단계에서 t-BuOMI가 승화성이 있기 때문에 열분해반응으로 고순도로 용이하게 제조된다. 전체적인 합성방법에 있어서 이소부틸렌 기체를 효과적으로 이용하므로 조작이 간편하고 경제적으로 대량생산이 가능한 장점이 있다. 또한 높은 수율로 t-BuOMI 단량체의 합성이 가능할 뿐만 아니라 본 발명에 의하여 제조된 t-BuOMI 단량체는 히드록시말레이미드에 t-부틸기가 도입되어 있어 감도와 내열성이 우수한 레지스트 재료의 제조에 적합하다.According to the present invention, isobutylene is reacted with an N-hydroxyl group of the compound of formula (III) under acid catalyzed conditions to produce a compound of formula (IV) having t-butyl group introduced therein. Since t-BuOMI is sublimable in the step, it is easily manufactured with high purity by pyrolysis reaction. Since the isobutylene gas is effectively used in the overall synthesis method, there is an advantage in that it is easy to operate and economically mass-produced. In addition, the synthesis of t-BuOMI monomers with high yield is possible, and the t-BuOMI monomers prepared according to the present invention have t-butyl groups introduced into hydroxymaleimide, which is suitable for preparing a resist material having excellent sensitivity and heat resistance.

본 발명에 의한 t-BuOMI 제조방법을 화학반응식으로 나타내면 다음과 같다.The t-BuOMI manufacturing method according to the present invention is represented by the chemical reaction formula below.

상기 반응식에서 알 수 있는 바와 같이 무수말레산과 퓨란을 반응시키면 딜스-알더반응에 의하여 구조식(II)의 3,6-에폭시-1,2,3,6-테트라히드로프탈릭 안히드리드가 정량적으로 생성되고, 구조식(II) 화합물과 히드록실아민을 반응시키면 구조식(Ⅲ)의 N-히드록시-3,6-에폭시-1,2,3,6-테트라히드로프탈이미드가 생성된다.산 촉매 조건하에 구조식(Ⅲ) 화합물과 이소부틸렌을 반응시키면 구조식(IV)의 N-(t-부톡시)-3,6-에폭시-1,2,3,6-테트라히드로프탈이미드가 생성되고, 구조식(IV) 화합물을 열분해하면 목적물인 구조식(I)의 t-BuOMI가 75%이상의 고수율로 생성된다. 생성된 t-BuOMI의 녹는점은 92℃였으며, 생성물은 적외선 분광분석, 탄소-13 및 양성자 핵자기 공명분석, 질량분석, 가스크로마토그라피 결합 질량분광분석, 원소분석에 의하여 그 화학구조가 확인되었다.As can be seen from the above scheme, when maleic anhydride and furan are reacted, 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride of the formula (II) is quantitatively reacted by Diels-Alder reaction. When the compound of formula (II) is reacted with hydroxylamine, N-hydroxy-3,6-epoxy-1,2,3,6-tetrahydrophthalimide of formula (III) is produced. Reaction of the compound of formula (III) with isobutylene under conditions yields N- (t-butoxy) -3,6-epoxy-1,2,3,6-tetrahydrophthalimide of formula (IV). When pyrolyzing the compound of formula (IV), t-BuOMI of the formula (I) as a target is produced in a high yield of 75% or more. The melting point of the produced t-BuOMI was 92 ° C, and the product was identified by infrared spectroscopy, carbon-13 and proton nuclear magnetic resonance analysis, mass spectrometry, gas chromatography coupled mass spectrometry, and elemental analysis. .

본 발명으로 제조한 t-BuOMI 단량체는 상업적으로 생산되는 일반 단량체와 용이하게 라디칼 공중합되고, 이로서 얻어진 중합체는 t-부틸기로 보호된 HOMI구조를 갖고 있어서 산에 의하여 t-부틸기의 제거가 매우 쉽고, 보호기를 제거하여 얻어진 중합체는 히드록시말레이미드 구조로 200℃이상의 높은 유리전이온도를 갖는다. 그러므로 반도체의 초미세가공에서 플라즈마 드라이 엣칭(dry-etching)등에 의한 화상전이(pattern transfer) 공정 등에서 레지스트 미세화상의 중요한 요구 물성인 200℃이상의 내열성을 만족시킨다.The t-BuOMI monomer prepared according to the present invention is easily radically copolymerized with commercially produced general monomers, and the polymer thus obtained has a HOMI structure protected with a t-butyl group, so that the t-butyl group is easily removed by acid. The polymer obtained by removing the protecting group has a high glass transition temperature of 200 ° C. or more with a hydroxymaleimide structure. Therefore, it satisfies the heat resistance of 200 ° C. or more, which is an important required property of the resist micro-image, in a pattern transfer process such as plasma dry etching or the like in ultra-fine processing of semiconductors.

또한 서브미크론 해상성 달성을 위하여 조사파장이 단파장인 원자외선영역(deep UV, 200∼300nm) 또는 보다 유리하게는 고출력의 불화크립톤 엑사이머 레이저(KrF excimer laser) 248nm 파장에서 레지스트의 광흡수가 높지 않고 적절하여야 하는데 본 발명 방법으로 제조한 t-BuOMI 단량체를 함유하는 중합체는 원자외선 영역의 광흡수도가 매우 낮아서 원자외선 및 감방사선 레지스트 응용에 매우 적절한 고분자로 기대된다.In order to achieve submicron resolution, the light absorption of the resist in the deep ultraviolet region (200-300 nm), or more advantageously, the high power KrF excimer laser 248 nm wavelength, has a short wavelength. The polymer containing the t-BuOMI monomer prepared by the method of the present invention has a very low light absorption in the far ultraviolet region, which is expected to be a very suitable polymer for the application of ultraviolet and radiation resists.

이하 t-BuOMI 단량체를 제조하는 본 발명의 실시예를 들어 자세히 설명한다. 그러나 이들 실시예가 본 발명의 범위를 한정하는 것은 아니다.Hereinafter, an embodiment of the present invention for preparing a t-BuOMI monomer will be described in detail. However, these examples do not limit the scope of the present invention.

실시예 1Example 1

t-Bu기로 보호된 구조식(IV) 화합물의 제조Preparation of Structural Formula (IV) Compound Protected with t-Bu Group

용량 2ℓ의 반응용기에 무수말레산 294.0g(3mol)과 퓨란 283.0g(3.5mol), 톨루엔 500ml를 넣고 4시간 환류시켰다. 반응물을 실온으로 식히고 여과 및 건조하여 구조식(II)의 화합물 441.0g(수율 90%)을 얻었다. 히드록실아민 메탄올용액 1ℓ(2M)를 만들어 반응용기에 넣고 구조식(II) 화합물 332.0g(2mol)을 천천히 부가하면서 실온에서 2시간 가량 저어주었다. 반응물을 여과하고 건조하여 N-히드록실기로 치환된 구조식(Ⅲ)의 화합물을 흰색 분말로서 294.0g(수율 81%)을 얻었다. 구조식(Ⅲ) 화합물 80.0g(0.44mol)과 디클로로메탄 500ml을 1ℓ 압력 반응기에 넣고 1시간 가량 냉동실에서 냉각시킨 후, 황산 1.0ml에서 이소부틸렌 200ml을 주가하고 110℃에서 8일간 반응시켰다. 반응후 여과하고 여액에서 용매를 감압증발시켜 t-Bu기가 치환된 구조식(IV) 화합물을 결정상태로 86.0g(수율 82%) 제조하였다.294.0 g (3 mol) of maleic anhydride, 283.0 g (3.5 mol) of furan, and 500 ml of toluene were added to a 2 L reaction vessel and refluxed for 4 hours. The reaction was cooled to room temperature, filtered and dried to give 441.0 g (90% yield) of the compound of formula II. 1 L (2 M) of hydroxylamine methanol solution was prepared, placed in a reaction vessel, and 332.0 g (2 mol) of the compound of formula (II) was slowly added and stirred at room temperature for 2 hours. The reaction was filtered and dried to obtain 294.0 g (yield 81%) of a compound of formula (III) substituted with N-hydroxyl group as a white powder. 80.0 g (0.44 mol) of the compound of the structural formula (III) and 500 ml of dichloromethane were placed in a 1 L pressure reactor, and cooled in a freezer for about 1 hour. 200 ml of isobutylene was added to 1.0 ml of sulfuric acid and reacted at 110 ° C. for 8 days. After the reaction was filtered and the solvent was evaporated under reduced pressure in the filtrate to give 86.0g (yield 82%) of the compound of formula (IV) substituted with t-Bu group in the crystal state.

실시예 2Example 2

구조식(I)의 t-BuOMI 단량체의 제조Preparation of t-BuOMI Monomer of Structural Formula (I)

t-부틸기로 보호된 구조식(IV) 화합물을 10.4g 취하여 145℃의 오일 중탕에서 감압 승화장치를 이용하여 2시간 동안 열분해시켰다. 열분해에 따른 중화로 깨끗한 흰색 결정체인 t-BuOMI를 5.6g(수율 75%) 얻었다. 생성된 고체를 톨루엔과 헥산 혹은 디클로로메탄과 헥산(1 : 10의 체적비율) 혼합 용매로 재결정하여 고순도의 t-BuOMI를 제조하였다. 얻어진 t-BuOMI는 녹는 점이 92℃로 관찰되었고 양성자 분석(NMR)에서 이중결합의 2개 프로톤(6.56ppm)과 t-부틸기의 9개 프로톤(1.30ppm)을 각각 단일 피크로 확인하였다. 적외선 분광분석에서 t-부틸에 해당하는 2980cm^{- 1}및 아미드에 해당하는 1730cm^-1의 흡수띠가 확인되었다.10.4 g of the compound of formula (IV) protected with t-butyl group was taken and pyrolyzed for 2 hours using a reduced pressure sublimator in an oil bath at 145 ° C. Neutralization by pyrolysis gave 5.6 g (yield 75%) of clear white crystals, t-BuOMI. The resulting solid was recrystallized with toluene and hexane or dichloromethane and hexane (volume ratio of 1: 10) mixed solvent to prepare t-BuOMI of high purity. The obtained t-BuOMI had a melting point of 92 ° C., and two protons (6.56 ppm) of double bonds and nine protons (1.30 ppm) of t-butyl groups were identified as single peaks in proton analysis (NMR). The absorption band of 1730cm ^-1 was observed for the ^first and ^amide-in infrared spectroscopic analysis 2980cm corresponding to t- butyl.

탄소-13양성자 분광분석에서 t-부틸의 메틸기의 탄소가 27.11, t-부틸기의 3차 탄소가 85.73, 올레핀의 탄소가 132.35, 말레이미드 고리의 카르보닐 탄소가 167.85ppm에서 확인되었다. 가스 크로마토그라피 결합질량 분석으로부터 t-BuOMI의 분자 이온 피크가 169.40에서 분자에서 메틸기가 이탈된 이온 피크가 154에서 t-부틸기가 이탈된 이온피크가 113, t-부틸기에서 기인된 이소부탄의 이온피크가 57에 확인되었다.In carbon-13 proton spectroscopy, the carbon of the t-butyl methyl group was 27.11, the tertiary carbon of the t-butyl group was 85.73, the carbon of the olefin was 132.35, and the carbonyl carbon of the maleimide ring was 167.85 ppm. Molecular ion peak of t-BuOMI from gas chromatographic binding mass spectrometry is 169.40.Ion peak from methyl group is ions peaked at 154. The peak was identified at 57.

원소분석에 의하여 탄소가 56.60%, 수소가 6.53% 질소가 8.14% 존재하는 것으로 나타났고 계산결과 C₈H_llNO₃의 분자식과 일치하였다.Elemental analysis showed 56.60% carbon, 6.53% hydrogen, and 8.14% nitrogen. The calculations were consistent with the molecular formula of C ₈ H _ll NO ₃ .

Claims

N-tertiary-butoxymaleimide (t-BuOMI) of formula (I)

Maleic anhydride and furan are reacted to prepare 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride of the following formula (II) to react the compound of formula (II) with hydroxylamine To prepare N-hydroxy-3,6-epoxy-1,2,3,6-tetrahydrodephthalimide of the following formula (III), and react the compound of formula (III) with isobutylene in the presence of an acid catalyst N- (t-butoxy) -3,6-epoxy-1,2,3,6-tetrahydrophthalimide of formula (IV) to thermally decompose the compound N-tertiary oxymaleimide (t-BuOMI) manufacturing method of 1).

The N- (t-butoxy) -3,6-epoxy-1,2,3,6 of formula (IV) is prepared by reacting a compound of formula (III) with isobutylene at 110 ° C under an acid catalyst. A process for producing N-tertiary-butoxy maleimide (t-BuOMI) of formula (I), characterized by producing tetrahydrophthalimide.

The process for producing N-tertiary-butoxymaleimide (t-BuOMI) of formula (I) according to claim 2, wherein the thermal decomposition temperature of the compound of formula (IV) is 145 ° C.