KR102544307B1 - Manufacturing method of aromatic diamine compound precursor - Google Patents
Manufacturing method of aromatic diamine compound precursor Download PDFInfo
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- 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
- C07D207/30—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 two double bonds between ring members or between ring members and non-ring members
- C07D207/32—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 two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/33—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 two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/335—Radicals substituted by nitrogen atoms not forming part of a nitro radical
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Abstract
폴리아믹산 및/또는 폴리이미드의 제조 원료인 디아민 화합물의 전구체인 디니트로 화합물을, 부생물이 적고, 고순도, 고수율로 제조하는 방법을 제공한다.
식 (1) 로 나타내는 방향족 디할로겐 화합물과 식 (2) 로 나타내는 N-알킬니트로아닐린 유도체를, 금속 착물 용매 및 염기의 존재하에 반응시키는 것에 의한, 식 (3) 으로 나타내는 N-(니트로페닐) 방향족 아민 화합물의 제조 방법.
[Ar 은 아릴렌기 또는 헤테로아릴렌기 ; X 는 할로겐 ; R 은 C1 ∼ C6 알킬]Provided is a method for producing a dinitro compound, which is a precursor of a diamine compound that is a raw material for producing polyamic acid and/or polyimide, with fewer by-products and with high purity and high yield.
N-(nitrophenyl) represented by formula (3) by reacting an aromatic dihalogen compound represented by formula (1) with an N-alkylnitroaniline derivative represented by formula (2) in the presence of a metal complex solvent and a base. A method for producing an aromatic amine compound.
[Ar is an arylene group or a heteroarylene group; X is halogen; R is C 1 -C 6 alkyl]
Description
본 발명은 액정 배향제 등에 사용되는 폴리이미드의 제조 원료인, 특정 디아민 화합물의 전구체인 디니트로 화합물을, 부생물이 적고, 고순도 또한 고수율로 제조하는 신규의 방법에 관한 것이다.The present invention relates to a novel method for producing a dinitro compound, which is a production raw material for polyimide used in a liquid crystal aligning agent or the like, and is a precursor of a specific diamine compound, with few by-products and with high purity and high yield.
현재, 액정 표시 소자에 사용되는 액정 배향막에는, 많은 경우, 폴리이미드막이 사용되고 있다. 이 폴리이미드막의 액정 배향막은, 폴리이미드의 전구체인 폴리아믹산의 용액 또는 용매 가용성의 폴리이미드의 용액을 기판에 도포하고, 소성하여 얻어지는 막을 러빙 처리 등의 배향 처리하는 방법에 의해 제조되고 있다 (특허문헌 1, 2 를 참조). 이 폴리아믹산이나 용매 가용성의 폴리이미드는, 일반적으로, 테트라카르복실산 2 무수물 등의 테트라카르복실산 유도체와, 디아민 화합물의 축중합 반응에 의해 제조되고 있다.Currently, in many cases, a polyimide film is used for a liquid crystal aligning film used for a liquid crystal display element. The liquid crystal alignment film of this polyimide film is produced by a method of applying a solution of a polyamic acid, which is a precursor of polyimide, or a solution of solvent-soluble polyimide to a substrate, followed by firing, and subjecting the obtained film to alignment treatment such as rubbing treatment (patented see literature 1, 2). This polyamic acid and solvent-soluble polyimide are generally manufactured by condensation polymerization of a tetracarboxylic acid derivative such as tetracarboxylic dianhydride and a diamine compound.
이러한 폴리아믹산이나 폴리이미드 등의 원료인 디아민 화합물은, 이것으로부터 얻어지는 액정 배향막의 특성, 나아가서는 액정 표시 소자의 특성에 영향을 주기 때문에 중요하며, 종래부터 다양한 디아민 화합물이 사용되고 있고, 제안되어 있다.Diamine compounds, which are raw materials such as polyamic acid and polyimide, are important because they affect the properties of the liquid crystal aligning film obtained therefrom and, by extension, the properties of the liquid crystal display element, and various diamine compounds have been conventionally used and proposed.
각종 특성이 우수한 디아민 화합물로서, 방향고리끼리가 결합된 구조를 갖는 것이 제안되어 있다. 이와 같은 디아민 화합물은, 일반적으로 전구체인 디니트로 화합물의 환원에 의해 제조되지만, 이들 디니트로 화합물 중 어떤 종류의 것은 제조 방법이 확립되어 있지 않아, 다단계의 공정을 필요로 하거나, 수율이 낮거나, 제조 비용이 높다는 문제점이 있다. 또, 방향족 디할로겐 화합물과 N-알킬니트로아닐린 유도체의 커플링 반응에 관해서는, 반응성이 낮아, 디니트로 화합물의 제조에 적용하는 것이 어려웠다.As diamine compounds excellent in various characteristics, those having a structure in which aromatic rings are bonded have been proposed. Such a diamine compound is generally produced by reduction of a dinitro compound as a precursor, but some types of these dinitro compounds do not have established production methods, require multi-step processes, have low yields, There is a problem that the manufacturing cost is high. In addition, the coupling reaction between an aromatic dihalogen compound and an N-alkylnitroaniline derivative has low reactivity, and it has been difficult to apply it to the production of a dinitro compound.
본 발명은 방향족 디할로겐 화합물과 N-알킬니트로아닐린 유도체의 커플링 반응을 이용하여 디니트로 화합물을 제조하는 경우에 있어서, 상기 문제를 해결함과 함께, 반응 속도가 높고, 부생물이 적고, 고순도이며, 또한 고수율로 목적물이 얻어지는 방법을 제공하는 것을 목적으로 한다.In the case of producing a dinitro compound using a coupling reaction between an aromatic dihalogen compound and an N-alkylnitroaniline derivative, the present invention solves the above problems, has a high reaction rate, low by-products, and high purity And, it is also an object to provide a method for obtaining a target product in high yield.
본 발명은 상기 목적을 달성하기 위해 예의 연구를 진행한 결과, 이하를 요지로 하는 신규의 제조 방법에 도달한 것이다.As a result of intensive research in order to achieve the above object, the present invention has arrived at a novel manufacturing method having the following gist.
1. 하기 식 (1) 로 나타내는 방향족 디할로겐 화합물과, 하기 식 (2) 로 나타내는 N-알킬니트로아닐린 유도체를, 금속 착물 촉매 및 염기의 존재하에 반응시키는 것에 의한, 하기 식 (3) 으로 나타내는 N-(니트로페닐) 방향족 아민 화합물의 제조 방법.1. An aromatic dihalogen compound represented by the following formula (1) and an N-alkylnitroaniline derivative represented by the following formula (2) are reacted in the presence of a metal complex catalyst and a base, represented by the following formula (3) A method for producing an N-(nitrophenyl) aromatic amine compound.
[화학식 1][Formula 1]
[식 중, Ar 은 아릴렌기 또는 헤테로아릴렌기를 나타내고, X 는 할로겐을 나타낸다.][Wherein, Ar represents an arylene group or a heteroarylene group, and X represents a halogen.]
[화학식 2][Formula 2]
[식 중, R 은 C1 ∼ C6 알킬을 나타낸다.][Wherein, R represents C 1 -C 6 alkyl.]
[화학식 3][Formula 3]
[식 중, Ar, X, 및 R 은 상기의 정의와 동일하다.][In the formula, Ar, X, and R are the same as defined above.]
2. 금속 착물 촉매가, 팔라듐 착물 또는 구리 착물인, 상기 1 에 기재된 제조 방법.2. The production method described in 1 above, wherein the metal complex catalyst is a palladium complex or a copper complex.
3. 염기가, 알칼리 금속 혹은 알칼리 토금속의 수산화물, 탄산염, 탄산수소염, 인산염, 인산수소염 또는 카르복실산염인, 상기 1 또는 2 에 기재된 제조 방법.3. The production method according to 1 or 2 above, wherein the base is a hydroxide, carbonate, hydrogen carbonate, phosphate, hydrogen phosphate or carboxylate of an alkali metal or alkaline earth metal.
4. 용매의 존재하에 반응시키는, 상기 1 ∼ 3 중 어느 한 항에 기재된 제조 방법.4. The production method according to any one of 1 to 3, wherein the reaction is performed in the presence of a solvent.
5. 상기 방향족 디할로겐 화합물이, 후기하는 식 (X1) ∼ (X6) 중 어느 것으로 나타내는 화합물인, 상기 1 ∼ 4 중 어느 한 항에 기재된 제조 방법.5. The manufacturing method according to any one of 1 to 4 above, wherein the aromatic dihalogen compound is a compound represented by any of formulas (X1) to (X6) described later.
6. 방향족 디할로겐 화합물이, 후기하는 식 (X1) ∼ (X3) 중 어느 것으로 나타내는 화합물인, 상기 1 ∼ 4 중 어느 한 항에 기재된 제조 방법.6. The production method according to any one of 1 to 4 above, wherein the aromatic dihalogen compound is a compound represented by any of formulas (X1) to (X3) described later.
7. 식 (1) 또는 식 (X1) ∼ (X6) 에 있어서의 X 가, Cl 또는 Br 인, 상기 1 ∼ 6 중 어느 한 항에 기재된 제조 방법.7. The manufacturing method according to any one of 1 to 6 above, wherein X in formula (1) or formulas (X1) to (X6) is Cl or Br.
8. N-알킬니트로아닐린 유도체가, N-메틸-p-니트로아닐린인, 상기 1 ∼ 7 중 어느 한 항에 기재된 제조 방법.8. The production method according to any one of 1 to 7 above, wherein the N-alkylnitroaniline derivative is N-methyl-p-nitroaniline.
9. 용매가, 톨루엔, 1,2-디메톡시에탄, 테트라하이드로푸란, 2-메틸테트라하이드로푸란, 디메틸포름아미드, 디메틸아세트아미드, 또는 N-메틸-2-피롤리돈인, 상기 4 ∼ 8 중 어느 한 항에 기재된 제조 방법.9. 4 to 8 above, wherein the solvent is toluene, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylformamide, dimethylacetamide, or N-methyl-2-pyrrolidone The manufacturing method according to any one of the above.
10. 염기가, 탄산세슘, 또는 인산삼칼륨인, 상기 1 ∼ 9 중 어느 한 항에 기재된 제조 방법.10. The manufacturing method according to any one of 1 to 9 above, wherein the base is cesium carbonate or tripotassium phosphate.
11. 팔라듐 착물에 있어서의 팔라듐이, Pd2(dba)3(dba)n (dba 는 디벤질리덴아세톤을 나타내고, n 은 0 내지 2 의 정수를 나타낸다) 으로 나타내어지는, 상기 2 ∼ 10 중 어느 한 항에 기재된 제조 방법.11. Any of 2 to 10 above, wherein palladium in the palladium complex is represented by Pd 2 (dba) 3 (dba) n (dba represents dibenzylidene acetone, and n represents an integer of 0 to 2) The manufacturing method according to claim 1.
12. 팔라듐 착물 또는 구리 착물에 있어서의 배위자가, 2-디시클로헥실포스피노-2',4',6'-트리이소프로필비페닐 및 2-디시클로헥실포스피노-2',6'-디이소프로폭시비페닐로 이루어지는 군에서 선택되는 적어도 1 종인, 상기 2 ∼ 11 중 어느 한 항에 기재된 제조 방법.12. The ligands in the palladium complex or copper complex are 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl and 2-dicyclohexylphosphino-2', 6'- The manufacturing method according to any one of 2 to 11 above, which is at least one selected from the group consisting of diisopropoxybiphenyl.
13. 상기 1 ∼ 12 중 어느 한 항에 기재된 제조 방법에 의해 얻어지는 식 (3) 으로 나타내는 N-(니트로페닐) 방향족 아민 화합물이 갖는 니트로기를 환원하는 것에 의한 N-(아미노페닐) 방향족 아민 화합물의 제조 방법.13. N- (aminophenyl) aromatic amine compound by reducing the nitro group of the N- (nitrophenyl) aromatic amine compound represented by formula (3) obtained by the production method according to any one of 1 to 12 above manufacturing method.
본 발명에 의하면, 반응성이 일반적으로 낮은 방향족 디할로겐 화합물과 N-알킬니트로아닐린 유도체의 커플링 반응에 의해, 디아민 화합물의 전구체인 디니트로 화합물을 고수율로 제조할 수 있다. 또, 본 발명에서 얻어지는 디니트로 화합물은, 금속 촉매의 사용량을 작게 할 수 있기 때문에, 전자 재료 분야에서 문제가 되는 잔류 금속의 함유량을 최소한으로 저감시킬 수 있고, 또한, 목적물과의 분리가 곤란한 반응 중간체인 모노커플링체의 함유량이 거의 없어, 칼럼 처리 등의 번잡한 정제를 필요로 하지 않는다.According to the present invention, a dinitro compound, which is a precursor of a diamine compound, can be produced in high yield by a coupling reaction between an aromatic dihalogen compound having generally low reactivity and an N-alkylnitroaniline derivative. In addition, since the dinitro compound obtained in the present invention can reduce the amount of metal catalyst used, the content of residual metal, which is a problem in the field of electronic materials, can be reduced to a minimum, and also a reaction in which separation from the target object is difficult. There is almost no content of intermediate monocoupling products, and cumbersome purification such as column treatment is not required.
본 발명에서 얻어지는 디니트로 화합물은, 폴리아믹산 및/또는 폴리이미드의 제조 원료인 디아민 화합물의 전구체 등으로서 사용된다.The dinitro compound obtained in the present invention is used as a precursor of a diamine compound that is a raw material for producing polyamic acid and/or polyimide.
이하에, 본 발명에 대해 더욱 상세하게 설명한다.Below, the present invention will be described in more detail.
또한, 본 명세서에 있어서의 「n」은 노르말을, 「s」는 세컨더리를, 「t」는 터셔리를, 「o」는 오르토를, 「m」은 메타를, 「p」는 파라를 나타낸다.In this specification, “n” represents normal, “s” represents secondary, “t” represents tertiary, “o” represents ortho, “m” represents meta, and “p” represents para. .
본 발명의 제조 방법에 있어서의 반응은, 하기 스킴 (A) 로 나타낸다. 즉, 식 (1) 로 나타내는 방향족 디할로겐 화합물과, 식 (2) 로 나타내는 N-알킬니트로아닐린을 금속 착물 촉매와 염기의 존재하에서 반응시킴으로써, 식 (3) 으로 나타내는 N-(니트로페닐) 방향족 아민 화합물을 제조하는 것이다.The reaction in the production method of the present invention is represented by the following scheme (A). That is, by reacting the aromatic dihalogen compound represented by formula (1) with N-alkylnitroaniline represented by formula (2) in the presence of a metal complex catalyst and a base, N-(nitrophenyl) aromatic represented by formula (3) It is to prepare an amine compound.
[화학식 4][Formula 4]
상기 식 (1) 중, Ar 및 X 는, 상기 1 에 기재한 바와 같다.In the formula (1), Ar and X are as described in 1 above.
Ar 로 나타내는 아릴렌기는, 아렌으로부터, 2 개의 고리 탄소 원자의 각각 1 개의 수소 원자를 제거함으로써 생성되는 2 가의 기이다. 또, 헤테로아릴렌기는, 헤테로아렌으로부터, 2 개의 고리 탄소 원자의 각각 1 개의 수소 원자를 제거함으로써 생성되는 2 가의 기이다.The arylene group represented by Ar is a divalent group produced by removing one hydrogen atom from each of two ring carbon atoms from arene. In addition, the heteroarylene group is a divalent group produced by removing one hydrogen atom from each of the two ring carbon atoms from the heteroarene.
또, X 로 나타내는 할로겐은, Cl, Br 또는 I 가 바람직하고, Cl 또는 Br 이 보다 바람직하다.Moreover, the halogen represented by X is preferably Cl, Br or I, and more preferably Cl or Br.
상기 식 (1) 로 나타내는 방향족 디할로겐 화합물로는, 하기 (X1) ∼ (X6) 중 어느 것으로 나타내는 것이 바람직하고, (X1) ∼ (X3) 중 어느 것으로 나타내는 것이 보다 바람직하다.As an aromatic dihalogen compound represented by the said formula (1), what is represented by any of the following (X1) - (X6) is preferable, and what is represented by any of (X1) - (X3) is more preferable.
[화학식 5][Formula 5]
상기 식 (3) 및 식 (X1) ∼ (X6) 중, X 는, 할로겐을 나타낸다. 할로겐으로는, Cl, Br 또는 I 가 바람직하고, Cl 또는 Br 이 보다 바람직하다.In the above formula (3) and formulas (X1) to (X6), X represents a halogen. As halogen, Cl, Br or I is preferable, and Cl or Br is more preferable.
상기 식 (3) 중의 R 로 나타내는 C1 ∼ C6 알킬은, 탄소 원자수가 1 ∼ 6 개 로 이루어지는 직사슬형 또는 분기사슬형의 지방족 탄화수소로부터 수소 1 원자가 소실되어 생성되는 1 가의 기를 나타낸다. R 은 C1 ∼ C3 알킬이 바람직하고, 메틸 또는 에틸이 보다 바람직하다.C 1 to C 6 alkyl represented by R in the formula (3) represents a monovalent group generated by loss of one hydrogen atom from a linear or branched aliphatic hydrocarbon having 1 to 6 carbon atoms. R is preferably C 1 -C 3 alkyl, more preferably methyl or ethyl.
R 의 예로는, 메틸, 에틸, n-프로필, 이소프로필, n-부틸, 이소부틸, s-부틸, t-부틸, n-펜틸, 이소펜틸, 네오펜틸, t-펜틸, 1,1-디메틸프로필, n-헥실, 또는 이소헥실이 바람직하고, 메틸이 보다 바람직하다.Examples of R include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, 1,1-dimethyl Preferred is propyl, n-hexyl, or isohexyl, and more preferred is methyl.
여기서 사용되는 방향족 디할로겐 화합물의 어느 것은 공지 화합물이며, 문헌에 기재된 공지된 방법에 준하여 합성할 수 있다. 예를 들어, 2,5-비스(4-브로모페닐)-1-메틸-1H-피롤은, J. Med. Chem. 1977년, 20권, 531-536 페이지에 기재된 방법에 준하여 반응시킴으로써, 화합물을 얻을 수 있다.Any of the aromatic dihalogen compounds used herein are known compounds, and can be synthesized according to known methods described in literature. For example, 2,5-bis(4-bromophenyl)-1-methyl-1H-pyrrole is described in J. Med. Chem. The compound can be obtained by reacting according to the method described in 1977, Vol. 20, pp. 531-536.
N-알킬니트로아닐린에 있어서의 니트로기의 아미노기에 대한 위치는, o 위치, m 위치, 또는 p 위치 중 어느 것이어도 되지만, p 위치가 보다 바람직하다.The position of the nitro group in the N-alkylnitroaniline relative to the amino group may be any of the o-position, m-position, and p-position, but the p-position is more preferable.
방향족 디할로겐 화합물과 N-알킬니트로아닐린을 반응시킬 때의 N-알킬니트로아닐린의 사용량은, 방향족 디할로겐 화합물의 할로겐 원자 1 몰당, 1.0 ∼ 1.5 몰이 바람직하고, 1.05 ∼ 1.2 몰이 특히 바람직하다.The amount of N-alkylnitroaniline used when the aromatic dihalogen compound and N-alkylnitroaniline are reacted is preferably 1.0 to 1.5 moles, particularly preferably 1.05 to 1.2 moles, per mole of the halogen atom of the aromatic dihalogen compound.
본 발명에 있어서, 상기 스킴 (A) 의 반응은, 금속 착물 촉매와 염기의 존재하에 실시된다. 금속 착물 촉매는, 금속 착물과 배위자를 사용하여 형성된다.In the present invention, the reaction of scheme (A) is carried out in the presence of a metal complex catalyst and a base. A metal complex catalyst is formed using a metal complex and a ligand.
금속 착물 촉매로는, 다양한 구조의 것을 사용할 수 있지만, 그 중에서도, 저원자가의 팔라듐 착물 또는 구리 착물이 바람직하다. 특히, 팔라듐 착물로는, 3 급 포스핀 또는 3 급 포스파이트를 배위자로 하는 0 가 금속 착물 촉매가 바람직하다.As a metal complex catalyst, although the thing of various structures can be used, among these, a low-valent palladium complex or copper complex is preferable. In particular, as the palladium complex, a zero-valent metal complex catalyst having a tertiary phosphine or a tertiary phosphite as a ligand is preferable.
본 발명에서는, 반응계 중에서 용이하게 0 가 금속 착물 촉매로 변환되는 전구체를 사용할 수도 있다. 나아가서는, 반응계 중에서, 3 급 포스핀이나 3 급 포스파이트를 배위자로서 포함하지 않는 금속 착물과, 배위자인 3 급 포스핀이나 3 급 포스파이트를 혼합하고, 3 급 포스핀 또는 3 급 포스파이트를 배위자로 하는 저원자가 금속 착물 촉매를 생성시켜 사용할 수도 있다.In the present invention, a precursor that is easily converted into a zero-valent metal complex catalyst in the reaction system can also be used. Furthermore, in the reaction system, a metal complex that does not contain tertiary phosphine or tertiary phosphite as a ligand is mixed with tertiary phosphine or tertiary phosphite as a ligand to obtain tertiary phosphine or tertiary phosphite. It is also possible to produce and use a low-valent metal complex catalyst as a ligand.
배위자인 3 급 포스핀 또는 3 급 포스파이트로는, 예를 들어, 트리페닐포스핀, 트리-o-톨릴포스핀, 디페닐메틸포스핀, 페닐디메틸포스핀, 1,2-비스(디페닐포스피노)에탄, 1,3-비스(디페닐포스피노)프로판, 1,4-비스(디페닐포스피노)부탄, 1,1'-비스(디페닐포스피노)페로센, 트리메틸포스파이트, 트리에틸포스파이트, 트리페닐포스파이트, 2-디시클로헥실포스피노-2',4',6'-트리이소프로필비페닐, 2-디-t-부틸포스피노-2',4',6'-트리이소프로필비페닐, 2-디시클로헥실포스피노-2',6'-디이소프로폭시비페닐, 2-디시클로헥실포스피노-2',6'-디메톡시비페닐, (2-비페닐)디 -t-부틸포스핀, (2-비페닐)디시클로헥실포스핀, 2-디시클로헥실포스피노-2'-메틸비페닐, 2-디시클로헥실포스피노-2'-(N,N-디메틸아미노)비페닐, 2-(디시클로헥실포스피노)-3,6-디메톡시-2',4',6'-트리이소프로필-1,1'-비페닐, 4,5-비스(디페닐포스피노)-9,9-디메틸크산텐, (옥시디-2,1-페닐렌)비스(디페닐포스핀) 등을 들 수 있다. 이들 배위자의 2 종 이상을 혼합하여 포함하는 금속 착물 촉매도 바람직하게 사용된다.As a ligand tertiary phosphine or tertiary phosphite, for example, triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis(diphenyl Phosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1'-bis (diphenylphosphino) ferrocene, trimethylphosphite, tri Ethyl phosphite, triphenylphosphite, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2-di-t-butylphosphino-2',4',6' -Triisopropylbiphenyl, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, (2- Biphenyl) di-t-butylphosphine, (2-biphenyl)dicyclohexylphosphine, 2-dicyclohexylphosphino-2'-methylbiphenyl, 2-dicyclohexylphosphino-2'-( N,N-dimethylamino)biphenyl, 2-(dicyclohexylphosphino)-3,6-dimethoxy-2',4',6'-triisopropyl-1,1'-biphenyl, 4, 5-bis(diphenylphosphino)-9,9-dimethylxanthene, (oxydi-2,1-phenylene)bis(diphenylphosphine), and the like. A metal complex catalyst containing a mixture of two or more of these ligands is also preferably used.
그 중에서도, 바람직한 배위자로는, 1,2-비스(디페닐포스피노)에탄, 1,3-비스(디페닐포스피노)프로판, 1,4-비스(디페닐포스피노)부탄, 2-디시클로헥실포스피노-2',4',6'-트리이소프로필비페닐, 2-디-t-부틸포스피노-2',4',6'-트리이소프로필비페닐, 2-디시클로헥실포스피노-2',6'-디이소프로폭시비페닐, 2-디시클로헥실포스피노-2',6'-디메톡시비페닐, (2-비페닐)디-t-부틸포스핀, (2-비페닐)디시클로헥실포스핀, 2-디시클로헥실포스피노-2'-메틸비페닐을 들 수 있고, 보다 바람직한 배위자로는, 2-디시클로헥실포스피노-2',4',6'-트리이소프로필비페닐, 2-디시클로헥실포스피노-2',6'-디이소프로폭시비페닐, 2-디시클로헥실포스피노-2',6'-디메톡시비페닐을 들 수 있다.Especially, as a ligand preferable, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 2-dicy Chlorhexylphosphino-2',4',6'-triisopropylbiphenyl, 2-di-t-butylphosphino-2',4',6'-triisopropylbiphenyl, 2-dicyclohexyl Phosphino-2',6'-diisopropoxybiphenyl, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, (2-biphenyl)di-t-butylphosphine, ( 2-biphenyl)dicyclohexylphosphine and 2-dicyclohexylphosphino-2'-methylbiphenyl, and more preferred ligands include 2-dicyclohexylphosphino-2',4', 6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl; can
금속 착물 촉매로서, 3 급 포스핀이나 3 급 포스파이트를 포함하지 않는 팔라듐 착물과, 3 급 포스핀 또는 3 급 포스파이트를 포함하는 금속 착물을 조합하여 사용하는 것도 바람직하다. 이 경우, 상기 배위자를 추가로 조합해도 된다. 3 급 포스핀이나 3 급 포스파이트를 포함하지 않는 팔라듐 착물로는, 비스(디벤질리덴아세톤)팔라듐, 트리스(디벤질리덴아세톤)디팔라듐, 비스(아세토니트릴)디클로로팔라듐, 비스(벤조니트릴)디클로로팔라듐, 아세트산팔라듐, 염화팔라듐, 팔라듐-활성탄 등을 들 수 있다. 3 급 포스핀이나 3 급 포스파이트를 배위자로서 포함하는 팔라듐 착물로는, (에틸렌)비스(트리페닐포스핀)팔라듐, 테트라키스(트리페닐포스핀)팔라듐, 비스(트리페닐포스핀)디클로로팔라듐 등을 들 수 있다.As the metal complex catalyst, it is also preferable to use a combination of a palladium complex containing no tertiary phosphine or tertiary phosphite and a metal complex containing tertiary phosphine or tertiary phosphite. In this case, you may further combine the said ligand. Palladium complexes not containing tertiary phosphine or tertiary phosphite include bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, bis(acetonitrile)dichloropalladium, bis(benzonitrile) dichloropalladium, palladium acetate, palladium chloride, and palladium-activated carbon. As the palladium complex containing tertiary phosphine or tertiary phosphite as a ligand, (ethylene)bis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)palladium, bis(triphenylphosphine)dichloropalladium etc. can be mentioned.
본 발명에 있어서의 바람직한 금속 착물 촉매로는, 비스(디벤질리덴아세톤)팔라듐, 트리스(디벤질리덴아세톤)디팔라듐, 아세트산팔라듐, 또는 팔라듐-활성탄을 들 수 있다. 그 중에서도, 비스(디벤질리덴아세톤)팔라듐, 또는 트리스(디벤질리덴아세톤)디팔라듐을 들 수 있다.As a preferable metal complex catalyst in this invention, bis (dibenzylidene acetone) palladium, tris (dibenzylidene acetone) dipalladium, palladium acetate, or palladium-activated carbon is mentioned. Especially, bis (dibenzylidene acetone) palladium or tris (dibenzylidene acetone) dipalladium is mentioned.
본 발명에 있어서의 금속 착물 촉매가 구리 착물인 경우, 구리 착물은 1 가의 것이 바람직하고, 예를 들어, 염화구리 (I), 브롬화구리 (I), 요오드화구리 (I), 아세트산구리 (I) 등을 들 수 있다. 그 중에서도, 염화구리 (I), 브롬화구리 (I), 또는 요오드화구리 (I) 가 바람직하다.When the metal complex catalyst in the present invention is a copper complex, the copper complex is preferably monovalent, for example, copper (I) chloride, copper (I) bromide, copper (I) iodide, copper (I) acetate etc. can be mentioned. Especially, copper chloride (I), copper bromide (I), or copper iodide (I) is preferable.
금속 착물 촉매로서 구리 착물을 사용하는 경우, 반응계 중에서 구리 착물과 배위자를 혼합하여 사용할 수도 있다. 반응계 중에서 구리 착물과 혼합하는 배위자로는, L-프롤린, 1,2-트랜스-시클로헥산디아민, 에틸렌디아민, 테트라메틸에틸렌디아민 (TMEDA), N,N'-디메틸에틸렌디아민 (DMEDA), 1,10-페난트롤린, 2,2'-비피리딜, 2-피콜릴아민, 18-크라운-6 이 바람직하고, L-프롤린, 트랜스-시클로헥산디카르복실산, 테트라메틸에틸렌디아민 (TMEDA) 이 보다 바람직하다.When using a copper complex as a metal complex catalyst, a copper complex and a ligand may be mixed and used in the reaction system. As the ligand to be mixed with the copper complex in the reaction system, L-proline, 1,2-trans-cyclohexanediamine, ethylenediamine, tetramethylethylenediamine (TMEDA), N,N'-dimethylethylenediamine (DMEDA), 1, 10-phenanthroline, 2,2'-bipyridyl, 2-picolylamine, 18-crown-6 are preferred, L-proline, trans-cyclohexanedicarboxylic acid, tetramethylethylenediamine (TMEDA) more preferable than this
본 발명에 있어서의 금속 착물 촉매의 사용량은, 이른바 촉매량이면 되고, 팔라듐 촉매를 사용하는 경우에는, 방향족 디할로겐 화합물에 대해, 바람직하게는 20 몰％ 이하이고, 보다 바람직하게는 10 몰％ 이하이다. 구리 촉매를 사용하는 경우에는, 방향족 디할로겐 화합물에 대해, 바람직하게는 100 몰％ 이하이고, 보다 바람직하게는 50 몰％ 이하이다. 금속 착물 촉매의 사용량은, 유효한 한 적은 편이 바람직하지만, 통상, 방향족 디할로겐 화합물에 대해, 0.001 몰％ 이상, 특히는 0.01 몰％ 이상이다.The amount of the metal complex catalyst used in the present invention may be a so-called catalytic amount, and in the case of using a palladium catalyst, it is preferably 20 mol% or less, more preferably 10 mol% or less, relative to the aromatic dihalogen compound. . When using a copper catalyst, it is preferably 100 mol% or less, and more preferably 50 mol% or less relative to the aromatic dihalogen compound. The usage amount of the metal complex catalyst is preferably as small as possible, but is usually 0.001 mol% or more, particularly 0.01 mol% or more, relative to the aromatic dihalogen compound.
본 발명에서 사용되는 염기로는, 예를 들어, 수산화물 ; 탄산염 ; 탄산수소염 ; 인산염 ; 인산수소염 ; 카르복실산염 ; 알콕시드 ; 아민류 ; 암모니아 등을 들 수 있다. 수산화물, 탄산염, 탄산수소염, 인산염, 인산수소염, 및 카르복실산염은, 알칼리 금속 또는 알칼리 토금속의 염이 바람직하다. 또, 염기는, 수화물이어도 되고, 수화물이 아니어도 된다.Examples of the base used in the present invention include hydroxide; carbonate; hydrogen carbonate; phosphate; hydrogen phosphate; Carboxylate; alkoxide; amines; Ammonia etc. are mentioned. The hydroxide, carbonate, hydrogen carbonate, phosphate, hydrogen phosphate, and carboxylate are preferably alkali metal or alkaline earth metal salts. In addition, the base may be a hydrate or may not be a hydrate.
상기 수산화물로는, 예를 들어, 수산화리튬, 수산화나트륨, 수산화칼륨, 수산화칼슘 등을 들 수 있다. 탄산염으로는, 예를 들어 탄산리튬, 탄산나트륨, 탄산칼륨, 탄산세슘, 탄산칼슘, 탄산바륨, 탄산나트륨칼륨 등을 들 수 있다. 탄산수소염으로는, 예를 들어 탄산수소리튬, 탄산수소나트륨, 탄산수소칼륨, 탄산수소암모늄 등을 들 수 있다. 인산염으로는, 예를 들어 오르토인산나트륨, 인산삼칼륨, 인산삼칼슘, 인산삼암모늄 등을 들 수 있다. 인산수소염으로는, 예를 들어 인산수소이나트륨, 인산수소이칼륨, 인산수소칼슘, 인산수소이암모늄, 인산이수소나트륨, 인산이수소칼륨, 인산이수소칼슘, 인산이수소암모늄 등을 들 수 있다. 알칼리 금속 및 알칼리 토금속의 카르복실산염으로는, 예를 들어 아세트산나트륨, 아세트산칼륨, 아세트산칼슘 등을 들 수 있다. 알콕시드로는, 예를 들어 리튬메톡시드, 나트륨메톡시드, 나트륨에톡시드, 나트륨t-부톡시드, 칼륨t-부톡시드 등을 들 수 있다. 아민류로는, 예를 들어 트리에틸아민, 트리-n-부틸아민, 디이소프로필에틸아민, N-메틸피페리딘, 4-메틸모르폴린, 4-에틸모르폴린, 피리딘, 4-(N,N-디메틸아미노)피리딘, 4-피롤리디노피리딘, 4-피롤리디노피리딘, 2,6-디(t-부틸)-4-메틸피리딘, 퀴놀린, N,N-디메틸아닐린, N,N-디에틸아닐린, 1,5-디아자비시클로[4.3.0]노난-5-엔 (DBN), 1,8-디아자비시클로[5.4.0]운데칸-7-엔 (DBU), 1,4-디아자비시클로[2.2.2]옥탄 (DABCO) 등을 들 수 있다.As said hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide etc. are mentioned, for example. Examples of the carbonate include lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate, barium carbonate, sodium potassium carbonate and the like. Examples of the hydrogen carbonate include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and ammonium hydrogen carbonate. As a phosphate, sodium orthophosphate, tripotassium phosphate, tricalcium phosphate, triammonium phosphate, etc. are mentioned, for example. Examples of the hydrogenphosphate salt include disodium hydrogenphosphate, dipotassium hydrogenphosphate, calcium hydrogenphosphate, diammonium hydrogenphosphate, sodium dihydrogenphosphate, potassium dihydrogenphosphate, calcium dihydrogenphosphate, and ammonium dihydrogenphosphate. As carboxylate of alkali metal and alkaline earth metal, sodium acetate, potassium acetate, calcium acetate etc. are mentioned, for example. As alkoxide, lithium methoxide, sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium t-butoxide etc. are mentioned, for example. Examples of amines include triethylamine, tri-n-butylamine, diisopropylethylamine, N-methylpiperidine, 4-methylmorpholine, 4-ethylmorpholine, pyridine, 4-(N, N-dimethylamino)pyridine, 4-pyrrolidinopyridine, 4-pyrrolidinopyridine, 2,6-di(t-butyl)-4-methylpyridine, quinoline, N,N-dimethylaniline, N,N- Diethylaniline, 1,5-diazabicyclo[4.3.0]nonane-5-ene (DBN), 1,8-diazabicyclo[5.4.0]undecane-7-ene (DBU), 1,4 -Diazabicyclo[2.2.2]octane (DABCO) etc. are mentioned.
바람직한 염기로는, 수산화칼륨, 탄산칼륨, 탄산세슘, 탄산수소나트륨, 인산삼칼륨, 인산수소이칼륨, 나트륨t-부톡시드, 칼륨t-부톡시드, 또는 트리에틸아민을 들 수 있다. 보다 바람직한 염기로는, 탄산세슘, 또는 인산삼칼륨을 들 수 있다. 이들 염기는 1 종 또는 2 종 이상 조합하여 사용할 수도 있다.Preferable bases include potassium hydroxide, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, tripotassium phosphate, dipotassium hydrogen phosphate, sodium t-butoxide, potassium t-butoxide, or triethylamine. As a more preferable base, cesium carbonate or tripotassium phosphate is mentioned. You may use these bases 1 type or in combination of 2 or more types.
본 발명의 제조 방법에 있어서의 반응은, 용매의 존재하에서 실시되는 것이 바람직하다. 반응 용매로는, 반응의 진행을 저해하지 않는 것이 바람직하다. 예를 들어, 벤젠, 톨루엔, 자일렌 등의 방향족 탄화수소류, 헥산, 헵탄 등의 지방족 탄화수소류, 시클로헥산 등의 지환식 탄화수소류, 클로로벤젠, 디클로로벤젠 등의 방향족 할로겐화 탄화수소류, 디클로로메탄, 클로로포름, 사염화탄소, 1,2-디클로로에탄, 1,1,1-트리클로로에탄, 트리클로로에틸렌, 테트라클로로에틸렌 등의 지방족 할로겐화 탄화수소류, 디에틸에테르, 이소프로필에테르, 1,2-디메톡시에탄, 테트라하이드로푸란, 2-메틸테트라하이드로푸란, 1,4-디옥산, 1-메톡시-2-(2-메톡시에톡시)에탄, TBME (t-부틸메틸에테르), CPME (시클로펜틸메틸에테르) 등의 에테르류, 아세트산에틸, 프로피온산에틸 등의 에스테르류, 디메틸포름아미드, 디메틸아세트아미드, N-메틸-2-피롤리돈 등의 아미드류, 트리에틸아민, 트리부틸아민, N,N-디메틸아닐린 등의 아민류, 피리딘, 피콜린 등의 피리딘류, 메탄올, 에탄올, n-프로판올, 에틸렌글리콜 등의 알코올류, 아세토니트릴, 디메틸술폭시드, 술포란, 1,3-디메틸-2-이미다졸리디논, 아세톤, 물 등을 들 수 있다.The reaction in the production method of the present invention is preferably carried out in the presence of a solvent. As the reaction solvent, one that does not inhibit the progress of the reaction is preferable. For example, aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, dichloromethane, and chloroform , aliphatic halogenated hydrocarbons such as carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethylene, and tetrachlorethylene, diethyl ether, isopropyl ether, 1,2-dimethoxyethane, Tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1-methoxy-2-(2-methoxyethoxy)ethane, TBME (t-butylmethyl ether), CPME (cyclopentylmethyl ether) ), ethers such as ethyl acetate and ethyl propionate, amides such as dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone, triethylamine, tributylamine, N,N- Amines such as dimethylaniline, pyridines such as pyridine and picoline, alcohols such as methanol, ethanol, n-propanol, and ethylene glycol, acetonitrile, dimethyl sulfoxide, sulfolane, and 1,3-dimethyl-2-imida Zolidinone, acetone, water, etc. are mentioned.
바람직한 용매로는, 톨루엔, 1,2-디메톡시에탄, 테트라하이드로푸란, 2-메틸테트라하이드로푸란, 디메틸포름아미드, 디메틸아세트아미드, 또는 N-메틸-2-피롤리돈을 들 수 있다. 보다 바람직한 용매로는 1,2-디메톡시에탄, 또는 테트라하이드로푸란을 들 수 있다. 용매는 단독이어도 되고 2 종류 이상을 사용해도 된다.Preferred solvents include toluene, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylformamide, dimethylacetamide, or N-methyl-2-pyrrolidone. A more preferable solvent is 1,2-dimethoxyethane or tetrahydrofuran. The solvent may be used alone or in combination of two or more.
반응 온도는, －100 ℃ 이상에서부터 사용하는 반응 용매의 비점의 온도까지의 범위를 선택할 수 있지만, 바람직하게는 －50 ∼ 150 ℃, 보다 바람직하게는 0 ∼ 100 ℃ 이다. 반응 시간은, 0.1 ∼ 1000 시간, 바람직하게는 0.5 ∼ 100 시간이다.The reaction temperature can be selected from a range from -100°C or higher to the temperature of the boiling point of the reaction solvent used, but is preferably -50 to 150°C, more preferably 0 to 100°C. The reaction time is 0.1 to 1000 hours, preferably 0.5 to 100 hours.
반응은, 상압이어도 되고 가압하여도 되고, 또 연속식이어도 되고 회분식이어도 된다.The reaction may be under normal pressure or pressurized, and may be continuous or batchwise.
상기 스킴 (A) 에 의해 제조된 식 (3) 으로 나타내는 디니트로 화합물은, 증류, 재결정 또는 실리카겔 등의 칼럼 크로마토그래피 등으로 정제해도 된다.The dinitro compound represented by Formula (3) manufactured by the above scheme (A) may be purified by distillation, recrystallization or column chromatography such as silica gel.
이와 같이 하여 얻어진 N-(니트로페닐) 방향족 아민 화합물은, 통상 알려진 기존의 방법으로 니트로기를 아미노기로 환원함으로써, N-(아미노페닐) 방향족 아민 화합물을 용이하게 제조할 수 있다.The N-(nitrophenyl) aromatic amine compound obtained in this way can be easily produced by reducing the nitro group to an amino group by a commonly known conventional method.
실시예Example
이하, 본 발명을 실시예에 의해 더욱 구체적으로 설명하지만, 이들 실시예에 의해 본 발명의 해석이 한정되는 것은 아니다. 또한, 실시예에서 사용한 분석 장치 및 분석 조건은, 하기와 같다.Hereinafter, the present invention will be described more specifically by examples, but the interpretation of the present invention is not limited by these examples. In addition, the analysis apparatus and analysis conditions used in the Example are as follows.
1H-NMR ; 1 H-NMR;
장치 : 니혼 전자사 제조 ECX-300 (300 ㎒),Device: ECX-300 (300 MHz) manufactured by Nihon Electric Co., Ltd.
측정 용매 : CDCl3, DMSO-d6, 기준 물질 : 테트라메틸실란 (TMS) (TMS 의 1H 의δ 값을 0.0 ppm 으로 한다)Measurement solvent: CDCl 3 , DMSO-d 6 , Reference substance: tetramethylsilane (TMS) (The δ value of 1H in TMS is set to 0.0 ppm)
HPLC ;HPLC;
장치 : HPLC, LC-20AD (시마즈 제작소사 제조)Device: HPLC, LC-20AD (manufactured by Shimadzu Corporation)
칼럼 : Inertsil ODS-3 (GL Science), 충전물의 평균 입자경 : 5 ㎛, 내경 : φ4.6 ㎜, 길이 : 250 ㎜ 의 칼럼 온도 : 40 ℃Column: Inertsil ODS-3 (GL Science), average particle diameter of packing: 5 μm, inner diameter: φ4.6 mm, length: 250 mm, column temperature: 40 ° C.
용리액 : 아세토니트릴/물 ＝ 80/20 (v/v), 유속 : 1.0 ㎖/minEluent: acetonitrile/water = 80/20 (v/v), flow rate: 1.0 ml/min
검출법 : UV (254 ㎚), 데이터 채취 시간 : 40 minDetection method: UV (254 nm), data acquisition time: 40 min
합성예 1 : 2,5-비스(N-(4-아미노페닐)-N-메틸-4-아미노페닐)-N-메틸피롤 (화합물 DA-1) 의 제조Synthesis Example 1: Preparation of 2,5-bis(N-(4-aminophenyl)-N-methyl-4-aminophenyl)-N-methylpyrrole (Compound DA-1)
(공정 a) ; 2,5-비스(N-(4-니트로페닐)-N-메틸-4-아미노페닐)-N-메틸피롤 (화합물 DN-1) 의 제조(Process a) ; Preparation of 2,5-bis(N-(4-nitrophenyl)-N-methyl-4-aminophenyl)-N-methylpyrrole (Compound DN-1)
[화학식 6][Formula 6]
(합성예 1-a-01)(Synthesis Example 1-a-01)
50 ㎖ 의 4 구 플라스크에 2,5-비스(4-브로모페닐)-1-메틸-1H-피롤 (1.5 g, 3.84 mmol), 트리스(디벤질리덴아세톤)디팔라듐 (70.2 mg, 0.08 mmol), 2-디시클로헥실포스피노-2',6'-디이소프로폭시비페닐 (71.6 mg, 0.15 mmol), 및 탄산세슘 (2.5 g, 7.68 mmol) 을 첨가하고, 반응 용기의 내부를 질소 가스로 치환한 후, 테트라하이드로푸란 (9.0 g) 을 주입하고, 환류하에서 30 분 교반하였다.In a 50 mL four-necked flask, 2,5-bis(4-bromophenyl)-1-methyl-1H-pyrrole (1.5 g, 3.84 mmol), tris(dibenzylideneacetone)dipalladium (70.2 mg, 0.08 mmol) ), 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl (71.6 mg, 0.15 mmol), and cesium carbonate (2.5 g, 7.68 mmol) were added, and the inside of the reaction vessel was filled with nitrogen. After replacing with gas, tetrahydrofuran (9.0 g) was injected and stirred for 30 minutes under reflux.
계속해서, 별도 조제한 N-메틸-4-니트로아닐린 (1.28 g, 8.45 mmol) 의 테트라하이드로푸란 용액 (10.5 g) 을 30 분에 걸쳐서 적하하고, 환류하에서 42 시간 교반하였다. 교반 종료 후, HPLC 로 목적물의 면적 백분율 (이하, LC 면백 (面百) 이라고 한다) 을 확인한 결과, 99.6 ％ 였다. 그 반응 혼합물을 20 ℃ ∼ 25 ℃ 까지 냉각시키고, 물 (15.0 g) 을 첨가하여, 30 분 교반하였다. 석출된 결정을 감압 여과하고, 결정을 테트라하이드로푸란과 물의 혼합 용매 (체적비 1 : 1, 7.5 g) 로 세정한 후, 건조시켜, 하기 NMR 분석 결과를 갖는 분말 결정 (DN-1) 을 얻었다 (수량 (收量) 1.91 g, 수율 96 ％).Then, a solution (10.5 g) of separately prepared N-methyl-4-nitroaniline (1.28 g, 8.45 mmol) in tetrahydrofuran was added dropwise over 30 minutes, and the mixture was stirred under reflux for 42 hours. It was 99.6% as a result of confirming the area percentage of the target object (hereinafter referred to as LC cotton white) by HPLC after completion of stirring. The reaction mixture was cooled to 20°C to 25°C, water (15.0 g) was added, and the mixture was stirred for 30 minutes. The precipitated crystals were filtered under reduced pressure, the crystals were washed with a mixed solvent of tetrahydrofuran and water (volume ratio 1:1, 7.5 g), and then dried to obtain powder crystals (DN-1) having the following NMR analysis results ( Yield 1.91 g, yield 96%).
(합성예 1-a-02 ∼ 1-a-12)(Synthesis Example 1-a-02 to 1-a-12)
배위자, 염기 및 용매를 변경한 것 이외에는, 합성예 1-a-01 에 기재된 방법에 준하여 반응을 실시하였다.The reaction was carried out according to the method described in Synthesis Example 1-a-01 except for changing the ligand, base and solvent.
합성예 1-a-01 ∼ 1-a-12 에 있어서의 배위자, 염기, 용매, 반응 온도, 반응 시간 및 LC 면백을 표 1 에 기재한다.Table 1 shows the ligand, base, solvent, reaction temperature, reaction time and LC cotton in Synthesis Examples 1-a-01 to 1-a-12.
표 1 에 있어서의 「XPhos」는 2-디시클로헥실포스피노-2',4',6'-트리이소프로필비페닐을 나타내고, 「RuPhos」는 2-디시클로헥실포스피노-2',6'-디이소프로폭시비페닐을 나타내고, 「DMF」는 디메틸포름아미드를 나타내고, 「THF」는 테트라하이드로푸란을 나타내고, 「NMP」는 N-메틸-2-피롤리돈을 나타내고, 「DMAc」는 디메틸아세트아미드를 나타내고, 「MeTHF」는 2-메틸테트라하이드로푸란을 나타내고, 「DME」는 1,2-디메톡시에탄을 나타낸다. 또, LC 면백이란, LC 로 반응을 추적했을 때의, 반응액 중의 목적물의 비율 (％) 을 나타낸다. 단, 용매, N-메틸-4-니트로아닐린 및 dba 는 제외한 수치이다."XPhos" in Table 1 represents 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, and "RuPhos" represents 2-dicyclohexylphosphino-2',6 '-diisopropoxybiphenyl, "DMF" represents dimethylformamide, "THF" represents tetrahydrofuran, "NMP" represents N-methyl-2-pyrrolidone, "DMAc" represents represents dimethylacetamide, "MeTHF" represents 2-methyltetrahydrofuran, and "DME" represents 1,2-dimethoxyethane. In addition, LC cotton white shows the ratio (%) of the target substance in the reaction solution when the reaction was tracked by LC. However, the solvent, N-methyl-4-nitroaniline and dba are excluded.
(합성예 1-a-13)(Synthesis Example 1-a-13)
500 ㎖ 의 4 구 플라스크에 2,5-비스(4-브로모페닐)-1-메틸-1H-피롤 (25.0 g, 63.9 mmol), N-메틸-4-니트로아닐린 (21.4 g, 140.58 mmol), 요오드화구리 (I) (4.87 g, 25.6 mmol), L-프롤린 (5.89 g, 51.12 mmol), 및 인산삼칼륨 (54.27 g, 255.6 mmol) 을 첨가하고, 반응 용기의 내부를 질소 가스로 치환한 후, NMP (125.0 g) 를 주입하고, 120 ℃ 에서 27 시간 교반하였다. 교반 종료 후, HPLC 로 목적물의 LC 면백을 확인한 결과, 48.2 ％ 였다.2,5-bis(4-bromophenyl)-1-methyl-1H-pyrrole (25.0 g, 63.9 mmol), N-methyl-4-nitroaniline (21.4 g, 140.58 mmol) in a 500 mL four-necked flask , copper (I) iodide (4.87 g, 25.6 mmol), L-proline (5.89 g, 51.12 mmol), and tripotassium phosphate (54.27 g, 255.6 mmol) were added, and the inside of the reaction vessel was purged with nitrogen gas. After that, NMP (125.0 g) was injected, and the mixture was stirred at 120°C for 27 hours. It was 48.2% as a result of confirming the LC cotton white of the target substance by HPLC after completion|finish of stirring.
(공정 b) ; 2,5-비스(N-(4-아미노페닐)-N-메틸-4-아미노페닐)-N-메틸피롤 (화합물 DA-1) 의 제조(Process b) ; Preparation of 2,5-bis(N-(4-aminophenyl)-N-methyl-4-aminophenyl)-N-methylpyrrole (Compound DA-1)
[화학식 7][Formula 7]
화합물 (DN-1) (12.0 g, 22.5 mmol), 5 질량％ Pd/C (41.3 ％ 함수형, 1.45 g), 활성탄 (1.2 g), 및 THF (120 g) 의 혼합물을, 게이지압 0.3 ㎫ 의 수소 분위기하, 50 ℃ 에서 4 시간 교반하였다. 반응 종료 후, 촉매 및 활성탄을 여과에 의해 분리한 후, 여과물을 THF (24.0 g) 로 2 회 세정하고, 여과액을 50 ℃ 에서 내용량이 48 g 이 될 때까지 감압 농축을 실시하고, 메탄올 (84.0 g) 을 첨가하고, 5 ℃ 까지 냉각시켜 1 시간 교반하였다. 석출된 결정을 여과하고, 메탄올 (24.0 g) 로 2 회 세정한 후, 50 ℃ 에서 감압 건조시켜, 분말 결정으로 하여, 하기 NMR 분석 결과를 갖는 분말 결정 (DA-1) 을 얻었다 (수량 8.93 g, 수율 84 ％).A mixture of compound (DN-1) (12.0 g, 22.5 mmol), 5% by mass Pd/C (41.3% hydrous form, 1.45 g), activated carbon (1.2 g), and THF (120 g) was prepared at a gauge pressure of 0.3 MPa. It stirred at 50 degreeC in hydrogen atmosphere for 4 hours. After completion of the reaction, the catalyst and activated carbon were separated by filtration, the filtrate was washed twice with THF (24.0 g), and the filtrate was concentrated under reduced pressure at 50°C until the net weight reached 48 g, followed by methanol (84.0 g) was added, cooled to 5°C, and stirred for 1 hour. The precipitated crystals were filtered, washed twice with methanol (24.0 g), and then dried under reduced pressure at 50°C to obtain powder crystals (DA-1) having the following NMR analysis results (amount: 8.93 g). , yield 84%).
본 발명에 따르면, 액정 배향제의 원료로서 유용한 디아민 화합물을, 부생물이 적고, 고순도 또한 고수율로 제조할 수 있다. 또, 본 발명의 제조 방법은, 대규모에 의한 생산이 실시 가능하여, 공업적으로 유용하다.ADVANTAGE OF THE INVENTION According to this invention, the diamine compound useful as a raw material of a liquid crystal aligning agent can be manufactured with few by-products and high purity and high yield. In addition, the production method of the present invention is industrially useful because large-scale production can be performed.
또한, 2017년 1월 13일에 출원된 일본 특허출원 2017-004140호의 명세서, 특허청구범위, 도면 및 요약서의 전체 내용을 여기에 인용하여, 본 발명의 명세서의 개시로서 받아들이는 것이다.In addition, all the content of the JP Patent application 2017-004140, a claim, drawing, and the abstract for which it applied on January 13, 2017 is referred here, and it takes in as an indication of the specification of this invention.
Claims (13)
[식 중, X 는 할로겐을 나타낸다.]
[식 중, R 은 C1 ∼ C6 알킬을 나타낸다.]
[식 중, Ar 은 하기 식 (X1-1) ∼ (X5-1) 중 어느 것으로 나타내는 기를 나타내고, R 은 상기의 정의와 동일하다.]
[식 중, * 은 상기 식 (3) 의 질소 원자와 결합하는 부분이다.]The following formula ( 3) A method for producing an N-(nitrophenyl) aromatic amine compound represented by
[In the formula, X represents halogen.]
[Wherein, R represents C 1 -C 6 alkyl.]
[Wherein, Ar represents a group represented by any of the following formulas (X1-1) to (X5-1), and R is as defined above.]
[In the formula, * is a moiety bonded to the nitrogen atom of the formula (3).]
금속 착물 촉매가, 팔라듐 착물 또는 구리 착물인, 제조 방법.According to claim 1,
A manufacturing method in which the metal complex catalyst is a palladium complex or a copper complex.
염기가, 알칼리 금속 혹은 알칼리 토금속의 수산화물, 탄산염, 탄산수소염, 인산염, 인산수소염 또는 카르복실산염인, 제조 방법.According to claim 1,
A manufacturing method in which the base is a hydroxide, carbonate, hydrogen carbonate, phosphate, hydrogen phosphate or carboxylate of an alkali metal or alkaline earth metal.
용매의 존재하에 반응시키는, 제조 방법.According to claim 1,
A method for producing a reaction in the presence of a solvent.
방향족 디할로겐 화합물이, 하기 식 (X1) ∼ (X3) 중 어느 것으로 나타내는 화합물인, 제조 방법.
[식 중, X 는 할로겐을 나타낸다.]According to claim 1,
A manufacturing method in which the aromatic dihalogen compound is a compound represented by any of the following formulas (X1) to (X3).
[In the formula, X represents halogen.]
식 (X1) ∼ (X5) 에 있어서의 X 가, Cl 또는 Br 인, 제조 방법.According to claim 1,
A manufacturing method in which X in formulas (X1) to (X5) is Cl or Br.
N-알킬니트로아닐린 유도체가, N-메틸-p-니트로아닐린인, 제조 방법.According to claim 1,
A manufacturing method wherein the N-alkylnitroaniline derivative is N-methyl-p-nitroaniline.
용매가, 톨루엔, 1,2-디메톡시에탄, 테트라하이드로푸란, 2-메틸테트라하이드로푸란, 디메틸포름아미드, 디메틸아세트아미드, 또는 N-메틸-2-피롤리돈인, 제조 방법.According to claim 4,
The manufacturing method in which the solvent is toluene, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylformamide, dimethylacetamide, or N-methyl-2-pyrrolidone.
염기가, 탄산세슘, 또는 인산삼칼륨인, 제조 방법.According to claim 1,
A manufacturing method in which the base is cesium carbonate or tripotassium phosphate.
팔라듐 착물에 있어서의 팔라듐이, Pd2(dba)3(dba)n (dba 는 디벤질리덴아세톤을 나타내고, n 은 0 내지 2 의 정수를 나타낸다) 으로 나타내어지는, 제조 방법.According to claim 2,
A manufacturing method in which palladium in a palladium complex is represented by Pd 2 (dba) 3 (dba) n (dba represents dibenzylideneacetone, and n represents an integer of 0 to 2).
팔라듐 착물 또는 구리 착물에 있어서의 배위자가, 2-디시클로헥실포스피노-2',4',6'-트리이소프로필비페닐 및 2-디시클로헥실포스피노-2',6'-디이소프로폭시비페닐로 이루어지는 군에서 선택되는 적어도 1 종인, 제조 방법.According to claim 2,
The ligands in the palladium complex or copper complex are 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl and 2-dicyclohexylphosphino-2',6'-diiso The manufacturing method which is at least 1 sort(s) selected from the group which consists of propoxy biphenyl.
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