KR920002795B1 - Process for the preparation of n.n'-substituted urea - Google Patents
Process for the preparation of n.n'-substituted urea Download PDFInfo
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- KR920002795B1 KR920002795B1 KR1019890015880A KR890015880A KR920002795B1 KR 920002795 B1 KR920002795 B1 KR 920002795B1 KR 1019890015880 A KR1019890015880 A KR 1019890015880A KR 890015880 A KR890015880 A KR 890015880A KR 920002795 B1 KR920002795 B1 KR 920002795B1
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- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
- C07C273/1809—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety
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- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
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- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
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- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/64—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups singly-bound to oxygen atoms
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Abstract
Description
본 발명은 방향족 모노니트로화합물, 방향족 제1급 아민 및 일산화탄소를 주촉매인 팔라듐 화합물, 조촉매인 할로겐원소를 포함한 암모니움염 또는 포스포늄염 및 비극성용매 존재하에서 반응시켜 하기 일반식(I)로 표시되는 N,N'-치환우레아를 제조하는 방법에 관한 것이다.The present invention is represented by the following general formula (I) by reacting an aromatic mononitro compound, an aromatic primary amine and carbon monoxide in the presence of an ammonium salt or a phosphonium salt containing a halogen element as a main catalyst, a halogen element as a promoter, and a nonpolar solvent. It relates to a method for producing a N, N'-substituted urea.
상기식에서, Ar1및 Ar2는 비치한 방향족기 또는 할로겐, 알킬, 알콕시 등으로 치환된 방향족기를 나타내며, 서로 같거나 상이하다.In the above formula, Ar 1 and Ar 2 represent an aromatic group or an aromatic group substituted with halogen, alkyl, alkoxy and the like, and are the same as or different from each other.
N,N'-치환우레아는 농약에 사용되는 카바메이트의 원료로 사용되는 유용한 물질이다.N, N'-substituted urea is a useful material used as a raw material for carbamate used in pesticides.
아민과 일산화탄소를 반응시켜 N,N'-치환우레아를 제조하는 종래의 방법은 코발트카르보닐(Can. J. Chem., 40,1718,1962), 초산온(J. Org. Chem., 37,2670,1972) 또는 초산수온 등의 백금족 이외의 금속화합물을 촉매로 사용하는 방법과, 황(J. Org. Chem., 26,3309,1691), 셀레늄(J. Amer. Chem. Soc., 93,6344,1971) 등의 비금속화합물을 촉매로 사용하는 방법 및 백금족화합물을 촉매로 사용하는 방법등이 알려져 있다.Conventional methods for preparing N, N'-substituted urea by reacting amines with carbon monoxide include cobalt carbonyl (Can. J. Chem., 40, 1718,1962), acetic acid (J. Org. Chem., 37, 2670,1972) or a metal compound other than platinum group such as acetic acid water temperature as a catalyst, sulfur (J. Org. Chem., 26,3309,1691), selenium (J. Amer. Chem. Soc., 93 (6363, 1971) and the like using a non-metal compound as a catalyst and a method using a platinum group compound as a catalyst.
이 중에서 백금족 이외의 금속화합물을 촉매로 사용하는 방법은 N,N'-치환우레아의 수율 및 선택도가 높지 못하고, 황이나 셀레늄 등의 비금속 화합물을 촉매로 사용하는 방법은 수율이나 선택도는 높으나, 촉매의 분리회수가 곤란하여 복잡한 조작을 필요로 하므로 경제성이 문제가 된다.Among them, the method of using a metal compound other than platinum group as a catalyst does not have high yield and selectivity of N, N'-substituted urea, and the method of using a nonmetallic compound such as sulfur or selenium as a catalyst has a high yield and selectivity. As a result, the recovery of the catalyst is difficult, and complicated operation is required, so economic efficiency is a problem.
백금족화합물을 촉매로 사용하는 방법은 일본특허공고 소 53-41123, 일본특개소 58-144363, 일본특개소 62-59253 및 문헌(J. Org. Chem. Vol. 40, No. 19, 2819, 1975)등에 나타나 있는데, 일본특허공고 소 53-41123 및 일본특개소 58-144363에는 고온고압하에서 아민을 일산화탄소 및 산소와 반응시켜서 N,N'-치환우레아를 제조하는 방법으로서, 이 방법은 기상 반응물이 두가지(일산화탄소 및 산소)이므로 연속반응시 두 기체의 분압조절이 어렵고, 산소를 사용하므로 폭발 위험성이 따르는 단점이 있다. 또한, J. Org. Chem.(Vol.40(19), 2819,1975) 및 일본특개소 62-59253에는 아민을 일산화탄소 및 니트로화합물과 반응시켜 N,N'-치환우레아를 제조하는 방법으로서, 전자의 방법은 수율이 낮고(64%), 용매와 함께 n-트리부틸아민을 사용해야 하며, 촉매의 활성이 급격히 떨어지는 단점이 있다.The method of using a platinum group compound as a catalyst is disclosed in Japanese Patent Publication No. 53-41123, Japanese Patent Application Laid-Open No. 58-144363, Japanese Patent Application Laid-Open No. 62-59253 and J. Org. Chem. Vol. 40, No. 19, 2819, 1975. Japanese Patent Laid-Open No. 53-41123 and Japanese Patent Laid-Open No. 58-144363 disclose a method for preparing N, N'-substituted urea by reacting amine with carbon monoxide and oxygen under high temperature and high pressure. Because of two (carbon monoxide and oxygen), it is difficult to control the partial pressure of the two gases in the continuous reaction, and there is a disadvantage that explosion risk is followed because oxygen is used. In addition, J. Org. Chem. (Vol. 40 (19), 2819, 1975) and Japanese Patent Laid-Open No. 62-59253 disclose a method for producing N, N'-substituted urea by reacting amine with carbon monoxide and nitro compounds. Low (64%), and n-tributylamine should be used together with the solvent, which has a disadvantage in that the activity of the catalyst drops sharply.
후자의 방법은 수율 및 선택도는 높으나 로듐(Rh) 및 루테늄(Ru)등의 값비싼 촉매를 사용해야 하며, 생성되는 N,N'-치환우레아의 성상이 깨끗하지 못하고, 아닐린이 부산물로 생성되며, 촉매가 열에 불안정화여 반응온도 부근에서 분해되는 문제점이 있다.The latter method has high yield and selectivity, but requires the use of expensive catalysts such as rhodium (Rh) and ruthenium (Ru) .The resulting N, N'-substituted urea is not clean and aniline is produced as a by-product. However, there is a problem that the catalyst destabilizes to heat and decomposes near the reaction temperature.
본 발명자는 방향족 모노니트로화합물, 방향족 제1급 아민 및 일산화탄소를 반응시켜서 상기 일반식(I)로 표시되는 N,N'-치환우레아를생성하는 반응에 있어서, 상기와 같은 문제점을 해결하기 위하여 부단한 노력을 기울여 연구를 계속한 결과, 방향족 모노니트로화합물에 대하여 방향족 제1급 아민을 2몰배 이상의 과량으로 사용하고, 팔라듐화합물을 주체로 하는 촉매와 할로겐 원소를 포함하는 조촉매를 사용하여 반응시킴으로써 반응부산물이 거의 없고, 수율이 아주 높으며, 촉매회수가 용이한 방법을 발명하게 되어 본 발명을 완성하게 되었다.MEANS TO SOLVE THE PROBLEM In the reaction which produces | generates the N, N'-substituted urea represented by the said general formula (I) by reacting an aromatic mononitro compound, an aromatic primary amine, and carbon monoxide, it is indefinite to solve such a problem. As a result of continued research, the reaction was carried out by using an aromatic primary amine in an excess of 2 moles or more with respect to the aromatic mononitro compound, and reacting it with a catalyst mainly composed of a palladium compound and a promoter containing a halogen element. Invented a method with little by-product, very high yield, and easy catalyst recovery to complete the present invention.
이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명에 사용되는 방향족 모노니트로화합물로는 니트로벤젠류, 니트로나프탈렌류, 니트로안트라센류, 니트로비페닐류 등이 있고, 구체적인 화합물로는 니트로벤젠, o-, m-, p-니트로톨루엔, o-니트로-p-크실렌, 2-메틸-1-니트로나프탈렌, o-, m-, p-클로로니트로벤젠, 1-브로모-4-니트로벤젠, 클로로니트로벤젠(각 이성질체), 2-클로로-6-니트로톨루엔, 4-클로로-3-니트로톨루엔, 1,4-디클로로-2-니트로벤젠, 3,4-디클로로-1-니트로벤젠,, α-클로로-m-니트로톨루엔, 1,2,4-트리클로로-5-니트로벤젠 등이 있다.Aromatic mononitro compounds used in the present invention include nitrobenzenes, nitronaphthalenes, nitroanthracenes, nitrobiphenyls, and the like. Nitrobenzene, o-, m-, p-nitrotoluene, o -Nitro-p-xylene, 2-methyl-1-nitronaphthalene, o-, m-, p-chloronitrobenzene, 1-bromo-4-nitrobenzene, chloronitrobenzene (each isomer), 2-chloro- 6-nitrotoluene, 4-chloro-3-nitrotoluene, 1,4-dichloro-2-nitrobenzene, 3,4-dichloro-1-nitrobenzene, α-chloro-m-nitrotoluene, 1,2, 4-trichloro-5-nitrobenzene and the like.
또한 본 발명에 사용되는 방향족 제1급 아민으로는 아닐린류, 아미노나프탈렌류, 아미노안트라센류, 아미노비페닐류 등이 있고, 구체적인 화합물로는 아닐린, o-, m-, p-톨루이딘, o-, m-, p-클로로아닐린, α- 또는 β-나프틸아민, 2-메틸-1-아미노 나프탈렌, 아미노톨루엔 등이 있다.Aromatic primary amines used in the present invention include aniline, aminonaphthalene, aminoanthracene, aminobiphenyl, and the like, and specific compounds include aniline, o-, m-, p-toluidine, and o-. , m-, p-chloroaniline, α- or β-naphthylamine, 2-methyl-1-amino naphthalene, aminotoluene and the like.
본 발명에 사용되는 방향족 제1급 아민은 반응물 뿐만 아니라, 촉매성분을 용해시켜 주는 용매로도 사용될 수 있는 보통 방향족 모노니트로화합물에 대하여 과량(몰비로 1 : 2 이상)으로 사용한다. 이렇게 함으로써 촉매의 비활성화를 방지하고, 촉매회수를 용이하게 할 수 있다.The aromatic primary amine used in the present invention is used in excess (more than 1: 2 in molar ratio) with respect to the usual aromatic mononitro compound which can be used not only as a reactant but also as a solvent for dissolving the catalyst component. In this way, deactivation of the catalyst can be prevented and catalyst recovery can be facilitated.
본 발명자들이 연구에 의하면 본 발명의 방법에 의한 일반식(I)의 N,N'-치환우레아의 생성반응은 하기 반응식(1) 및 (2)의 반응이 경쟁적으로 동시에 진행되는 것으로 사료된다.According to the researches of the present inventors, it is considered that the reaction of the N, N'-substituted urea of the general formula (I) according to the method of the present invention proceeds competitively simultaneously with the reactions of the following reaction formulas (1) and (2).
이때, 방향족 모노니트로화합물과 방향족 제1급 아민의 몰비에 따라 N,N'-치환우레아의 생성량이 크게 달라지는데 방향족 모노니트로화합물의 양이 같을때 방향족 제1급 아민의 양이 많아짐에 따라 N,N'-치환우레아의 생성량이 증가한다.At this time, the amount of N, N'-substituted urea varies greatly according to the molar ratio of the aromatic mononitro compound and the aromatic primary amine. When the amount of the aromatic mononitro compound is the same, the amount of the aromatic primary amine increases as N, The amount of N'-substituted urea increases.
그 이유는 방향족 아민의 농도가 커지면 반응식(1) 반응에 비하여 반응식(2) 반응이 상대적으로 빠르게 진행되어 생성되는 N,N'-치환우레아의 생성량이 많아지기 때문이다.The reason for this is that when the concentration of the aromatic amine increases, the amount of N, N'-substituted urea generated by the reaction of Reaction (2) proceeds relatively faster than that of Reaction (1).
본 발명에 사용되는 팔라듐 화합물을 주체로 하는 촉매는 2가 상태의 팔라듐 원소를 포함하는 화합물을 말한다.A catalyst mainly composed of a palladium compound used in the present invention refers to a compound containing a palladium element in a divalent state.
팔라듐 화합물에는 일반식 PdX2로 표시되는 팔라듐염과 일반식 PdX2L2로 표시되는 착체화합물이 있다. 여기에서 X는 할로겐, NO3, OCOCH3, OCOF3등을 나타내며, L은 리간드로서 PR3(식 중, R은 메틸, 에틸 또는 부틸을 나타낸다), PPh3, C6H5NH2, CH3CN, P-ClC6H4NH2, P-CH3C6H4NH2등을 나타낸다.Palladium compound has a complex compound represented by the palladium salt with the general formula L 2 PdX 2 represented by the general formula PdX 2. Where X represents halogen, NO 3 , OCOCH 3 , OCOF 3, etc., L is a ligand PR 3 (wherein R represents methyl, ethyl or butyl), PPh 3 , C 6 H 5 NH 2 , CH 3 CN, P-ClC 6 H 4 NH 2 , P-CH 3 C 6 H 4 NH 2 , and the like.
구체적인 화합물로는 PdCl2, PdBr2, PdI2, Pd(NO3)2, PdSO4등의 무기염류; Pd(OCOCH3)2, Pd(OCOCF3)2등의 유기산염류; PdCl2(PPh3)2, Pd(OCOCH3)2(PPh3)2등의 착체화합물 등이 있다.Specific compounds include inorganic salts such as PdCl 2 , PdBr 2 , PdI 2 , Pd (NO 3 ) 2 , and PdSO 4 ; Pd (OCOCH 3) 2, Pd (OCOCF 3) organic acid salts of 2, and the like; Complex compounds such as PdCl 2 (PPh 3 ) 2 and Pd (OCOCH 3 ) 2 (PPh 3 ) 2 ;
사용되는 촉매의 양은 몰수로 방향족 모노니트로 화합물의 1/10~1/3000의 양을 사용하는 것이 바람직하다. PdX2형태의 촉매를 사용할 경우, 위에서 언급한 리간드를 사용하여 촉매의 비활성화를 방지해 주는 것이 필요한데, 리간드로서는 PPh3, PR3(식중, R은 메틸, 에틸 또는 부틸을 나타낸다)등의 인화합물이 특히 바람직하다. 리간드는 촉매사용 몰수의 2배 이상의 양을 사용하는 것이 좋다.It is preferable to use the quantity of the catalyst of 1/10-1/3000 of an aromatic mononitro compound in the number of moles of catalyst used. When using a PdX 2 type catalyst, it is necessary to prevent the deactivation of the catalyst by using the above-mentioned ligand. As the ligand, phosphorus compounds such as PPh 3 and PR 3 (where R represents methyl, ethyl or butyl) are used. This is particularly preferred. The ligand is preferably used at least twice the number of moles used catalyst.
한편, 본 발명의 방법에서 조촉매로 사용하는 할로겐원소를 포함하는 화합물에는 일반식[R4N+]X-로 표시되는 암모니움염과 일반식[R4P+]X-로 표시되는 포스포니움염이 있다(여기에서 R은 수소, 지방족기, 치환족기, 방향족기, 방향지방족기로부터 선택되는 기를 표시하며 서로 같거나 다를 수 있으며, X는 할로겐원소를 나타낸다). 구체적인 화합물로는 암모니움염으로서 테트라에틸암모니움클로라이드, 테트라메틸암모니움클로라이드, 테트라부틸암모니움클로라이드, 테트라에틸암모니움브로마이드, 테트라메틸암모니움브로마이드, 테트라부틸암모니움브로마이드, 테트라에틸암모니움요오드, 테트라메틸암모니움요오드, 테트라부틸암모니움요오드, 트리메틸벤질암모니움클로라이드 등이 있고, 포스포니움염으로서는 테트라부틸포스포니움브로마이드, 테트라메틸포스포니움클로라이드, 테트라에틸포스포니움브로마이드, 테트라에틸포스포니움클로라이드, 테트라메틸포스포니움클로라이드, 테트라부틸포스포니움클로라이드, 테트라메틸포스포니움요오드, 테트라부틸포스포니움요오드, 테트라에틸포스포니움요오드 등이 있다. 조촉매로 사용되는 화합물은 팔라듐화합물에 대하여 1~10배의 몰수를 사용한다. 1몰배 이하의 양을 사용하면 충분히 반응이 진행되지 않고 10몰배 이상의 양을 사용하면 경제적으로 불합리하다.On the other hand, a compound containing a halogen element to use as a co-catalyst in the process of the present invention the general formula [R 4 N +] X - ammonium salts with the formula represented by [R 4 P +] X - phosphine represented by the pony There is a hum salt (where R represents a group selected from hydrogen, aliphatic, substituted, aromatic, aromatic aliphatic groups and can be the same or different and X represents a halogen element). Specific compounds include tetraethylammonium chloride, tetramethylammonium chloride, tetrabutylammonium chloride, tetraethylammonium bromide, tetramethylammonium bromide, tetrabutylammonium bromide, tetraethylammonium iodine and tetramethyl as ammonium salts. Methyl ammonium iodine, tetrabutyl ammonium iodine, trimethylbenzyl ammonium chloride, and the like, and as the phosphonium salt, tetrabutyl phosphonium bromide, tetramethyl phosphonium chloride, tetraethyl phosphonium bromide, tetraethyl phosphonium Chloride, tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium iodine, tetrabutylphosphonium iodine, tetraethylphosphonium iodine and the like. Compounds used as cocatalysts use moles of 1 to 10 times the palladium compound. If an amount of 1 mole or less is used, the reaction does not proceed sufficiently, and an amount of 10 mole or more is economically unreasonable.
팔라듐화합물을 주체로 하는 촉매(리간드포함) 및 리간드의 양은 반응시에 완전히 용해되어 액상으로 존재하도록 각 성분의 용해도, 반응온도, 방향족 제1급 아민의 사용량, 용매의 종류 및 사용량 등의 반응조건에 따라 조절해주는 것이 바람직하다.Reaction conditions such as solubility of each component, reaction temperature, amount of aromatic primary amine, type of solvent and amount of solvent so that the amount of catalyst (including ligands) and ligand mainly composed of palladium compounds are completely dissolved and present in the liquid phase during the reaction. It is desirable to adjust according to.
본 반응에서 사용된 촉매 및 조촉매의 회수는 고체상태인 N,N'-치환우레아를 여과시켜 분리함으로써 쉽게 달성할 수 있다. 생성물을 여과한 후 N,N'-치환우레아를 방향족 제1급 아민으로 세척함으로써 촉매를 거의 완벽하게 회수할 수 있다.Recovery of the catalyst and cocatalyst used in the present reaction can be easily accomplished by filtering off the solid N, N'-substituted urea. The catalyst can be recovered almost completely by filtering the product and then washing the N, N'-substituted urea with an aromatic primary amine.
본 발명에 사용되는 용매로는 N,N'-치환우레아의 용해도가 크지 않은 비극성 용매가 적합하며 벤젠, 톨루엔, 크실렌 등이 특히 바람직하다. 상기의 용매는 필요에 따라 사용하여도 좋고 사용하지 않아도 무방하다.As the solvent used in the present invention, a nonpolar solvent having a low solubility of N, N'-substituted urea is suitable, and benzene, toluene, xylene and the like are particularly preferable. The solvent may be used as necessary or may not be used.
본 발명의 방법에 의한 반응온도는 50~200℃의 온도범위에서, 바람직하게는 80~140℃의 범위에서 진행시킨다. 반응온도가 너무 낮으면 미반응 모노니트로화합물의 양이 많아지게 되고, 반응온도가 너무 높으면 촉매의 비활성화가 일어나 촉매의 활성이 떨어지거나 촉매가 분해된다. 반응압력은 1기압 이상의 압력에서 진행시키며, 통상적으로는 5~100기압에서 반응시킨다. 5기압 이하의 압력에서는 반응이 빨리 진행되지 않고, 100기압 이상의 압력에서는 장치비가 비싸지므로 경제성이 문제가 된다. 반응시간은 10분~600분인데 사용되는 반응물의 종류, 반응압력, 온도, 촉매의 종류 및 사용량에 따라 달라지게 된다.Reaction temperature by the method of the present invention is carried out in a temperature range of 50 ~ 200 ℃, preferably in the range of 80 ~ 140 ℃. If the reaction temperature is too low, the amount of unreacted mononitro compound is increased. If the reaction temperature is too high, the catalyst is deactivated to deactivate the catalyst or decompose the catalyst. The reaction pressure proceeds at a pressure of 1 atm or higher, and is usually reacted at 5 to 100 atm. The reaction does not proceed quickly at pressures of 5 atm or lower, and the cost of equipment is high at pressures of 100 atm or higher, thereby causing economic problems. The reaction time is 10 minutes to 600 minutes, depending on the type of reactants used, reaction pressure, temperature, type of catalyst, and amount used.
이하, 본 발명을 실시예로서 좀더 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail as examples.
실시예에서 기재된 반응은 모두 300ml 오토클레이브에서 배치(batch)로 수행한 것이다. 반응물의 가열은 반응기 외부에 장치된 가열기로 하였으며 반응이 끝난후, 반응기 내부에 장치된 냉각코일을 따라 흐르는 냉각수에 의해 냉각시켰다. 반응물은 t-부틸벤젠을 내부표준 물질로 사용하여 가스크로마토그래피아 고속액체크로마토그래피로 분석하였다.All reactions described in the examples were performed in batches in a 300 ml autoclave. The reaction was heated with a heater installed outside the reactor, and after the reaction was completed, it was cooled by cooling water flowing along the cooling coil installed inside the reactor. The reaction product was analyzed by gas chromatography and high performance liquid chromatography using t-butylbenzene as an internal standard.
N,N'-치환우레아의 수율은 아래의 공식에 의해 계산하였다.The yield of N, N'-substituted urea was calculated by the following formula.
[실시예 1]Example 1
300ml 오토클레이브에 니트로벤젠 6.15g(50밀리몰), 아닐린 27.9g(300밀리몰), 팔라듐 아세테이트(Pd(CH3COO)2) 0.15g 트리페닐포스핀(PPh3) 1g, 테트라에틸암모니움 클로라이드(NEt4Cl) 2g, t-부틸벤젠(가스크로마토그래피 분석을 위한 내부표준물질)과 크실렌 60g을 투입하였다. 10기압의 일산화탄소로 기상 부분을 3회 치환한 후 상온에서 일산화탄소압을 가하여 40기압이 되게 하였다. 반응기를 교반시키면서 온도를 올려 120℃에서 1.5시간 동안 반응시킨 후, 샘플 밸브를 통하여 샘플을 취하여 가스크로마토그래피로 분석하였다. 반응기를 상온까지 냉각시킨 후 가스를 배출시켰다. 반응물을 감압 여과한 후 아닐린(18.6g, 200밀리몰)과 크실렌(50g)으로 세척하고 건조하여 흰색의 고체 18.4g을 얻었다. 가스크로마토그래피 분석결과, 니트로벤젠의 전화율은 100% 이었으며, N,N'-디페닐 우레아(DPU)의 수율은 97.3%였다.Nitrobenzene 6.15 g (50 mmol), aniline 27.9 g (300 mmol) in 300 ml autoclave, palladium acetate (Pd (CH 3 COO) 2 ) 0.15g triphenylphosphine (PPh 3 ) 1g, tetraethylammonium chloride ( 2 g of NEt 4 Cl), t-butylbenzene (internal standard for gas chromatography analysis) and 60 g of xylene were added. After replacing the gas phase part three times with 10 atm of carbon monoxide, carbon monoxide was applied at room temperature to 40 atm. The temperature was raised while stirring the reactor and reacted at 120 ° C. for 1.5 hours. Then, a sample was taken through a sample valve and analyzed by gas chromatography. After cooling the reactor to room temperature, the gas was discharged. The reaction was filtered under reduced pressure, washed with aniline (18.6 g, 200 mmol) and xylene (50 g) and dried to give 18.4 g of a white solid. As a result of gas chromatography analysis, the conversion of nitrobenzene was 100%, and the yield of N, N'-diphenyl urea (DPU) was 97.3%.
[실시예 2]Example 2
실시예 1의 촉매함유 여과액(생성물 분리후의 반응여과액 및 아닐린세척액)에 니트로벤젠 6.15g(50밀리몰)을 첨가한 후 실시예 1과 같은 반응조건에서 실험하였다. 니트로벤젠의 전화율은 100%였으며, N,N'-디페닐우레아 수율은 98%로서 회수된 촉매의 활성감소는 나타나지 않았다.Nitrobenzene 6.15g (50 mmol) was added to the catalyst-containing filtrate of Example 1 (reaction filtrate after product separation and aniline wash), and the reaction was carried out under the same reaction conditions as in Example 1. The conversion of nitrobenzene was 100% and the yield of N, N'-diphenylurea was 98%, indicating no deactivation of the recovered catalyst.
[실시예 3]Example 3
테트라에틸 암모니움 클로라이드(NEt4Cl) 대신에 테트라부틸포스포니움 브로마이드(Bu4PBr)을 사용하여 4시간 반응시킨 외에는 실시예 1과 동일한 조건에서 실험하였다. 니트로벤젠의 전화율은 97.8%였고, N,N'-디페닐우레아의 수율은 96.4%였다.The reaction was carried out under the same conditions as in Example 1 except that the reaction was performed for 4 hours using tetrabutylphosphonium bromide (Bu 4 PBr) instead of tetraethyl ammonium chloride (NEt 4 Cl). The conversion of nitrobenzene was 97.8%, and the yield of N, N'-diphenylurea was 96.4%.
[실시예 4]Example 4
팔라듐 아세테이트(Pd(CH3COO)2) 대신에 팔라듐 트리플루오로 아세테이트(Pd(CF3COO)2) 0.5g을 사용하여 62기압, 100℃에서 7시간 반응시킨 외에는 실시예 1과 동일한 조건에서 실험하였다. 니트로벤젠의 전화율은 96.2%였고, N,N'-디페닐우레아의 수율은 93.4%였다.Under the same conditions as in Example 1, except that 0.5 g of palladium trifluoro acetate (Pd (CF 3 COO) 2 ) was used instead of palladium acetate (Pd (CH 3 COO) 2 ) at 62 atmospheres and 100 ° C. for 7 hours. Experiment. The conversion of nitrobenzene was 96.2%, and the yield of N, N'-diphenylurea was 93.4%.
[실시예 5]Example 5
팔라듐 아세테이트(Pd(CH3COO)2) 대신에 PdCl2(0.15g)를 사용하여 6시간 반응시킨 외에는 실시예 1과 동일한 조건에서 실험하였다. 니트로벤젠의 전화율은 88.9%였고, N,N'-디페닐우레아의 수율은 86.1%였다.The reaction was conducted under the same conditions as in Example 1 except that the reaction was carried out for 6 hours using PdCl 2 (0.15 g) instead of palladium acetate (Pd (CH 3 COO) 2 ). The conversion of nitrobenzene was 88.9%, and the yield of N, N'-diphenylurea was 86.1%.
[실시예 6]Example 6
크실렌 대신에 톨루엔 60g을 사용하여 53기압, 100℃에서 6시간 동안 반응시킨 외에는 실시예 1과 동일한 조건에서 실험하였다. 니트로벤젠의 전화율은 95.2%였으며, N,N'-디페닐우레아의 수율은 92.4%였다.The experiment was carried out under the same conditions as in Example 1 except that 60 g of toluene was used instead of xylene and reacted at 53 atmospheres and 100 ° C. for 6 hours. The conversion of nitrobenzene was 95.2%, and the yield of N, N'-diphenylurea was 92.4%.
[비교예 1]Comparative Example 1
테트라에틸암모니움 클로라이드(NEt4Cl) 없이 실험한 외에는 실시예 1과 동일한 조건에서 실험하였다. 니트로벤젠의 전화율은 11.5%였고, N,N'-디페닐우레아(DPU)의 수율은 11.4%였다.The experiment was conducted under the same conditions as in Example 1 except that the experiment was performed without tetraethylammonium chloride (NEt 4 Cl). The conversion of nitrobenzene was 11.5%, and the yield of N, N'-diphenylurea (DPU) was 11.4%.
[비교예 2]Comparative Example 2
아닐린 없이 실험한 외에는 실시예 1과 동일한 조건에서 실험하였다. 그 결과, 아닐린 생성은 없었으며 반응이 일어나지 않았다.The experiment was conducted under the same conditions as in Example 1 except that the experiment was performed without aniline. As a result, there was no aniline production and no reaction occurred.
[비교예 3]Comparative Example 3
니트로벤젠 없이 실험한 외에는 실시예 1과 동일한 조건에서 실험하였다. 그 결과 반응이 일어나지 않았다.The experiment was conducted under the same conditions as in Example 1 except that the experiment was performed without nitrobenzene. As a result, no reaction occurred.
[비교예 4][Comparative Example 4]
테트라에틸암모니움 클로라이드(NEt4Cl) 대신에 KCl(2g)을 사용하여 5.5시간 반응시킨 외에는 실시예 1과 동일한 조건에서 실험하였다. 니트로벤젠의 전화율은 55.5%였고, N,N'-디페닐우레아(DPU)의 수율은 55.1%였다.The reaction was carried out under the same conditions as in Example 1 except that the reaction was performed for 5.5 hours using KCl (2 g) instead of tetraethylammonium chloride (NEt 4 Cl). The conversion of nitrobenzene was 55.5%, and the yield of N, N'-diphenylurea (DPU) was 55.1%.
[비교예 5][Comparative Example 5]
테트라에틸암모니움 클로라이드(NEt4Cl) 대신에 CuCl2(2g)을 사용하여 55기압에서 5시간 반응시킨 외에는 실시예 1과 동일한 조건에서 실험하였다. 그 결과 반응은 일어나지 않았다.Tetraethylammonium chloride (NEt 4 Cl) was used in the same conditions as in Example 1 except for reacting for 5 hours at 55 atm using CuCl 2 (2g). As a result, no reaction occurred.
[비교예 6]Comparative Example 6
팔라듐 아세테이트(Pd(CH3COO)2) 대신에 금속팔라듐(0.15g)을 사용하여 50기압, 100℃에서 4.5시간 반응시킨 외에는 실시예 1과 동일한 조건에서 실험하였다. 그 결과 반응은 일어나지 않았다.Metal palladium (0.15 g) was used instead of palladium acetate (Pd (CH 3 COO) 2 ), and the reaction was carried out under the same conditions as in Example 1 except that the reaction was carried out at 50 atmospheres and 100 ° C. for 4.5 hours. As a result, no reaction occurred.
[비교예 7]Comparative Example 7
크실렌 대신에 아세톤 700ml를 사용하여 실시예 6과 동일한 조건에서 실험하였다. 니트로벤젠의 전화율은 25.4%였으며, N,N'-디페닐우레아의 수율은 25.1%였다.700 ml of acetone instead of xylene was used under the same conditions as in Example 6. The conversion of nitrobenzene was 25.4%, and the yield of N, N'-diphenylurea was 25.1%.
Claims (8)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019890015880A KR920002795B1 (en) | 1989-11-02 | 1989-11-02 | Process for the preparation of n.n'-substituted urea |
| JP2252030A JPH06104651B2 (en) | 1989-11-02 | 1990-09-25 | Method for producing N, N'-substituted urea |
| US07/606,721 US5091571A (en) | 1989-11-02 | 1990-10-31 | Process for preparing N,N'-disubstituted urea |
| US07/780,197 US5198582A (en) | 1989-11-02 | 1991-10-22 | Process for preparing symmetric N,N'-disubstituted aromatic urea |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019890015880A KR920002795B1 (en) | 1989-11-02 | 1989-11-02 | Process for the preparation of n.n'-substituted urea |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR910009632A KR910009632A (en) | 1991-06-28 |
| KR920002795B1 true KR920002795B1 (en) | 1992-04-03 |
Family
ID=19291290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019890015880A KR920002795B1 (en) | 1989-11-02 | 1989-11-02 | Process for the preparation of n.n'-substituted urea |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR920002795B1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19990002169A (en) * | 1997-06-19 | 1999-01-15 | 구자홍 | Bottom panel structure of plasma display panel |
| KR100493375B1 (en) * | 2003-01-21 | 2005-06-07 | 한국과학기술연구원 | Method for preparing n,n'-disubstituted urea using imidazolium alkylselenite catalyst |
-
1989
- 1989-11-02 KR KR1019890015880A patent/KR920002795B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR910009632A (en) | 1991-06-28 |
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