KR100195580B1 - Process for producing 1,4-naphthoquinone - Google Patents
Process for producing 1,4-naphthoquinone Download PDFInfo
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- KR100195580B1 KR100195580B1 KR1019960048982A KR19960048982A KR100195580B1 KR 100195580 B1 KR100195580 B1 KR 100195580B1 KR 1019960048982 A KR1019960048982 A KR 1019960048982A KR 19960048982 A KR19960048982 A KR 19960048982A KR 100195580 B1 KR100195580 B1 KR 100195580B1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C50/00—Quinones
- C07C50/10—Quinones the quinoid structure being part of a condensed ring system containing two rings
- C07C50/12—Naphthoquinones, i.e. C10H6O2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
- C07C46/06—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring
- C07C46/08—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring with molecular oxygen
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Abstract
본 발명은 1,4-벤조퀴논류를 1,3-부타디엔류 [2+4] 디즈-알더 반응시켜서 얻은 4a, 5, 8, 8a-테트라하이드로-1,4-나프토퀴논류를 탈수소화하여, 1,4-나프토퀴논류를 제조하는 방법에 관한 것이며, 특히 탈수소화 촉매하에서 과산화수소, 염소산 나트륨계, 산소등의 산화제를 사용하여 산화성 탈수소화하는 것으로 이루어진 1,4-나프토퀴논류의 제조방법에 관한 것이다.The present invention relates to a process for the dehydrogenation of 4a, 5,8,8a-tetrahydro-1,4-naphthoquinones obtained by subjecting 1,4-benzoquinones to 1,3-butadiene [2 + 4] And 1,4-naphthoquinones. More particularly, the present invention relates to a process for producing 1,4-naphthoquinones, which comprises oxidizing dehydrogenation using an oxidizing agent such as hydrogen peroxide, sodium chlorate, oxygen, etc. under a dehydrogenation catalyst .
본 발명의 제조방법에 사용된 산화제들은 탈수소화 반응후 공해문제를 야기시키지 않으며, 반응 선택성이 높이 부생성물의 발생이 없고 높은 수율로 생성물을 얻을 수 있다.The oxidizing agents used in the production process of the present invention do not cause pollution problems after the dehydrogenation reaction and produce products with high reaction selectivity without generation of byproducts and with a high yield.
Description
[발명의 명칭][Title of the Invention]
1,4-나프토퀴논류의 제조방법Preparation of 1,4-naphthoquinones
[발명의 상세한 설명]DETAILED DESCRIPTION OF THE INVENTION [
[발명의 목적][Object of the invention]
본 발명의 목적은 1,4-벤조퀴논류를 1,3-부타디엔류와 [2+4] 딜즈-알더 반응 시켜서 얻은 4a, 5, 8, 8a-테트라하이드로-1,4-나프토퀴논류를 탈수소화 촉매하에서 탈수소화하여 1,4-나프토퀴논류를 제조하는 방법에 관한 것이며, 보다 구체적으로는 탈수소화 공정에서 활성탄에 담지된 팔라듐의 탈수소화 촉매존재하에 산화제로서 과산화수소, 염소산나트륨계 산화제 또는 산소를 사용하여 산화성 탈수소화하는 것으로 이루어진 1,4-나프토퀴논류의 제조방법에 관한 것이다.The object of the present invention is to provide 4a, 5,8,8a-tetrahydro-1,4-naphthoquinones obtained by reacting 1,4-benzoquinones with 1,3-butadiene in a [2 + 4] More specifically, the present invention relates to a method for producing 1,4-naphthoquinone by dehydration under a dehydrogenation catalyst, and more particularly, to a method for producing 1,4-naphthoquinone by dehydrogenation in the presence of a dehydrogenation catalyst of palladium supported on activated carbon in a dehydrogenation process, And oxidative dehydrogenation using oxygen to produce 1,4-naphthoquinones.
[발명이 속하는 기술분야 및 그 분야의 종래 기술][TECHNICAL FIELD OF THE INVENTION AND RELATED ART OF THE SAME]
본 발명은 1,4-벤조퀴논류(1,4-benzoquinone)와 1,3-부타디엔류(1,3-butadienes)를 [2+4] 딜즈-알더(Diels-Alder) 반응 시켜 4a, 5, 8, 8a-테트라하이드로-1,4-나프토퀴논류(4a, 5, 8, 8a-tetraghydro-1,4-naphtrhoquinones)를 합성한후, 산화성 탈수소화 반응으로 1,4-나프토퀴논류(1,4-naphthoquinones)를 제조하는 법에 관한것이다.The present invention relates to a process for producing 4a, 5a, 5a, 5b and 5c by reacting 1,4-benzoquinone and 1,3-butadienes with a [2 + 4] Diels- , 8,8a-tetrahydro-1,4-naphthoquinones (4a, 5,8,8a-tetraghydro-1,4-naphtrhoquinones) were synthesized and then 1,4-naphthoquinones 1,4-naphthoquinones. ≪ / RTI >
1,4-나프토퀴논류는 안트라퀴논류(anthraquinones)의 제조 원료로 알려져 있으며, 디크론, 모게톤 등의 농약, 비타민 K류, 난연제, 방청제, 반응억제제, 탈황촉매, 염료중간체 등의 합성원료로서 중요한 정밀화학 제품이다.1,4-naphthoquinones are known as raw materials for the production of anthraquinones and are used as synthetic raw materials for pesticides such as dicron and mogetone, vitamin K, flame retardant, rust inhibitor, reaction inhibitor, desulfurization catalyst, Is an important fine chemical product.
종래에는 나프탈렌류(naphthalenes) 를 산화시켜 1,4-나프토퀴논류를 제조하였으며, 이때 산화시키는 방법으로는 산화바나디움을 촉매로 하여 산소를 이용하는 기체상태로 산화시키는 방법과 크롬 또는 망간 등과 같은 중금속의 산화물인 산화체를 이용하여 액체상태에서 산화시키는 방법이 있다.(Ullmann's Enchclopedia of Industial Chemistry, A17권, 61∼71쪽, 1991년, VCH 독일)Conventionally, naphthalenes have been oxidized to produce 1,4-naphthoquinones. Oxidation methods include oxidizing vanadium oxide to a gaseous state using oxygen, and a method of oxidizing heavy metals such as chromium or manganese (Ullmann ' s Enchclopedia of Industial Chemistry, vol. A17, pp. 61-71, 1991, VCH Germany).
이들 일예의 특허문헌으로서 일본 특허공개공보 평3-275642호(1991년), 평6-9485호(1994년)는 2-메틸나프탈렌(2-methylnaphtalene)을 기상반응으로 산화시켜 비타민 K3로 알려진 2-메틸-1,4-나프토퀴논(2-methyl-1,4-naphthoquinone)을 제조하는 방법에 관한 것이고, 일본 특허 공개공보 소64-90151호(1989년), 평6-172253호(1994년)는 2-메틸-1-나프톨(2-methyl-1-napthol)을 액상으로 산화시켜 2-메탈-1,4-나프토퀴논을 제조하는 방법에 관한 것이다.Japanese Patent Application Laid-Open Nos. 3-275642 (1991) and Hei 6-9485 (1994) disclose a method of oxidizing 2-methylnaphthalene by a gas phase reaction, which is known as vitamin K 3 (2-methyl-1,4-naphthoquinone), and Japanese Patent Application Laid-Open Nos. 64-90151 (1989), 6-172253 1994) relates to a process for preparing 2-methyl-1,4-naphthoquinone by oxidizing 2-methyl-1-napthol into a liquid phase.
상기의 기체상태로 산화시키는 방법은 반응성은 뛰어나나 고온에서 반응시켜야 하는 단점으로 인하여 생성물의 반이상이 무스프탈산(phthalic anhydride)과 같은 부산물이 생성되어 제품의 정제와 부산물을 처리하여야 한다는 문제점이 있다.The above-mentioned method of oxidizing to a gaseous state is excellent in reactivity but has a disadvantage that it must be reacted at a high temperature, and therefore, half of the products have a problem of producing by-products such as phthalic anhydride, .
기상 산화반응의 문제점을 해결하기 위하여 나프탈렌 용액으로 하는 액상 산화반응이 개발되었으나, 촉매로 중금속을 사용하여야 하므로 폐기물을 처리하여야 하는 문제점이 있다.In order to solve the problems of the gas phase oxidation reaction, a liquid phase oxidation reaction using a naphthalene solution has been developed. However, since heavy metals should be used as a catalyst, the waste must be treated.
유럽특허 제 636,598호(1995년), 일본 특허공개공보 평7-223993호(1995년), 미국특허 제 5,412,124호(1995년)는 나프탈렌류를 산화시키지 않고 1,4-나프토퀴논류를 제조하는 방법에 관한것으로 1,3-부타디엔과 2-메틸-1,4-벤조퀴논을 [2+4] 딜즈-알더 반응을 시킨 다음 생성된 2-메틸-4a, 5, 8, 8a-테트라하이드로-1,4-나프토퀴논을 탈수소화하여 2-메틸-1,4-나프토퀴논류(비타민 K3)을 제조할 수 있다는 것을 특징으로 한다. 이때, 산화제로 2,3-디클로로-5, 6-디시아노-1,4-벤조퀴논(2, 3-dichloro- 5,6-dicyano-1,4-benzoquinone ; DDQ)를 사용하여 산화시켰다. 그러나, 여기에서 사용되는 산화제인 DDQ는 유기물로서 반응 후에도 같은 유기반응에서 분리를 하기가 곤란하다는 단점이 있다.European Patent No. 636,598 (1995), Japanese Patent Application Laid-Open No. 7-223993 (1995), and US Patent No. 5,412,124 (1995) disclose that 1,4-naphthoquinones are prepared without oxidizing naphthalenes Methyl-1,4-benzoquinone is subjected to a [2 + 4] Diels-Alder reaction of 1,3-butadiene and the resulting 2-methyl-4a, 5,8,8a-tetrahydro- And 1,4-naphthoquinone is dehydrogenated to produce 2-methyl-1,4-naphthoquinones (vitamin K 3 ). At this time, oxidation was performed using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) as an oxidizing agent. However, DDQ, which is an oxidizing agent used here, is disadvantageous in that it can not be separated in the same organic reaction even after the reaction as an organic substance.
또한 대한민국 특허출원 제 96-12872호에서는 [2+4] 딜즈-알더 반응 생성물인 2-메탈-4a, 5, 8, 8a-테트라하이드로-1,4-나프토퀴논을 분리, 정제하지 않고 동일 반응기에서 디메틸술폭사이드를 반응용매겸 탈수소화제로 사용하고, 탈수소화 반응 촉매로 루이스산 또는 브뢴스테드산을 사용하여 산화성 탈수소화하여 2-메탈-1,4-나프토퀴논을 제조하는 방법을 제시하고 있다.In Korean Patent Application No. 96-12872, 2-metal-4a, 5,8,8a-tetrahydro-1,4-naphthoquinone, which is the [2 + 4] Metal-1,4-naphthoquinone is prepared by using dimethylsulfoxide as a reaction solvent and dehydrogenating agent in a reactor and oxidizing dehydrogenation using Lewis acid or Bronsted acid as a dehydrogenation catalyst I am suggesting.
한편, 방향족화 반응의 대표적인 화합물인 사이클로헥센류(cyclohexenes)의 산화성 탈수소화 반응에 사용되는 산화제로는 황과 브롬이 대표적인 산화제이나, 반응시 황화수소 브롬화수소가 발생되는 단점이 있어, 환경오염이 심각하여 실제 공업적인 생산에 사용할 수가 없다.On the other hand, sulfuric acid and bromine are representative oxidizing agents for the oxidative dehydrogenation reaction of cyclohexenes, which is a typical compound of aromaticization reaction, but hydrogen sulfide hydrogen bromide is generated in the reaction, And can not be used for actual industrial production.
[발명이 이루고자 하는 기술적 과제][Technical Problem]
본 발명은 1,4-나프토퀴논류의 제조방법중 탈수소화 공정에서 탈수소화반응후 공해를 유발하지 않는 산화제를 연구하던차 과산화수소, 염소산나트륨계 산화제, 산소등이 유용한 산화제임을 발견하여 본 발명을 완성하기에 이르렀다.The present invention is based on the finding that hydrogen peroxide, sodium chlorate oxidant, oxygen and the like are useful oxidizing agents in studying oxidizing agents that do not cause pollution after dehydrogenation in the dehydrogenation process in 1,4-naphthoquinone production process It came to the following.
[발명의 구성 및 작용][Structure and operation of the invention]
본 발명은 1,4-벤조퀴논류를 1,3-부타디엔류 와 [2+4] 딜즈-알더 반응시켜서 얻은 4a, 5, 8, 8a-테트라하이드로-1,4-나프토퀴논류를 탈수소화 촉매하에서 과산화수소, 염소산나트륨계, 산소등의 산화제를 사용하여 산화성 탈수소화하는 것으로 이루어진 1,4-나프토퀴논류의 제조방법이다.The present invention relates to a process for the preparation of 4a, 5,8,8a-tetrahydro-1,4-naphthoquinones obtained by reacting 1,4-benzoquinones with 1,3-butadiene in a [2 + 4] And oxidative dehydrogenation using an oxidizing agent such as hydrogen peroxide, sodium chlorate system or oxygen under a catalyst.
본 발명은 1,4-벤조퀴논류를 [2+4] 딜즈-알더 반응의 친디엔체(dienophile)로 이용하고 1,3-부타디엔류를 공액 디엔체(conjugated dienes)로 이용하여 반응 시켜 4a, 5, 8, 8a-테트라하이드- 1,4-나프토퀴논류를 제조하고, 이 제조된 [2+4] 딜즈-알더 반응 생성물의 방향족화(aromatization)을 위하여 이중결합은 산화시키지 않고 탈수소화 시킬 수 있는 산화제를 사용하여 산화성 탈수소화 반응시켜 1,4-나프토퀴논류를 제조하는 방법에 관한 것이다. 이때 산화제로는 과산화수소, 염소산나트륨계등이 가능하며, 산소 또는 공기를 사용하는 기-액 반응도 가능하다.In the present invention, 1,4-benzoquinone is used as a dienophile of the [2 + 4] Diels-Alder reaction and 1,3-butadiene is used as conjugated dienes to form 4a , 5,8,8a-tetrahydro-1,4-naphthoquinones and for the aromatization of the resulting [2 + 4] Diels-Alder reaction product, the double bond is dehydrogenated To an oxidative dehydrogenation reaction using an oxidizing agent capable of producing 1,4-naphthoquinones. The oxidizing agent may be hydrogen peroxide, sodium chlorate or the like, or a gas-liquid reaction using oxygen or air may be used.
본 발명의 일예로 1,4-벤조퀴논류과 2,3-디메틸-1,3-부타디엔(2, 3-dimethyl-1,3-butadiene)을 정량적으로 [2+4] 딜즈-알더 반응을 시켜본 결과 예상된 반응 경로와는 다르게 6, 7-디메틸-4a, 5, 8, 8a-테트라하이드로-1,4-나프토퀴논(6,7-dimethyl-4a, 5, 8, 8a-tetrahydro-1,4 naphthoquinone) 이 부산물 없이 생성되었다. 이와같이 [2+4] 딜즈-알더 반응 반응물이 더 이상의 반응을 하지 않는 이유로는 [2+4] 딜즈-알더 반응 생성물의 친디엔체 부분이 동일 평면에 있지 않아 가능하다고 판단된다. [2+4] 딜즈-알더 반응 생성물인 4a, 5, 8, 8a-테트라하이드-1,4-나프토퀴논류를 중금속과 같이 공해를 유발하는 산화제 대신 공해를 유발하지 않는 산화제를 선택하고, 산화성 탈수소화 반응과정을 거쳐 방향족 화합물인 1,4-나프토퀴논류를 제조하는 것이다.In an example of the present invention, the [2 + 4] Diels-Alder reaction is carried out quantitatively with 1,4-benzoquinone and 2,3-dimethyl-1,3-butadiene As a result, unlike the expected reaction pathway, 6,7-dimethyl-4a, 5,8,8a-tetrahydro-1,4-naphthoquinone (6,7- 1,4 naphthoquinone) was produced without byproducts. Thus, the reason why the [2 + 4] Diels-Alder reaction product does not react further is judged to be possible because the diene portion of the [2 + 4] Diels-Alder reaction product is not in the same plane. 4a, 5,8,8a-tetrahydro-1,4-naphthoquinones, which are [2 + 4] Diels-Alder reaction products, are replaced with oxidants that do not cause pollution instead of pollutants such as heavy metals, And 1,4-naphthoquinone, which is an aromatic compound, is produced through a dehydrogenation reaction process.
본 발명에서는 낮은 반응온도를 요구하며, 부산물의 발생이 적은 균일계 액상반응과 높은 반응온도에서 높은 전환율을 갖는 불균일계 기상반응의 장점만을 선택한 불균일계 액상반응인 촉매수소전달반응(catalytic transfer hydrogenation)을 응용하였으며 , 산화제로는 반응 후 공해를 유발하지 않는 과산화수소, 염소산나트륨계[NaClOn(n=1-4)], 산소 등을 사용하였다. 사용된 산화제의 양은 테트라하이드로-1,4-벤조퀴논에 대해서 당량비로 1:0.5∼1:2를 사용함이 적절하다.In the present invention, catalytic transfer hydrogenation reaction, which is a heterogeneous liquid-phase reaction which requires a low reaction temperature and produces only a homogeneous liquid-phase reaction with low occurrence of byproducts and only the merits of a heterogeneous gas- Hydrogen peroxide, sodium chlorate (NaClOn (n = 1-4)), and oxygen were used as oxidants. The amount of the oxidizing agent used is suitably 1: 0.5 to 1: 2 in terms of equivalents relative to tetrahydro-1,4-benzoquinone.
본 발명에서 사용된 산화제중 과산화수소는 반응 후 물로 전환되며, 물에 30% 희석시킨 것을 사용하여 위험성을 줄여 사용하였다. 염소산나트륨계 산화제는 반응 후 반응성이 없는 염화나트륨을 생성하므로, 반응 후 처리시 공해문제를 야기시키지 않는 산화제이다.Among the oxidants used in the present invention, hydrogen peroxide was converted into water after the reaction, and a 30% dilution in water was used to reduce the risk. The sodium chlorate-based oxidizing agent produces sodium chloride which is not reactive after the reaction, so it is an oxidizing agent that does not cause pollution problems during the post-reaction treatment.
본 발명에서의 탈수소화 반응은 불균일계 촉매를 사용하여 낮은 온도, 상압의 격렬하지 않는 조건에서의 반응으로 반응의 위험도를 최소화 시킬 수 있으며, 촉매의 회수가 용이한 촉매수소전달 반응을 응용하였다. 여기에서 반응에 사용된 불균일계 촉매는 팔라듐을 활성탄에 담지시킨 촉매로서, 기공의 크기가 약 40μm이상이고, 팔라듐이 5wt% 담지된 것을 사용하였으며 촉매 비표면적(specific surface area)은 약 600㎡/g였다. 그러나, 탈수소화반응을 액상에서 상압의 촉매수소전달 반응을 할 경우, 기상의 불균일계 촉매 반응과는 달리 수소공여 용매로 지방족 또는 방향족 알콜류, 물 등이 사용된다.The dehydrogenation reaction in the present invention employs a heterogeneous catalyst to minimize the risk of reaction by reaction at low temperature and atmospheric pressure in a nonvolatile condition and to apply a catalytic hydrogen transfer reaction which facilitates recovery of the catalyst. Here, the heterogeneous catalyst used in the reaction was a catalyst in which palladium was supported on activated carbon. The catalyst had a pore size of about 40 μm or more and a palladium loading of 5 wt%, and a specific surface area of about 600 m 2 / g. However, when the dehydrogenation reaction is carried out in a liquid phase at atmospheric catalytic hydrogen transfer reaction, aliphatic or aromatic alcohols and water are used as a hydrogen donating solvent, unlike the heterogeneous catalytic reaction in the gas phase.
본 발명에서는 테트라하이드로-1,4-나프토퀴논류의 용해도를 고려하여 반응용매로 알콜류를 사용하였으며, 산화성 탈수소화 반응온도는 50∼80℃가 적절하였다.In the present invention, alcohols were used as a reaction solvent in consideration of the solubility of tetrahydro-1,4-naphthoquinones. The temperature of the oxidative dehydrogenation reaction was suitably in the range of 50 to 80 ° C.
본 발명은 균일계 촉매반응의 전형적인 반응을 이용하였으며 반응기는 회분식으로 가압이 가능한 반응기를 사용하였다. 반응물의 분석은 핵자기공명(NMR) 스펙트럼과 기체크로마토그라피-질량분석검출기(GC-MSD)를 이용하여 확인하였다. 면적비를 환산하여 사용하였다.The present invention utilizes the typical reaction of a homogeneous catalyst reaction and the reactor employs a batch pressurizable reactor. Analysis of the reactants was confirmed by nuclear magnetic resonance (NMR) spectroscopy and gas chromatography-mass spectrometry (GC-MSD). Area ratio.
본 발명을 실시예에서 상세히 설명하면 다음과 같다. 그러나 본 발명이 실시예에 의하여 국한되는 것은 아니다.The present invention will be described in detail in the following examples. However, the present invention is not limited to the examples.
[실시예 1][Example 1]
냉각기와 교반기가 있는 100㎖의 반응기에 다음 표 1에 제시된 바와 같이 퀴논류 26.5mmol 을 유기용매 50㎖에 교반하면서 용해시킨 후 반응기의 온도를 상승시키면서 부타디엔류 26.5㎖을 주입한후 240분간 반응시킨다. 반응용액을 시간별로 일정량 취하여 핵자기공명 스펙트럼과 기체크로마토그라피를 이용 확인 및 정량하여 딜즈-알더 반응 생성물을 표 1에 표시된 결과와 같이 얻었다.In a 100 ml reactor equipped with a condenser and a stirrer, 26.5 mmol of quinone was dissolved in 50 ml of an organic solvent while stirring, as shown in the following Table 1, 26.5 ml of butadiene was injected while the temperature of the reactor was increased, and the reaction was carried out for 240 minutes . A certain amount of the reaction solution was taken over time, and nuclear magnetic resonance spectra and gas chromatography were used to identify and quantify the Dil-Alder reaction product as shown in Table 1.
[실시예 2][Example 2]
가압반응이 가능하고 교반기가 있는 250㎖의 반응기에 1,4-벤조퀴논류 108g (1.0mmol)을 클로로포름 200㎖에 교반하면서 용해시킨후 1,3-부타디엔류 60g(1.1 mmol)을 주입하고 반응기의 온도를 80℃까지 올려 1시간 반응시켰다. 초기의 압력은 80℃에서 62psiG였으나 1시간 후에는 43psiG로 감소하였다. 반응물을 감압증류하여 클로로포름을 제거한 후 에틸알콜에서 재결정하여 4a, 5, 8, 8a-테트라하이드로-1,4-나프토퀴논 130g (수율 80%)을 얻었다.108 g (1.0 mmol) of 1,4-benzoquinone were dissolved in 200 ml of chloroform with stirring, and 60 g (1.1 mmol) of 1,3-butadiene was introduced into a 250 ml reactor equipped with a stirrer, Was heated to 80 DEG C and reacted for 1 hour. Initial pressure was 62 psi G at 80 ° C, but decreased to 43 psi G after 1 hour. The reaction mixture was distilled under reduced pressure to remove chloroform and recrystallized in ethyl alcohol to obtain 130 g (yield 80%) of 4a, 5,8,8a-tetrahydro-1,4-naphthoquinone.
[실시예 3][Example 3]
실시예 1, 2에서 제조한 딜즈-알더 반응 생성물 10mmol을 냉각기와 교반기가 있는 10㎖의 반응기에 넣고 용매로 에틸알콜을 15㎖ 첨가하여 용해시킨다. 이 용액에 5wt%-팔라듐 /활성탄 0.3g을 넣어 현탁액을 만든 후 반응온도를 75℃로 조절한다. 물 1㎖에 산화제로 NaClO10mmol을 용해시킨후 10분동안 적하(dropping)하면서 교반시키고, 75℃에서 2시간 반응시킨다. 가스크로마토그라피로 분석된 전환율 및 나프토퀴논의 수율은 표 2와 같다.10 mmol of the product of the Diels-Alder reaction product prepared in Examples 1 and 2 was placed in a 10 ml reactor equipped with a condenser and a stirrer, 15 ml of ethyl alcohol was added as a solvent and dissolved. To this solution, a suspension is prepared by adding 0.3 g of 5 wt% -palladium / activated carbon, and the reaction temperature is adjusted to 75 ° C. 10 mmol of NaClO was dissolved in 1 ml of water as an oxidizing agent, and the mixture was stirred for 10 minutes while dropping, and reacted at 75 ° C for 2 hours. Table 2 shows conversion ratios and yields of naphthoquinone analyzed by gas chromatography.
[실시예 4][Example 4]
실시예 2에서 제조된 4a, 5, 8, 8a-테트라하이드로-1,4-나프토퀴논을 사용하고 다음 표3에 제시된 산화제를 사용한 것 이외에는 실시예3과 동일하게 실시하여 표 3과 같은 전환율 및 나프토퀴논의 수율을 얻었다.Using the 4a, 5,8,8a-tetrahydro-1,4-naphthoquinone prepared in Example 2 and the oxidizing agent shown in the following Table 3, the same procedure as in Example 3 was carried out, And the yield of naphthoquinone.
[실시예 5][Example 5]
상기 실시예 1에서 제조된 2-메틸-4a, 5, 8, 8a-테트라하이드로-1,4-나프토퀴논을 사용하고 다음 표4에 제시된 바와같이 산화제를 달리한 것 이외에는 실시예 3과 동일하게 실시하여 전환율 및 2-메틸-1,4-나프토퀴논의 수율을 다음 표4와 같이 얻었다.Using the 2-methyl-4a, 5,8,8a-tetrahydro-1,4-naphthoquinone prepared in Example 1 and the oxidizing agent as shown in Table 4 below, the same procedure as in Example 3 And the conversion and the yield of 2-methyl-1,4-naphthoquinone were obtained as shown in Table 4 below.
[실시예 6][Example 6]
실시예 3에서 산화제를 NaClO로 바꾸고 실시예 1에서 제조한 2,6,7-트리메틸-4a, 5, 8, 8a-테트라하이드로-1,4-나프토퀴논을 사용한 것외에는 실시예 3과 동일하게 실시하여 전환율 91%, 수율 100%의 결과를 얻었다.In the same manner as in Example 3 except that the oxidizing agent in Example 3 was changed to NaClO and the 2,6,7-trimethyl-4a, 5,8,8a-tetrahydro-1,4-naphthoquinone prepared in Example 1 was used To obtain a conversion rate of 91% and a yield of 100%.
[실시예 7][Example 7]
실시예 1에서 제조된 2,7-디메틸-4a, 5, 8, 8a-테트라하이드로-1,4-나프토퀴논으로 바꾸고, 산화제를 NaClO 와 NaClO를 사용한 것외에는 실시예 3과 동일하게 실시하여 표5와 같은 결과를 얻었다.Dimethyl-4a, 5,8,8a-tetrahydro-1,4-naphthoquinone prepared in Example 1 was replaced with NaClO and NaClO as oxidizing agents, the procedure of Example 3 was repeated to give Table 5 shows the results.
[발명의 효과][Effects of the Invention]
본 발명은 [2+4] 딜즈-알더 반응이 열허용(thermal allowd)반응으로 촉매없이도 반응온도만 높여주기만 하면 반응이 진행되고 반응후 처리시 공해문제를 야기시키지 않는 산화제를 사용하여 공해의 발생소지를 줄일 수 있고, 반응 선택성이 높이 부생성물의 발생이 없고 높은 수율로 1,4-벤조퀴논류로부터 1,4-나프토퀴논류를 제조할 수 있다.The present invention relates to the use of an oxidizing agent which does not cause a pollution problem when the reaction proceeds and only after the [2 + 4] Diels-Alder reaction undergoes a thermal allowd reaction, 1,4-naphthoquinones can be prepared from 1,4-benzoquinones at a high yield without reducing generation of byproducts and high reaction selectivity.
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