KR0129115B1 - Process for preparation of 3-brumocamphor - Google Patents

Process for preparation of 3-brumocamphor

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Publication number
KR0129115B1
KR0129115B1 KR1019940021919A KR19940021919A KR0129115B1 KR 0129115 B1 KR0129115 B1 KR 0129115B1 KR 1019940021919 A KR1019940021919 A KR 1019940021919A KR 19940021919 A KR19940021919 A KR 19940021919A KR 0129115 B1 KR0129115 B1 KR 0129115B1
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camphor
mole
amount
organic solvent
solvent
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KR1019940021919A
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Korean (ko)
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KR960007525A (en
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김영규
이상협
이희봉
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이종학
한양종합화학주식회사
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/385—Saturated compounds containing a keto group being part of a ring
    • C07C49/457—Saturated compounds containing a keto group being part of a ring containing halogen
    • C07C49/467—Saturated compounds containing a keto group being part of a ring containing halogen polycyclic
    • C07C49/473—Saturated compounds containing a keto group being part of a ring containing halogen polycyclic a keto group being part of a condensed ring system
    • C07C49/477—Saturated compounds containing a keto group being part of a ring containing halogen polycyclic a keto group being part of a condensed ring system having two rings

Abstract

Synthetic method of 3-bromocamphor is provided in this invention. Camphor represented by structural formula(II) and brome are reacted in the presence of 5-80 mole parts of organic solvent such as ethanol, dichloroethane, carbon tetrachloride, etc, for 1 to 8 hours at the temperature of 60-110 degree Celsius, distilled under reduced pressure to eliminate solvent, refluxed with mixed solvent of water and alcohol and base such as sodium hydroxide, potassium hydroxide, etc, then recrystallized by cooling down to room temperature to yield 3-bromocamphor.

Description

3-브로모캠퍼의 제조방법Method of manufacturing 3-bromo camphor

본 발명은 하기 구조식(Ⅰ)로 표시되는 3-브로모캠퍼의 제조방법에 관한 것으로, 좀 더 구체적으로는 유기용매하에서 하기 구조식(Ⅱ)로 표시되는 캠퍼를 브롬화반응시킨 후, 염기로 후처리하고 재결정시켜 하기 구조식(Ⅰ)로 표시되는 3-브로모캠퍼를 고수율로 제조하는 방법에 관한 것이다.The present invention relates to a method for producing 3-bromo camphor represented by the following structural formula (I), and more specifically, after the bromination reaction of the camphor represented by the following structural formula (II) under an organic solvent, followed by post-treatment with a base. And recrystallization to produce a 3-bromo camphor represented by the following structural formula (I) in high yield.

일반적으로 상기 구조식(Ⅰ)로 표시되는 3-브로모캠퍼는 입체 이성질체의 광학분할제로 사용되는 3-브로모캠퍼-9-슐폰산의 중간체 화합물로써, 상기 구조식(Ⅱ)로 표시되는 캠퍼는 출발물질로 하여 Agric. Biol. Chem. 43(20, 395-396p, 1979에 기재된 방법에 의해 제조되어 왔다.In general, 3-bromo camphor represented by the structural formula (I) is an intermediate compound of 3-bromo camphor-9-sulfonic acid used as an optical splitting agent of stereoisomer, and the camphor represented by the structural formula (II) starts Agric as a substance. Biol. Chem. 43 (20, 395-396p, 1979).

상기 문헌에 따르면, 상기 구조식(Ⅱ)로 표시되는 캠퍼에 브롬(Br2)을 80℃에서 3시간동안 적가한 후 3시간동안 교반한 다음, 교반을 마친 반응액을 냉수에 부가시킨다. 그후, 생성된 침전물을 에탄올(CH3CH2OH)에서 재결정시킨 후 건조시켜 66%의 수율로 상기 구조식(Ⅰ)로 표시되는 목적화합물을 제조하였다.According to this document, bromine (Br 2 ) is added dropwise to the camphor represented by the structural formula (II) at 80 ° C. for 3 hours, followed by stirring for 3 hours, and then the reaction solution is stirred and added to cold water. Thereafter, the resulting precipitate was recrystallized in ethanol (CH 3 CH 2 OH) and dried to prepare the target compound represented by the above formula (I) in a yield of 66%.

그러나, 상기 방법은 용매를 사용하지 않은 방응이므로 대량생산을 위한 공장에 적용시 교반에 문제점이 있을 뿐만 아니라 에탄올을 사용하여 재결정시킬 경우, 결정화되지 않은 하기 구조식(Ⅲ)으로 표시되는 상기 3-브로모캠퍼의 이성질체 및 하기 구조식(Ⅳ)로 표시되는 더브로 모캠퍼가 여액에 다량함유되어 있어 수율이 낮을 뿐만아니라 처리해야 할 폐기물이 다량 발생하는 단점이 있다.However, since the method does not use a solvent, it is not only a problem in agitation when applied to a factory for mass production, and when recrystallized using ethanol, the 3-broken is represented by the following structural formula (III) which is not crystallized. Isomers of the parent camphor and Dubro, which is represented by the following structural formula (IV), are contained in the filtrate in a large amount in the filtrate, so that the yield is low as well as a large amount of waste to be treated.

이러한 문제점들을 해결하기 위하여 본 발명자는 광범위한 연구를 수행하였고, 그 결과 본 발명에 이르게 되었다. 따라서, 본 발명은 적절한 용매의 선정을 통해 대량생산시 교반을 효율적으로 수행하면서 수율을 향상시키는 방법과 반응의 부산물일 상기 구조식(Ⅲ)으로 표시되는 브로모캠퍼 이성질체 및 상기 구조식(Ⅳ)으로 표시되는 디브로모 캠퍼의 양을 최소화할 수 있는 방법을 제공하는데 그 목적이 있다.In order to solve these problems, the inventors have conducted extensive research, and as a result, the present invention has been reached. Therefore, the present invention is a bromo camphor isomer represented by the structural formula (III) and the structural formula (IV) to be a by-product of the reaction and a method of improving the yield while efficiently performing agitation during mass production through the selection of a suitable solvent. It is an object of the present invention to provide a method for minimizing the amount of dibromo camphor.

상기 목적을 달성하기 위한 본 발명의 제조방법은 하기 구조식(Ⅰ)로 표시되는 3-브로모캠퍼의 제조방법에 있어서, 하기 구조식(Ⅱ)로 표시되는 캠퍼와 브롬을 유기용매하에서 1~8시간 반응시킨 후 감압증류 시켜 상기 용매를 제거한 다음, 물과 알콜의 혼합용매 및 염기를 부가하여 환류시키고, 환류종료 후 천천히 상온까지 냉각시켜 재결정시키는 것으로 구성된다.The production method of the present invention for achieving the above object is 1 to 8 hours in the manufacturing method of 3-bromo camphor represented by the following structural formula (I), the camphor and bromine represented by the following structural formula (II) under an organic solvent. After the reaction, the mixture is distilled under reduced pressure to remove the solvent, and then refluxed by adding a solvent and a base of a mixture of water and alcohol, and slowly recrystallizing the mixture after cooling to room temperature.

이하 본 발명을 좀 더 구체적으로 살펴보면 다음과 같다.Looking at the present invention in more detail as follows.

본 발명에 따르면, 상기 구조식(Ⅱ)로 표시되는 캠퍼를 유기용매하에서 브롬을 적가한 후 교반한 다음, 감압하에서 용매를 제거하고 물과 에탄올의 혼합용매 및 염기를 부가하여 환류시키므로써 반응 부산물인 상기 구조식(Ⅲ)로 표시되는 브로모캠퍼 이성질체의 이성질화반응과 상기 구조식(Ⅳ)으로 표시되는 디브로모캠퍼의 탈브롬화 반응을 동시에 수행하였으며 환류를 마친 후 천천히 냉각시키면서 재결정을 시도하였다.According to the present invention, the camphor represented by Structural Formula (II) is added dropwise after stirring bromine under an organic solvent, and then the solvent is removed under reduced pressure, and a mixed solvent of water and ethanol and a base are added to reflux to produce a reaction product. Isomerization of the bromo camphor isomer represented by Structural Formula (III) and debromination of the dibromo camphor represented by Structural Formula (IV) were carried out at the same time, and recrystallization was attempted while cooling slowly after reflux.

본 발명에 사용된 바람직한 유기용매로는 에탄올(C2H5OH), 디콜로로에탄(CICH2CH2CI), 사염화탄산(CCI4), 프로판올(C3H7OH), 클로로포름(CHCI3), 메탄올(CH3OH), 디클로로메탄(CH2CI2), 엑산(C6H14), 사이클로헥산(C6H12) 또는 초산(CH3COOH)등이 있고, 에탄올, 사염화탄소, 디클로로에탄, 사이클로헥산 또는 초산 등이 좀 더 바람직하다. 본 발명에 사용된 바람직한 염기로는 수산화나트륨(NaOH), 수산화칼륨(KOH), 피리딘(C5H10N), 수산화리튬(LiOH),메톡시나트륨(NaOCH3), 에톡시나트륨(NaOC2H5) 또는 수산화칼슘(Ca(OH)2)등이 있으며, 수산화나트륨, 수산화칼륨, 수산화칼슘 또는 수산화리튬 등이 좀 더 바람직하다.Preferred organic solvents used in the present invention include ethanol (C 2 H 5 OH), dichloroloethane (CICH 2 CH 2 CI), carbon tetrachloride (CCI 4 ), propanol (C 3 H 7 OH), chloroform (CHCI 3 ), methanol (CH 3 OH), dichloromethane (CH 2 CI 2 ), exo acid (C 6 H 14 ), cyclohexane (C 6 H 12 ) or acetic acid (CH 3 COOH), and the like, and ethanol, carbon tetrachloride, Dichloroethane, cyclohexane or acetic acid and the like are more preferred. Preferred bases used in the present invention include sodium hydroxide (NaOH), potassium hydroxide (KOH), pyridine (C 5 H 10 N), lithium hydroxide (LiOH), methoxy sodium (NaOCH 3 ), ethoxy sodium (NaOC 2 H 5 ) or calcium hydroxide (Ca (OH) 2 ), and the like, and sodium hydroxide, potassium hydroxide, calcium hydroxide or lithium hydroxide is more preferable.

본 발명에서는 상기 유기용매를 상기 구조식(Ⅱ)로 표시되는 캠퍼 0.1몰당 0.5∼8.0ml를 사용하여 60∼110℃에서 브롬 0.09∼0.20몰을 적가시켜 교반하므로써 전체 브롬화 반응시간을 1∼8시간으로 하였고, 상기 반응을 마친 반응물을 감압증류시켜 상기 유기용매를 제거시키고 상기 염기 0.01∼0.10몰과 물과 알콜, 바람직하게 에탄올의 혼합용매(60∼95%에탄올)를 부가시켜 10∼120분 동안 환류시키므로써 반응 부산물인 상기 브로모캠퍼 이성질체의 이성질화 반응과 상기 구조식(Ⅳ)로 표시되는 디브로모캠퍼의 탈브로화 반응을 동시에 수행하였다. 이 반응을 통하여 상기 반응부산물들을 상기 구조식(Ⅰ)의 목적화합물로 90%이상 전환시키므로써 수율을 크게 향상시킬 수 있었다.In the present invention, by using the organic solvent 0.5 to 8.0 ml per 0.1 mole of the camphor represented by the formula (II) dropwise to 0.09 to 0.20 mol bromine at 60 to 110 ℃ dropwise, the entire bromination reaction time to 1 to 8 hours The reaction was completed by distillation under reduced pressure to remove the organic solvent, and the mixture was refluxed for 10 to 120 minutes by adding a mixed solvent (60 to 95% ethanol) of 0.01 to 0.10 mol of the base and water and alcohol, preferably ethanol. In this case, the isomerization of the bromocamper isomer as a reaction by-product and the debromination reaction of the dibromo camphor represented by the structural formula (IV) were simultaneously performed. Through this reaction, the yield was greatly improved by converting the reaction by-products to 90% or more of the target compound of Structural Formula (I).

따라서, 본 발명의 특징은 상기 구조식(Ⅱ)로 표시되는 캠퍼와 브롬을 유기용매하에서 반응시키므로써 종래에 공장에서 상기 구조식(Ⅰ)로 표시되는 3-브로모캠퍼를 대량생산시 문제되었던 교반의 문제점을 해결할 수 있었을 뿐만 아니라 수산화나트륨을 비롯한 염기를 이용하여 반응 부산물인 상기 브로모캠퍼 이성질체의 이성질화 반응과 상기 디브로모캠퍼의 탈브롬화 반응을 동시에 수행하므로써 이들을 대부분 목적화합물로 전환시켰다.Therefore, the characteristics of the present invention is that the reaction of the agitation that has been a problem during mass production of the 3-bromo camphor represented by the structural formula (I) in the factory by reacting the camphor and bromine represented by the structural formula (II) under an organic solvent. Not only could the problem be solved, but most of them were converted to the target compound by simultaneously performing isomerization of the bromocamper isomer and debromination of the dibromocamper as a reaction by-product using a base including sodium hydroxide.

본 발명에 사용된 염기의 사용량은 상기 캠퍼 0.1몰당 0.01∼0.10몰, 바람직하게는 0.03∼0.05몰 이하에서는 반응부산물의 이성질화 반응과 탈브롬화반응이 효과적으로 수행되지 못하였고 0.10몰 이상에서는 반응부산물이 목적화합물로 전환되나 목적화합물이 염기에 의해 분해되는 문제점이었다. 본 발명에서 사용한 유기용매량은 상기 캠퍼 0.1몰당 0.5∼8.0ml이며, 바람직하게는 1.0∼3.0ml이다. 0.5ml보다 적을 경우에는 교반이 원활하지 못했으며 8.0ml이상일 때에는 반응부산물이 많이 생성되는 단점이 있다. 이때 사용된 브롬은 캠피 0.1몰당 0.09∼0.20몰이며, 바람직하게는 0.11∼0.13몰이다. 0.09몰 이하에서는 반응하지 않은 캠퍼가 많이 존재하였고 0.20몰 이상에서는 반응부산물인 상기 구조식(Ⅲ)의 브로모캠퍼 이성질체와 상기 구조식(Ⅳ)의 디브로모캠퍼로의 반응진행이 증가하였다. 반응온도범위는 60∼100℃, 바람직하게는 80∼100℃인데, 60℃이하에서는 반응속도가 느려 반응시간을 6시간이상 수행하여도 원활한 목적화합물을 얻을 수 없었고 110℃이상에서는 생성물의 파괴로 인해 수율이 감소할 뿐만아니라 착색도가 심해져 백색의 결정을 얻을 수 없었다. 반응 후 재결정용매로는 60∼95% 에탄올이 사용되며, 바람직하게는 75∼85%의 에탄올이 사용되는데, 에탄올이 60%이하에서는 결정이 생성되지 않고 오일 형태로 존재하며 95%이상에서는 용해도의 증가에 의해 수율이 감소하는 경향이 있다.The amount of base used in the present invention is 0.01 to 0.10 moles per 0.1 mole of the camphor, preferably 0.03 to 0.05 moles or less, isomerization and debromination reaction of the reaction byproducts were not effectively performed, and the reaction byproducts were more than 0.10 moles. It was converted into the target compound, but the target compound was decomposed by the base. The amount of organic solvent used in the present invention is 0.5 to 8.0 ml per 0.1 mol of the camphor, preferably 1.0 to 3.0 ml. When less than 0.5ml, the stirring was not smooth, and when more than 8.0ml, there are disadvantages in that a lot of reaction by-products are generated. The bromine used at this time is 0.09 to 0.20 mol per 0.1 mol of campy, preferably 0.11 to 0.13 mol. At 0.09 mole or less, a large amount of unreacted camphor was present, and at 0.20 mole or more, the reaction progression of the bromo camphor isomer of Structural Formula (III) and the dibromo camphor of Structural Formula (IV) increased. The reaction temperature range is 60 to 100 ° C, preferably 80 to 100 ° C. Under 60 ° C, the reaction rate is slow, and even if the reaction time is performed for 6 hours or more, the target compound cannot be obtained smoothly. As a result, not only the yield was reduced, but also the color was too high to obtain white crystals. After the reaction, 60-95% ethanol is used as the recrystallization solvent. Preferably, 75-85% ethanol is used. When the ethanol is 60% or less, crystals do not form and exist in the form of oil. The yield tends to decrease with increasing.

따라서, 본 발명에서는 적절한 반응용매의 선정, 반응조건의 최적화 및 반응 후 처리공정을 획기적으로 개선시키므로써 종래방법의 수율 66%보다 크게 향상된 90%이상의 수율로 원하는 목적 화합물을 얻을 수 있었다.Therefore, in the present invention, by selecting the appropriate reaction solvent, optimizing the reaction conditions and significantly improving the post-reaction treatment process, the desired target compound can be obtained with a yield of 90% or more, which is significantly improved than the yield of 66% of the conventional method.

이하 실시예를 통해 본 발명의 제조방법 및 그 효과에 대해서 좀 더 구체적으로 설명하지만, 하기 예에 본 발명의 범주가 한정되는 것은 아니다.Hereinafter, the production method and effects of the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the following examples.

(실시예1)Example 1

캠퍼 15.2g(0.1몰)을 디클로로에탄 1.0ml에 녹인 후 105℃에서 브롬 9.2(0.11몰)을 3시간동안 적가하였다. 적가 종료후 2시간동안 교반하였으며 온도를 상온까지 내렸다. 반응용매인 디클로로에탄올 감압 증류하여 제거하고 80% 에탄올 5.0ml와 수산화나트륨 1.60g(0.04몰)을 부가하여 45분간 환류시켰다. 환류후 서서히 사온까지 냉각시키면서 재결정을 시도하였으며 결정화된 브로모캠퍼는 여과후 건조시켜 19.3g(수율 ; 83.5%)을 얻었다. 가스 크로마토그래피로 분석한 결과 순도는 99.5%였다.15.2 g (0.1 mol) of camphor was dissolved in 1.0 ml of dichloroethane, and then bromine 9.2 (0.11 mol) was added dropwise at 105 DEG C for 3 hours. After the addition was completed, the mixture was stirred for 2 hours and the temperature was lowered to room temperature. Dichloroethanol, a reaction solvent, was distilled off under reduced pressure, and 5.0 ml of 80% ethanol and 1.60 g (0.04 mol) of sodium hydroxide were added thereto, and the mixture was refluxed for 45 minutes. After reflux, recrystallization was attempted while gradually cooling to room temperature. The crystallized bromocamphor was filtered and dried to obtain 19.3 g (yield: 83.5%). Purity was 99.5% when analyzed by gas chromatography.

(실시예2)Example 2

캠퍼 15.2g(0.1몰)을 사염화탄소 3.0ml에 녹인 후 80℃에서 브롬 8.0g(0.1몰)을 1시간동안 적가하였다. 적가 종료 후 5시간동안 교반하였으며 온도를 상온까지 내렸다. 반응용매인 사염화탄소를 감압증류하여 제거하고 95% 에탄올 10.0ml와 수산화나트륨 0.80g(0.02몰)을 부가하여 120분간 환류시켰다. 환류 후 서서히 상온까지 냉각시키면서 재결정을 시도하였으며 결정화된 브로모캠퍼는 여과 후 건조시켜 19.8g(수율;85.8%)을 얻었다. 가스 크로마토그래피로 분석한 결과 순도는 99.0%였다.15.2 g (0.1 mol) of camphor was dissolved in 3.0 ml of carbon tetrachloride, and then 8.0 g (0.1 mol) of bromine was added dropwise at 80 ° C for 1 hour. After the dropwise addition was stirred for 5 hours and the temperature was lowered to room temperature. Carbon tetrachloride as a reaction solvent was removed by distillation under reduced pressure, and 10.0 ml of 95% ethanol and 0.80 g (0.02 mol) of sodium hydroxide were added to reflux for 120 minutes. After reflux, recrystallization was attempted while gradually cooling to room temperature. The crystallized bromocamphor was filtered and dried to obtain 19.8 g (yield: 88.5%). Purity was 99.0% when analyzed by gas chromatography.

(실시예3)Example 3

캠퍼 15.2g(0,1몰)을 시이클로헥산 2.0ml에 녹인 후 75℃에서 브롬 10.4g(0,14몰)을 3시간동안 적가하였다. 적가 종료후 4시간동안 교반하였으며 온도를 상온까지 내렸다. 반응용매인 사이클로헥산을 감압증류하여 제거하고 75% 에탄올 5.0ml와 수산화나트륨 2,40g(0.06몰)을 부가하여 10분간 환류시켰다. 환류후 서서히 상온까지 냉각시키면서 재결정을 시도하였으며 결정화된 브로모캠퍼는 여과 후 건조시켜 18.5g(수율; 80.1%)을 얻었다. 가스 크로마토그래피로 분석한 결과 순도는 99.7%였다.15.2 g (0,1 mole) of camphor was dissolved in 2.0 ml of cyclohexane, and 10.4 g (0,14 mole) of bromine was added dropwise at 75 ° C for 3 hours. After the addition was completed, the mixture was stirred for 4 hours and the temperature was lowered to room temperature. The reaction solvent cyclohexane was removed by distillation under reduced pressure, and 5.0 ml of 75% ethanol and 2,40 g (0.06 mol) of sodium hydroxide were added and refluxed for 10 minutes. After reflux, recrystallization was attempted while gradually cooling to room temperature. The crystallized bromocamphor was filtered and dried to obtain 18.5 g (yield; 80.1%). Purity was 99.7% when analyzed by gas chromatography.

(실시예4)Example 4

캠퍼 15.2g(0.1몰)을 초산 4.0ml에 녹인 후 110℃에서 브롬 9.2(0.12몰)을 4시간동안 적가하였다. 적가 종료 후 1시간동안 교반하였으며 온도를 상온까지 내렸다. 반응용매인 디클로로에탄올을 감압증류하여 제거하고 80% 에탄올 5.0ml와 수산화나트륨 1.60g(0.05몰)을 부가하여 30분간 환류시켰다. 환류 후 서서히 상온까지 냉각시키면서 재결정을 시도하였으며 결정화된 브로모캠퍼는 여과 후 건조하여 16.9g(수율; 73.2%)을 얻었다. 가스 크로마토그래피로 분석한 결과 순도는 98.0%였다.15.2 g (0.1 mole) of camphor was dissolved in 4.0 ml of acetic acid, and bromine 9.2 (0.12 mole) was added dropwise at 110 ° C for 4 hours. After the dropwise addition was stirred for 1 hour and the temperature was lowered to room temperature. Dichloroethanol, the reaction solvent, was removed by distillation under reduced pressure, and 5.0 ml of 80% ethanol and 1.60 g (0.05 mol) of sodium hydroxide were added to reflux for 30 minutes. After reflux, recrystallization was attempted while gradually cooling to room temperature. The crystallized bromocamphor was filtered and dried to obtain 16.9 g (yield; 73.2%). Purity was 98.0% when analyzed by gas chromatography.

(실시예 5∼18)(Examples 5-18)

실시예 1에서 브롬의 사용량, 유기용매의 종류, 반응온도, 염기의 종류, 염기 사용량, 재결정용매의 종류와 사용량 그리고 반응 후 환류 시간을 하기 표1에 기재된 조건으로 변경시키는 것을 제외하고는 동일하게 실시하였다. 그 결과 또한 하기 표 1에 기재하였다.Except for changing the amount of bromine, the type of organic solvent, the reaction temperature, the type of the base, the amount of the base, the amount and amount of the recrystallization solvent and the reflux time after the reaction to the conditions shown in Table 1 in Example 1 Was carried out. The results are also listed in Table 1 below.

[표 1]TABLE 1

Claims (13)

하기 구조식(Ⅰ)로 표시된 3-브로모캠퍼의 제조방법에 있어서, 하기 구조식(Ⅱ)로 표시되는 캠퍼와 브롬을 유기용매하에서 1∼8시간 반응시킨 후 감압증류시켜 상기 용매를 제거한 다음, 물과 알콜의 혼합용매 및 염기를 부가하여 환류시키고, 환류 종료 후 천천히 상온까지 냉각시켜 재결정시키는 것을 특징으로 하는 3-브로모캠퍼 제조방법.In the method for producing a 3-bromo camphor represented by the following structural formula (I), the camphor and bromine represented by the following structural formula (II) are reacted under an organic solvent for 1 to 8 hours, and then distilled under reduced pressure to remove the solvent, followed by water And a mixed solvent of a alcohol and a base to reflux, and after the reflux is completed, the mixture is slowly cooled to room temperature and recrystallized. 제1항에 있어서, 상기 유기용매가 에탄올(C2H5OH), 디클로로에탄(CIH2CH|2CI), 사염화탄산(CCI4), 프로판올(C3H7OH),클로로포름(CHCI3), 메탄올(CH|3OH), 디클로로메탄(CH2CI2), 헥산(C6H14) 클로헥산(C6H12) 또는 초산(CH3COOH)임을 특징으로 하는 3-브로모캠퍼의 제조방법.The method of claim 1, wherein the organic solvent is ethanol (C 2 H 5 OH), dichloroethane (CIH 2 CH | 2 CI), carbon tetrachloride (CCI 4 ), propanol (C 3 H 7 OH), chloroform (CHCI 3 ), Methanol (CH | 3 OH), dichloromethane (CH 2 CI 2 ), hexane (C 6 H 14 ) clohexane (C 6 H 12 ) or acetic acid (CH 3 COOH) Manufacturing method. 제2항에 있어서, 상기 유기용매가 에탄올, 사염화탄소, 디클로로에탄, 사이클로헥산 또는 초산임을 특징으로 하는 3-브로모캠퍼의 제조방법.The method of claim 2, wherein the organic solvent is ethanol, carbon tetrachloride, dichloroethane, cyclohexane or acetic acid. 제1항에 또는 제2항에 있어서, 상기 유기용매의 사용량이 캠퍼 0.1몰당 0.5∼8.0ml임을 특징으로 하는 3-브로모캠퍼의 제조방법.The method of claim 1 or 2, wherein the amount of the organic solvent is 0.5 to 8.0 ml per 0.1 mole of the camphor. 제4항에 있어서, 상기 유기용매의 사용량이 캠퍼 0.1 몰당 1.0∼3.0ml임을 특징으로 하는 3-브로모캠퍼의 제조방법.The method of claim 4, wherein the organic solvent is used in an amount of 1.0 to 3.0 ml per 0.1 mole of camphor. 제1항에 있어서, 상기 염기가 수산화나트륨(NaOH), 수산화칼륨(KOH), 피리딘(C5H10N), 수산화리튬(LiOH), 메톡시나트륨(NaOCH3), 에톡시나트륨(NaOC2H5) 또는 수산화칼슘(Ca(OH)2)임을 특징으로 하는 3-브로모캠퍼의 제조방법.The method of claim 1, wherein the base is sodium hydroxide (NaOH), potassium hydroxide (KOH), pyridine (C 5 H 10 N), lithium hydroxide (LiOH), methoxy sodium (NaOCH 3 ), ethoxy sodium (NaOC 2 H 5 ) or calcium hydroxide (Ca (OH) 2 ) method for producing a 3-bromo camphor. 제6항에 있어서, 상기 염기가 수산화나트륨, 수산화칼륨, 수산화칼슘 또는 수산화리튬임을 특징으로 하는 3-브로모캠퍼의 제조방법.The method of claim 6, wherein the base is sodium hydroxide, potassium hydroxide, calcium hydroxide or lithium hydroxide. 제1항에 또는 제6항에 있어서, 상기 염기의 사용량이 캠퍼 0.1몰당 0.01∼0.10몰임을 특징으로 하는 3-브로모캠퍼의 제조방법.The method of claim 1 or 6, wherein the base is used in an amount of 0.01 to 0.10 moles per 0.1 mole of camphor. 제8항에 있어서, 상기 염가의 사용량이 캠퍼 0,1몰당 0.03∼0,05몰임을 특징으로 하는 3-브로모캠퍼의 제조방법.The method of claim 8, wherein the use amount of the cheap is 0.03 to 0,05 mol per 0,1 mol of the camphor. 제1항에 있어서, 상기 브롬의 사용량이 캠퍼 0.1몰당 0.09∼0.20몰임을 특징으로 하는 3-브로모캠퍼의 제조방법.The method of claim 1, wherein the bromine is used in an amount of 0.09 to 0.20 moles per 0.1 mole of the camphor. 제10항에 있어서, 상기 브롬의 사용량이 캠퍼 0.1몰당 0.10∼0.13몰임을 특징으로 하는 3-브로모캠퍼의 제조방법.The method of claim 10, wherein the bromine is used in an amount of 0.10 to 0.13 moles per 0.1 mole of the camphor. 제1항에 있어서, 상기 반응온도가 60∼110℃임을 특징으로 하는 3-브로모캠퍼의 제조방법.The method of claim 1, wherein the reaction temperature is 60 ~ 110 ℃. 제12항에 있어서, 상기 혼합용매가 60∼95%에탄올임을 특징으로 하는 3-브로모캠퍼의 제조방법.The method of claim 12, wherein the mixed solvent is 60 to 95% ethanol.
KR1019940021919A 1994-08-31 1994-08-31 Process for preparation of 3-brumocamphor KR0129115B1 (en)

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