KR0143017B1 - Precess for 2-chlow-1, 4-dialkoxy benzene - Google Patents
Precess for 2-chlow-1, 4-dialkoxy benzeneInfo
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- KR0143017B1 KR0143017B1 KR1019940020112A KR19940020112A KR0143017B1 KR 0143017 B1 KR0143017 B1 KR 0143017B1 KR 1019940020112 A KR1019940020112 A KR 1019940020112A KR 19940020112 A KR19940020112 A KR 19940020112A KR 0143017 B1 KR0143017 B1 KR 0143017B1
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- dimethoxybenzene
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- chloro
- chlorination
- reaction temperature
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
본 발명은 1,4-디알콕시벤젠 또는 하이드로퀴논을 유기용매를 사용함이 없이염소화제인 술푸릴 클로라이드(SO2Cl2)를 사용하여 염소화하여 해당 염소화된 2-클로로-1,4-디알콕시벤젠 또는 2-클로로하이드로퀴논을 선택적으로 합성하거나 또는 물 존재하에서 염소화제인 술푸릴 클로라이드(S02Cl2)를 사용하여 염소화하여 해당 염소화된 2-클로로-1,4-디알콕시벤젠 또는 2-클로로하이드로퀴논을 선택적으로 합성하는 제조방법에 관한 것이다.The present invention provides chlorinated 2-chloro-1,4-dialkoxy by chlorination of 1,4-dialkoxybenzene or hydroquinone using sulfuryl chloride (SO 2 Cl 2 ), a chlorinating agent, without the use of an organic solvent. Selective synthesis of benzene or 2-chlorohydroquinone or chlorination with the chlorinating agent sulfuryl chloride (S02Cl2) in the presence of water to give the corresponding chlorinated 2-chloro-1,4-dialkoxybenzene or 2-chlorohydroquinone It relates to a production method for selectively synthesizing a.
Description
[발명의명칭][Name of invention]
2-클로로-1,4-디 알콕시 벤젠의 제조방법Method for preparing 2-chloro-1,4-dialkoxy benzene
[발명의 상세판 설명][Detailed edition of the invention]
본 발명은 1,4-디알콕시벤젠 또는 하이드로퀴논을 유기용매를 사용함이 없이 염소화제인 술푸릴 클로라이드(SO2C12)를 사용하여 염소화하여 해당 염소화된 2-클로로-1,4-디알콕시벤젠 또는 2-클로로하이드로퀴논을 선택적으로 합성하거나 또는 물 존재하에서 염소화제인 술푸릴 클로라이드(SO2Cl2)를 사용하여 염소화하여 해당 염소화된 2-클로로-1,4-디알콕시벤젠 또는 2-클로로하이드로퀴논을 선택적으로 합성하는 제조방법에 관한 것이다.The present invention provides chlorinated 2-chloro-1,4-dialkoxy by chlorination of 1,4-dialkoxybenzene or hydroquinone using sulfuryl chloride (SO 2 C1 2 ), a chlorinating agent, without the use of an organic solvent. Selective synthesis of benzene or 2-chlorohydroquinone or chlorination with the chlorinating agent sulfuryl chloride (SO 2 Cl 2 ) in the presence of water to give the corresponding chlorinated 2-chloro-1,4-dialkoxybenzene or 2- It relates to a process for the selective synthesis of chlorohydroquinone.
본 화학물질은 염료 및 안료, 살충제, 제약의 중간체 및 중합반응체의 단량체 등 여러 가지 용도로서 다양하게 쓰인다.The chemical is used in a variety of applications, including dyes and pigments, pesticides, pharmaceutical intermediates and monomers of polymerization reactants.
본 화학물질은 1933년에 처음 합성되었고(미국 특허 1,919,580), 이 방법에서는 1-아미노-2,5-디메톡시벤젠을 디아조화시켜 이를 CuCl을 이용한 잔트마이어 반응(Sandmeyer reaction)에 의하여 아민기를 염소기로 치환하여 제조하였다.This chemical was first synthesized in 1933 (US Pat. No. 1,919,580), which diazotizes 1-amino-2,5-dimethoxybenzene and uses the CuCl Sandmeyer reaction to produce amine groups. It was prepared by substituting with a group.
그 후 본 화학물질을 만들기 위해서 p-벤조퀴논 테트라메틸 디케탈즈에서 만드는 방법[1976년 독일특허 제 2,522,854호, 1978년 미국특허 제 4,066,708호3, 1,4-디메톡시벤젠(DMB)에서 HCI를 이용하여 전기분해에 의해 합성하는 방법[198l년 일본특허 소56-133480호 2-클로로하이드로 퀴논에서 디메틸설페이드를 사용하여 메틸화시키는 방법이 시도되었다. 현재 가장 많이 쓰는 합성방법은 p-벤조퀴논 레트라메틸 디케탈즈에 의한 합성법이나, 반응물을 구하거나 합성하는 것이 용이하지 않고, 합성반응시에 수율이 높지 않다.HCI was then prepared in p-benzoquinone tetramethyl diketals to make this chemical [Germany Patent No. 2,522,854 in 1976, US Patent No. 4,066,708 3 in 1978, 1,4-dimethoxybenzene (DMB). Method of synthesizing by electrolysis using a method of methylation using dimethyl sulfide in Japanese Patent No. 56-133480 2-chlorohydro quinone in 198l was attempted. Currently, the most widely used synthetic method is a synthesis method using p-benzoquinone retramethyl diketals, it is not easy to obtain or synthesize a reactant, and the yield is not high during the synthesis reaction.
표 1은 각 문헌에 발표된 실험 결과로서 다음과 같다.Table 1 shows the results of the experiments published in each document.
1. Tetrahedron Letters, 24, 30, 3117∼3120, 1983Tetrahedron Letters, 24, 30, 3117-3120, 1983
2. J. Chem. Soc. Perkin Trans. Ⅱ, 385, 19882. J. Chem. Soc. Perkin Trans. Ⅱ, 385, 1988
3. Chem. Soc. of Jpn, Chemistry Letters, 415, 19893. Chem. Soc. of Jpn, Chemistry Letters, 415, 1989
이상에서 보듯이 특별한 염소화제를 사용한 경우도 수율 및 순도을 놀게 얻기 힘듬을 알 수 있다.As can be seen from the above, even when a special chlorinating agent is used, it is difficult to obtain yield and purity.
특히 표 I에서 나타난 결과를 보면 염소화제(chlorinatin agent:예 ; BTMA ICl4, NCP 또는 NCTA)에 관계없이 수율이 떨어지는 현상을 볼 수 있다.In particular, the results shown in Table I show a drop in yield regardless of the chlorinating agent (eg BTMA ICl4, NCP or NCTA).
또한 일반적으로 염소화 반응에 염소 가스를 주로 사용하고 있으나 이는 방향족에테르의 염소화제펄는 부적당하였다.In general, chlorine gas is mainly used for the chlorination reaction, but the chlorinating agent pearl of the aromatic ether is inadequate.
염소를 이용하여 디메톡시벤젠을 염소화하떤 과잉의 반응이 진행되어 2, 5-디클로로-1,4-디메톡시벤젠, 2, 3-디클로로-1,4-디메톡시 벤젠, 그리고 2, 6-디클로로-1,4-디메톡시벤젠(이하, 상기 디클로로 화합물을 디클로로 1,4-디메톡시벤젠이라 총칭한다)이 형성되며 반응물 등이 분해되어 2-클로로-1,4-디메톡시벤젠을 얻기 힘들다.Any excess reaction of chlorination of dimethoxybenzene with chlorine proceeds, resulting in 2, 5-dichloro-1,4-dimethoxybenzene, 2, 3-dichloro-1,4-dimethoxy benzene, and 2, 6-dichloro -1,4-dimethoxybenzene (hereinafter, referred to collectively as dichloro 1,4-dimethoxybenzene) is formed and the reactants and the like are decomposed to obtain 2-chloro-1,4-dimethoxybenzene.
본 발명에서는 유기용매 사용없이 염소화제로 SO2Cl2를 이용하였는데, 본 발명에서 염소화제로서 상기 선행기술에서 사용한 Cl2가스 대신 SO2Cl2를 사용하여 수행한 결과 반웅성이 아주 우수하였으며 선택성도 좋게 나타난다.In the present invention, SO 2 Cl 2 was used as a chlorinating agent without using an organic solvent. In the present invention, as a chlorinating agent, SO 2 Cl 2 was used instead of the Cl 2 gas used in the prior art. Appears good.
여기서, 본 발명에서 사용되는 염소화제는 SO2Cl2만을 한정하는 것은 아니며, 이와 치환, 대체 할 수 있는 동일,유사한 균등물에 해당되는 염소화제는 모두 본 발명의 기술사상의 범주에 포함되는 것이다.Here, the chlorinating agent used in the present invention is not limited to SO 2 Cl 2 only, and all chlorinating agents corresponding to the same or similar equivalents that can be substituted and substituted therein are all included in the scope of the technical idea of the present invention. .
이와 같은 본 발명은 기존의 염소화 반응의 단점을 보완하여 수율, 순도 및 제조비용 절감 등의 위 선행기술에서 발생되었던 제반 문제점들을 해결함으로써 염소화의 공업화에 기여하고자 하는데 그 목적이 있다.The present invention is intended to contribute to the industrialization of chlorination by solving the problems of the prior art such as reducing the yield, purity and manufacturing cost by supplementing the disadvantages of the existing chlorination reaction.
본 발명의 반응식은 다음과 같으며,The reaction scheme of the present invention is as follows.
여기서 R은 -H,-CH3,-C2H5등이며, 이와 치환, 대체 할 수 있는 동일·유사한 균등물에 해당되는 화합물도 모두 본 발명의 기술사상의 범주에 포함되는 것이다.Here, R is -H, -CH 3 , -C 2 H 5 and the like, and all compounds corresponding to the same and similar equivalents that can be substituted and replaced with them are also included in the scope of the technical idea of the present invention.
선행 문헌을 조사한 바에 의하면 1984년 Irwin과 Del[미국 특허 제 4,439,596호 1984년]에 의해 하이드로퀴논의 염소화반응으로서 빙초산 용매하에SO2Cl2를 이용하는 방법이 제시되어 있으나, 본 발명은 이와는 반응물(출발물질)이 다르며, 특히 본 발명에서는 유기용매를 사용하지 않고 반응을 완결하는데 그 특징이 있다. 생성물의 조성 중 2-클로로-하이드로퀴논의 순도는 약 80%였다.According to a review of the literature, Irwin and Del (US Pat. No. 4,439,596, 1984) proposed a method of using SO 2 Cl 2 in a glacial acetic acid solvent by chlorination of hydroquinone in 1984. Materials) are different, and in particular, the present invention is characterized in completing the reaction without using an organic solvent. The purity of the 2-chloro-hydroquinone in the composition of the product was about 80%.
본 발명의 합성방법으로 DMB(1,4-디메톡시벤젠)을 반응기에 넣고 60℃로 온도를 올리면서 반응물(출발물질)을 온전히 녹인다음, SO2Cl2를 천천히 적가하면서 반응을 진행시키는 한편, 반응중에 GC(가스 크로마토그래피)를 이용하여 반응율 및 선택도를 분석한다.In the synthesis method of the present invention, DMB (1,4-dimethoxybenzene) was put in a reactor, and the reaction product (starting material) was dissolved completely while raising the temperature to 60 ° C., and the reaction was carried out while slowly dropwise adding SO 2 Cl 2 . During the reaction, the reaction rate and selectivity are analyzed using gas chromatography (GC).
반응이 진행되면 반응 온도를 천천히 낮추어 과반응의 진행을 억제한다.As the reaction proceeds, the reaction temperature is lowered slowly to suppress the progress of the reaction.
반응은 일반적인 연속 반응의 형태를 가지며, 2-클로로-1,4-디메톡시벤젠의 전환율이 80%이상 이루어지면 보통 부생성물인 디클로로-1,4-디메톡시벤젠이 8-10%정도의 농도로 생성된다. 이후 SO2Cl2계속 적가할 경우 반응물은 2-클로로-1,4-디메톡시벤젠보다 부생성물인 디클로로-1,4-디메톡시벤젠으로 반응이 급격히 더 진행된다. 즉 반응물질인 1,4-디메톡시벤젠이 남지 않을때까지 SO2Cl2를 적가할 경우 부생성물인 디클로로-1,4-디메톡시벤젠의 농도는 20-25%정도로 계속 증가하는 결과를 보였다.The reaction takes the form of a general continuous reaction. When the conversion rate of 2-chloro-1,4-dimethoxybenzene is more than 80%, the concentration of the byproduct dichloro-1,4-dimethoxybenzene is about 8-10%. Is generated. If SO 2 Cl 2 is continuously added dropwise, the reaction proceeds more rapidly with dichloro-1,4-dimethoxybenzene as a by-product than 2-chloro-1,4-dimethoxybenzene. In other words, when SO 2 Cl 2 was added dropwise until no reactant 1,4-dimethoxybenzene was left, the concentration of byproduct dichloro-1,4-dimethoxybenzene was increased to about 20-25%. .
본 실험의 결과 반응이 끝난 생성물의 색상은 맑은 색을 띠고 있으며, 실온으로 서서히 냉각하거나 방치시 디클로로-1,4-디메톡시벤젠의 백색 결정이 생벙되어 침전된다.As a result of this experiment, the color of the reaction product is clear, and white crystals of dichloro-1,4-dimethoxybenzene are precipitated when slowly cooled or left at room temperature.
또한 용매로 각각 CH3OH, DCE(1,2-Dichloroethane), CH3CN을 사용하여 염소화반응을 진행시킨 결과, 유기용매를 사용하지 않은 상기의 염소화반응 결과와 비슷한 반응성을 보였으나, 선택성에 있어서는 떨어지며, 상기 용매중 MeOH을 사용한 경우, SO2Cl2가 MeOH과 극렬한 반응성을 갖음으로써 오히려 용매로서 좋지 못한 결과를 가져 왔다.In addition, as a solvent, CH 3 OH, DCE (1,2-Dichloroethane), and CH 3 CN were used for the chlorination reaction, and showed similar reactivity with the above chlorination reaction without using an organic solvent. In the case of using MeOH in the solvent, SO 2 Cl 2 has an extreme reactivity with MeOH, which is rather poor as a solvent.
유기용매를 사용하지 않는 본 발명에서의 반응의 특징은 초기에 반응물을 녹이기 위하여 반응온도를 약 65℃로 올린 후 SO2Cl2을 적가하고 반응이 약15%정도 이루어지면 반응온도를 천천히 낮추면서 약 40℃로 유지하며 계속반응을 시키는 방법과 일정한 반응온도에서 계속 반응을 진행시키는 두가지 공정이 있으나, 바람직하게는 합성시 작업 조건의 간단화를 위해 일정 온도에서 합성하는 것이 좋다.The characteristics of the reaction in the present invention that does not use an organic solvent is to raise the reaction temperature to about 65 ℃ initially to dissolve the reactants, and then dropwise SO 2 Cl 2 and slowly lowering the reaction temperature when the reaction is about 15% There are two processes to keep the reaction at about 40 ℃ and continue the reaction at a constant reaction temperature, but preferably synthesized at a constant temperature in order to simplify the working conditions in the synthesis.
이러한 염소화반응에서의 반응온도(45-65C)에 따른 선택성은 큰 차이를 보이지 않았으나 보다 고온에서 반응시 약간 과반응 생성물이 증가됨을 알 수 있었다.The selectivity according to the reaction temperature (45-65C) in this chlorination reaction did not show a big difference, but it was found that the reaction products slightly increased at higher temperatures.
반응시간은 4시간에서 9시간정도로 반응시간에 따른 선택성은 크게 차이가 나지 않는 결과를 얻었다.The reaction time was about 4 hours to 9 hours, the selectivity according to the reaction time did not differ significantly.
1,4-디메톡시벤젠외에 하이드로퀴논이나 1,4-디에톡시벤젠의 SO2Cl2를 사용한 염소화반응도 상기의 1,4-디메톡시벤젠의 경우와 유사하다.The chlorination reaction using SO 2 Cl 2 of hydroquinone or 1,4-diethoxybenzene in addition to 1,4-dimethoxybenzene is similar to that of 1,4-dimethoxybenzene.
이와같은 SO2Cl2를 사용한 본 합성방법을 타특허 문헌과 비교하여 볼 때 본 발명은 유기용매 사용과 무관하게 수율과 선택성, 반응성이 우수하며 반응이 일정하게 일어나는 결과로 인하여 유기용매를 사용하지 않아도 되므로 인해 원가가 절감되고, 작업 조건이 용하하는 등 큰 잇점이 있다.When comparing this synthesis method using SO 2 Cl 2 with other patent literatures, the present invention is excellent in yield, selectivity, and reactivity regardless of the use of organic solvents. There is a big advantage, such as cost savings and lower working conditions.
즉 본 발명은 기존 기술과 다르게 유기용매를 사용하지 않고도 수율과 선택성이 높아 반응전후 정제를 위하여 다량의 에너지와 유기용매를 사용하지 않으므로써 유기용매 회수에 대한 문제가 없고, 폐수의 생성을 줄일 수 있으며 또한 이를 처리하기 위한 경비를 대폭 절감 할 수 있고, 환경공해가 발생되지 않는 등의 유리한 점이 있다.That is, the present invention has a high yield and selectivity without using an organic solvent, unlike the existing technology, and thus, there is no problem of recovering the organic solvent by using a large amount of energy and an organic solvent for purification before and after the reaction, and it is possible to reduce the generation of waste water. In addition, there is an advantage that can greatly reduce the costs for handling this, and does not cause environmental pollution.
이상에서 합성된 반응 생성물은 분별진공증류 또는 결정화 등의 일반적인 정제 방법에 의하여 고순도의 제품으로 얻어질 수 있다.The reaction product synthesized above may be obtained as a high purity product by a general purification method such as fractional vacuum distillation or crystallization.
이렇게 얻어진 제품은 염료, 살충제 제약의 중간체 및 중합반응체의 단량체로 쓰이며, 특히 더 나아가서는 니트로화 반응 및 수소화 반응클 거침으로써 4-클로로-2,5-디메톡시아닐린을 합성할 수 있다.The products thus obtained are used as monomers for dyes, pesticide pharmaceutical intermediates and polymerization reactants, and in particular, 4-chloro-2,5-dimethoxyaniline can be synthesized by nitration and hydrogenation.
이하 본 발명 실시예를 통해서 구체적으로 설명한다.Hereinafter, the present invention will be described in detail.
[실시예 1]Example 1
1,4-디메톡시벤젠 1.0 mole(138 g)을 반응기에 투입하고 온도를 올려 약55℃에서 완전히 용융시킨후 SO2Cl21.3 mole(175.5g)을 천천히 적가하면서 시간마다 GC분석 하였다.1.0 mole (138 g) of 1,4-dimethoxybenzene was added to the reactor, the temperature was raised, and completely melted at about 55 ° C., and 1.3 g of SO 2 Cl 2 (175.5 g) was slowly added dropwise to analyze GC every hour.
반응결과 2-클로로-1,4-디메톡시벤젠이 약 15%정도되면 온도를 천천히 낮추면서 약 40℃로 유지하였다. 반응시간은 8시간으로 반응을 완료했다.When the reaction resulted in about 15% of 2-chloro-1,4-dimethoxybenzene, the temperature was maintained at about 40 ° C. while slowly decreasing the temperature. The reaction time was 8 hours to complete the reaction.
반응 종료 후 반응 생성물의 GC분석 결과는 1,4-디메톡시벤젠이 0.6%, 2-클로로-],4-디메톡시벤젠이 78%, 디클로로-1,4-디메톡시벤젠이 23%로 나타났다.GC analysis of the reaction product after the reaction showed 0.6% of 1,4-dimethoxybenzene, 78% of 2-chloro-], 4-dimethoxybenzene and 23% of dichloro-1,4-dimethoxybenzene. .
2-클로로-1,4-디메톡시벤젠의 조성은 약 84%가 형성된 후 이를 정점으로 반응이 더 진행됨에 따라 감소되었다. 이는 반응물의 감소보다 과반응물인 디클로로화합물이 증가함을 의미한다.The composition of 2-chloro-1,4-dimethoxybenzene decreased as about 84% formed and then the reaction proceeded to its peak. This means that dichloro compounds, which are overreactants, increase rather than decreases in reactants.
이 반응물을 실온에서 방치 냉각시켜 과반응 생성물인 디클로로-1,4-디메톡시벤젠의 결정을 여과하고 여액의 조성을 분석한 결과 2-클로로-1,4-디메톡시벤젠이 90%, 디클로로-1,4-디메톡시벤젠이 7%로 나타났으며 결정의 조성중에 2-끌로로-1,4-디메톡시벤젠이 52%,디클로로-1,4-디메톡시벤젠이 45%로 나타났다.The reactant was left to cool at room temperature, and the crystals of dichloro-1,4-dimethoxybenzene, a product of overreaction, were filtered and the composition of the filtrate was analyzed. As a result, 90% of 2-chloro-1,4-dimethoxybenzene was obtained and dichloro-1. , 4-Dimethoxybenzene was found to be 7%, 2-chloro-1,4-dimethoxybenzene was 52%, and dichloro-1,4-dimethoxybenzene was 45% in the composition of the crystal.
이상과 같은 GC분석결봐를 표로 정리하면 다음 표 2와 같다The above GC analysis results are summarized in the table below.
[실시예 2]Example 2
1,4-디메톡시벤젠 1.0 mole(138g)과 SO2Cl21.3 mole(175.5g)을 45, 55, 65℃로 분류하여 각각 동일 온도에서 실시예 1과 동일 방법으로 실시하였다.1.0 mole (138 g) of 1,4-dimethoxybenzene and 1.3 mole (175.5 g) of SO 2 Cl 2 were classified into 45, 55, and 65 ° C., respectively, and were carried out in the same manner as in Example 1 at the same temperature.
반응완료 후 맑은 적색의 오일(클로로디메톡시벤젠)과 횐 결정(디클로로디메톡시벤젠)을 얻었다.After completion of the reaction, a clear red oil (chlorodimethoxybenzene) and crystallites (dichlorodimethoxybenzene) were obtained.
이때 GC의 결과는 다음 표 3과 같다.The results of the GC are shown in Table 3 below.
실시예 2의 결과와 같이 약 65℃에서의 염소화 반응은 과반응 생성물인 DCDMB가 크게 늘어났음을 알 수 있다.As in the result of Example 2, it can be seen that the chlorination reaction at about 65 ° C. significantly increased the DCDMB as a reaction product.
[실시예 3]Example 3
원료인 1,4-디메톡시벤젠 1 mole(138g)을 약 55℃에서 완전히 용해한 후 CH3OH80ml와 SO2Cl21.2 mole(162g)을 6시간에 걸쳐 동시에 적가하였다.After dissolving 1 mole (138 g) of 1,4-dimethoxybenzene as a raw material at about 55 ° C., 80 ml of CH 3 OH and 1.2 mole (162 g) of SO 2 Cl 2 were simultaneously added dropwise at 6 hours.
반응중 결정이 생성되지 않게 온도를 유지하였다 이때의 온도는 약 28℃였다.The temperature was maintained so that no crystals formed during the reaction. The temperature was about 28 ° C.
적사 완료후 GC분석결과는 1,4-디메톡시벤젠이 4%, 2-클로로-1,4-디메톡시벤젠이 79.5%, 디를로로-1,4-디메톡시벤젠이 15.2%로 구성되었다.After completion of the redox, GC analysis showed 4% of 1,4-dimethoxybenzene, 79.5% of 2-chloro-1,4-dimethoxybenzene, and 15.2% of dilo-1,4-dimethoxybenzene. It became.
[실시예 4]Example 4
1,4-디메톡시벤젠 1 mole(138g)을 H2O 200ml존재하에 반응기 온도를 약 55℃로 올렸다. 반응물이 완전히 용응된 후 SO2C121.4 mole(162g)을 40∼55℃로 유지하면서 7시간에 걸쳐 적가하였다. 적가 완료후 GC분석결과는 1,4-디메톡시벤젠이 3.9%, 2-클로로-1,4-디메톡시벤젠이 77.9%, 디클로로-1,4-디메록시벤젠이 16.4%이었다.1 mole (138 g) of 1,4-dimethoxybenzene was raised to about 55 ° C. in the presence of 200 ml of H 2 O. After the reaction completely dissolved, 1.4 mole (162 g) of SO 2 C1 2 was added dropwise over 7 hours while maintaining the temperature at 40-55 ° C. After completion of the addition, GC analysis showed that 1,4-dimethoxybenzene was 3.9%, 2-chloro-1,4-dimethoxybenzene was 77.9%, and dichloro-1,4-dimethoxybenzene was 16.4%.
[비교예 1]Comparative Example 1
1,4-디메톡시벤젠 1 mole(138g)을 DCE 100ml에 완전히 용해후 SO2Cl21.2After dissolving 1 mole of 1,4-dimethoxybenzene (138 g) in 100 ml of DCE, SO 2 Cl 2 1.2
mo1e (l62g)을 25∼30℃로 유지하면서 7시간에 걸쳐 적가하였다.mo1e (l62g) was added dropwise over 7 hours while maintaining at 25-30 占 폚.
적가 완료후 GC분석결과는 1,4-디메톡시벤젠이 0.8%, 2-클로로-1,4-디메톡시벤젠이 68.2%,디클로로-1,4-디메톡시벤젠이 28.6%이었다.After completion of the addition, GC analysis showed 0.8% of 1,4-dimethoxybenzene, 68.2% of 2-chloro-1,4-dimethoxybenzene, and 28.6% of dichloro-1,4-dimethoxybenzene.
[비교예 2]Comparative Example 2
1,4-디메톡시벤젠 1 mole(138g)을 CH3OH 200ml에 완전히 용해후 SO2Cl21.2mole(l62g)을 30∼35℃로 유지하면서 7시간에 걸쳐 적가하였다.One mole (138 g) of 1,4-dimethoxybenzene was completely dissolved in 200 ml of CH 3 OH, and then 1.2 mole (l 62 g) of SO 2 Cl 2 was added dropwise over 7 hours while maintaining the temperature at 30 to 35 ° C.
적가 완료후 GC분석결과는 1,4-디메톡시벤젠이 1.25%, 2-츨로로-1,4-디메톡시벤젠이 74%, 디클로로-1,4-디메톡시벤젠이 21%이었다.After completion of the dropwise addition, GC analysis showed 1.25% for 1,4-dimethoxybenzene, 74% for 2-chloro-1,4-dimethoxybenzene, and 21% for dichloro-1,4-dimethoxybenzene.
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