KR910001998B1 - Process for the preparation of 2-(2-naphthyloxy) proponic acid derivation - Google Patents
Process for the preparation of 2-(2-naphthyloxy) proponic acid derivation Download PDFInfo
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- KR910001998B1 KR910001998B1 KR1019880006086A KR880006086A KR910001998B1 KR 910001998 B1 KR910001998 B1 KR 910001998B1 KR 1019880006086 A KR1019880006086 A KR 1019880006086A KR 880006086 A KR880006086 A KR 880006086A KR 910001998 B1 KR910001998 B1 KR 910001998B1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
- C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
- C07C59/66—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings
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Abstract
Description
본 발명은 하기 일반식 (Ⅰ)의 2-(2-나프틸옥시)프로피온산 유도체의 제조방법에 관한 것이다.The present invention relates to a process for the preparation of 2- (2-naphthyloxy) propionic acid derivatives of the general formula (I).
상기식 중, R은 수소 또는 메틸기이며, n은 0~2까지의 정수이다.In said formula, R is hydrogen or a methyl group, n is an integer of 0-2.
본 발명에 따른 상기 일반식 (Ⅰ)의 화합물은 다음 일반식 (Ⅱ)의 2-(2-나프틸옥시)프로피온아닐라이드 유도체 합성의, 중간체로서 유용하다.The compounds of the general formula (I) according to the present invention are useful as intermediates for the synthesis of 2- (2-naphthyloxy) propionanilide derivatives of the following general formula (II).
상기식 중, R 및 n은 전술한 바와 같다.In the above formula, R and n are as described above.
일본공개공보 제 74-35, 533호에는 일반식(Ⅱ)로 나타나는 화합물 중 R이 메틸기이고, n이 0일 때, 일발처리로써 수전(水田) 잡초에 대한 광범위한 살균력과 다년생 잡초까지의 제초효과를 갖는 우수한 수전용 제초제로 사용될 수 있다고 기재되어 있다.Japanese Patent Application Laid-Open No. 74-35, 533 discloses a broad range of bactericidal activity against hydrangea weeds and herbicidal effects to perennial weeds in a single treatment when R is a methyl group and n is 0 among the compounds represented by general formula (II). It is described that it can be used as an excellent herbicide having a hydrogel.
상기 일반식 (Ⅰ)의 화합물은 일본공개공보 제 74-35, 533호 미합중국 특허 제 3, 740, 437호 및 체코슬로바키아 특허 제 229, 091호에 그의 제조방법이 개시되어 있는데 이들 방법에서는 통상적으로 2-나프톨과 하기 일반식(Ⅲ)의 할로카르본산의 금속염을 물속에서 반응시킴으로서 일반식 (Ⅰ) 화합물을 제조하는 것으로 되어 있다.Compounds of the general formula (I) are disclosed in Japanese Patent Application Laid-Open Nos. 74-35, 533, U.S. Patent Nos. 3, 740, 437 and Czechoslovak Patent Nos. 229, 091. A compound of the general formula (I) is prepared by reacting 2-naphthol with a metal salt of halocarboxylic acid of the general formula (III) below in water.
상기식 중, R 및 n는 전술한 바와 같으며 X는 염소 또는 브롬을 나타내며, Y는 나트륨 또는 칼륨을 나타낸다.Wherein R and n are as described above, X represents chlorine or bromine and Y represents sodium or potassium.
전술한 종래의 방법으로 상기 일반식(Ⅰ)의 화합물을 제조하는 경우, 반응시간이 24시간 이상으로 길며 pH를 8로 적절하게 조절하여야 하고 특히 부생성물이 과량 생성되어 수율이 떨어지므로 (83% 정도) 공업적인 제조방법으로는 부적당하다.When preparing the compound of the general formula (I) by the above-described conventional method, the reaction time is longer than 24 hours, the pH should be properly adjusted to 8, especially because the by-products are excessively produced, yield is reduced (83% Degree) It is not suitable as an industrial manufacturing method.
본 발명자들은 상기의 문제점들을 해결하기 위하여 연구를 거듭해 온 결과, 용매로서 물 대신 유기 용매를 사용하고 일반식 (Ⅲ)의 할로카르본산의 금속염 대신에 산과 알칼리금속염기를 혼합 사용하므로써 종래의 문제점을 완전히 해결하고 일반식 (Ⅰ)의 화합물을 용이하게 제조할 수 있음을 발견하고 본 발명을 완성하였다.The present inventors have been studied to solve the above problems, and as a result, by using an organic solvent instead of water as a solvent and using an acid and an alkali metal base instead of the metal salt of halocarboxylic acid of the general formula (III), the conventional problem is solved. The present invention has been completed by finding that it is possible to solve completely and to easily prepare a compound of general formula (I).
본 발명의 목적은 하기 일반식 (Ⅳ)의 할로카르본산을 유기용매 및 알칼리금속염기 존재하에서 2-나프톨과 반응시킴으로써 일반식 (Ⅰ)의 2-(2-나프틸옥시)프로피온산 유도체의 제조방법을 제공하는 것이다.An object of the present invention is to prepare a 2- (2-naphthyloxy) propionic acid derivative of the general formula (I) by reacting halocarboxylic acid of the general formula (IV) with 2-naphthol in the presence of an organic solvent and an alkali metal base. To provide.
상기식 중, R, X 및 n은 전술한 바와 같다.In the above formula, R, X and n are as described above.
일반식 (Ⅳ)의 할로카르본산의 제조방법은 이미 널리 알려진 것으로서 독일공개특허 제 3, 422, 672호 등에 자세히 기술되어 있다.The preparation method of the halocarboxylic acid of the general formula (IV) is already well known and is described in detail in German Patent Publication Nos. 3, 422, 672 and the like.
본 발명에서 사용되는 유기용매로서는 벤젠, 톨루엔, 아세톤, 테트라하이드로푸란, 1, 4-디옥산이고, 알칼리금속염기로서는 수산화칼륨, 수산화나트륨, 탄산칼륨, 탄산나트륨이며, 알칼리금속 염기의 사용량은 2-나프톨에 대하여 2.0 내지 3.0몰비가 바람직하며 염기를 2.0몰비 이하로 사용하는 경우에는 수율이 감소하게 된다. 또한 일반식 (Ⅳ)의 할로카르본산의 사용량은 2-니프톨에 대하여 1.0 내지 1.5몰비이고 반응시간은 3 내지 6시간이다. 한편, 본 발명의 반응은 상온에서 실시하되 발열반응이므로 알칼리금속 염기를 가하기 전에 0 내지 5℃의 냉각과정을 필요로 한다.The organic solvent used in the present invention is benzene, toluene, acetone, tetrahydrofuran, 1, 4-dioxane, and the alkali metal base is potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, and the amount of alkali metal base used is 2- A molar ratio of 2.0 to 3.0 molar ratios is preferred with respect to naphthol, and the yield is reduced when the base is used at a molar ratio of 2.0 or less. In addition, the usage-amount of the halocarboxylic acid of General formula (IV) is 1.0-1.5 molar ratio with respect to 2-niphthol, and reaction time is 3-6 hours. On the other hand, the reaction of the present invention is carried out at room temperature but exothermic reaction requires a cooling process of 0 to 5 ℃ before adding the alkali metal base.
전술한 조건으로 본 발명을 실시함으로써 반응중 pH를 조절해야 하는 번거로움이 없어지므로 공정이 간단해졌을 뿐만 아니라 반응시간이 현저히 짧아지고 부생성물이 생성되지 않으므로 순도와 수율이 대단히 높아진다는 놀라운 결과를 얻게 되었다.By carrying out the present invention under the above-mentioned conditions, there is no need to adjust the pH during the reaction, which not only simplifies the process but also significantly shortens the reaction time and produces no by-products, resulting in surprisingly high purity and yield. I got it.
이하 본 발명을 실시예로서 보다 상세히 설명한다. 그러나 이러한 실시예가 본 발명을 한정하는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples. However, these examples do not limit the present invention.
[실시예]EXAMPLE
2-(2-나프틸옥시)프로피온산의 제조Preparation of 2- (2-naphthyloxy) propionic acid
2
그런 다음 상기 혼합물을 4시간 동안 가열환류시키고, 감압 농축시켜 용매를 제거한다. 농축된 반응물을 물 800ml로 녹이고, 분액깔대기를 사용하여 메틸렌클로라이드로 2회 세척한다. 물층을 진한 염산 용액(170ml)를 적가하여 생성된 고체를 여과하고 여과된 고체를 물로 2회 세척하고 시클로헥산으로 1회 세척한다. 얻어진 고체를 감압오븐에서 건조시키면 상기 목적화합물 205.5g(수율 : 95.0%)이 얻어진다. 얻어진 생성물을 가스크로마토그래피로 분석한 결과 2-(2-나프틸옥시)프로피온산 99.8%가 함유되어 있음을 알 수 있었다.The mixture is then heated to reflux for 4 hours and concentrated under reduced pressure to remove the solvent. The concentrated reaction was dissolved in 800 ml of water and washed twice with methylene chloride using a separatory funnel. The aqueous layer was added dropwise with concentrated hydrochloric acid solution (170 ml) to filter the resulting solid, and the filtered solid was washed twice with water and once with cyclohexane. The obtained solid was dried in a vacuum oven to obtain 205.5 g (yield: 95.0%) of the target compound. Analysis of the obtained product by gas chromatography showed that 99.8% of 2- (2-naphthyloxy) propionic acid was contained.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019880006086A KR910001998B1 (en) | 1988-05-24 | 1988-05-24 | Process for the preparation of 2-(2-naphthyloxy) proponic acid derivation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019880006086A KR910001998B1 (en) | 1988-05-24 | 1988-05-24 | Process for the preparation of 2-(2-naphthyloxy) proponic acid derivation |
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| Publication Number | Publication Date |
|---|---|
| KR890017226A KR890017226A (en) | 1989-12-15 |
| KR910001998B1 true KR910001998B1 (en) | 1991-03-30 |
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| Application Number | Title | Priority Date | Filing Date |
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| KR1019880006086A KR910001998B1 (en) | 1988-05-24 | 1988-05-24 | Process for the preparation of 2-(2-naphthyloxy) proponic acid derivation |
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| KR (1) | KR910001998B1 (en) |
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- 1988-05-24 KR KR1019880006086A patent/KR910001998B1/en not_active IP Right Cessation
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| KR890017226A (en) | 1989-12-15 |
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