KR19990047155A - Method for preparing 3- (hydroxymethyl) tetrahydrofuran derivative - Google Patents
Method for preparing 3- (hydroxymethyl) tetrahydrofuran derivative Download PDFInfo
- Publication number
- KR19990047155A KR19990047155A KR1019970065411A KR19970065411A KR19990047155A KR 19990047155 A KR19990047155 A KR 19990047155A KR 1019970065411 A KR1019970065411 A KR 1019970065411A KR 19970065411 A KR19970065411 A KR 19970065411A KR 19990047155 A KR19990047155 A KR 19990047155A
- Authority
- KR
- South Korea
- Prior art keywords
- hydroxymethyl
- tetrahydrofuran
- formula
- butyl
- reaction
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/12—Radicals substituted by oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Furan Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
본 발명은 각종 산업 분야 특히, 의약 및 살충제 등과 같은 농약의 중간원료로 유용하게 사용되는 화학식 1로 표시되는 3-(하이드록시메틸)테트라하이드로퓨란[3-(hydroxymethyl)tetrahydrofuran]을 제조하는 방법에 관한 것으로, 반응물질인 화학식 2로 표시되는 2-하이드록시메틸-4-알켄-1-올 유도체(2-hydroxymethyl- 4-alkene-1-ol Derivatives)를 요오드(I2) 존재 하에서 고리화 반응시켜 목적화합물인 3-(하이드록시메틸)테트라하이드로퓨란을 기존의 방법에 비해 쉽고 간편하게 제조할 수 있는 방법이다.The present invention relates to a method for producing 3- (hydroxymethyl) tetrahydrofuran [3- (hydroxymethyl) tetrahydrofuran] represented by Chemical Formula 1, which is usefully used as an intermediate raw material of agrochemicals such as medicines and insecticides. In the present invention, 2-hydroxymethyl-4-alkene-1-ol derivatives represented by Chemical Formula 2, which are reactants, are cyclized in the presence of iodine (I 2 ). 3- (hydroxymethyl) tetrahydrofuran, which is a target compound, can be easily and conveniently prepared as compared to the conventional method.
(상기 화학식에서 R1, R2및 R3 은 명세서에 정의한 바와 같다.)(R in the above formulaOne, R2And R3 Is as defined in the specification.)
Description
본 발명은 화학식 1로 표시되는 3-(하이드록시메틸)테트라하이드로퓨란 유도체의 제조방법에 관한 것이다.The present invention relates to a process for the preparation of 3- (hydroxymethyl) tetrahydrofuran derivative represented by the formula (1).
더욱 상세하게는 본 발명은 화학식 2로 표시되는 2-하이드록시메틸-4-알켄-1-올 유도체를 반응물질로 하여 각종 유기용매하에서 촉매를 이용하여 고리화 반응을 시켜 목적화합물인 3-(하이드록시메틸)테트라하이드로퓨란 유도체를 제조하는 방법에 관한 것이다.More specifically, the present invention is a 2-hydroxymethyl-4-alkene-1-ol derivative represented by the general formula (2) as a reaction material is subjected to a cyclization reaction using a catalyst under various organic solvents 3- ( Hydroxymethyl) tetrahydrofuran derivative.
화학식 1Formula 1
상기 화학식에서 R1, R2및 R3 은 명세서에 정의한 바와 같다.R in the above formulaOne, R2And R3 Is as defined in the specification.
화학식 2Formula 2
상기 화학식에서 R1, R2및 R3 은 명세서에 정의한 바와 같다.R in the above formulaOne, R2And R3 Is as defined in the specification.
3-(하이드록시메틸)테트라하이드로퓨란 유도체는 각종 산업분야에 유용하게 사용되는 물질로서, 특히 의약품 및 살충제 등과 같은 농약의 중간체로 유용하게 사용되는 물질이다.3- (hydroxymethyl) tetrahydrofuran derivatives are useful materials for various industrial fields, and are particularly useful as intermediates of pesticides such as pharmaceuticals and insecticides.
종래에는 하기 반응식 1에서 보는 바와 같이, 2-하이드록시메틸-1,4-부탄디올(2-hydroxymethyl-1,4-butanediol)을 인산(H3PO4)과 반응시켜 3-(하이드록시메틸)테트라하이드로퓨란 유도체를 제조하였는데 (Bull. Soc. Chem., 1972, Fr.(9), 3614∼3624), 이 반응은 화학식 1로 표시되는 3-(하이드록시메틸)테트라하이드로퓨란 유도체를 제조하기 위하여 과량의 인산(H3PO4)을 사용하기 때문에 반응종료후 탄산칼륨(K2CO3) 등으로 반응물을 중화시켜야 하고, 또한 목적화합물인 3-(하이드록시메틸)테트라하이드로퓨란 유도체를 추출하고 정제하는 과정이 필요하기 때문에 공업적으로 바람직하지 않은 방법이다.Conventionally, as shown in Scheme 1 below, 2-hydroxymethyl-1,4-butanediol is reacted with phosphoric acid (H 3 PO 4 ) to give 3- (hydroxymethyl). Tetrahydrofuran derivatives were prepared (Bull. Soc. Chem., 1972, Fr. (9), 3614 to 3624), and the reaction was performed to prepare 3- (hydroxymethyl) tetrahydrofuran derivative represented by the formula (1). In order to use excess phosphoric acid (H 3 PO 4 ) in order to neutralize the reactants with potassium carbonate (K 2 CO 3 ), etc. It is an industrially undesirable method because it requires a process of purification.
한편, 일본특허 제 291159호에 기재된 하기 반응식 2로 표시되는 3-(하이드록시메틸)테트라하이드로퓨란 유도체의 제조방법은 반응물질인 2-하이드록시메틸-1,4-부탄디올을 벤젠 등의 유기용매하에서나 용매 없이 산촉매하에서 고리화시켜 3-(하이드록시메틸)테트라하이드로퓨란 유도체를 제조하는 것으로, 이 방법을 통하여 3-(하이드록시메틸)테트라하이드로퓨란 유도체를 제조하기 위해서는 높은 반응온도가 요구되며, 장시간 동안 반응을 지속시켜야 하기 때문에 공업적으로는 바람직하지 않다는 단점이 있다.On the other hand, the manufacturing method of 3- (hydroxymethyl) tetrahydrofuran derivative represented by following Reaction Scheme 2 described in Japanese Patent No. 291159 is an organic solvent such as benzene, 2-hydroxymethyl-1,4-butanediol The 3- (hydroxymethyl) tetrahydrofuran derivative was prepared by cyclization under an acid catalyst without or under a solvent. A high reaction temperature is required to prepare 3- (hydroxymethyl) tetrahydrofuran derivative through this method. However, there is a disadvantage in that it is not industrially preferable because the reaction must be continued for a long time.
이에 본 발명자들은 3-(하이드록시메틸)테트라하이드로퓨란 유도체를 제조하는 기존의 방법에서 나타나는 문제점들을 해결하고자 연구를 계속해 오던 중, 기존의 방법에 비해 경제적이며, 공업적으로 용이하게 3-(하이드록시메틸)테트라하이드로퓨란 유도체를 제조하는 방법을 개발하여 본 발명을 완성하였다.Accordingly, the present inventors continue to study to solve the problems appearing in the existing method for preparing 3- (hydroxymethyl) tetrahydrofuran derivative, and are economically and industrially easier than the existing method. The present invention has been completed by developing a method for preparing oxymethyl) tetrahydrofuran derivative.
본 발명의 목적은 3-(하이드록시메틸)테트라하이드로퓨란 유도체를 경제적이며, 공업적으로 용이하게 제조하는 방법을 제공하는 것이다.It is an object of the present invention to provide a process for the production of 3- (hydroxymethyl) tetrahydrofuran derivatives economically and industrially.
상기 목적을 달성하기 위하여, 본 발명에서는 화학식 2의 2-하이드록시메틸-4-알켄-1-올 유도체를 유기용매하에서 요오드 촉매를 이용하여 고리화 반응시켜 화학식 1의 3-(하이드록시메틸)테트라하이드로퓨란 유도체를 제조하는 방법을 제공한다.In order to achieve the above object, in the present invention, the 2-hydroxymethyl-4-alkene-1-ol derivative of the formula (2) is cyclized using an iodine catalyst under an organic solvent to give 3- (hydroxymethyl) of the formula (1). Provided are methods for preparing tetrahydrofuran derivatives.
화학식 1Formula 1
상기 화학식 1에서,In Chemical Formula 1,
R1, R2및R3는 각각 수소, 메틸, 에틸, n-프로필, i-프로필, n-부틸, i-부틸 또는 t-부틸기 중에서 선택되는 C1∼C4의 알킬기 또는 페닐기를 나타낸다.R 1 , R 2 and R 3 each represent a C 1 to C 4 alkyl or phenyl group selected from hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl groups .
화학식 2Formula 2
상기 화학식 2에서,In Chemical Formula 2,
R1, R2및R3는 각각 수소, 메틸, 에틸, n-프로필, i-프로필, n-부틸, i-부틸 또는 t-부틸기 중에서 선택되는 C1∼C4의 알킬기 또는 페닐기를 나타낸다.R 1 , R 2 and R 3 each represent a C 1 to C 4 alkyl or phenyl group selected from hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl groups .
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
하기 반응식 3은 본 발명의 화학식 1의 화합물을 제조하는 과정을 도시한 것이다.Scheme 3 below illustrates a process for preparing the compound of Formula 1 of the present invention.
상기 반응식 3에 나타낸 본 발명의 화합물인 3-(하이드록시메틸)테트라하이드로퓨란 유도체는 반응물질인 2-하이드록시메틸-4-알켄-1-올 유도체를 유기용매하에서 촉매량의 요오드로 고리화 반응시켜 제조한다.The 3- (hydroxymethyl) tetrahydrofuran derivative of the compound of the present invention shown in Scheme 3 is a cyclization reaction of a reactant 2-hydroxymethyl-4-alkene-1-ol derivative with a catalytic amount of iodine in an organic solvent. To make it.
구조식 1의 2-하이드록시메틸-4-알켄-1-올 유도체는 각종 유기용매하에서 촉매량의 요오드(I2)를 사용하여 고리화 반응을 시켜 화학식 1의 화합물인 3-(하이드록시메틸)테트라하이드로퓨란 유도체를 얻는다.2-hydroxymethyl-4-alkene-1 -ol derivative of formula 1 is subjected to cyclization reaction using catalytic amount of iodine (I 2 ) under various organic solvents to give 3- (hydroxymethyl) tetra Hydrofuran derivatives are obtained.
이때 반응용매로는 헥산(hexane), 벤젠(benzene), 에테르(ether) 및 메틸렌 클로라이드(methylene chloride) 등이 사용될 수 있는데, 반응용매로 테트라하이드로퓨란(THF), 디메틸아미노포름아마이드(dimethylaminoformamide) 또는 알콜 등을 사용하여 반응을 시키면 요오드화된 부생성물이 생성될 수 있다.In this case, hexane, benzene, ether, and methylene chloride may be used as the reaction solvent, and tetrahydrofuran (THF), dimethylaminoformamide or dimethylaminoformamide may be used as the reaction solvent. Reaction with alcohol or the like can produce iodinated byproducts.
본 발명의 화학식 1의 화합물을 제조하는데 있어서 적절한 반응온도는 실온의 범위(20∼40℃)가, 반응시간은 30분 정도가 바람직하다.In preparing the compound of Formula 1 of the present invention, the reaction temperature is preferably in the range of room temperature (20 to 40 ° C), and the reaction time is preferably about 30 minutes.
본 발명의 방법에 따라 제조할 수 있는 화학식 1의 화합물 중 대표적인 화합물에는 다음과 같은 물질이 있다.Representative compounds of the compound of Formula 1 that may be prepared according to the method of the present invention include the following materials.
1) 2,2-디메틸-4-n-부틸-4-하이드록시메틸 테트라하이드로퓨란1) 2,2-dimethyl-4-n-butyl-4-hydroxymethyl tetrahydrofuran
2) 2,2-디메틸-4-하이드록시메틸 테트라하이드로퓨란2) 2,2-dimethyl-4-hydroxymethyl tetrahydrofuran
3) 2,2-디메틸-4-메틸-4-하이드록시메틸 테트라하이드로퓨란3) 2,2-dimethyl-4-methyl-4-hydroxymethyl tetrahydrofuran
4) 2,2-디메틸-4-에틸-4-하이드록시메틸 테트라하이드로퓨란4) 2,2-dimethyl-4-ethyl-4-hydroxymethyl tetrahydrofuran
5) 2,2-디메틸-4-벤질-4-하이드록시메틸 테트라하이드로퓨란5) 2,2-dimethyl-4-benzyl-4-hydroxymethyl tetrahydrofuran
한편, 구조식 1로 표시되는 2-하이드록시메틸-4-알켄-1-올 유도체는 하기 반응식 4에 도시된 바와 같이 말론산 에스테르 유도체를 공지의 환원반응을 통하여 용이하게 제조할 수 있으며, 제조된 2-하이드록시메틸-4-알켄-1-올 유도체는 정제하거나 별도의 정제과정이 없이 3-(하이드록시메틸)테트라하이드로퓨란 유도체를 제조하는 반응의 반응물질로 사용할 수 있다. 하기 반응식 4에서 R4는 C1∼C3의 알킬기를 나타낸다.Meanwhile, the 2-hydroxymethyl-4-alkene-1-ol derivative represented by Structural Formula 1 can be easily prepared through a known reduction reaction of malonic ester derivative, as shown in Scheme 4 below, The 2-hydroxymethyl-4-alkene-1-ol derivative may be used as a reactant of a reaction for preparing 3- (hydroxymethyl) tetrahydrofuran derivative without purification or separate purification. In Reaction Scheme 4, R 4 represents an alkyl group having 1 to 3 carbon atoms.
이하, 실시예를 통하여 본 발명을 상세히 설명하기로 한다.Hereinafter, the present invention will be described in detail through examples.
실시예는 본 발명의 예시 일뿐 본 발명이 실시예에 의하여 한정되는 것은 아니다.The examples are only examples of the present invention and the present invention is not limited by the examples.
〈실시예 1〉 2,2-디메틸-4-n-부틸-4-하이드록시메틸 테트라하이드로퓨란의 제조Example 1 Preparation of 2,2-dimethyl-4-n-butyl-4-hydroxymethyl tetrahydrofuran
2-n-부틸-2-(β-메트알릴)프로판-1,3-디올(0.2g, 5mmol)을 정제된 메틸렌클로라이드(CH2Cl2)에 녹인 후 반응물을 교반하면서 요오드(I2; 0.05g, 0.2mmol)를 첨가하였다. 반응은 30분 동안 지속시킨 뒤 5% 나트륨 티오설페이트(sodium thiosulfate) 수용액으로 추출하여 잔존하는 요오드를 제거하고 유기층은 증류수와 염화나트륨 수용액으로 세척하였다. 다음 용매는 감압 증류하여 제거하고 실리카겔크로마토그래피로 분리하여 순수한 표제화합물(0.19g, 수율: 95%)을 얻었다.2-n-butyl-2- (β-methallyl) propane-1,3-diol (0.2 g, 5 mmol) was dissolved in purified methylene chloride (CH 2 Cl 2 ), followed by stirring the reaction with iodine (I 2 ; 0.05 g, 0.2 mmol) was added. The reaction was continued for 30 minutes, extracted with 5% sodium thiosulfate aqueous solution to remove residual iodine, and the organic layer was washed with distilled water and aqueous sodium chloride solution. The solvent was then distilled off under reduced pressure and separated by silica gel chromatography to obtain the pure title compound (0.19 g, yield: 95%).
1H NMR(CDCl3, ppm) δ 0.91(t, 3H), 1.25(s, 3H), 1.28(s, 3H), 1.36∼1.63(m, 6H), 1.58(d, 2H), 2.57(brs, 1H), 3.48(s, 2H), 3.50(d, J=9.2㎐, 1H), 3.75(d, J=9.2㎐, 1H). 1 H NMR (CDCl 3 , ppm) δ 0.91 (t, 3H), 1.25 (s, 3H), 1.28 (s, 3H), 1.36 to 1.63 (m, 6H), 1.58 (d, 2H), 2.57 (brs , 1H), 3.48 (s, 2H), 3.50 (d, J = 9.2 Hz, 1H), 3.75 (d, J = 9.2 Hz, 1H).
bp: 94∼95℃(0.01 mmHg)bp: 94-95 degreeC (0.01 mmHg)
〈실시예 2〉 2,2-디메틸-4-하이드록시메틸 테트라하이드로퓨란의 제조<Example 2> Preparation of 2,2-dimethyl-4-hydroxymethyl tetrahydrofuran
2-n-부틸-2-(β-메트알릴)프로판-1,3-디올 대신 2-(β-메트알릴)프로판-1,3-디올 (0.2g, 5mmol)을 사용하여 실시예 1과 같은 방법으로 제조하여 표제화합물을 (0.134g, 수율: 67%)을 얻었다.Example 1 using 2- (β-methallyl) propane-1,3-diol (0.2 g, 5 mmol) instead of 2-n-butyl-2- (β-methallyl) propane-1,3-diol Prepared in the same manner to obtain the title compound (0.134g, yield: 67%).
1H NMR(CDCl3, ppm) δ 1.22(s, 3H), 1.30(s, 3H), 1.46(dd, J=12.4㎐, 1H), 1.90(dd, J=12.4㎐, 1H), 2.62(m, 1H), 2.77(brs, 1H), 3.58(dd, J=7.2㎐, 2H), 3.66(dd, J=9.0㎐, 1H), 3.97(dd, J=9.0㎐, 1H). 1 H NMR (CDCl 3 , ppm) δ 1.22 (s, 3H), 1.30 (s, 3H), 1.46 (dd, J = 12.4 ㎐, 1H), 1.90 (dd, J = 12.4 ㎐, 1H), 2.62 ( m, 1H), 2.77 (brs, 1H), 3.58 (dd, J = 7.2 Hz, 2H), 3.66 (dd, J = 9.0 Hz, 1H), 3.97 (dd, J = 9.0 Hz, 1H).
bp: 72℃(0.01 mmHg).bp: 72 ° C. (0.01 mmHg).
〈실시예 3〉 2,2-디메틸-4-메틸-4-하이드록시메틸 테트라하이드로퓨란의 제조<Example 3> Preparation of 2,2-dimethyl-4-methyl-4-hydroxymethyl tetrahydrofuran
2-n-부틸-2-(β-메트알릴)프로판-1,3-디올 대신 2-메틸-2-(β-메트알릴)프로판-1,3-디올 (0.2g, 5mmol)을 사용하여 실시예 1과 같은 방법으로 제조하여 표제화합물을 (0.142g, 수율: 71%)을 얻었다.2-methyl-2- (β-methallyl) propane-1,3-diol (0.2 g, 5 mmol) instead of 2-n-butyl-2- (β-methallyl) propane-1,3-diol Prepared in the same manner as in Example 1, obtaining the title compound (0.142 g, yield: 71%).
1H NMR(CDCl3, ppm) δ 1.12(s, 3H), 1.28(s, 6H), 1.50(dd, J=12.8㎐, 1H), 1.71(d, J=12.8㎐, 1H), 2.90(brs, 1H), 3.58(q, J=9.0㎐, 2H), 3.49(d, J=9.0㎐, 1H), 3.78(d, J=9.0㎐, 1H). 1 H NMR (CDCl 3 , ppm) δ 1.12 (s, 3H), 1.28 (s, 6H), 1.50 (dd, J = 12.8 Hz, 1H), 1.71 (d, J = 12.8 Hz, 1H), 2.90 ( brs, 1H), 3.58 (q, J = 9.0 Hz, 2H), 3.49 (d, J = 9.0 Hz, 1H), 3.78 (d, J = 9.0 Hz, 1H).
bp: 72℃(0.01 mmHg).bp: 72 ° C. (0.01 mmHg).
〈실시예 4〉 2,2-디메틸-4-에틸-4-하이드록시메틸 테트라하이드로퓨란의 제조Example 4 Preparation of 2,2-dimethyl-4-ethyl-4-hydroxymethyl tetrahydrofuran
2-에틸-2-(β-메트알릴)프로판-1,3-디올(0.2g, 5mmol)을 정제된 메틸렌클로라이드에 녹인 후 반응물을 교반하면서 요오드(0.05g, 0.2mmol)를 첨가하였다. 반응은 30분 동안 지속시킨 뒤 5% 나트륨 티오설페이트(sodium thiosulfate) 수용액으로 추출하여 잔존하는 요오드를 제거하고 유기층은 증류수와 염화나트륨 수용액으로 세척하였다. 다음 용매는 감압 증류하여 제거하고 감압 분별 증류하여 순수한 표제화합물(0.144g, 수율: 72%)을 얻었다.2-ethyl-2- (β-methallyl) propane-1,3-diol (0.2 g, 5 mmol) was dissolved in purified methylene chloride and iodine (0.05 g, 0.2 mmol) was added while stirring the reaction. The reaction was continued for 30 minutes, extracted with 5% sodium thiosulfate aqueous solution to remove residual iodine, and the organic layer was washed with distilled water and aqueous sodium chloride solution. The solvent was then distilled off under reduced pressure and fractional distillation under reduced pressure yielded the pure title compound (0.144 g, yield: 72%).
1H NMR(CDCl3, ppm) δ 0.88(t, 3H), 1.24(s, 3H), 1.28(s, 3H), 1.36∼1.58(m, 2H), 1.57(s, 2H), 2.31(brs, 1H), 3.51(d, 2H), 3.53(d, J=9.2㎐, 1H), 3.77(d, J=9.2㎐, 1H). 1 H NMR (CDCl 3 , ppm) δ 0.88 (t, 3H), 1.24 (s, 3H), 1.28 (s, 3H), 1.36-1.58 (m, 2H), 1.57 (s, 2H), 2.31 (brs , 1H), 3.51 (d, 2H), 3.53 (d, J = 9.2 Hz, 1H), 3.77 (d, J = 9.2 Hz, 1H).
bp: 80℃(0.01 mmHg).bp: 80 ° C. (0.01 mmHg).
〈실시예 5〉 2,2-디메틸-4-벤질-4-하이드록시메틸 테트라하이드로퓨란의 제조Example 5 Preparation of 2,2-dimethyl-4-benzyl-4-hydroxymethyl tetrahydrofuran
2-에틸-2-(β-메트알릴)프로판-1,3-디올 대신 2-벤질-2-(β-메트알릴)프로판-1,3-디올 (0.2g, 5mmol)을 사용하여 실시예 4와 같은 방법으로 제조하여 표제화합물을 (0.194g, 수율: 97%)을 얻었다.Example using 2-benzyl-2- (β-methallyl) propane-1,3-diol (0.2 g, 5 mmol) instead of 2-ethyl-2- (β-methallyl) propane-1,3-diol Prepared in the same manner as 4 to obtain the title compound (0.194g, yield: 97%).
1H NMR(CDCl3, ppm) δ 1.23(s, 3H), 1.26(s, 3H), 1.51(d, J=13.0㎐, 1H), 1.74(d, J=13.0㎐, 1H), 2.29(brs, 1H), 2.80(q, J=13.4㎐, 2H), 3.43(d, J=11.0㎐, 2H), 3.72(d, J=9.2㎐, 2H), 7.17∼7.33(m, 5H). 1 H NMR (CDCl 3 , ppm) δ 1.23 (s, 3H), 1.26 (s, 3H), 1.51 (d, J = 13.0 μs, 1H), 1.74 (d, J = 13.0 μs, 1H), 2.29 ( brs, 1H), 2.80 (q, J = 13.4 kPa, 2H), 3.43 (d, J = 11.0 kPa, 2H), 3.72 (d, J = 9.2 kPa, 2H), 7.17 to 7.33 (m, 5H).
bp: 135℃(0.01 mmHg).bp: 135 ° C. (0.01 mmHg).
이상에서 살펴 본 바와 같이, 촉매량의 요오드를 사용하여 2-하이드록시메틸-4-알켄-1-올 유도체를 고리화 반응시켜 3-(하이드록시메틸)테트라하이드로퓨란 유도체를 얻는 본 발명의 제조방법은 비교적 온화한 반응조건(30분, 실온)에서 반응시켜 목적화합물인 3-(하이드록시메틸)테트라하이드로퓨란 유도체를 얻을 수 있고 중화, 추출 및 정제 등 별도의 후처리 공정이 필요없어 공업적으로 용이한 반응이다. 또한, 반응물질인 2-하이드록시메틸-4-알켄-1-올 유도체를 말론산 에스테르 화합물로부터 공지의 반응으로 용이하게 제조할 수 있을 뿐만 아니라, 목적화합물의 수율도 높아 매우 경제적이고 효과적으로 3-(하이드록시메틸)테트라하이드로퓨란 유도체를 제조할 수 있다. 따라서, 본 발명은 각종 산업에 유용하게 사용되는 중간체인 3-(하이드록시메틸)테트라하이드로퓨란 유도체를 공업적으로 합성할 수 있는 유용한 제조방법이다.As described above, the preparation method of the present invention provides a 3- (hydroxymethyl) tetrahydrofuran derivative by cyclizing a 2-hydroxymethyl-4-alkene-1-ol derivative using a catalytic amount of iodine. Is reacted under relatively mild reaction conditions (30 minutes, room temperature) to obtain 3- (hydroxymethyl) tetrahydrofuran derivative as a target compound, and it is industrially easy because it does not require a separate post-treatment process such as neutralization, extraction and purification. It is a reaction. In addition, 2-hydroxymethyl-4-alkene-1-ol derivatives, which are reactants, can be easily produced from known malonic ester compounds by known reactions, and the yield of target compounds is high. (Hydroxymethyl) tetrahydrofuran derivatives can be prepared. Accordingly, the present invention is a useful manufacturing method capable of industrially synthesizing 3- (hydroxymethyl) tetrahydrofuran derivative, which is an intermediate useful for various industries.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019970065411A KR100250838B1 (en) | 1997-12-02 | 1997-12-02 | Process for preparation of 3-(hydroxymethyl)tetrahydrofuran derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019970065411A KR100250838B1 (en) | 1997-12-02 | 1997-12-02 | Process for preparation of 3-(hydroxymethyl)tetrahydrofuran derivatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR19990047155A true KR19990047155A (en) | 1999-07-05 |
| KR100250838B1 KR100250838B1 (en) | 2000-05-01 |
Family
ID=19526284
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019970065411A KR100250838B1 (en) | 1997-12-02 | 1997-12-02 | Process for preparation of 3-(hydroxymethyl)tetrahydrofuran derivatives |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100250838B1 (en) |
-
1997
- 1997-12-02 KR KR1019970065411A patent/KR100250838B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR100250838B1 (en) | 2000-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101158132B1 (en) | Manufacture of vitamin b6 | |
| EP1794140B1 (en) | Process for the preparation of escitalopram | |
| KR100250838B1 (en) | Process for preparation of 3-(hydroxymethyl)tetrahydrofuran derivatives | |
| KR100511534B1 (en) | Amide compound, process for the production | |
| KR100369274B1 (en) | Improved process for producing 4-hydroxy-2-pyrrolidone | |
| JPWO2006080339A1 (en) | Process for producing 5-chloro-2,4-dihydroxypyridine | |
| CA1196000A (en) | Process for production of methyl 2- tetradecylglycidate | |
| JPH06172301A (en) | Production of r/s-gamma-lipoic acid or r/s-alpha- lipoic acid, 8-alkoxy-6-formyloxyoctanoic acid and its production | |
| KR100936306B1 (en) | Process for the preparation of 3-[2-3,4-dimethoxy-benzoyl-4,5-dimethoxy-phenyl]-pentan-2-one | |
| EP1018503B1 (en) | Process of producing cyclopropanecarboxylate compounds | |
| JP3047582B2 (en) | Method for producing threo-4-alkoxy-5- (arylhydroxymethyl) -2 (5H) -furanone | |
| JPH0696564B2 (en) | α- (ω-hydroxyalkyl) furfuryl alcohol and process for producing the same | |
| JP3777407B2 (en) | Method for producing carboxylic acid derivative | |
| KR101548886B1 (en) | Method for preparing (r)-rolipram precursor by catalytic enantioselective micahel reaction and method for preparing (r)-rolptram using the (r)-rolipram precursor | |
| KR100343551B1 (en) | Process for preparing 4-alkoxycarbonyl-5-chloropyrazole derivatives | |
| KR100449310B1 (en) | preparation method of 2-deoxy-L-ribose | |
| JP3634874B2 (en) | Trifluoromethylacetylene derivative, method for producing the same, and method for producing the intermediate | |
| JP4294130B2 (en) | Method for producing α, β-unsaturated ketone compound | |
| JP2000063321A (en) | Production of long-chain beta-hydroxycarboxylic acid of high optical purity | |
| KR100199042B1 (en) | Process for preparation of 2-aminothiazolecarboxylic acid derivative | |
| JP2734646B2 (en) | Novel synthetic method of 2,2-difluorocarboxylic acid derivatives | |
| JP5773850B2 (en) | Method for producing optically active α-alkylserine derivative | |
| JPH0159266B2 (en) | ||
| JPS6152811B2 (en) | ||
| JPH11322663A (en) | Production of gamma-fluoroacetoacetic acid derivative |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20021224 Year of fee payment: 4 |
|
| LAPS | Lapse due to unpaid annual fee |