JPH0360827B2 - - Google Patents
Info
- Publication number
- JPH0360827B2 JPH0360827B2 JP57218113A JP21811382A JPH0360827B2 JP H0360827 B2 JPH0360827 B2 JP H0360827B2 JP 57218113 A JP57218113 A JP 57218113A JP 21811382 A JP21811382 A JP 21811382A JP H0360827 B2 JPH0360827 B2 JP H0360827B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- ester
- epoxysuccinic acid
- triethylamine
- epoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- DCEMCPAKSGRHCN-UHFFFAOYSA-N oxirane-2,3-dicarboxylic acid Chemical compound OC(=O)C1OC1C(O)=O DCEMCPAKSGRHCN-UHFFFAOYSA-N 0.000 claims description 55
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 36
- 150000002148 esters Chemical class 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 239000004593 Epoxy Substances 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- -1 epoxysuccinic acid monoethyl ester Chemical class 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ITAMCOCNZJPJDF-UHFFFAOYSA-N 1-(6-aminopurin-9-yl)propan-2-yloxymethyl-phenoxyphosphinic acid Chemical compound C1=NC2=C(N)N=CN=C2N1CC(C)OCP(O)(=O)OC1=CC=CC=C1 ITAMCOCNZJPJDF-UHFFFAOYSA-N 0.000 description 1
- QJQZRLXDLORINA-UHFFFAOYSA-N 2-cyclohexylethanol Chemical compound OCCC1CCCCC1 QJQZRLXDLORINA-UHFFFAOYSA-N 0.000 description 1
- IBMXMCXCSPGCDQ-UHFFFAOYSA-N 3-cyclopentylpropan-1-ol Chemical compound OCCCC1CCCC1 IBMXMCXCSPGCDQ-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- ISQVBYGGNVVVHB-UHFFFAOYSA-N cyclopentylmethanol Chemical compound OCC1CCCC1 ISQVBYGGNVVVHB-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- OTGHWLKHGCENJV-UHFFFAOYSA-N glycidic acid Chemical compound OC(=O)C1CO1 OTGHWLKHGCENJV-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 208000010125 myocardial infarction Diseases 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229940124597 therapeutic agent Drugs 0.000 description 1
Description
本発明は次の一般式（）
（式中、Ｒはアルキル基、フエニル基、フエニ
ル基で置換された炭素数１〜３のアルキル基、シ
クロアルキル基又はシクロアルキル基で置換され
た炭素数１〜３のアルキル基を示す）
で表わされるエポキシコハク酸モノエステルの新
規な製造法に関する。
本発明方法で得られる（）式で表わされるエ
ポキシコハク酸モノエステルはある種の生理活性
物質の合成中間体、例えばエポキシコハク酸モノ
エチルエステルは心筋梗塞の予防及び治療剤であ
る３−〔３−メチル−１−｛４−（２，３，４−ト
リメトキシフエニルメチル）ピペラジン−１−イ
ルカルボニル｝ブチルカルバモイル〕オキシラン
−２−カルボン酸エステルの合成中間体として有
用な化合物である。
従来、エポキシコハク酸モノエステルを製造す
る方法としては、エポキシコハク酸ジアルキルエ
ステルを半ケン化する方法が知られている（特開
昭52−31024号）。しかしながら、この方法による
と、半ケン化されたエポキシコハク酸モノエステ
ルはアルカリ金属塩の形で沈殿するが、この光学
活性体の沈殿は過が極めて困難であるため、そ
の単離操作が厄介であり、また斯くして得たアル
カリ金属塩は更に遊離酸の形にしなければならな
いという欠点があつた。
そこで、本発明者は斯かる欠点を克服せんと鋭
意研究を行つた結果、エポキシコハク酸ジハライ
ドに、これとほぼ等モルのアルコールを作用させ
るとモノエステルが容易に得られることを見出
し、本発明を完成した。
本発明方法は次の反応式によつて示される。
（式中、Ｘはハロゲン原子を示し、Ｒは前記の
意味を有する）
すなわち、本発明は、エポキシコハク酸ジハラ
イド（）に、これとほぼ等モルのアルコール
（）を反応せしめてエポキシコハク酸モノエス
テル（）を製造する方法である。
本発明方法を実施するには、エポキシコハク酸
ジハライド（）と、これとほぼ等モルのアルコ
ール（）とを、不活性溶媒中塩基の存在下反応
させる。不活性溶媒としては、例えばヘキサン、
ベンゼン等の炭化水素類、クロロホルム、ジクロ
ルエタン等のハロ炭化水素類、エチルエーテル、
テトラヒドロフラン、ジオキサン等のエーテル
類、アセトン、メチルエチルケトン類のケトン
類、酢酸エチル、酢酸ブチル等のエステル類を単
独又は混合して使用できる。また、塩基として
は、トリエチルアミン、ピリジン、メチルモルホ
リン等の有機塩基が好ましい。反応は−50℃ない
し溶媒の沸点の温度で数分〜数時間行うのが好ま
しい。
斯くして得られる反応混合物から目的化合物
（）を単離するには、反応液に水を加えて有機
層を分離し、この有機層にアルカリ性水溶液を加
えて水層に移行させ、次いでこの水層を酸性に調
整したのち、有機溶媒で抽出すればよい。
叙上の如く、本発明方法は、従来法に比較して
反応操作及び単離操作が簡単であつて、収率も優
れており、しかもエポキシコハク酸モノエステル
が遊離酸の形で得られるので、そのまま合成原料
として使用できる利点を有する。
次に実施例を挙げて説明する。
実施例 １
エポキシコハク酸モノメチルエステルの製造：
エポキシコハク酸ジクロリド2.01ｇをベンゼン
100mlに溶かした溶液に、メタノール0.32ｇとト
リエチルアミン1.01ｇをベンゼン20mlに溶かした
溶液を撹拌冷却下（０〜10℃）に滴下し、30分間
撹拌した。この反応液に水100mlを加え、ベンゼ
ン層を分取し、飽和食塩水で洗浄した。このベン
ゼン層に重炭酸ナトリウム1.68ｇを水100mlに溶
かした溶液を加えて振盪し、水層を分取した。こ
の水層を1N硫酸で酸性とし、酢酸エチル100mlで
２回抽出した。酢酸エチル層を飽和食塩水で洗浄
後、硫酸ナトリウム上で乾燥し、溶媒を留去して
目的物の白色結晶0.33ｇを得た。収率23％。
IRνKBr naxcm-1：1760（エステル），900（エポキシ
）
NMR（CDCl3）δ＝3.77（2H，ｓ，
The present invention is based on the following general formula () (In the formula, R represents an alkyl group, a phenyl group, an alkyl group having 1 to 3 carbon atoms substituted with a phenyl group, a cycloalkyl group, or an alkyl group having 1 to 3 carbon atoms substituted with a cycloalkyl group) The present invention relates to a novel method for producing the epoxysuccinic acid monoester. The epoxysuccinic acid monoester represented by the formula () obtained by the method of the present invention is a synthetic intermediate for certain physiologically active substances, for example, the epoxysuccinic acid monoethyl ester is a preventive and therapeutic agent for myocardial infarction 3-[3 -Methyl-1-{4-(2,3,4-trimethoxyphenylmethyl)piperazin-1-ylcarbonyl}butylcarbamoyl] It is a compound useful as an intermediate in the synthesis of oxirane-2-carboxylic acid ester. Conventionally, as a method for producing epoxysuccinic acid monoester, a method of semi-saponifying epoxysuccinic acid dialkyl ester is known (Japanese Patent Application Laid-open No. 31024/1983). However, according to this method, semi-saponified epoxysuccinic acid monoester is precipitated in the form of an alkali metal salt, but it is extremely difficult to precipitate this optically active substance, making its isolation operation cumbersome. However, the alkali metal salt obtained in this way had to be further converted into a free acid form. Therefore, the present inventor conducted intensive research to overcome such drawbacks, and as a result, discovered that a monoester can be easily obtained by reacting epoxysuccinic acid dihalide with alcohol in an approximately equimolar amount. completed. The method of the present invention is shown by the following reaction formula. (In the formula, X represents a halogen atom, and R has the above-mentioned meaning.) That is, in the present invention, epoxysuccinic acid dihalide () is reacted with approximately equimolar amount of alcohol () to form epoxysuccinic acid mono This is a method for producing ester (). To carry out the method of the present invention, epoxysuccinic acid dihalide () and approximately equimolar amount of alcohol () are reacted in an inert solvent in the presence of a base. Examples of inert solvents include hexane,
Hydrocarbons such as benzene, halohydrocarbons such as chloroform and dichloroethane, ethyl ether,
Ethers such as tetrahydrofuran and dioxane, ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate and butyl acetate can be used alone or in combination. Furthermore, as the base, organic bases such as triethylamine, pyridine, and methylmorpholine are preferred. The reaction is preferably carried out at a temperature of -50°C to the boiling point of the solvent for several minutes to several hours. To isolate the target compound () from the reaction mixture thus obtained, water is added to the reaction mixture to separate the organic layer, an alkaline aqueous solution is added to this organic layer to transfer it to the aqueous layer, and then this water is added to the organic layer to separate the organic layer. After adjusting the layer to be acidic, it may be extracted with an organic solvent. As mentioned above, the method of the present invention has simpler reaction operations and isolation operations than conventional methods, and has an excellent yield, and moreover, the epoxysuccinic acid monoester is obtained in the form of a free acid. , which has the advantage of being able to be used as a raw material for synthesis. Next, an example will be given and explained. Example 1 Production of epoxysuccinic acid monomethyl ester: 2.01g of epoxysuccinic acid dichloride was added to benzene.
A solution of 0.32 g of methanol and 1.01 g of triethylamine dissolved in 20 ml of benzene was added dropwise to the solution in 100 ml while stirring and cooling (0 to 10°C), and the mixture was stirred for 30 minutes. 100 ml of water was added to this reaction solution, and the benzene layer was separated and washed with saturated brine. A solution of 1.68 g of sodium bicarbonate dissolved in 100 ml of water was added to the benzene layer and shaken, and the aqueous layer was separated. This aqueous layer was acidified with 1N sulfuric acid and extracted twice with 100 ml of ethyl acetate. The ethyl acetate layer was washed with saturated brine, dried over sodium sulfate, and the solvent was distilled off to obtain 0.33 g of white crystals. Yield 23%. IRν KBr nax cm -1 : 1760 (ester), 900 (epoxy) NMR (CDCl 3 ) δ=3.77 (2H, s,
【式】）
3.88（3H，ｓ，−Ｏ−ＣH3 ）
実施例 ２
エポキシコハク酸モノエチルエステルの製造：
実施例１と同様にしてエポキシコハク酸ジクロ
リド2.01ｇ、エタノール0.46ｇ、トリエチルアミ
ン1.01ｇより目的物0.86ｇを得た。収率54％。
IRνneat naxcm-1：1750（エステル），9.05（エポキ
シ）
NMR（CDCl3）δ＝1.30（3H，ｔ，Ｊ＝7.0Hz，
−ＣH3 ）
3.60（2H，ｓ，[Formula]) 3.88 (3H, s, -O-C H 3 ) Example 2 Production of epoxysuccinic acid monoethyl ester: 2.01 g of epoxy succinic acid dichloride, 0.46 g of ethanol, 1.01 g of triethylamine in the same manner as in Example 1. 0.86 g of the target product was obtained. Yield 54%. IRν neat nax cm -1 : 1750 (ester), 9.05 (epoxy) NMR (CDCl 3 ) δ=1.30 (3H, t, J=7.0Hz,
−C H 3 ) 3.60 (2H, s,
【式】）
4.24（2H，ｑ，Ｊ＝7.0Hz，−Ｏ−ＣH2 −）
実施例 ３
エポキシコハク酸モノｎ−プロピルエステルの
製造：
実施例１と同様にしてエポキシコハク酸ジクロ
リド2.01ｇ、ｎ−プロパノール0.60ｇ、トリエチ
ルアミン1.01ｇより目的物0.90ｇを得た。収率52
％。
IRνneat naxcm-1：1750（エステル），900（エポキシ
）
NMR〔（CD3）2CO〕δ＝0.96（3H，ｔ，Ｊ＝
7.0Hz，−ＣH3 ）
1.62（2H，ｍ，−ＣH2 −）
3.60（2H，dd，Ｊ＝2.0Hz，[Formula]) 4.24 (2H, q, J = 7.0Hz, -O-C H 2 -) Example 3 Production of epoxysuccinic acid mono-n-propyl ester: 2.01 g of epoxysuccinic acid dichloride in the same manner as in Example 1 , n-propanol (0.60 g), and triethylamine (1.01 g) to obtain 0.90 g of the desired product. Yield 52
%. IRν neat nax cm -1 : 1750 (ester), 900 (epoxy) NMR [(CD 3 ) 2 CO] δ = 0.96 (3H, t, J =
7.0Hz, -C H 3 ) 1.62 (2H, m, -C H 2 -) 3.60 (2H, dd, J = 2.0Hz,
【式】）
4.12（2H，ｔ，Ｊ＝7.0Hz，−Ｏ−ＣH2 −）
実施例 ４
エポキシコハク酸モノドデシルエステルの製
造：
実施例１と同様にしてエポキシコハク酸ジクロ
リド2.01ｇ、ドデシルアルコール1.86ｇ、トリエ
チルアミン1.01ｇより目的物1.07ｇを得た。収率
36％。
IRKBr naxcm-1：1750（エステル），9.00（エポキシ）
NMR〔（CD3）2CO〕δ＝0.88（3H，ｔ，Ｊ＝
7.0Hz，−ＣH3 ）
1.30（20H，ｍ，−（ＣH2）10 −）
3.60（2H，dd，Ｊ＝2.0Hz，[Formula]) 4.12 (2H, t, J = 7.0Hz, -O-C H 2 -) Example 4 Production of epoxysuccinic acid monododecyl ester: 2.01 g of epoxysuccinic acid dichloride, dodecyl 1.07 g of the desired product was obtained from 1.86 g of alcohol and 1.01 g of triethylamine. yield
36%. IR KBr nax cm -1 : 1750 (ester), 9.00 (epoxy) NMR [(CD 3 ) 2 CO] δ=0.88 (3H, t, J=
7.0Hz, -C H 3 ) 1.30 (20H, m, -(C H 2 ) 10 -) 3.60 (2H, dd, J = 2.0Hz,
【式】）
4.18（2H，ｔ，Ｊ＝7.0Hz，−Ｏ−ＣH2 −）
実施例 ５
エポキシコハク酸モノフエニルエステルの製
造：
実施例１と同様にしてエポキシコハク酸ジクロ
リド2.01ｇ、フエノール0.94ｇ、トリエチルアミ
ン1.01ｇより目的物0.54ｇを得た。収率25％。
IRνKBr naxcm-1：1760（エステル），900（エポキシ
）
NMR〔（CD3）2CO〕δ＝3.85（2H，dd，Ｊ＝
2.0Hz，[Formula]) 4.18 (2H, t, J = 7.0Hz, -O-C H 2 -) Example 5 Production of epoxysuccinic acid monophenyl ester: 2.01 g of epoxysuccinic acid dichloride, phenol in the same manner as in Example 1 0.54 g of the target product was obtained from 0.94 g and 1.01 g of triethylamine. Yield 25%. IRν KBr nax cm -1 : 1760 (ester), 900 (epoxy) NMR [(CD 3 ) 2 CO] δ = 3.85 (2H, dd, J =
2.0Hz,
【式】） 7.30（5H，ｍ，【formula】) 7.30 (5H, m,
【式】）
実施例 ６
エポキシコハク酸−２−フエネチルエステルの
製造：
実施例１と同様にしてエポキシコハク酸ジクロ
リド2.01ｇ、フエネチルアルコール1.22ｇ、トリ
エチルアミン1.01ｇより目的物1.0ｇを得た。収
率42％。
IRνneat naxcm-1：1755（エステル），900（エポキシ
）
NMR〔（CD3）2CO〕δ＝2.96（2H，ｔ，Ｊ＝
7.0Hz，−ＣH2 −）
3.60（2H，dd，Ｊ＝2.0Hz，[Formula]) Example 6 Production of epoxysuccinic acid-2-phenethyl ester: In the same manner as in Example 1, 1.0 g of the target product was obtained from 2.01 g of epoxysuccinic acid dichloride, 1.22 g of phenethyl alcohol, and 1.01 g of triethylamine. Ta. Yield 42%. IRν neat nax cm -1 : 1755 (ester), 900 (epoxy) NMR [(CD 3 ) 2 CO] δ = 2.96 (2H, t, J =
7.0Hz, -C H 2 -) 3.60 (2H, dd, J = 2.0Hz,
【式】） 4.40（2H，ｔ，Ｊ＝7.0Hz，−Ｏ−ＣH2 −） 7.20（5H，ｓ，[Formula]) 4.40 (2H, t, J=7.0Hz, -O-C H 2 -) 7.20 (5H, s,
【式】）
実施例 ７
エポキシコハク酸−３−フエニルプロピルエス
テルの製造：
実施例１と同様にしてエポキシコハク酸ジクロ
リド2.01ｇ、３−フエニルプロパノール1.36ｇ、
トリエチルアミン1.01ｇより目的物1.27ｇを得
た。収率51％。
IRνneat naxcm-1：1750（エステル），895（エポキシ
）
NMR〔（CD3）2CO〕δ＝2.00（2H，ｍ，−ＣH2
−）
2.68（2H，ｔ，Ｊ＝7.0Hz，−ＣH2 −）
3.60（2H，dd，Ｊ＝2.0Hz，[Formula]) Example 7 Production of epoxysuccinic acid-3-phenylpropyl ester: In the same manner as in Example 1, 2.01 g of epoxysuccinic acid dichloride, 1.36 g of 3-phenylpropanol,
1.27 g of the target product was obtained from 1.01 g of triethylamine. Yield 51%. IRν neat nax cm -1 : 1750 (ester), 895 (epoxy) NMR [(CD 3 ) 2 CO] δ = 2.00 (2H, m, -C H 2
-) 2.68 (2H, t, J = 7.0Hz, -CH 2 -) 3.60 (2H, dd, J = 2.0Hz,
【式】） 4.20（2H，ｔ，Ｊ＝7.0Hz，−Ｏ−ＣH2 −） 7.20（5H，ｍ，[Formula]) 4.20 (2H, t, J=7.0Hz, -O-C H 2 -) 7.20 (5H, m,
【式】）
実施例 ８
エポキシコハク酸シクロペンタンメチルエステ
ルの製造：
実施例１と同様にしてエポキシコハク酸ジクロ
リド2.01ｇ、シクロペンタンメタノール1.0ｇ、
トリエチルアミン1.01ｇより目的物1.30ｇを得
た。収率56％。
IRνneat naxcm-1：1745（エステル），900（エポキシ
）
NMR〔（CD3）2CO〕δ＝1.00〜2.00（9H，ｍ，
[Formula]) Example 8 Production of epoxysuccinic acid cyclopentane methyl ester: In the same manner as in Example 1, 2.01 g of epoxysuccinic acid dichloride, 1.0 g of cyclopentane methanol,
1.30 g of the target product was obtained from 1.01 g of triethylamine. Yield 56%. IRν neat nax cm -1 : 1745 (ester), 900 (epoxy) NMR [(CD 3 ) 2 CO] δ = 1.00 to 2.00 (9H, m,
【式】） 3.50（2H，dd，Ｊ＝2.0Hz，【formula】) 3.50 (2H, dd, J=2.0Hz,
【式】）
4.00（2H，ｄ，Ｊ＝7.0Hz，−Ｏ−ＣH2 −）
実施例 ９
エポキシコハク酸−３−シクロペンタンプロピ
ルエステルの製造：
実施例１と同様にしてエポキシコハク酸ジクロ
リド2.01ｇ、３−シクロペンタン−プロパノール
1.28ｇ、トリエチルアミン1.01ｇより目的物1.28
ｇを得た。収率53％。
IRνneat naxcm-1：1750（エステル），900（エポキシ
）
NMR〔（CD3）2CO〕δ＝0.80−2.00（13H，ｍ，
[Formula]) 4.00 (2H, d, J = 7.0Hz, -O-C H 2 -) Example 9 Production of epoxysuccinic acid-3-cyclopentanepropyl ester: Epoxysuccinic acid dichloride was prepared in the same manner as in Example 1. 2.01g, 3-cyclopentane-propanol
1.28g, triethylamine 1.01g, target product 1.28
I got g. Yield 53%. IRν neat nax cm -1 : 1750 (ester), 900 (epoxy) NMR [(CD 3 ) 2 CO] δ=0.80−2.00 (13H, m,
【式】） 3.60（2H，dd，Ｊ＝2.0Hz，【formula】) 3.60 (2H, dd, J=2.0Hz,
【式】）
4.18（2H，ｔ，Ｊ＝7.0Hz，−Ｏ−ＣH2 −）
実施例 10
エポキシコハク酸シクロヘキサンメチルエステ
ルの製造：
実施例１と同様にしてエポキシコハク酸ジクロ
リド2.01ｇ、シクロヘキサンメタノール1.14ｇ、
トリエチルアミン1.01ｇより目的物1.23ｇを得
た。収率54％。
IRνneat naxcm-1：1750（エステル），895（エポキシ
）
NMR〔（CD3）2CO〕δ＝0.80〜2.00（11H，ｍ，
[Formula]) 4.18 (2H, t, J = 7.0Hz, -O-C H 2 -) Example 10 Production of epoxysuccinic acid cyclohexane methyl ester: 2.01 g of epoxysuccinic acid dichloride, cyclohexane in the same manner as in Example 1 1.14g of methanol,
1.23 g of the target product was obtained from 1.01 g of triethylamine. Yield 54%. IRν neat nax cm -1 : 1750 (ester), 895 (epoxy) NMR [(CD 3 ) 2 CO] δ = 0.80 to 2.00 (11H, m,
【式】） 3.60（2H，dd，Ｊ＝2.0Hz，【formula】) 3.60 (2H, dd, J=2.0Hz,
【式】）
3.96（2H，ｄ，Ｊ＝7.0Hz，−Ｏ−ＣH2 −）
実施例 11
エポキシコハク酸−２−シクロヘキサンエチル
エステルの製造：
実施例１と同様にしてエポキシコハク酸ジクロ
リド2.01ｇ、２−シクロヘキサンエタノール1.28
ｇ、トリエチルアミン1.01ｇより目的物1.00ｇを
得た。収率41％。
IRνneat naxcm-1：1745（エステル），900（エポキシ
）
NMR〔（CD3）2CO〕δ＝0.70−1.96（13H，ｍ，
[Formula]) 3.96 (2H, d, J = 7.0Hz, -O-C H 2 -) Example 11 Production of epoxysuccinic acid-2-cyclohexane ethyl ester: Epoxysuccinic acid dichloride 2.01 in the same manner as in Example 1 g, 2-cyclohexaneethanol 1.28
1.00 g of the target product was obtained from 1.01 g of triethylamine. Yield 41%. IRν neat nax cm -1 : 1745 (ester), 900 (epoxy) NMR [(CD 3 ) 2 CO] δ=0.70−1.96 (13H, m,
【式】） 3.60（2H，dd，Ｊ＝2.0Hz，【formula】) 3.60 (2H, dd, J=2.0Hz,
【式】） 4.20（2H，ｔ，Ｊ＝7.0Hz，−Ｏ−ＣH2 −）[Formula]) 4.20 (2H, t, J=7.0Hz, -O-C H 2 -)
Claims (1)
とほぼ等モルの一般式（）、 Ｒ−OH （） （式中、Ｒはアルキル基、フエニル基、フエニ
ル基で置換された炭素数１〜３のアルキル基、シ
クロアルキル基又はシクロアルキル基で置換され
た炭素数１〜３のアルキル基を示す） で表されるアルコールを反応せしめることを特徴
とする一般式（）、 （式中、Ｒは前記の意味を有する） で表されるエポキシコハク酸モノエステルの製造
法。[Claims] 1 General formula () (wherein, An alkyl group having 1 to 3 carbon atoms substituted with a group, a cycloalkyl group, or an alkyl group having 1 to 3 carbon atoms substituted with a cycloalkyl group). formula(), (In the formula, R has the above meaning.) A method for producing an epoxysuccinic acid monoester represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21811382A JPS59108774A (en) | 1982-12-13 | 1982-12-13 | Preparation of epoxysuccinic acid monoester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21811382A JPS59108774A (en) | 1982-12-13 | 1982-12-13 | Preparation of epoxysuccinic acid monoester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59108774A JPS59108774A (en) | 1984-06-23 |
| JPH0360827B2 true JPH0360827B2 (en) | 1991-09-17 |
Family
ID=16714828
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21811382A Granted JPS59108774A (en) | 1982-12-13 | 1982-12-13 | Preparation of epoxysuccinic acid monoester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59108774A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115895752A (en) * | 2021-09-30 | 2023-04-04 | 中国石油化工股份有限公司 | Antiwear additive, preparation method thereof and application thereof in oil products |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54141737A (en) * | 1978-04-20 | 1979-11-05 | Taisho Pharmaceut Co Ltd | Epoxysuccinic acid diester |
| JPS54141735A (en) * | 1978-04-20 | 1979-11-05 | Taisho Pharmaceut Co Ltd | Epoxysuccinic acid ester |
| JPS54141750A (en) * | 1978-04-20 | 1979-11-05 | Taisho Pharmaceut Co Ltd | Epoxysuccinic acid diester derivative |
-
1982
- 1982-12-13 JP JP21811382A patent/JPS59108774A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54141737A (en) * | 1978-04-20 | 1979-11-05 | Taisho Pharmaceut Co Ltd | Epoxysuccinic acid diester |
| JPS54141735A (en) * | 1978-04-20 | 1979-11-05 | Taisho Pharmaceut Co Ltd | Epoxysuccinic acid ester |
| JPS54141750A (en) * | 1978-04-20 | 1979-11-05 | Taisho Pharmaceut Co Ltd | Epoxysuccinic acid diester derivative |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59108774A (en) | 1984-06-23 |
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