JPH02145539A - Dibasic acid ester - Google Patents
Dibasic acid esterInfo
- Publication number
- JPH02145539A JPH02145539A JP30141688A JP30141688A JPH02145539A JP H02145539 A JPH02145539 A JP H02145539A JP 30141688 A JP30141688 A JP 30141688A JP 30141688 A JP30141688 A JP 30141688A JP H02145539 A JPH02145539 A JP H02145539A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- acid ester
- reaction
- dibasic acid
- parts
- 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.)
- Granted
Links
- 150000002148 esters Chemical class 0.000 title claims abstract description 11
- 239000002253 acid Substances 0.000 title claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 150000003839 salts Chemical class 0.000 abstract description 11
- 239000003377 acid catalyst Substances 0.000 abstract description 5
- -1 acrylate ester Chemical class 0.000 abstract description 4
- 239000004593 Epoxy Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000004952 Polyamide Substances 0.000 abstract description 2
- 239000003990 capacitor Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000003085 diluting agent Substances 0.000 abstract description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 abstract description 2
- 239000004014 plasticizer Substances 0.000 abstract description 2
- 229920002647 polyamide Polymers 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 abstract 1
- 239000003822 epoxy resin Substances 0.000 abstract 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000314 lubricant Substances 0.000 abstract 1
- 238000003754 machining Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 abstract 1
- 229920000647 polyepoxide Polymers 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- 239000011790 ferrous sulphate Substances 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000006355 carbonyl methylene group Chemical group [H]C([H])([*:2])C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000010730 cutting oil Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- CFUNAYGQFFNNSD-UHFFFAOYSA-L ferrous ammonium sulfate heptahydrate Chemical compound [NH4+].[NH4+].O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O CFUNAYGQFFNNSD-UHFFFAOYSA-L 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- JKJJSJJGBZXUQV-UHFFFAOYSA-N methyl 2-methylidenebutanoate Chemical compound CCC(=C)C(=O)OC JKJJSJJGBZXUQV-UHFFFAOYSA-N 0.000 description 1
- DKSFGNGSHIVGLY-UHFFFAOYSA-N methyl 3,3-dimethyl-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)(C)C DKSFGNGSHIVGLY-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、二塩基酸エステルに関する。[Detailed description of the invention] Industrial applications The present invention relates to dibasic acid esters.
発明の開示
本発明の二塩基酸エステルは、文献未記載の新規化合物
であって、下記−取代（１）で表わされる。Disclosure of the Invention The dibasic acid ester of the present invention is a novel compound that has not been described in any literature, and is represented by the following - removal amount (1).
〔式中Ｒ１、Ｒ２及びＲ３は、それぞれ低級アルキル基
を示す。〕
本発明の二塩基酸エステルは、例えば電解コンデンサ駆
動用電解液、潤滑油、切削油、可塑剤等に好適に使用さ
れ得る。更に本発明の二塩基酸エステルは、グリシジル
エステル、ポリエステル、ポリアミド等の製造原料とし
て、またエポキシ硬化剤、エポキシ反応希釈剤等として
も使用され得る。[In the formula, R1, R2 and R3 each represent a lower alkyl group. ] The dibasic acid ester of the present invention can be suitably used, for example, as an electrolytic solution for driving an electrolytic capacitor, a lubricating oil, a cutting oil, a plasticizer, and the like. Further, the dibasic acid ester of the present invention can be used as a raw material for producing glycidyl esters, polyesters, polyamides, etc., and also as an epoxy curing agent, an epoxy reaction diluent, etc.
本明細書において、Ｒ１、Ｒ２及びＲ３で示される低級
アルキル基としては、例えばメチル、エチル、ｎ−プロ
ピル、イソプロピル、ｎ−ブチル、イソブチル、ｔｅｒ
ｔ−ブチル基等の直鎖又は分枝鎖状の炭素数１〜４のア
ルキル基を挙げることができる。In this specification, examples of lower alkyl groups represented by R1, R2 and R3 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, ter
Examples include straight chain or branched alkyl groups having 1 to 4 carbon atoms such as t-butyl group.
本発明の一般式（１）で表わされる二塩基酸エステルは
、例えば酸触媒の存在下−取代％式％（２）
〔式中Ｒ１は前記に同じ。〕
で表わされる低級アルコール中でシクロヘキサノンと過
酸化水素とを反応させ、次いで得られる反応液に一般式
〔式中Ｒ２及びＲ３は前記に同じ。〕
で表わされるアクリル酸エステル誘導体を金属塩の存在
下に反応させることにより製造される。The dibasic acid ester represented by the general formula (1) of the present invention can be prepared, for example, in the presence of an acid catalyst by the following formula: % (2) [wherein R1 is the same as above. ] Cyclohexanone and hydrogen peroxide are reacted in a lower alcohol represented by the formula, and then the resulting reaction solution is mixed with the general formula [where R2 and R3 are the same as above]. ] It is produced by reacting an acrylic ester derivative represented by the following in the presence of a metal salt.
更に詳しくは、まず−取残（２）の低級アルコール中、
シクロヘキサノンと過酸化水素とを酸触媒の存在下に反
応させて低級アルコキシシクロへキシルパーオキサイド
とする。ここで低級アルコールとしては、例えば無水の
メタノール、エタノール、イソプロパツール、ｎ−ブタ
ノール、ｔｅｒｔ−ブタノール等を挙げることができる
。また酸触媒としては、例えば硫酸、塩酸、リン酸、ト
リフルオロ酢酸等を挙げることができ、これらの中でも
硫酸及びリン酸が特に好適である。シクロヘキサノンと
過酸化水素との反応において、両者の使用割合としては
、特に限定されるものではないが、通常前者１００重串
部（以下単に１部」と記す）当り、８０〜１３０部程度
、好ましくは１００〜１１０部程度とするのがよい。上
記低級アルコールは、シクロへキサノン１００部当り、
通常２００〜７００部程度、好ましくは２５０〜３５０
部程度用いるのがよい。また酸触媒は、シクロヘキサノ
ン１００部当り、通常５〜１０部程度、好ましくは６〜
８部程度用いるのがよい。該反応は、通常冷却下、好ま
しくは一２０〜１０’Ｃ付近にて好適に進行し、短時間
で該反応は終了する。More specifically, first - in the lower alcohol of the remainder (2),
Cyclohexanone and hydrogen peroxide are reacted in the presence of an acid catalyst to form lower alkoxycyclohexyl peroxide. Examples of the lower alcohol include anhydrous methanol, ethanol, isopropanol, n-butanol, and tert-butanol. Further, examples of the acid catalyst include sulfuric acid, hydrochloric acid, phosphoric acid, trifluoroacetic acid, etc. Among these, sulfuric acid and phosphoric acid are particularly preferred. In the reaction between cyclohexanone and hydrogen peroxide, the proportion of the two used is not particularly limited, but is usually about 80 to 130 parts per 100 parts (hereinafter simply referred to as 1 part) of the former, preferably about 80 to 130 parts. is preferably about 100 to 110 parts. The above lower alcohol is per 100 parts of cyclohexanone,
Usually about 200 to 700 parts, preferably 250 to 350 parts
It is best to use about 30%. The acid catalyst is usually about 5 to 10 parts, preferably 6 to 10 parts, per 100 parts of cyclohexanone.
It is best to use about 8 parts. The reaction normally proceeds suitably under cooling, preferably around -20 to 10'C, and is completed in a short time.
上記反応で低級アルコキシシクロへキシルパーオキサイ
ドが生成するが、本発明ではこれを単離することなく、
反応液のまま次の反応に供するのがよい。Lower alkoxycyclohexyl peroxide is produced in the above reaction, but in the present invention, it is not isolated, but
It is best to use the reaction solution as is for the next reaction.
引続く反応で用いられる一般式（３）のアクリル酸エス
テル誘導体としては、上記−取残（３）に該当するもの
である限り、従来公知のものを広く使用でき、例えばメ
タクリル酸メチル、メタクリル酸エヂル、メタクリルＩ
ｎ−プロピル、メタクリル酸イソプロピル、メタクリル
ｌｎ−ブチル、２−エチルアクリル酸メチル、２−（ｎ
−プロピル）アクリル酸メチル、２−イソプロピルアク
リル酸メチル、２−（ｎ−ブチル）アクリル酸メチル、
２−（ｔｅｒｔ−ブチル）アクリル酸メチル等を挙げる
ことができる。As the acrylic acid ester derivative of the general formula (3) used in the subsequent reaction, a wide variety of conventionally known derivatives can be used as long as they fall under the above-mentioned residue (3), such as methyl methacrylate, methacrylic acid, etc. Egil, Methacrylic I
n-propyl, isopropyl methacrylate, ln-butyl methacrylate, methyl 2-ethyl acrylate, 2-(n
-propyl) methyl acrylate, 2-isopropylacrylate methyl, 2-(n-butyl) methyl acrylate,
Examples include methyl 2-(tert-butyl)acrylate.
上記反応液と一般式（３）のアクリル酸エステル誘導体
とを反応させるに際しては、金属塩が触媒として用いら
れる。ここで金属塩としては、例えば鉄、銅、コバルト
、チタン、錫等の金属の硫酸塩、塩化物、アンモニウム
塩等の塩やこれらの水和物等が挙げられる。この中でも
第一鉄塩が好適で必る。第一鉄塩とし−Ｃは、例えば硫
酸第一鉄、塩化第一鉄、硫酸第一・鉄アンモニウム塩等
やこれらの水和物等が挙げられる。これらの中で特に硫
酸第一鉄が好ましく、硫酸第一鉄は反応後にこれを硫酸
と鉄で還元して５ＡＨ第一鉄を回収し、再使用を有利に
行なうことができる。上記金属塩は、１種単独で、又は
２種以上混合して用いられる。When reacting the above reaction solution with the acrylic acid ester derivative of general formula (3), a metal salt is used as a catalyst. Examples of the metal salt include salts such as sulfates, chlorides, and ammonium salts of metals such as iron, copper, cobalt, titanium, and tin, and hydrates thereof. Among these, ferrous salts are preferred. Examples of the ferrous salt -C include ferrous sulfate, ferrous chloride, ferrous ammonium sulfate, and hydrates thereof. Among these, ferrous sulfate is particularly preferred, and after the reaction, ferrous sulfate can be reduced with sulfuric acid and iron to recover ferrous 5AH, which can be advantageously reused. The above metal salts may be used alone or in combination of two or more.
上記反応液と一般式（３）のアクリル酸エステル誘導体
とは、シクロへキサノン１００部当り、取残（３）のア
クリル酸エステル誘導体を通常１００〜２７０部程度、
好ましくは２３０〜２５０部程度となるように、使用さ
れるのがよい。The reaction solution and the acrylic ester derivative of general formula (3) are usually about 100 to 270 parts of the acrylic ester derivative of the residue (3) per 100 parts of cyclohexanone.
Preferably, it is used in an amount of about 230 to 250 parts.
該反応を実施するに当っては、上記反応液に上記アクリ
ル酸エステル誘導体を加えて、撹拌下、金属塩をそのま
ま用いるか又は予め低級アルコールにできるだけ溶解し
て得た懸濁液乃至均一溶液を徐々に滴下する。ここで低
級アルコールは、上記シクロヘキサノンと過酸化水素と
の反応で用いられる低級アルコールと同種のものとする
のがよい。To carry out the reaction, the acrylic acid ester derivative is added to the reaction solution and, under stirring, the metal salt is used as it is or a suspension or homogeneous solution obtained by dissolving as much as possible in a lower alcohol in advance is prepared. Drip gradually. Here, the lower alcohol is preferably of the same type as the lower alcohol used in the reaction between cyclohexanone and hydrogen peroxide.
上記金属塩の低級アルコール懸濁液乃至均一溶液は、窒
素ガス中金属塩に対して２〜４倍量の低級アルコール中
に金属塩を懸濁乃至溶解させて調製するのがよい。金属
塩の懸濁乃至溶解に当り、窒素ガスを存在させると、上
記反応を効率よく行なうことができる。上記反応は、冷
却下、通常−２０〜１０℃付近、好ましくは一１０〜５
℃付近にて好適に進行し、一般に０．３〜２時間程度で
該反応は完結する。The lower alcohol suspension or homogeneous solution of the metal salt is preferably prepared by suspending or dissolving the metal salt in a lower alcohol in an amount of 2 to 4 times the amount of the metal salt in nitrogen gas. When nitrogen gas is present during suspension or dissolution of the metal salt, the above reaction can be carried out efficiently. The above reaction is carried out under cooling, usually around -20 to 10°C, preferably around -10 to 5°C.
The reaction proceeds suitably at around 0.degree. C. and is generally completed in about 0.3 to 2 hours.
斯くして１ｑられる本発明の一般式（１）の二塩基酸エ
ステルは、慣用の分離精製手段、例えば蒸留等により反
応混合物から容易に単離、精製される。また上記反応で
用いられる低級アルコールも、無水の状態で容易に回収
され得る。The dibasic acid ester of the general formula (1) of the present invention, which is thus 1q, can be easily isolated and purified from the reaction mixture by conventional separation and purification means, such as distillation. Furthermore, the lower alcohol used in the above reaction can also be easily recovered in an anhydrous state.
！−−度一−Ｖ
以下に実施例を掲げて／を発明をより一層明らかにする
。! --Degree-V Examples are given below to further clarify the invention.
実施例１
撹拌機付反応容器に無水メタノール４６０ｋｇを入れ、
これを５℃に冷却し、シクロへキサノン１６０ｋｇ及び
′ａ硫酸１０ｋ（］を加えて撹拌しながら更に３５％過
酸化水素水１６０ｋｃ＋を徐々に加えて５℃を保ちなが
ら１０分間撹拌を続けて反応させる。この反応液にメタ
クリル酸メチル４００ｋｑを溶解し、別に窒素ガス中で
硫酸第一鉄（７水塩）４８０に！；ｌを反応温度を−２
０〜−５℃に保ちながら徐々に添加して反応させる。反
応後、静置分液し、上層のエステル層と下層の第二鉄塩
溶液を分離する。エステル層を水洗、乾燥し、次いで１
４０〜ｂ
Ｒ２及びＲ３が共にメチル基である一般式（１）の化合
物を３２６ｋｇ得る。収率６１％元素分析値（Ｃ＋ ７
Ｒ３ｏ Ｏｓとして）Ｈ
理論値（％）： ６１．７９ ９．１５実測値（％）
： ６２．０１ ８．９２沸点：１５３〜１５５℃／
’ｌ ｍｍＨｇＨＮＭＲ（ＣＤＣＱ３．２７０ＭＨｚ
１ ｐｐｍ／ＴＭＳ）
１．１０ （ｄ、Ｊ＝５．４Ｈｚ、３Ｈ，Ｃ旦３）１．
１５ （ｓ、３Ｈ，Ｃ旦３）
１．２０＝１．８０ （ｍ、１２Ｈ，メチレン）２．２
７ （ｔ、Ｊ＝６．８Ｈｚ、２ｔ−１゜ＣＯＣＨ２）
２．４０〜２．６０ （ｃ、１Ｈ，ＣＯＯ旦）２．６３
．３．６４及び３．６７（各Ｓ、９Ｈ。Example 1 460 kg of anhydrous methanol was placed in a reaction vessel equipped with a stirrer,
Cool this to 5℃, add 160kg of cyclohexanone and 10k of 'a sulfuric acid (), and gradually add 160kc+ of 35% hydrogen peroxide while stirring, and continue stirring for 10 minutes while maintaining the temperature at 5℃ to react. Dissolve 400 kq of methyl methacrylate in this reaction solution, and separately add 480 kq of ferrous sulfate (heptahydrate) to the reaction temperature at -2
The mixture is gradually added and reacted while maintaining the temperature at 0 to -5°C. After the reaction, the mixture is allowed to stand still and separated into an upper ester layer and a lower ferric salt solution. The ester layer was washed with water, dried, and then 1
40-b 326 kg of a compound of general formula (1) in which R2 and R3 are both methyl groups is obtained. Yield: 61% Elemental analysis value (C+ 7
R3o Os) H Theoretical value (%): 61.79 9.15 Actual value (%)
: 62.01 8.92 Boiling point: 153-155℃/
'l mmHgHNMR (CDCQ3.270MHz
1 ppm/TMS) 1.10 (d, J=5.4Hz, 3H, Cdan3) 1.
15 (s, 3H, Cdan3) 1.20=1.80 (m, 12H, methylene) 2.2
7 (t, J=6.8Hz, 2t-1°COCH2) 2.40~2.60 (c, 1H, COOdan) 2.63
．． 3.64 and 3.67 (each S, 9H.
０ＣＲ３）
マススペクトル（ｍ／ｅ）：
３３０ （Ｐ” ）、２９９ （Ｐ” −０ＣＨ
３）。0CR3) Mass spectrum (m/e): 330 (P”), 299 (P”-0CH
3).
０＋
２７１ （Ｐ” −ＣＯＣＨ３）
ＩＲスペクトルに−ト、 ｃｍ−１） ：２９５０．２
８５５，１７４５，１４３０゜１３６０．１２０５
ＣＮＭＲ（ＣＤＣＱ３．２７０ＭＨｚ、ｐｐｍ／ＴＭＳ
）
１７．１（ΩＲ３＞、１９．６ （ΩＲ３）。0+ 271 (P''-COCH3) IR spectrum, cm-1): 2950.2
855,1745,1430゜1360.1205 CNMR (CDCQ3.270MHz, ppm/TMS
) 17.1 (ΩR3>, 19.6 (ΩR3).
２１．２，２４．３．２４．６，２８．９゜２９．７，
３３．９，３５．８．３９．４゜４３．１，５１．５
（ＯΩＨ３＞、５１．６（ＯΩＨ３＞、５１．７ （Ｏ
ΩＨ３）。21.2, 24.3.24.6, 28.9°29.7,
33.9, 35.8.39.4゜43.1, 51.5
(OΩH3>, 51.6 (OΩH3>, 51.7 (O
ΩH3).
１７４．３ （Ｃ＝０）、１７７．３ （Ｃ＝Ｏ）。174.3 (C=0), 177.3 (C=O).
１７７．５ （Ｃ＝Ｏ） （以 上）177.5 (C=O) (that's all)
Claims (1)
キル基を示す。〕 で表わされる二塩基酸エステル。[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R^1, R^2 and R^3 each represent a lower alkyl group. ] A dibasic acid ester represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30141688A JP2681202B2 (en) | 1988-11-28 | 1988-11-28 | Tribasic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30141688A JP2681202B2 (en) | 1988-11-28 | 1988-11-28 | Tribasic acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02145539A true JPH02145539A (en) | 1990-06-05 |
| JP2681202B2 JP2681202B2 (en) | 1997-11-26 |
Family
ID=17896614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30141688A Expired - Lifetime JP2681202B2 (en) | 1988-11-28 | 1988-11-28 | Tribasic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2681202B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1005053A2 (en) | 1998-11-26 | 2000-05-31 | Okamura Oil Mills, Ltd. | Composition comprising long chain dibasic acids and electrolytic solution using thereof |
| JP2006070020A (en) * | 2004-08-03 | 2006-03-16 | Okamura Seiyu Kk | Long-chained polybasic acid mixture |
-
1988
- 1988-11-28 JP JP30141688A patent/JP2681202B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1005053A2 (en) | 1998-11-26 | 2000-05-31 | Okamura Oil Mills, Ltd. | Composition comprising long chain dibasic acids and electrolytic solution using thereof |
| EP1005053A3 (en) * | 1998-11-26 | 2004-01-07 | Okamura Oil Mills, Ltd. | Composition comprising long chain dibasic acids and electrolytic solution using thereof |
| KR100566581B1 (en) * | 1998-11-26 | 2006-05-25 | 오카무라 세이유 가부시키가이샤 | Long chain dibasic acid composition and electrolyte using the same |
| JP2006070020A (en) * | 2004-08-03 | 2006-03-16 | Okamura Seiyu Kk | Long-chained polybasic acid mixture |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2681202B2 (en) | 1997-11-26 |
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