JPH02145540A - Production of dibasic acid ester - Google Patents
Production of dibasic acid esterInfo
- Publication number
- JPH02145540A JPH02145540A JP63301418A JP30141888A JPH02145540A JP H02145540 A JPH02145540 A JP H02145540A JP 63301418 A JP63301418 A JP 63301418A JP 30141888 A JP30141888 A JP 30141888A JP H02145540 A JPH02145540 A JP H02145540A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- acid ester
- cyclohexanone
- expressed
- dibasic acid
- 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.)
- Pending
Links
- 150000002148 esters Chemical class 0.000 title claims abstract description 19
- 239000002253 acid Substances 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 239000003377 acid catalyst Substances 0.000 claims abstract description 7
- 125000005396 acrylic acid ester group Chemical group 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 6
- 235000003891 ferrous sulphate Nutrition 0.000 abstract description 5
- 239000011790 ferrous sulphate Substances 0.000 abstract description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 abstract description 5
- 239000004593 Epoxy Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 3
- 239000010687 lubricating oil Substances 0.000 abstract description 3
- 150000002978 peroxides 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
- 239000010730 cutting oil 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
- 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 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- -1 acrylic ester Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 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
- 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
- 239000003054 catalyst Substances 0.000 description 2
- 238000001816 cooling Methods 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 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
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 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
- 238000003754 machining Methods 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
- 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
- IJMWNARRWGXIEF-UHFFFAOYSA-N methyl 3-methyl-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)C IJMWNARRWGXIEF-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000203 mixture Substances 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
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical compound P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【発明の詳細な説明】 Ｌ！上辺五里方１ 本発明は、二塩基酸エステルの製造法に関する。[Detailed description of the invention] L! Kamibegori direction 1 The present invention relates to a method for producing a dibasic acid ester.
の 術及びその問題点 従来、−取代 〔式中Ｒ２及びＲ３はそれぞれ低級アルキル基を示す。technique and its problems Conventionally, - machining allowance [In the formula, R2 and R3 each represent a lower alkyl group.
〕
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一般式Ｃ式中Ｒ１、Ｒ２及び
Ｒ３は、それぞれ低級アルキル基を示す。〕
で表わされる二塩基酸エステルのうち、Ｒ１Ｒ２及びＲ
３が共にメチル基を示す化合物は、例えば式
％式％
で表わされる化合物をパラジウム−ホスフィン触媒の存
在下にジカルボニレーションすることにより製造されて
いる（米国特許第４６２９８０７号明細書参照）。しか
しながら、この方法によれば、目的とする二塩基酸エス
テルが、１９．１％という低収率で１９られるに過ぎな
い。] By reacting the acrylic ester derivative represented by the following in the presence of a metal salt, R1, R2 and R3 each represent a lower alkyl group in the general formula C. ] Of the dibasic acid esters represented by R1R2 and R
A compound in which 3 both represent a methyl group is produced, for example, by dicarbonylating a compound represented by the formula % in the presence of a palladium-phosphine catalyst (see US Pat. No. 4,629,807). However, according to this method, the desired dibasic acid ester can only be obtained with a low yield of 19.1%.
問題点を解決するための手段
本発明の目的は、上記−取代（１）で表わされる二塩基
酸エステルを高収率で製造し得る方法を提供することに
ある。Means for Solving the Problems An object of the present invention is to provide a method for producing the dibasic acid ester represented by the above-mentioned -removal allowance (1) in high yield.
本発明によれば、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％（３）
（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一般式（１）で表わされる二
基Ｌ［エステルを得ることを特徴とする二塩基酸エステ
ルの製造法が提供される。According to the present invention, in the presence of an acid catalyst - removal rate % 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 an acrylic ester represented by the general formula % (3) (wherein R2 and R3 are the same as above). Provided is a method for producing a dibasic acid ester, characterized in that a dibasic L[ester represented by general formula (1) is obtained by reacting a derivative in the presence of a metal salt.
本発明の方法で製造される一般式（１）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
方法で製造される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１ｑる。The dibasic acid ester of general formula (1) produced by the method of the present invention can be used, for example, as an electrolytic solution for driving an electrolytic capacitor, a lubricating oil,
It can be suitably used as cutting oil, plasticizer, etc. Furthermore, the dibasic acid ester produced by the method of the present invention can be used as a raw material for producing glycidyl esters, polyesters, polyamides, etc.
It is also used as an epoxy curing agent, 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.
本発明においては、まず−取代（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おる。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
重量部（以下単に「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２５０〜３
５０部程度用いるのがよい。また酸触媒は、シクロへキ
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。In the present invention, first, cyclohexanone and hydrogen peroxide are reacted in the lower alcohol (removal allowance (2)) in the presence of an acid catalyst to form lower alkoxycyclohexyl peroxide. Examples of the lower alcohol include anhydrous methanol, ethanol, isopropanol, n-
Examples include butanol, tert-butanol, and the like. 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 suitable. In the reaction between cyclohexanone and hydrogen peroxide, the ratio of the two used is not particularly limited, but the former is usually 100%
The amount per part by weight (hereinafter simply referred to as "parts") is about 80 to 130 parts, preferably about 100 to 110 parts. The above lower alcohol is usually about 200 to 700 parts, preferably 250 to 3 parts, per 100 parts of cyclohexanone.
It is recommended to use about 50 copies. The acid catalyst is usually used in an amount of about 5 to 10 parts, preferably about 6 to 8 parts, per 100 parts of cyclohexanone. The reaction is usually carried out under cooling.
Preferably, the reaction proceeds suitably at around -20 to 10'C, and the reaction 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−取代（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、メタクリル酸エチル、メタクリルｌ
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−エチルアクリル駿メチル、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 meet the above-mentioned allowance (3), such as methyl methacrylate, ethyl methacrylate, etc. , methacrylic
n-propyl, isopropyl methacrylate, ln-butyl methacrylate, 2-ethyl acrylic methyl, 2-(n
Examples include methyl -propyl)acrylate, methyl 2-isopropylacrylate, methyl 2'-(n-butyl)acrylate, and 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
第一鉄塩が好適である。第一鉄塩としては、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５Ａ酸第−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 ferrous salts 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 5A acid, 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、−取代（３）の
アクリル酸エステル誘導体を通常１００〜２５０部程度
、好ましくは１２０〜１４０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 250 parts, preferably about 120 to 140 parts, of the acrylic ester derivative of -removal allowance (3) per 100 parts of cyclohexanone. It is better to use it as such.
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１ｑだ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 dissolved in lower alcohol as much as possible to form a 1q suspension or homogeneous solution. 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
°Ｃ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 °C and is generally completed in about 0.3 to 2 hours.
斯くして得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 thus obtained 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.
発明の効果
本発明の方法によれば、上記−取代（１）の二塩基酸エ
ステルが、極めて高収率で製造される。Effects of the Invention According to the method of the present invention, the above-mentioned dibasic acid ester (1) is produced in an extremely high yield.
Ｘ−一度一一舅 以下に実施例を掲げて本発明をより一層明らかにする。X-once eleven father-in-law Examples are given below to further clarify the present invention.
実施例１
撹拌機付反応容器に無水メタノール４６０ｋｏを入れ、
これを５℃に冷却し、シクロへキサノン１６０ｋａ及び
濃硫酸１０ｋａを加えて撹拌しながら更に３５％過酸化
水素水１６０ｋｇ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２００ｋｇを溶解し、別に窒素ガス中で硫酸第
一鉄（７水塩）４８０ｋｇを反応温度を−２０〜−５°
Ｃ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’ｉ ００
〜１２０’Ｃ／ １ ｍｍ１１ｇで蒸留して、Ｒ１Ｒ２
及びＲ３が共にメチル基である一般式（１）の化合物を
２６３ ｋｇ得る。収率７０％元素分析値（Ｃ１２Ｒ２
２０４として）Ｈ
理論値（％）： ６２．５８ ９．６３実測値（％）
： ６２．３４ ９．９１沸点：１０８〜１１０℃／
１ ｍｍ１−１゜ＨＮＭＲ（ＣＤＣＱ３．２７０ＭＨ
ｚ、ｐｐｍ／ＴＭＳ）
１．１４ （ｄ、Ｊ＝５．４Ｈ１，３Ｈ，ＣＨ３）１．
２５〜１．８０ （ｂｒ、１０Ｈ，メチレン）２．３０
（ｔ、Ｊ＝８．１Ｈｚ、２Ｈ。Example 1 460 ko of anhydrous methanol was placed in a reaction vessel equipped with a stirrer,
Cool this to 5°C, add 160 ka of cyclohexanone and 10 ka of concentrated sulfuric acid, and gradually add 160 kg of 35% hydrogen peroxide while stirring.
Continue stirring for a minute to allow the reaction to occur. Dissolve 200 kg of methyl methacrylate in this reaction solution, and separately add 480 kg of ferrous sulfate (heptahydrate) in nitrogen gas at a reaction temperature of -20 to -5°.
While maintaining the temperature at C, gradually add and react. 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 'i 00
Distilled at ~120'C/1 mm 11 g, R1R2
and R3 are both methyl groups, 263 kg of a compound of general formula (1) is obtained. Yield 70% Elemental analysis value (C12R2
204) H Theoretical value (%): 62.58 9.63 Actual value (%)
: 62.34 9.91 Boiling point: 108-110℃/
1 mm1-1°HNMR (CDCQ3.270MH
z, ppm/TMS) 1.14 (d, J=5.4H1,3H,CH3)1.
25-1.80 (br, 10H, methylene) 2.30
(t, J=8.1Hz, 2H.
−ＣＯＣＨ２） ２．４３ （ｓｅｘｔｅｔ、Ｊ＝５，４Ｈ２，１Ｈ。-COCH2) 2.43 (sextet, J=5,4H2,1H.
ＣＨ−ＣＨ３）
３．６７ （ｓ、６Ｈ，ＱＣＣ８４
マススペクトル（ｍ／ｅ）：
２３０ （Ｐ” ）、１９９ （Ｐ” −０’ＣＨ３）
。CH-CH3) 3.67 (s, 6H, QCC84 Mass spectrum (m/e): 230 (P"), 199 (P"-0'CH3)
.
０＋
１７１ （Ｐ” −ＣＯＣＨ３）
ＩＲスペクトルに−ト、 ｃｍ” ） ：２９３０．２
８５０，１７４０，１４３０゜１３６０．１２００
ＣＮＭＲ（ＣＤＣＱ３．２７０ＭＨｚ、ｐｐｍ／ＴＭＳ
）
１７、Ｏ（ΩＨ３＞、２４．７．２７．０゜２８．７，
２９．３，３３．６，３４．０゜３９．３，５１．４
（ＯΩ１１３）、５’１．７（０ΩＨ３）、１７４．２
（Ｃ＝Ｏ）。0+ 171 (P”-COCH3) IR spectrum, cm”): 2930.2
850,1740,1430゜1360.1200 CNMR (CDCQ3.270MHz, ppm/TMS
) 17, O(ΩH3>, 24.7.27.0°28.7,
29.3, 33.6, 34.0°39.3, 51.4
(OΩ113), 5'1.7 (0ΩH3), 174.2
(C=O).
１７７．２ （Ｃ＝Ｏ）177.2 (C=O)
Claims (1)
酸化水素とを反応させ、次いで得られる反応液に一般式 ▲数式、化学式、表等があります▼ 〔式中Ｒ＾２及びＲ＾３はそれぞれ低級アルキル基を示
す。〕 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一般式 ▲数式、化学式、表等があります▼ 〔式中Ｒ＾１、Ｒ＾２及びＲ＾３は前記に同じ。〕で表
わされる二塩基酸エステルを得ることを特徴とする二塩
基酸エステルの製造法。(1) In the presence of an acid catalyst, the general formula R^1OH [wherein R^1 represents a lower alkyl group]. ] Cyclohexanone and hydrogen peroxide are reacted in a lower alcohol represented by the formula, and then the reaction solution obtained has the general formula ▲ mathematical formula, chemical formula, table, etc. ▼ [In the formula, R^2 and R^3 are each lower alkyl Indicates the group. ] By reacting the acrylic acid ester derivative represented by in the presence of a metal salt, a general formula ▲ mathematical formula, chemical formula, table, etc. can be obtained ▼ [In the formula, R^1, R^2 and R^3 are the same as above. ] A method for producing a dibasic acid ester, characterized by obtaining a dibasic acid ester represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63301418A JPH02145540A (en) | 1988-11-28 | 1988-11-28 | Production of dibasic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63301418A JPH02145540A (en) | 1988-11-28 | 1988-11-28 | Production of dibasic acid ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02145540A true JPH02145540A (en) | 1990-06-05 |
Family
ID=17896635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63301418A Pending JPH02145540A (en) | 1988-11-28 | 1988-11-28 | Production of dibasic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02145540A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55139336A (en) * | 1979-04-13 | 1980-10-31 | Okamura Seiyu Kk | Preparation of polycarboxylic acid and its ester |
-
1988
- 1988-11-28 JP JP63301418A patent/JPH02145540A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55139336A (en) * | 1979-04-13 | 1980-10-31 | Okamura Seiyu Kk | Preparation of polycarboxylic acid and its ester |
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