CN101397246B - Method for preparing 2,3-dialkyl succinic acid and ester compounds thereof - Google Patents
Method for preparing 2,3-dialkyl succinic acid and ester compounds thereof Download PDFInfo
- Publication number
- CN101397246B CN101397246B CN2007101752829A CN200710175282A CN101397246B CN 101397246 B CN101397246 B CN 101397246B CN 2007101752829 A CN2007101752829 A CN 2007101752829A CN 200710175282 A CN200710175282 A CN 200710175282A CN 101397246 B CN101397246 B CN 101397246B
- Authority
- CN
- China
- Prior art keywords
- alkyl
- following
- succinic acid
- group
- general structure
- 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.)
- Active
Links
Images
Abstract
The invention relates to a preparation method of 2, 3-dialkyl succinic acid and ester compounds thereof. 1, 2-dialkyl-1, 1, 2, 2-tetra (alkoxy carbonyl)ethane is prepared through the dimerization coupling reaction of 2-alkyl-malonic ester compounds, then the 2, 3-dialkyl succinic acid is prepared by carrying out hydrolysis and decarboxylation reaction, and the 2, 3-dialkyl succinate compounds are prepared by further esterification. The preparation method is conductive to the commercial production of the 2, 3-dialkyl succinate and can be used for preparing a Ziegler-Natta polypropylene catalyst as an internal electron donor compound. The preparation method can be used in the technical field of petrochemical polypropylene.
Description
Technical field
The present invention relates to the preparation method of organic compound, be specifically related to 2, the preparation method of 3-dialkyl succinic acid and ester compound thereof.
Background technology
Seek the focus that ideal electron donor compound is novel polypropylene catalyst research always.Existing document CN1313869A discloses the succinate compounds as one of catalyst component, is used for the preparation of the solid catalyst of olefinic polymerization.Wherein, the succinate of structural formula (IV) is a kind of particularly preferred internal electron donor compound.This series succinate is the internal electron donor of Ziegler-Natta catalyst, has improved the controllability of catalyzer to relative molecular mass distribution, degree of isotacticity and the oligomer of olefin polymer.Adopt this catalyzer, can improve the resistance to impact shock of product, can keep modulus in flexure again simultaneously; Perhaps when improving modulus in flexure (the bending amount of touching is higher than 2100MPa), keep shock strength again; Even can accomplish that the two improves simultaneously.It is reported (contemporary petrochemical complex, 2003,11 (10), 4-11), have equilibrated rigidity and impact property with this impact copolymer of doing the novel propylene polymerizing catalyst production of electron donor with succinate, higher by 20%～30% than the old trade mark.
The CN1313869A document also discloses the preparation method of the succinate of structural formula (IV), is raw material with 2-alkyl acetic ester, and by the existing literature method oxidative coupling preparation of quoting, wherein embodiment 18 has illustrated that Valeric acid ethylester is at lithium diisopropylamine and TiCl
4Effect oxidative coupling down obtains 2,3-dipropyl ethyl succinate.But the prior art synthetic method is difficulty comparatively.Need to use lithium diisopropylamine (LDA) mostly, and temperature requirement is-70 ℃ by the preparation of hazardous product n-Butyl Lithium.So should not realize industrialization.Though the CN1313869A document discloses 2,3-dicyclohexyl ethyl succinate embodiment and it can be by 2, and the esterification and the reduction reaction of 3-phenylbenzene succsinic acid prepare, and do not disclose 2, the concrete preparation method of 3-phenylbenzene succsinic acid.
Summary of the invention
The technical problem to be solved in the present invention is:
The purpose of this invention is to provide a kind of be convenient to the suitability for industrialized production general structure for (III) 2,3-dialkyl succinic acid and general structure thereof are the preparation method of the ester compound of (IV), this helps commercially producing 2,3-dialkyl succinic acid ester, and be used for the preparation of Ziegler-Natta polypropylene catalyst as the internal electron donor compound.
Technical scheme of the present invention is:
A kind of 2, the preparation method of 3-dialkyl succinic acid; May further comprise the steps:
With general structure is 1 of (II) formula, 2-dialkyl-1,1,2, and 2-four (-oxyl carbonyl) ethane is raw material;
4 ester groups in the general structure of described raw material (II) are under acidic conditions or alkaline condition, hydrolysis reaction all takes place, any two ester groups that connect with different carbon atoms in above-mentioned 4 ester groups, decarboxylic reaction after obtaining carboxyl, has taken place again in hydrolysis, the generating structure general formula be (III) 2, the 3-dialkyl succinic acid;
In general structure (II), (III):
R
1Group is selected from a kind of in following: the C of straight chain
1～C
20The C of alkyl, side chain
1～C
20Alkyl, C
3～C
20Cycloalkyl, C
4～C
20Alkyl-cycloalkyl, C
4～C
20Cycloalkylalkyl, C
6～C
20Aryl, C
7～C
20Alkaryl, C
7～C
20Aralkyl;
R
3Group is selected from a kind of in following: the C of straight chain
1～C
20The C of alkyl, side chain
1～C
20Alkyl, C
4～C
20Cycloalkylalkyl, C
7～C
20Aralkyl.
On above-mentioned basic technical scheme basis, further increase and to comprise raw material (II) preparation process
Technical scheme:
Described general structure prepares by following manner for the compound of (II) formula:
React with active metal or alkali earlier with the 2-alkyl-malonic ester compounds of general structure for (I) formula, and in non-protonic solvent, be dissolved as reaction solution, after oxygenant is dissolved in aprotic solvent, join in the described reaction solution, the dimerization linked reaction takes place, the generating structure general formula is 1 of (II) formula, 2-dialkyl-1,1,2,2-four (-oxyl carbonyl) ethane;
(I)
In general structure (I):
R
1Group is selected from a kind of in following: the C of straight chain
1～C
20The C of alkyl, side chain
1～C
20Alkyl, C
3～C
20Cycloalkyl, C
4～C
20Alkyl-cycloalkyl, C
4～C
20Cycloalkylalkyl, C
6～C
20Aryl, C
7～C
20Alkaryl, C
7～C
20Aralkyl;
R
3Group is selected from a kind of in following: the C of straight chain
1～C
20The C of alkyl, side chain
1～C
20Alkyl, C
4～C
20Cycloalkylalkyl, C
7～C
20Aralkyl.
Promptly go out the compound of general structure (II) earlier from the compound of general structure (I), refabrication goes out the compound of general structure (III).
For step from (I) formula compound (II) formula compound, dual mode can be arranged, first kind above-mentioned is the product that dissolves (I) formula compound and active metal or alkali reaction with non-protonic solvent, and the dimerization linked reaction takes place under the oxygenant effect, the generating structure general formula is 1 of (II) formula, 2-dialkyl-1,1,2,2-four (-oxyl carbonyl) ethane; Second kind is to use electrochemical oxidation.
Wherein the qualification of first kind of scheme is:
Described non-protonic solvent is selected from a kind of in the following solvent: tetrahydrofuran (THF), dimethyl formamide, dimethyl sulfoxide (DMSO), acetonitrile;
Described active metal or alkali are selected from a kind of in following: the alkoxide of basic metal, alkaline-earth metal, alkalimetal hydride, alkaline earth metal hydride, alkali alcoholate, alkaline-earth metal, alkaline carbonate, alkaline earth metal carbonate;
Described oxygenant is selected from a kind of in following: halogen, superoxide, transiting metal oxidation attitude compound.
Further preferred version is:
Described non-protonic solvent is selected from a kind of in the following solvent: tetrahydrofuran (THF), dimethyl formamide, dimethyl sulfoxide (DMSO);
Described active metal or alkali are selected from a kind of in following: sodium Metal 99.5, potassium metal, potassium ethylate, sodium ethylate, sodium hydride;
Described oxygenant is selected from a kind of in following: superoxide, transiting metal oxidation attitude compound.
Another kind of preferred version is:
Described non-protonic solvent is selected from a kind of in the following solvent: tetrahydrofuran (THF), dimethyl formamide, dimethyl sulfoxide (DMSO);
Described active metal or alkali are selected from a kind of in following: potassium ethylate, sodium hydride;
Described oxygenant is: iodine.
For step, can also adopt the scheme of prior art electrochemical oxidation from (I) formula compound (II) formula compound:
Described general structure prepares by following manner for the compound of (II) formula:
With general structure is the 2-alkyl-malonic ester compounds of (I) formula, and the method by electrochemical oxidation (referring to Chem.Ber., 127 (7), 1257-1262,1994.), the generating structure general formula is 1 of (II) formula, 2-dialkyl-1,1,2,2-four (-oxyl carbonyl) ethane;
In general structure (I):
R
1Group is selected from a kind of in following: the C of straight chain
1～C
20The C of alkyl, side chain
1～C
20Alkyl, C
3～C
20Cycloalkyl, C
4～C
20Alkyl-cycloalkyl, C
4～C
20Cycloalkylalkyl, C
6～C
20Aryl, C
7～C
20Alkaryl, C
7～C
20Aralkyl;
R
3Group is selected from a kind of in following: the C of straight chain
1～C
20The C of alkyl, side chain
1～C
20Alkyl, C
4～C
20Cycloalkylalkyl, C
7～C
20Aralkyl.
Step for from (II) formula compound (III) formula compound can adopt dual mode, and a kind of is that described hydrolysis and decarboxylic reaction take place under the acidic hydrolysis condition, and another kind is that described hydrolysis and decarboxylic reaction take place under the alkaline hydrolysis condition.
Wherein the qualification of acidic hydrolysis and decarboxylic reaction scheme is:
Described general structure is the compound of (II) formula, under strong acid condition, under room temperature to 100 ℃ temperature, described hydrolysis and decarboxylic reaction takes place, the generating structure general formula be (III) 2, the 3-dialkyl succinic acid.
Further preferred:
Described general structure is the compound of (II) formula, under concentrated hydrochloric acid or 50%～90% vitriolic condition, under 90 ℃～100 ℃ temperature, described hydrolysis and decarboxylic reaction takes place, the generating structure general formula be (III) 2, the 3-dialkyl succinic acid.
For the step from (II) formula compound (III) formula compound, the qualification of alkaline hydrolysis and decarboxylic reaction scheme is:
With described general structure is the compound of (II) formula, with the dissolving of low-carbon alcohol kind solvent, under refluxad, with the oxyhydroxide reaction of alkali-metal oxyhydroxide or alkaline-earth metal, 1 hour～20 hours reaction times;
The solvent in the reaction solution is sloughed in evaporation then, adds entry in residual reaction liquid, extracts reaction solution with the organic solvent extracting that is insoluble in water again, isolates water; Above-mentioned water is neutralized with protonic acid, obtain containing general structure for (III) 2, the mixture of 3-dialkyl succinic acid; Through separation and purification, obtain 2,3-dialkyl succinic acid product.
For above-mentioned fundamental sum optimized technical scheme, especially for following preferred group:
In general structure (I), (II), (III):
R
1Group is selected from a kind of in following: the C of straight chain
1～C
8The C of alkyl, side chain
1～C
8Alkyl, C
3～C
9Cycloalkyl, C
4～C
9Alkyl-cycloalkyl, C
4～C
9Cycloalkylalkyl, C
6～C
10Aryl, C
7～C
10Alkaryl, C
7～C
10Aralkyl;
R
3Group is selected from a kind of in following: the C of straight chain
1～C
8The C of alkyl, side chain
1～C
8Alkyl, C
4～C
9Cycloalkylalkyl, C
7～C
10Aralkyl.
Further preferred, in general structure (I), (II), (III):
R
1Group is selected from a kind of in following: the C of straight chain
3～C
8The C of alkyl, side chain
3～C
8Alkyl, C
3～C
9Cycloalkyl, C
6～C
10Aryl, C
7～C
10Alkaryl, C
7～C
10Aralkyl;
R
3Group is selected from a kind of in following: the C of straight chain
1～C
8The C of alkyl, side chain
1～C
8Alkyl, C
7～C
10Aralkyl.
Further preferred again, in general structure (I), (II), (III):
R
1Group is selected from a kind of in following: sec.-propyl, isobutyl-, sec-butyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, neo-pentyl, isohexyl, Sec-Hexyl, 5-methyl hexyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, p-methylphenyl;
R
3Group is selected from a kind of in following: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, phenmethyl.
Further preferred again, in general structure (I), (II), (III):
R
1Group is selected from a kind of in following: sec.-propyl, isobutyl-, cyclopentyl, cyclohexyl, phenyl, p-methylphenyl;
R
3Group is selected from a kind of in following: methyl, ethyl, phenmethyl.
Preferred especially, in general structure (I), (II), (III):
R
1Group is selected from a kind of in following: phenyl, sec.-propyl;
R
3Group is selected from a kind of in following: methyl, ethyl;
Promptly prepare: 2,3-phenylbenzene succsinic acid, 2,3-di-isopropyl succsinic acid.
For 2, the preparation method of 3-dialkyl succinic acid ester compound is above-mentioned 2, on the preparation method basis of 3-dialkyl succinic acid, has increased esterif iotacation step, goes out the compound of general structure (IV) from the compound of general structure (III).
Basic technical scheme is:
With general structure is 1 of (II) formula, 2-dialkyl-1,1,2, and 2-four (-oxyl carbonyl) ethane is raw material;
4 ester groups in the general structure of described raw material (II) are under acidic conditions or alkaline condition, hydrolysis reaction all takes place, any two ester groups that connect with different carbon atoms in above-mentioned 4 ester groups, decarboxylic reaction after obtaining carboxyl, has taken place again in hydrolysis, the generating structure general formula be (III) 2, the 3-dialkyl succinic acid;
Described general structure be (III) 2, the 3-dialkyl succinic acid is under the protonic acid catalytic condition, again with R
2OH reaction, generating structure general formula be (IV) 2,3-dialkyl succinic acid ester compound;
In general structure (II), (III), (IV):
R
1Group is selected from a kind of in following: the C of straight chain
1～C
20The C of alkyl, side chain
1～C
20Alkyl, C
3～C
20Cycloalkyl, C
4～C
20Alkyl-cycloalkyl, C
4～C
20Cycloalkylalkyl, C
6～C
20Aryl, C
7～C
20Alkaryl, C
7～C
20Aralkyl;
R
2Group is selected from a kind of in following: the C of straight chain
1～C
20The C of alkyl, side chain
1～C
20Alkyl, C
3～C
20Cycloalkyl, C
4～C
20Alkyl-cycloalkyl, C
4～C
20Cycloalkylalkyl, C
6～C
20Aryl, C
7～C
20Alkaryl, C
7～C
20Aralkyl;
R
3Group is selected from a kind of in following: the C of straight chain
1～C
20The C of alkyl, side chain
1～C
20Alkyl, C
4～C
20Cycloalkylalkyl, C
7～C
20Aralkyl;
R
2R among the OH
2Group and (IV) formula R
2Group is identical.
Above-mentioned 2, on preparation method's basic technical scheme basis of 3-dialkyl succinic acid ester compound, further increase the technical scheme that comprises raw material (II) preparation process:
Described general structure prepares by following manner for the compound of (II) formula:
React with active metal or alkali earlier with the 2-alkyl-malonic ester compounds of general structure for (I) formula, and in non-protonic solvent, be dissolved as reaction solution, after oxygenant is dissolved in aprotic solvent, join in the described reaction solution, the dimerization linked reaction takes place, the generating structure general formula is 1 of (II) formula, 2-dialkyl-1,1,2,2-four (-oxyl carbonyl) ethane;
In general structure (I):
R
1Group is selected from a kind of in following: the C of straight chain
1～C
20The C of alkyl, side chain
1～C
20Alkyl, C
3～C
20Cycloalkyl, C
4～C
20Alkyl-cycloalkyl, C
4～C
20Cycloalkylalkyl, C
6～C
20Aryl, C
7～C
20Alkaryl, C
7～C
20Aralkyl;
R
3Group is selected from a kind of in following: the C of straight chain
1～C
20The C of alkyl, side chain
1～C
20Alkyl, C
4～C
20Cycloalkylalkyl, C
7～C
20Aralkyl.
Promptly go out the compound of general structure (II) earlier from the compound of general structure (I), refabrication goes out the compound of general structure (III).
For step from (I) formula compound (II) formula compound, dual mode can be arranged, first kind of product that is above-mentioned with non-protonic solvent dissolving (I) formula compound and active metal or alkali reaction, and the dimerization linked reaction takes place under the oxygenant effect, the generating structure general formula is 1 of (II) formula, 2-dialkyl-1,1,2,2-four (-oxyl carbonyl) ethane; Second kind is to use electrochemical oxidation.
Wherein the qualification of first kind of scheme is:
Described non-protonic solvent is selected from a kind of in the following solvent: tetrahydrofuran (THF), dimethyl formamide, dimethyl sulfoxide (DMSO), acetonitrile;
Described active metal or alkali are selected from a kind of in following: the alkoxide of basic metal, alkaline-earth metal, alkalimetal hydride, alkaline earth metal hydride, alkali alcoholate, alkaline-earth metal, alkaline carbonate, alkaline earth metal carbonate;
Described oxygenant is selected from a kind of in following: halogen, superoxide, transiting metal oxidation attitude compound.
Further preferred version is:
Described non-protonic solvent is selected from a kind of in the following solvent: tetrahydrofuran (THF), dimethyl formamide, dimethyl sulfoxide (DMSO);
Described active metal or alkali are selected from a kind of in following: sodium Metal 99.5, potassium metal, potassium ethylate, sodium ethylate, sodium hydride;
Described oxygenant is selected from a kind of in following: superoxide, transiting metal oxidation attitude compound.
Another kind of preferred version is:
Described non-protonic solvent is selected from a kind of in the following solvent: tetrahydrofuran (THF), dimethyl formamide, dimethyl sulfoxide (DMSO);
Described active metal or alkali are selected from a kind of in following: potassium ethylate, sodium hydride;
Described oxygenant is: iodine.
For step, can also adopt the scheme of prior art electrochemical oxidation from (I) formula compound (II) formula compound:
Described general structure prepares by following manner for the raw material of (II) formula:
With general structure is the 2-alkyl-malonic ester compounds of (I) formula, and the method by electrochemical oxidation (referring to Chem.Ber., 127 (7), 1257-1262,1994.), the generating structure general formula is 1 of (II) formula, 2-dialkyl-1,1,2,2-four (-oxyl carbonyl) ethane;
In general structure (I):
R
1Group is selected from a kind of in following: the C of straight chain
1～C
20The C of alkyl, side chain
1～C
20Alkyl, C
3～C
20Cycloalkyl, C
4～C
20Alkyl-cycloalkyl, C
4～C
20Cycloalkylalkyl, C
6～C
20Aryl, C
7～C
20Alkaryl, C
7～C
20Aralkyl;
R
3Group is selected from a kind of in following: the C of straight chain
1～C
20The C of alkyl, side chain
1～C
20Alkyl, C
4～C
20Cycloalkylalkyl, C
7～C
20Aralkyl.
Step for from (II) formula compound (III) formula compound can adopt dual mode, and a kind of is that described hydrolysis and decarboxylic reaction take place under the acidic hydrolysis condition, and another kind is that described hydrolysis and decarboxylic reaction take place under the alkaline hydrolysis condition.
Wherein the qualification of acidic hydrolysis and decarboxylic reaction scheme is:
Described general structure is the raw material of (II) formula, under strong acid condition, under room temperature to 100 ℃ temperature, described hydrolysis and decarboxylic reaction takes place, the generating structure general formula be (III) 2, the 3-dialkyl succinic acid.
Further preferred:
Described general structure is the raw material of (II) formula, under concentrated hydrochloric acid or 50%～90% vitriolic condition, under 90 ℃～100 ℃ temperature, described hydrolysis and decarboxylic reaction takes place, the generating structure general formula be (III) 2, the 3-dialkyl succinic acid.
For the step from (II) formula compound (III) formula compound, the qualification of alkaline hydrolysis scheme is:
With described general structure is the raw material of (II) formula, with the dissolving of low-carbon alcohol kind solvent, under refluxad, with the oxyhydroxide reaction of alkali-metal oxyhydroxide or alkaline-earth metal, 1 hour～20 hours reaction times;
The solvent in the reaction solution is sloughed in evaporation then, adds entry in residual reaction liquid, extracts reaction solution with the organic solvent extracting that is insoluble in water again, isolates water; Above-mentioned water is neutralized with protonic acid, obtain containing general structure for (III) 2, the mixture of 3-dialkyl succinic acid; Through separation and purification, obtain 2,3-dialkyl succinic acid product.
For above-mentioned 2, the preparation method's of 3-dialkyl succinic acid ester compound fundamental sum optimal technical scheme, especially for following preferred group:
In general structure (I), (II), (III), (IV):
R
1Group is selected from a kind of in following: the C of straight chain
1～C
8The C of alkyl, side chain
1～C
8Alkyl, C
3～C
9Cycloalkyl, C
4～C
9Alkyl-cycloalkyl, C
4～C
9Cycloalkylalkyl, C
6～C
10Aryl, C
7～C
10Alkaryl, C
7～C
10Aralkyl;
R
2Group is selected from a kind of in following: the C of straight chain
1～C
8The C of alkyl, side chain
1～C
8Alkyl, C
3～C
9Cycloalkyl, C
4～C
9Alkyl-cycloalkyl, C
4～C
9Cycloalkylalkyl, C
6～C
10Aryl, C
7～C
10Alkaryl, C
7～C
10Aralkyl;
R
3Group is selected from a kind of in following: the C of straight chain
1～C
8The C of alkyl, side chain
1～C
8Alkyl, C
4～C
9Cycloalkylalkyl, C
7～C
10Aralkyl.
Further preferred, in general structure (I), (II), (III), (IV):
R
1Group is selected from a kind of in following: the C of straight chain
3～C
8The C of alkyl, side chain
3～C
8Alkyl, C
3～C
9Cycloalkyl, C
6～C
10Aryl, C
7～C
10Alkaryl, C
7～C
10Aralkyl;
R
2Group is selected from a kind of in following: the C of straight chain
1～C
8The C of alkyl, side chain
1～C
8Alkyl, C
7～C
10Aralkyl;
R
3Group is selected from a kind of in following: the C of straight chain
1～C
8The C of alkyl, side chain
1～C
8Alkyl, C
7～C
10Aralkyl.
Further preferred again, in general structure (I), (II), (III), (IV):
R
1Group is selected from a kind of in following: sec.-propyl, isobutyl-, sec-butyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, neo-pentyl, isohexyl, Sec-Hexyl, 5-methyl hexyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, p-methylphenyl;
R
2Group is selected from a kind of in following: phenmethyl, to methylbenzyl, styroyl, methyl, ethyl, n-propyl, normal-butyl, isobutyl-, n-pentyl, isopentyl, n-hexyl, isohexyl, 5-methyl hexyl;
R
3Group is selected from a kind of in following: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, phenmethyl.
Further preferred again, in general structure (I), (II), (III), (IV):
R
1Group is selected from a kind of in following: sec.-propyl, isobutyl-, cyclopentyl, cyclohexyl, phenyl, p-methylphenyl;
R
2Group is selected from a kind of in following: phenmethyl, methyl, ethyl, n-propyl, normal-butyl, isobutyl-;
R
3Group is selected from a kind of in following: methyl, ethyl, phenmethyl.
Preferred especially, in general structure (I), (II), (III), (IV):
R
1Group is selected from a kind of in following: phenyl, sec.-propyl;
R
2Group is selected from a kind of in following: ethyl, n-propyl, normal-butyl, isobutyl-;
R
3Group is selected from a kind of in following: methyl, ethyl.
Promptly prepare: 2,3-phenylbenzene Succinic acid dimethylester, 2,3-phenylbenzene ethyl succinate, 2,3-phenylbenzene succsinic acid di-n-propyl ester, 2,3-phenylbenzene dibutyl succinate, 2,3-phenylbenzene di-iso-octyl succinate, 2,3-phenylbenzene succsinic acid diisoamyl ester, 2,3-phenylbenzene succsinic acid two dissident's esters, 2,3-phenylbenzene succsinic acid two (2-methyl hexyl) ester, 2,3-di-isopropyl Succinic acid dimethylester, 2,3-di-isopropyl ethyl succinate, 2,3-di-isopropyl succsinic acid di-n-propyl ester, 2,3-di-isopropyl dibutyl succinate, 2,3-di-isopropyl di-iso-octyl succinate, 2,3-di-isopropyl succsinic acid diisoamyl ester, 2,3-di-isopropyl succsinic acid two dissident's esters, 2,3-di-isopropyl succsinic acid two (2-methyl hexyl) ester, 2,3-dicyclohexyl Succinic acid dimethylester, 2,3-dicyclohexyl ethyl succinate, 2,3-dicyclohexyl succsinic acid di-n-propyl ester, 2,3-dicyclohexyl dibutyl succinate, 2,3-dicyclohexyl di-iso-octyl succinate, 2,3-dicyclohexyl succsinic acid diisoamyl ester, 2,3-dicyclohexyl succsinic acid two dissident's esters, 2,3-dicyclohexyl succsinic acid two (2-methyl hexyl) ester.
For above-mentioned 2, the preparation method of 3-dialkyl succinic acid ester compound, esterif iotacation step is preferred:
Described general structure be (III) 2, the 3-dialkyl succinic acid is under the sulphuric acid catalysis condition, again with R
2OH reaction, generating structure general formula be (IV) 2,3-dialkyl succinic acid ester compound.
The invention has the beneficial effects as follows:
Preparation method of the present invention has opened up one new 2, the synthetic method of 3-dialkyl succinic acid ester compound, make its internal electron donor realize industrialization easily as polypropylene catalyst, make this novel polypropylene catalyst can be used to produce the high-performance polymer commodity on a large scale, thereby can improve polyacrylic production technology level.
Description of drawings
Fig. 1 is 2,3-dialkyl succinic acid ester compound synthetic route synoptic diagram.
Embodiment
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not subjected to the restriction of these embodiment, and scope of the present invention proposes in claims.
Embodiment 1～5, preparation 1,2-dialkyl-1,1,2,2-four (-oxyl carbonyl) ethane.
Embodiment 1: preparation 1,2-phenylbenzene-1,1,2,2-four (ethoxy carbonyl) ethane
In 250ml single port flask, add the 3.0g sodium hydride.The sherwood oil that adds 25ml then, vibration is dissolved in the sherwood oil mineral oil of protection sodium hydride.Leave standstill again, make sodium hydride avale.Topple over and sherwood oil, the single port bottle adds the 25ml sherwood oil again.So washing is three times.With rotatory evaporator residual sherwood oil is removed then.Take off the single port bottle, claim to such an extent that sodium hydride 1.7g adds the dry tetrahydrofuran (THF) of crossing of 50ml rapidly with the heavy method of difference.
Take by weighing phenyl ethyl malonate 11.8g, slowly be added drop-wise in the single port bottle that fills sodium hydride.Carrying out along with dripping has bubble to emerge in the reaction solution.After dropwising, continue reaction 1 hour, get reaction solution.
Take by weighing the 6.3g iodine and be dissolved in the 30ml tetrahydrofuran (THF), color is dark violet redness.Slowly be added drop-wise in the above-mentioned reaction solution then.After the tetrahydrofuran solution of iodine was added drop-wise to reaction solution, red-purple disappeared immediately.Along with the continuous adding of iodine, color begins slowly to deepen.After dropwising Deng iodine solution, color becomes red-purple.Be heated to backflow then, reaction is 10 hours under reflux state.
After reaction finishes, add 100ml water, add sodium bisulfite again, vibration, until color become light yellow till.Use each consumption 80ml extracted with diethyl ether three times then.Merge organic layer, add one night of anhydrous magnesium sulfate drying.
Remove by filter sal epsom, rotary evaporation is removed ether, obtains pale brown look liquid crude product.Separate with the chromatography column that is filled with silica gel again.Earlier doing eluting solvent with sherwood oil, is that 5: 1 sherwood oil and ethyl acetate mixture done eluting solvent with mol ratio then.Separate at last and obtain liquid target compound 1,2-phenylbenzene-1,1,2,2-four (ethoxy carbonyl) ethane, yield 58.9%.Mass spectroscopy MS (EI, m/s): 470 (M
+).
IR(cm
-1)：2983，2939，2905，1736，1497，1448，1389，1367，1243，1096，1031，861，739，698。
1H-NMR(CDCl
3/TMS，300MHz)(δ，ppm)：1.22～1.31(12H，4OCH
2CH
3)，4.27～4.33(8H，4OCH
2CH
3)，7.11～7.61(10H，10ArH)。
Embodiment 2: preparation 1,2-phenylbenzene-1,1,2,2-four (ethoxy carbonyl) ethane
Claim potassium metal 0.39g with the heavy method of difference, divide to join in the 10ml dehydrated alcohol for three times, make the ethanolic soln of potassium ethylate.
In 100ml single port flask, add the 2.36g phenyl ethyl malonate, add the 15ml dehydrated alcohol again.Under condition of stirring, be added drop-wise in the phenyl ethyl malonate then, reacted 1 hour with the ethanolic soln of constant pressure funnel with potassium ethylate.Under reduced pressure remove ethanol then, obtain white solid.To wherein adding 15ml dimethyl sulfoxide (DMSO) (DMSO), white solid dissolves fully, gets reaction solution.
Take by weighing the 1.27g iodine, be dissolved in the dimethyl sulfoxide (DMSO) (DMSO) of 10ml, make the solution of iodine.Under room temperature (about 20 ℃), in above-mentioned reaction solution, slowly drip the DMSO solution of iodine by constant pressure funnel, and constantly stir then.Dropwise the back and continue reaction 10 hours.In reaction solution, add 200ml water then, use the extracted with diethyl ether three times of 50ml again.Combined ether layer is with one night of anhydrous magnesium sulfate drying.
Remove by filter desiccant sal epsom, slough ether under the decompression and obtain pale brown look liquid.Separate with the chromatography column that is filled with silica gel again and purify.With mol ratio is that 5: 1 sherwood oil and ethyl acetate done eluting solvent.Obtain target compound 1,2-phenylbenzene-1,1,2,2-four (ethoxy carbonyl) ethane.
Embodiment 3: preparation 1,2-phenylbenzene-1,1,2,2-four (ethoxy carbonyl) ethane
Change reaction solvent, use N, dinethylformamide (DMF) replaces dimethyl sulfoxide (DMSO), and other are operated with embodiment 2, obtain target compound 1,2-phenylbenzene-1,1,2,2-four (ethoxy carbonyl) ethane.Mass spectroscopy: with electron spray(ES) (ESI) mass spectrometric analysis method, recording its molecular weight is 470.
Embodiment 4: preparation 2,5-dimethyl-3,3,4,4-four (ethoxy carbonyl) hexane
Take by weighing diethyl isopropyl 1.0g, join in the 100ml single port flask.Weighing potassium metal 0.20g joins in the 20ml dehydrated alcohol at twice, and reaction makes the ethanolic soln of potassium ethylate.Potassium ethylate solution is joined in the single port bottle that fills the raw material diethyl isopropyl, start stirring simultaneously.React after 1 hour, stop to stir, take out rotor.On rotatory evaporator, remove ethanol, obtain white solid matter.
Get the tetrahydrofuran (THF) of 20ml, be added in the top white solid through no water treatment.Solid dissolves fully, obtains water white solution.Being heated to 65 ℃ refluxes tetrahydrofuran (THF).
Take by weighing the 0.60g iodine with the dissolving of 20ml tetrahydrofuran (THF), in reaction flask, drip at a slow speed by constant pressure funnel.Iodine solution is once adding, and redness is taken off fast.Along with the continuous adding of iodine solution, it is muddy that reaction solution becomes gradually, has solid to generate the flavescence gradually of reaction solution color.After iodine solution adds fully, continue reaction 10 hours down at 65 ℃ again.
Behind the stopped reaction, leave standstill for some time, the solid deposits of generation is got off.Reaction solution is a deep yellow.Add 50ml water, start stirring, solids disappeared.With the ethyl acetate extraction of each consumption 30ml three times.Merge organic layer, add one night of anhydrous magnesium sulfate drying.
Filter, remove sal epsom.Slough solvent ethyl acetate, chromatography column separates purifies, and obtains product 2,5-dimethyl-3,3,4,4-four (ethoxy carbonyl) hexane.Mass spectroscopy: with electron spray(ES) (ESI) mass spectrometric analysis method, recording its molecular weight is 402.
Embodiment 5: preparation 1,2-di-isopropyl-1,1,2,2-four (methoxycarbonyl) ethane
Claim potassium metal 0.27g, divide to join in the 20ml anhydrous methanol for three times, make the methanol solution of potassium methylate.In 100ml single port flask, add 1.0g isopropyl-malonic acid dimethyl ester, add the 15ml anhydrous methanol again.Under condition of stirring, be added drop-wise in the isopropyl-malonic acid dimethyl ester reaction 1h then with the methanol solution of constant pressure funnel with potassium methylate.Remove methyl alcohol under the decompression, obtain white solid, i.e. the product of isopropyl-malonic acid dimethyl ester and potassium methylate reaction is called for short sylvite 1.The tetrahydrofuran (THF) of 20ml is added in the above-mentioned sylvite 1, stir back sylvite 1 and be partly dissolved.
Take by weighing the 1.46g iodine, be dissolved in the tetrahydrofuran (THF) of 10ml, make the tetrahydrofuran solution of iodine.Then at room temperature, in the reaction flask that above-mentioned sylvite 1 is housed, slowly drip the tetrahydrofuran solution of iodine, and constantly stir by constant pressure funnel.Dropwise the back and continue reaction 1h, filter out solid afterwards, obtain containing Iod R liquid.
Weighing potassium metal 0.27g divides to join in the 20ml anhydrous methanol for three times again, makes the methanol solution of potassium methylate.In 100ml single port flask, add 1.0g isopropyl-malonic acid dimethyl ester, add the 15ml anhydrous methanol again.Under condition of stirring, be added drop-wise in the isopropyl-malonic acid dimethyl ester reaction 1h then with the methanol solution of constant pressure funnel with potassium methylate.Remove methyl alcohol under the decompression, obtain white solid, i.e. the product of isopropyl-malonic acid dimethyl ester and potassium methylate reaction is called for short sylvite 2.The tetrahydrofuran (THF) of 20ml is added in the above-mentioned sylvite 2, stir back sylvite 2 and be partly dissolved,, and constantly stir then to wherein dripping the above-mentioned Iod R liquid that contains, dropwise back back flow reaction 12 hours under 65 degree oil baths, with electron spray(ES) (ESI) mass spectrometric analysis method, record that to contain molecular weight in the product liquid be 346 compound, promptly with 1,2-di-isopropyl-1,1,2,2-four (methoxycarbonyl) ethane molecule amount matches.
In the present embodiment, the tetrahydrofuran solution method for making of the tetrahydrofuran solution of sylvite 1 and sylvite 2 is just the same, in fact be equivalent to prepare respectively the tetrahydrofuran solution of two parts of sylvite, first tetrahydrofuran solution with iodine splashes into a copy of it and obtains containing Iod R liquid, will contain the Iod R drop again and go into another part.
Embodiment 6～8, preparation 1,2-dialkyl succinic acid.
Embodiment 6: preparation 2,3-phenylbenzene succsinic acid
In 100ml single port flask, add 1,2-phenylbenzene-1,1,2,2-four (ethoxy carbonyl) ethane 0.41g.Adding the 15ml dehydrated alcohol, sample dissolves fully.Take by weighing 0.25g potassium hydroxide solid again, be added in the single port bottle, stir.Heat temperature raising to reflux state reacted 20 hours down.
Reaction is cooled to room temperature after finishing.Slough etoh solvent at 30 ℃ of following rotary evaporations again.Add 50ml water then.Extracted with diethyl ether with each consumption 15ml.After extracting three times, aqueous phase is with 10% hydrochloric acid soln acidifying, till the pH value is 2.And then the extracted with diethyl ether of each consumption 15ml four times.Merge organic layer, add one night of anhydrous magnesium sulfate drying.
Remove sal epsom, slough solvent ether, obtain solid crude product.Crude product is purified with the method for column chromatography, the eluting solvent ethyl acetate.Obtain product 2 at last, 3-phenylbenzene succsinic acid.Yield 85.6%.Mass spectroscopy MS (EI, m/s): 270 (M
+).
IR(cm
-1)：2983，1708，1603，1514，1496，1453，1411，1242，1024，936，857，806，700，525。
1H-NMR(CDCl
3/TMS，300MHz)(δ，ppm)：12.3(2H，2COOH)，7?37～7.46(10H，10ArH)，
Embodiment 7: preparation 2,3-phenylbenzene succsinic acid
In 100ml single port flask, add 1,2-phenylbenzene-1,1,2,2-four (ethoxy carbonyl) ethane 0.50g.The concentrated hydrochloric acid of measuring 15ml again is added in the single port bottle, starts stirring.Heat temperature raising extremely refluxes, and reacts 20 hours under reflux state.
Reaction is cooled to room temperature after finishing.Add 50ml water then.Extracted with diethyl ether with each consumption 15ml.Extract three times, merge organic layer, and with the saturated sodium bicarbonate aqueous solution thorough washing of 50ml.Tell water, the hydrochloric acid soln acidifying with 10% is till the pH value is at 2 o'clock.And then with the extracted with diethyl ether of each consumption 15ml four times.Merge organic layer, add one night of anhydrous magnesium sulfate drying.
Remove by filter sal epsom, slough solvent ether.Obtain the solids crude product.Thick product is purified by the method for column chromatography.The eluting solvent ethyl acetate.Obtain product 2 at last, 3-phenylbenzene succsinic acid.
Embodiment 8: preparation 2,3-di-isopropyl succsinic acid
Embodiment 4 obtain 2,5-dimethyl-3,3,4,4-four (ethoxy carbonyl) hexane adopts 78% sulfuric acid of its 6 times of quality, 100 ℃ oil bath hydrolysis more than 30 minutes, after reaction finishes, cooling in the water with 5 times of volumes of reaction solution impouring, is used extracted with diethyl ether, concentrates.In 10% potassium hydroxide aqueous solution of 10 times of quality of concentrated solution adding, reflux.Cooling, it is till 2 o'clock that concentrated hydrochloric acid is neutralized to the pH value, separates out precipitation, separates to obtain 2,3-di-isopropyl succsinic acid.Mass spectroscopy MS (EI, m/s): 185 (M-17)
+
IR(cm
-1)：2969，2695，1700，1602.8，1467，1426，1392，1377，1289，1257，1193，1113，943，745，649。
Embodiment 9～10, preparation 1,2-dialkyl succinic acid ester.
Embodiment 9: preparation 2,3-phenylbenzene ethyl succinate
Add 2 in 100ml single port flask, 3-phenylbenzene succsinic acid 0.2g adds the 15ml dehydrated alcohol again.In reaction flask, drip the vitriol oil of 0.1ml again.Start stirring.Be warming up to backflow, reaction is 2.5 hours under reflux state.
Reaction is cooled to room temperature after finishing.Add 100ml water, with the extracted with diethyl ether of each 20ml four times.Merge organic layer, slough solvent ether then.In raffinate, add the saturated sodium hydrogen carbonate solution of 50ml.And then with the extracted with diethyl ether of each consumption 20ml three times.Merge organic layer, add one night of anhydrous magnesium sulfate drying.
Remove by filter desiccant sal epsom.Slough solvent ether, obtain target compound 2 at last, 3-phenylbenzene ethyl succinate.Mass spectroscopy MS (EI, m/s): 326 (M
+).
IR(cm
-1)：3061，3029，2980，2934，2872，1733，1601，1514，1454，1367，1257，1148，1096，1023，731，698，511。
Embodiment 10: preparation 2,3-phenylbenzene ethyl succinate
Embodiment 7 obtain 2,3-phenylbenzene succsinic acid gets compound 2 by embodiment 9 working method, 3-phenylbenzene ethyl succinate.
Claims (20)
1. one kind 2, the preparation method of 3-dialkyl succinic acid; It is characterized in that, may further comprise the steps:
With general structure is 1 of (II) formula, 2-dialkyl-1,1,2, and 2-four (-oxyl carbonyl) ethane is raw material;
4 ester groups in the general structure of described raw material (II) are under acidic conditions or alkaline condition, hydrolysis reaction all takes place, any two ester groups that connect with different carbon atoms in above-mentioned 4 ester groups, decarboxylic reaction after obtaining carboxyl, has taken place again in hydrolysis, the generating structure general formula be (III) 2, the 3-dialkyl succinic acid;
Described acidic hydrolysis condition is: under strong acid condition, under room temperature to 100 ℃ temperature, described hydrolysis and decarboxylic reaction take place; The generating structure general formula be (III) 2, the 3-dialkyl succinic acid;
Described alkaline hydrolysis condition is: with the alcohol solvent dissolving, under refluxad, with the oxyhydroxide reaction of alkali-metal oxyhydroxide or alkaline-earth metal, 1 hour～20 hours reaction times; The solvent in the reaction solution is sloughed in evaporation then, adds entry in residual reaction liquid, extracts reaction solution with the organic solvent extracting that is insoluble in water again, isolates water; Above-mentioned water is neutralized with protonic acid, obtain containing general structure for (III) 2, the mixture of 3-dialkyl succinic acid; Through separation and purification, obtain 2,3-dialkyl succinic acid product;
In general structure (II), (III):
R
1Group is selected from a kind of in following: the C of straight chain
1～C
20The C of alkyl, side chain
1～C
20Alkyl, C
3～C
20Cycloalkyl, C
4～C
20Alkyl-cycloalkyl, C
4～C
20Cycloalkylalkyl, C
6～C
20Aryl, C
7～C
20Alkaryl, C
7～C
20Aralkyl;
R
3Group is selected from a kind of in following: straight chain
C1～C
20The C of alkyl, side chain
1～C
20Alkyl, C
4～C
20Cycloalkylalkyl, C
7～C
20Aralkyl.
2. according to claim 12, the preparation method of 3-dialkyl succinic acid is characterized in that:
Described general structure prepares by following manner for the compound of (II) formula:
React with active metal or alkali earlier with the 2-alkyl-malonic ester compounds of general structure for (I) formula, and in non-protonic solvent, be dissolved as reaction solution, after oxygenant is dissolved in aprotic solvent, join in the described reaction solution, the dimerization linked reaction takes place, the generating structure general formula is 1 of (II) formula, 2-dialkyl-1,1,2,2-four (-oxyl carbonyl) ethane;
In general structure (I):
R
1Group is selected from a kind of in following: the C of straight chain
1～C
20The C of alkyl, side chain
1～C
20Alkyl, C
3～C
20Cycloalkyl, C
4～C
20Alkyl-cycloalkyl, C
4～C
20Cycloalkylalkyl, C
6～C
20Aryl, C
7～C
20Alkaryl, C
7～C
20Aralkyl;
R
3Group is selected from a kind of in following: the C of straight chain
1～C
20The C of alkyl, side chain
1～C
20Alkyl, C
4～C
20Cycloalkylalkyl, C
7～C
20Aralkyl;
Described non-protonic solvent is selected from a kind of in the following solvent: tetrahydrofuran (THF), dimethyl formamide, dimethyl sulfoxide (DMSO), acetonitrile;
Described active metal or alkali are selected from a kind of in following: the alkoxide of basic metal, alkaline-earth metal, alkalimetal hydride, alkaline earth metal hydride, alkali alcoholate, alkaline-earth metal, alkaline carbonate, alkaline earth metal carbonate;
Described oxygenant is selected from a kind of in following: halogen, superoxide, transiting metal oxidation attitude compound.
3. according to claim 22, the preparation method of 3-dialkyl succinic acid is characterized in that:
Described non-protonic solvent is selected from a kind of in the following solvent: tetrahydrofuran (THF), dimethyl formamide, dimethyl sulfoxide (DMSO);
Described active metal or alkali are selected from a kind of in following: sodium Metal 99.5, potassium metal, potassium ethylate, sodium ethylate, sodium hydride;
Described oxygenant is selected from a kind of in following: superoxide, transiting metal oxidation attitude compound.
4. according to claim 22, the preparation method of 3-dialkyl succinic acid is characterized in that:
Described non-protonic solvent is selected from a kind of in the following solvent: tetrahydrofuran (THF), dimethyl formamide, dimethyl sulfoxide (DMSO);
Described active metal or alkali are selected from a kind of in following: potassium ethylate, sodium hydride;
Described oxygenant is: iodine.
5. according to claim 12, the preparation method of 3-dialkyl succinic acid is characterized in that:
Described general structure is the compound of (II) formula, under concentrated hydrochloric acid or 50%～90% vitriolic condition, under 90 ℃～100 ℃ temperature, described hydrolysis and decarboxylic reaction takes place, the generating structure general formula be (III) 2, the 3-dialkyl succinic acid.
6. described 2 according to one of claim 1 to 5, the preparation method of 3-dialkyl succinic acid is characterized in that:
In general structure (I), (II), (III):
R
1Group is selected from a kind of in following: the C of straight chain
1～C
8The C of alkyl, side chain
1～C
8Alkyl, C
3～C
9Cycloalkyl, C
4～C
9Alkyl-cycloalkyl, C
4～C
9Cycloalkylalkyl, C
6～C
10Aryl, C
7～C
10Alkaryl, C
7～C
10Aralkyl;
R
3Group is selected from a kind of in following: the C of straight chain
1～C
8The C of alkyl, side chain
1～C
8Alkyl, C
4～C
9Cycloalkylalkyl, C
7～C
10Aralkyl.
7. according to claim 62, the preparation method of 3-dialkyl succinic acid is characterized in that:
In general structure (I), (II), (III):
R
1Group is selected from a kind of in following: the C of straight chain
3～C
8The C of alkyl, side chain
3～C
8Alkyl, C
3～C
9Cycloalkyl, C
6～C
10Aryl, C
7～C
10Alkaryl, C
7～C
10Aralkyl;
R
3Group is selected from a kind of in following: the C of straight chain
1～C
8The C of alkyl, side chain
1～C
8Alkyl, C
7～C
10Aralkyl.
8. according to claim 72, the preparation method of 3-dialkyl succinic acid is characterized in that:
In general structure (I), (II), (III):
R
1Group is selected from a kind of in following: sec.-propyl, isobutyl-, sec-butyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, neo-pentyl, isohexyl, Sec-Hexyl, 5-methyl hexyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, p-methylphenyl;
R
3Group is selected from a kind of in following: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, phenmethyl.
9. according to claim 82, the preparation method of 3-dialkyl succinic acid is characterized in that:
In general structure (I), (II), (III):
R
1Group is selected from a kind of in following: sec.-propyl, isobutyl-, cyclopentyl, cyclohexyl, phenyl, p-methylphenyl;
R
3Group is selected from a kind of in following: methyl, ethyl, phenmethyl.
10. according to claim 92, the preparation method of 3-dialkyl succinic acid is characterized in that:
In general structure (I), (II), (III):
R
1Group is selected from a kind of in following: phenyl, sec.-propyl;
R
3Group is selected from a kind of in following: methyl, ethyl.
11. one kind 2, the preparation method of 3-dialkyl succinic acid ester compound; It is characterized in that:
Prepare in accordance with the method for claim 1 general structure for (III) 2, the 3-dialkyl succinic acid; Described general structure be (III) 2, the 3-dialkyl succinic acid is under the protonic acid catalytic condition, again with R
2OH reaction, generating structure general formula be (IV) 2,3-dialkyl succinic acid ester compound;
(Ⅳ)
In general structure (IV):
R
1Group is selected from a kind of in following: the C of straight chain
1～C
20The C of alkyl, side chain
1～C
20Alkyl, C
3～C
20Cycloalkyl, C
4～C
20Alkyl-cycloalkyl, C
4～C
20Cycloalkylalkyl, C
6～C
20Aryl, C
7～C
20Alkaryl, C
7～C
20Aralkyl;
R
2Group is selected from a kind of in following: the C of straight chain
1～C
20The C of alkyl, side chain
1～C
20Alkyl, C
3～C
20Cycloalkyl, C
4～C
20Alkyl-cycloalkyl, C
4～C
20Cycloalkylalkyl, C
6～C
20Aryl, C
7～C
20Alkaryl, C
7～C
20Aralkyl;
R
2R among the OH
2Group and (IV) formula R
2Group is identical.
12. according to claim 11 2, the preparation method of 3-dialkyl succinic acid ester compound is characterized in that:
Prepare in accordance with the method for claim 2 general structure for (III) 2, the 3-dialkyl succinic acid.
13. according to claim 12 2, the preparation method of 3-dialkyl succinic acid ester compound is characterized in that:
Described non-protonic solvent is selected from a kind of in the following solvent: tetrahydrofuran (THF), dimethyl formamide, dimethyl sulfoxide (DMSO);
Described active metal or alkali are selected from a kind of in following: sodium Metal 99.5, potassium metal, potassium ethylate, sodium ethylate, sodium hydride;
Described oxygenant is selected from a kind of in following: superoxide, transiting metal oxidation attitude compound.
14. according to claim 12 2, the preparation method of 3-dialkyl succinic acid ester compound is characterized in that:
Described non-protonic solvent is selected from a kind of in the following solvent: tetrahydrofuran (THF), dimethyl formamide, dimethyl sulfoxide (DMSO);
Described active metal or alkali are selected from a kind of in following: potassium ethylate, sodium hydride;
Described oxygenant is: iodine.
15. according to claim 11 2, the preparation method of 3-dialkyl succinic acid ester compound is characterized in that:
Described general structure is the compound of (II) formula, under concentrated hydrochloric acid or 50%～90% vitriolic condition, under 90 ℃～100 ℃ temperature, described hydrolysis and decarboxylic reaction takes place, the generating structure general formula be (III) 2, the 3-dialkyl succinic acid.
16. described 2 according to one of claim 11 to 15, the preparation method of 3-dialkyl succinic acid ester compound is characterized in that:
In general structure (I), (II), (III), (IV):
R
1Group is selected from a kind of in following: the C of straight chain
1～C
8The C of alkyl, side chain
1～C
8Alkyl, C
3～C
9Cycloalkyl, C
4～C
9Alkyl-cycloalkyl, C
4～C
9Cycloalkylalkyl, C
6～C
10Aryl, C
7～C
10Alkaryl, C
7～C
10Aralkyl;
R
2Group is selected from a kind of in following: the C of straight chain
1～C
8The C of alkyl, side chain
1～C
8Alkyl, C
3～C
9Cycloalkyl, C
4～C
9Alkyl-cycloalkyl, C
4～C
9Cycloalkylalkyl, C
6～C
10Aryl, C
7～C
10Alkaryl, C
7～C
10Aralkyl;
R
3Group is selected from a kind of in following: the C of straight chain
1～C
8The C of alkyl, side chain
1～C
8Alkyl, C
4～C
9Cycloalkylalkyl, C
7～C
10Aralkyl.
17. according to claim 16 2, the preparation method of 3-dialkyl succinic acid ester compound is characterized in that:
In general structure (I), (II), (III), (IV):
R
1Group is selected from a kind of in following: the C of straight chain
3～C
8The C of alkyl, side chain
3～C
8Alkyl, C
3～C
9Cycloalkyl, C
6～C
10Aryl, C
7～C
10Alkaryl, C
7～C
10Aralkyl;
R
2Group is selected from a kind of in following: the C of straight chain
1～C
8The C of alkyl, side chain
1～C
8Alkyl, C
7～C
10Aralkyl;
R
3Group is selected from a kind of in following: the C of straight chain
1～C
8The C of alkyl, side chain
1～C
8Alkyl, C
7～C
10Aralkyl.
18. according to claim 17 2, the preparation method of 3-dialkyl succinic acid ester compound is characterized in that:
In general structure (I), (II), (III), (IV):
R
1Group is selected from a kind of in following: sec.-propyl, isobutyl-, sec-butyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, neo-pentyl, isohexyl, Sec-Hexyl, 5-methyl hexyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, p-methylphenyl;
R
2Group is selected from a kind of in following: phenmethyl, to methylbenzyl, styroyl, methyl, ethyl, n-propyl, normal-butyl, isobutyl-, n-pentyl, isopentyl, n-hexyl, isohexyl, 5-methyl hexyl;
R
3Group is selected from a kind of in following: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, phenmethyl.
19. according to claim 18 2, the preparation method of 3-dialkyl succinic acid ester compound is characterized in that:
In general structure (I), (II), (III), (IV):
R
1Group is selected from a kind of in following: sec.-propyl, isobutyl-, cyclopentyl, cyclohexyl, phenyl, p-methylphenyl;
R
2Group is selected from a kind of in following: phenmethyl, methyl, ethyl, n-propyl, normal-butyl, isobutyl-;
R
3Group is selected from a kind of in following: methyl, ethyl, phenmethyl.
20. described 2 according to one of claim 17 to 19, the preparation method of 3-dialkyl succinic acid ester compound is characterized in that:
Described general structure be (III) 2, the 3-dialkyl succinic acid is under the sulphuric acid catalysis condition, again with R
2OH reaction, generating structure general formula be (IV) 2,3-dialkyl succinic acid ester compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101752829A CN101397246B (en) | 2007-09-28 | 2007-09-28 | Method for preparing 2,3-dialkyl succinic acid and ester compounds thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101752829A CN101397246B (en) | 2007-09-28 | 2007-09-28 | Method for preparing 2,3-dialkyl succinic acid and ester compounds thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101397246A CN101397246A (en) | 2009-04-01 |
| CN101397246B true CN101397246B (en) | 2011-08-03 |
Family
ID=40516114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101752829A Active CN101397246B (en) | 2007-09-28 | 2007-09-28 | Method for preparing 2,3-dialkyl succinic acid and ester compounds thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101397246B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313869A (en) * | 1999-04-15 | 2001-09-19 | 巴塞尔技术有限公司 | Components and catalysts for the polymerization of olefins |
-
2007
- 2007-09-28 CN CN2007101752829A patent/CN101397246B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313869A (en) * | 1999-04-15 | 2001-09-19 | 巴塞尔技术有限公司 | Components and catalysts for the polymerization of olefins |
Non-Patent Citations (1)
| Title |
|---|
| Yoshihiro Matsumura, et al..stereoselective homocoupling of phenylacetic acid derivatives utilizing electrochemically generated base.《Electrochimica Acta》.1997,2233-2239. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101397246A (en) | 2009-04-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108047261B (en) | Preparation method of clitorium | |
| CN101811983B (en) | Preparation method of 2,3-diisopropyl-2-cyano diethyl succinate compound | |
| CN101811982B (en) | 2,3-diisopropyl-2.3-dicyano-diethyl succinate compound, preparation method and application thereof | |
| CN101570550A (en) | Method for synthesizing chiral ferrocene diphosphine ligand | |
| CN102093245A (en) | Preparation method of sitagliptin intermediate, sitagliptin or salts thereof | |
| CN103539773B (en) | Method for preparing ticagrelor key intermediate | |
| WO2006117800A2 (en) | Novel 3, 4-propylenedioxythiophene derivatives with pendant functional groups | |
| CN101397246B (en) | Method for preparing 2,3-dialkyl succinic acid and ester compounds thereof | |
| CN103897025A (en) | Preparation method of pidotimod | |
| CN102702191A (en) | Synthesis method of vinpocetine | |
| CN110981779B (en) | Synthesis method of R-2- (2, 5-difluorophenyl) pyrrolidine | |
| DK170233B1 (en) | Process for the preparation of alkoxymethyl ether and alkoxymethyl ester derivatives of glycerols | |
| CN103601706A (en) | Method for synthesizing natural product Jaspine B isomer | |
| CN102336656B (en) | High-selectivity synthesis method of benzoyl formic acid | |
| CN103483201A (en) | Synthetic method of (R)-2-methyl-4-nitro-1-butanol | |
| CN105032473A (en) | Method for preparing formaldehydedibutylacetal by adopting sulfuric acid modified process nano-grade HZSM-5 catalyst | |
| Kupai et al. | Synthesis of new enantiopure dimethyl-and diisobutyl-substituted pyridino-18-crown-6 ethers containing a halogen atom or a methoxy group at position 4 of the pyridine ring for enantiomeric recognition studies | |
| CN109776568B (en) | Axisymmetric hexahydric bridged naphthalene nucleus micromolecule receptor material and preparation method and application thereof | |
| CN102432558B (en) | Method for synthesizing irbesartan and intermediate thereof | |
| CN106928057A (en) | The method of one kind synthesis maleic acid two (2 ethyl hexyl) ester | |
| CN1950324B (en) | Process for production of cyclopentanone-2,3,5-tri- carboxylic triesters | |
| CN101654454B (en) | Preparation method of mitrazapine and intermediate product thereof | |
| CN104447784A (en) | Statin medicine intermediate as well as preparation method and application thereof | |
| JP2002322181A (en) | Production method for quinoline derivative | |
| CN116515089A (en) | Preparation method for synthesizing phenanthrenedione unit-containing conjugated polymer through direct functionalization of C-H bond |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |