CN100509763C - Preparation of alpha, beta unsaturated nitrile addition product - Google Patents
Preparation of alpha, beta unsaturated nitrile addition product Download PDFInfo
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- CN100509763C CN100509763C CNB2005100888305A CN200510088830A CN100509763C CN 100509763 C CN100509763 C CN 100509763C CN B2005100888305 A CNB2005100888305 A CN B2005100888305A CN 200510088830 A CN200510088830 A CN 200510088830A CN 100509763 C CN100509763 C CN 100509763C
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- alkyl
- hydrogen
- unsaturated nitrile
- reaction
- independently
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Abstract
The present invention relates to a preparation method of alpha-beta unsaturated nitrile additive product. Said invention also provides its general formula, and its preparation method includes reaction of active methane compound with alpha, beta unsaturated nitrile under the action of metal alcohol salt. Said invention can raise the conversion rate of alpha, beta unsaturated nitrile addition reaction and product yield.
Description
Technical field
The present invention relates to the preparation method of unsaturated nitrile addition product, relate more specifically to α, the preparation method of the adduct of beta unsaturated nitrile and active methylene compound.
Background technology
Since on double key carbon, be connected with-the CN key, α, and the cloud density on the two keys of beta unsaturated nitrile class reduces, thereby easier generation nucleophilic addition(Adn) and free radical addition reaction.α, beta unsaturated nitrile addition product is of a great variety, is widely used as synthon, plastics, coating, tackiness agent, tensio-active agent and medical material or the like.For example, vinyl cyanide and divinyl, cinnamic terpolymer are a kind of excellent engineering plastics, are called for short ABS resin; The cyano group ether compound that unsaturated nitrile and alcohols addition obtain is important spices; α, the adduct of beta unsaturated nitrile and active methylene radical compounds as (2-cyanoethyl)-propanedioic acid oxalic acid, is important pharmaceutical intermediate.
α, the reaction of beta unsaturated nitrile and active methylene compound is typical Michael addition (Michaeladdition) reaction.Reaction formula following (wherein A and A ' are electron withdrawing group), this reaction is carried out under base catalysis usually.
Because the addition reaction of Michael's nucleophilic methylene radical is a reversible, so catalyst system therefor, temperature and other reaction conditions have very big influence to reaction conversion ratio and yield.Up to now, lot of documents is discussed with regard to the used catalyzer of this reaction system, but more or less there is the lower problem of catalyzer complexity and reaction conversion ratio or product yield in existing catalystic converter system.
In Izv.Akad.Navk SSSR.Ser Khim, 5,1210-1211,1980; Izv.Akad.NavkSSSR.Ser Khim, 5,1107-1112,1982 and Uzb.Khim.Zh., 5,77-9, the complex system that proposes with iron carbonyl, iodine, bromine and three (dimethylin) phosphinylidyne and Al-Ni-Ti-Mo in 1990 is a catalyzer, prepare (2-cyanoethyl)-propanedioic acid oxalic acid from vinyl cyanide, but can only obtain the yield of 55-59.7%.
Song Wenyan etc. are at " cyanoethylation reaction of diethyl malonate and methyl aceto acetate ", disclosing with salt of wormwood in " Xiamen University's journal " 1988 the 27th volumes the 4th phase 470-472 page or leaf is catalyzer, ethyl acetate is a solvent, diethyl malonate and methyl aceto acetate are the method for feedstock production vinyl cyanide adduct, and its product yield is respectively 78～83% and 57%.
United States Patent (USP) the 5th, 319, No. 125 disclose with tetramethyleneimine and small amount of acid is catalyzer, and from cyclopentanone and α, beta unsaturated nitrile prepares the method for 2-(2-cyanoethyl)-cyclopentanone, and the nitrile transformation efficiency of this method can reach 97%, and product yield reaches 85-89%.
" journal of Shandong university " the 39th the 3rd phase of volume discloses with nanometer KF/Al
2O
3Be catalyzer, from the method for vinyl cyanide preparation (2-cyanoethyl)-propanedioic acid oxalic acid, its yield can only reach 88.3%.
Summary of the invention
The object of the present invention is to provide the preparation α of a kind of high conversion, high yield, the method for beta unsaturated nitrile addition product.
The present invention relates to the preparation method of general formula (I) compound, be included in and make general formula (II) compound and the reaction of general formula (III) compound under the effect of metal alkoxide.
Wherein,
R
1, R
2Be electron withdrawing group independently;
R
3, R
4Be hydrogen, C independently
1-C
8Alkyl, C
3-C
8Cycloalkyl or C
6-C
20Aryl;
R
5Be hydrogen, C
1-C
8Alkyl, C
3-C
8Cycloalkyl, C
6-C
20Aryl or electron withdrawing group.
In the present invention's one preferred embodiment, R
1And R
2Be independently selected from COR
6, COOR
6, CONH
2, CN, NO
2, SOR
6And SO
2R
6Group, and each R
6Be hydrogen, C independently
1-C
8Alkyl, C
3-C
8Cycloalkyl or C
6-C
20Aryl.More preferably, R
1And R
2Be COR independently
6, COOR
6, CN or NO
2
In another preferred embodiment of the present invention, R
3And R
4Be hydrogen, C independently
1-C
6Alkyl, C
3-C
6Cycloalkyl or C
6-C
10Aryl, more preferably hydrogen, C
1-C
6Alkyl or phenyl.
In another preferred embodiment of the present invention, R
5Be hydrogen, C
1-C
6Alkyl, C
3-C
6Cycloalkyl, C
6-C
20Aryl or such as COR
6, COOR
6, CN or NO
2Electron withdrawing group, and each R
6Be hydrogen, C independently
1-C
8Alkyl, C
3-C
8Cycloalkyl or C
6-C
20Aryl, more preferably hydrogen, C
1-C
6Alkyl or phenyl.
In a preferred embodiment of the invention, described metal alkoxide is alkali metal alcoholates or alkaline-earth alkoxides, as the alkoxide of Li, Na, K, Mg or Ca, more preferably alkaline-earth alkoxides.Magnesium ethylate is most preferred catalyzer in the present invention.
In a further preferred embodiment, the alcohol that forms described metal alkoxide is lower alcohol.
In the preferred embodiment of the invention, can use inert solvent such as benzene, ether as solvent, more preferably with polar organic solvent such as ethyl acetate, diox and pure as solvent, especially preferably with C
1-C
6Alkanol is a solvent.
Preferably, the present invention is reflected under the temperature condition of room temperature to 100 ℃ or solvent for use boiling point and carries out.More preferably, described temperature of reaction is the boiling point of about 40 ℃ to 80 ℃ or solvent for use, more preferably about 50-60 ℃.
Use the inventive method, can improve α, the transformation efficiency of beta unsaturated nitrile addition reaction and product yield.And the used catalyst system of the inventive method is simple relatively and cheap, can use the on-the-spot preparation of conventional raw material.
Embodiment
As mentioned above, the present invention relates to the α shown in the general formula (I), the preparation method of beta unsaturated nitrile addition product is included under the effect of metal alkoxide and makes the α shown in active methylene compound shown in the general formula (II) and the general formula (III), the beta unsaturated nitrile reaction.
Wherein,
R
1, R
2Be electron withdrawing group independently;
R
3, R
4Be hydrogen, C independently
1-C
8Alkyl, C
3-C
8Cycloalkyl or C
6-C
20Aryl;
R
5Be hydrogen, C
1-C
8Alkyl, C
3-C
8Cycloalkyl, C
6-C
20Aryl or electron withdrawing group.
Term used herein " electron withdrawing group " refers to make the electronic cloud that closes on the carbon atom to be offset to it, thereby the group that the cloud density on the adjacent carbons is reduced includes but not limited to NO
2, CN, SO
3H, CHO, COOH, COR, CONH
2, COOR, Cl, Br, OR, SR, SOR, SO
2The R group.More preferably, described electron withdrawing group is NO
2, CN, CHO, COOH, COR, CONH
2, COOR, SOR and SO
2R, more preferably NO
2, CN, CHO, COOH, COR and COOR.
" alkyl " of the present invention is often referred to the saturated fatty alkyl of straight or branched, is preferably C
1-C
8Alkyl, more preferably C
1-C
6Alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, tertiary butyl or the like.Consider sterically hindered influence to reaction, alkyl of the present invention is preferably straight chained alkyl, as methyl, ethyl, n-propyl or the like.
" cycloalkyl " of the present invention is often referred to saturated alicyclic hydrocarbon radical, is preferably C
3-C
8Cycloalkyl, more preferably C
3-C
6Cycloalkyl, for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
" aryl " of the present invention refers to be preferably C by aromatic hydrocarbyl
6-C
20Aryl, more preferably C
6-C
10Aryl, for example phenyl and naphthyl, more preferably phenyl.
" lower alcohol " of the present invention refers to contain the alcohol of 1-8 carbon atom, more preferably C
1-C
6Alkanol, for example methyl alcohol, ethanol, propyl alcohol and butanols or the like.
In the present invention's one preferred embodiment, R
1And R
2Be independently selected from COR
6, COOR
6, CONH
2, CN, NO
2, SOR
6And SO
2R
6, and each R
6Be hydrogen, C independently
1-C
8Alkyl, C
3-C
8Cycloalkyl or C
6-C
20Aryl.
In a further preferred embodiment, R
1And R
2Be independently selected from COR
6, COOR
6, NO
2And CN, and each R
6Be hydrogen, C independently
1-C
8Alkyl, C
3-C
8Cycloalkyl or C
6-C
20Aryl.More preferably, each R
6Be hydrogen, C independently
1-C
6Alkyl, C
3-C
6Cycloalkyl or C
6-C
10Aryl, more preferably hydrogen, C
1-C
6Alkyl or phenyl.
In another preferred embodiment of the present invention, R
3And R
4Be hydrogen, C independently
1-C
6Alkyl, C
3-C
6Cycloalkyl or C
6-C
10Aryl, more preferably hydrogen, C
1-C
6Alkyl or phenyl.
In the present invention again in the preferred embodiment, R
5Be hydrogen, C
1-C
6Alkyl, C
3-C
6Cycloalkyl, C
6-C
20Aryl or COR
6, COOR
6, NO
2Or CN group, and each R
6Be hydrogen, C independently
1-C
8Alkyl, C
3-C
8Cycloalkyl or C
6-C
20Aryl.More preferably, R
5Be hydrogen, C
1-C
6Alkyl or phenyl.
In a preferred embodiment of the invention, catalyst system therefor is alkali metal alcoholates or alkaline-earth alkoxides, as the alkoxide of Li, Na, K, Mg or Ca.But because basic metal is too active, it is preserved and is all wayward with the reaction of alcohol, therefore more preferably alkaline-earth alkoxides, preferred especially magnesium alkoxide.The alcohol that forms described alkoxide is preferably lower alcohol, more preferably C
1-C
6Alkanol, for example methyl alcohol, ethanol, propyl alcohol and butanols.
In the present invention's one preferred embodiment, use alcohol as solvent.More preferably described alcohol is pure identical with the described metal alkoxide of formation.The mol ratio of the amount of solvent for use and formula (III) compound amount is preferably 3～5:1.Certainly, will be understood by those skilled in the art that and also can use more substantial solvent to react.
Because addition reaction of the present invention is a reversible exothermic reaction, elevated temperature helps fast reaction speed when temperature is low, but when temperature acquires a certain degree, continues the elevated temperature product yield and reduce on the contrary.Therefore, the used temperature of reaction of the present invention is preferably the boiling point of room temperature to 100 ℃ or solvent for use.More preferably, temperature of reaction of the present invention is about 40 ℃ to 80 ℃ or solvent for use boiling point, more preferably about 50-60 ℃.
In the inventive method, mol ratio to formula (II) compound and formula (III) compound does not have strict requirement, but, the adduct shown in the minimizing formula (I) and formula (III) compound be shaped as the secondary adduct for further adding, the mol ratio of preferred formula (II) compound and formula (III) compound is greater than 1:1, more preferably about 2:1.
In the inventive method, catalyst levels has certain influence to product yield and selectivity, and catalytic effect is poor when catalytic amount is not enough, but secondary adduct growing amount increases when catalyst excess.Therefore, the mol ratio of the amount of catalyst system therefor of the present invention and formula (III) compound amount is preferably about 0.2～1.0:1, more preferably about 0.4～0.6:1.
The inventive method can also significantly reduce the generation of secondary adduct when improving nitrile feed stock conversion and product yield, selectivity of product is improved.
Below the present invention is described in detail by specific embodiment, but the present invention is not limited to these embodiment.
Embodiment
Agitator is being housed, and thermometer adds dehydrated alcohol 18g (0.4 mole) and magnesium powder 9.7g (0.4 mole) in the 1L four-hole boiling flask of dropping funnel and reflux exchanger, splash into the CCl of 1ml
4, have a large amount of gases to emit.Refluxing appears in still liquid, and reaction causes.Slowly drip ethanol 100g (126.7ml, 2.17 moles) when reducing, continue reaction, till no bubble produces when refluxing.Reaction solution is cooled to 50-60 ℃, under this temperature, drips diethyl malonate 288g (1.8 moles) in the 1h, dropwise at 60 ℃ of insulation reaction 1h.Be cooled to 50 ℃ again, and in 50 ± 2 ℃ of following 47.7g (59.2ml that drip, 0.9 mole) vinyl cyanide and 50ml (39.6g, 0.86 alcoholic acid mixing solutions mole), dropwise and be warming up to 60 ℃ of insulation reaction 6h, add 20% hydrochloric acid 150g, branch vibration layer behind the stirring 0.5h obtains colourless to faint yellow limpid organic solution.
Gas Chromatographic Determination vinyl cyanide transformation efficiency is greater than 99%, and (2-cyanoethyl)-the diethyl malonate selectivity is greater than 95%, and yield reaches more than 94%.
Mass spectrum (m/z): 213,186,168,141,140,101,96,73,69,55,41,29.
IR composes (cm
-1): 2983,2941,2247,1741,1467,1371,1095,1047,1024.
More than describe and in an exemplary fashion the preferred embodiments of the invention are illustrated.Those skilled in the art should be appreciated that under the condition that does not break away from essence spirit of the present invention and scope can make various modifications or replacement to it, and these embodiments must be included in the scope of the present invention.
Claims (9)
1. the preparation method of general formula (I) compound is included under the effect of alkaline-earth alkoxides catalyzer and makes general formula (II) compound and the reaction of general formula (III) compound,
Wherein,
R
1, R
2Be electron withdrawing group independently;
R
3, R
4Be hydrogen, C independently
1-C
8Alkyl, C
3-C
8Cycloalkyl or C
6-C
20Aryl;
R
5Be hydrogen, C
1-C
8Alkyl, C
3-C
8Cycloalkyl, C
6-C
20Aryl or electron withdrawing group.
2. the method for claim 1, wherein said electron withdrawing group is selected from COR
6, COOR
6, CN and NO
2, and each R
6Be hydrogen, C independently
1-C
8Alkyl, C
3-C
8Cycloalkyl or C
6-C
20Aryl.
3. method as claimed in claim 2, wherein R
3, R
4, R
5And R
6Be hydrogen, C independently
1-C
6Alkyl or phenyl.
4. as the described method of arbitrary claim among the claim 1-3, wherein said alkaline-earth alkoxides is a magnesium alkoxide.
5. method as claimed in claim 4, the alcohol that wherein forms described alkaline-earth alkoxides is C
1-C
6Alkanol.
6. the method for claim 1 is carried out under the wherein said temperature condition that is reflected at 40 ℃ to 80 ℃ or solvent for use boiling point.
7. method as claimed in claim 6 is carried out under the wherein said 50-60 of being reflected at ℃ the temperature.
8. the method for claim 1, the mol ratio of wherein said catalyst levels and general formula (III) compound amount is 0.4～0.6:1.
9. the method for claim 1, the wherein said C that is reflected at
1-C
6Carry out in the alkanol solvent.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100888305A CN100509763C (en) | 2005-07-29 | 2005-07-29 | Preparation of alpha, beta unsaturated nitrile addition product |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100888305A CN100509763C (en) | 2005-07-29 | 2005-07-29 | Preparation of alpha, beta unsaturated nitrile addition product |
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| Publication Number | Publication Date |
|---|---|
| CN1903837A CN1903837A (en) | 2007-01-31 |
| CN100509763C true CN100509763C (en) | 2009-07-08 |
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|---|---|---|---|
| CNB2005100888305A Expired - Fee Related CN100509763C (en) | 2005-07-29 | 2005-07-29 | Preparation of alpha, beta unsaturated nitrile addition product |
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| Country | Link |
|---|---|
| CN (1) | CN100509763C (en) |
-
2005
- 2005-07-29 CN CNB2005100888305A patent/CN100509763C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| a synthesis of DL-proline. journal of american chemical society,Vol.71 . 1949 |
| a synthesis of DL-proline. journal of american chemical society,Vol.71 . 1949 * |
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|---|---|
| CN1903837A (en) | 2007-01-31 |
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Granted publication date: 20090708 Termination date: 20110729 |