CN103319368A - Synthesis method of 2-methylene glutaronitrile - Google Patents
Synthesis method of 2-methylene glutaronitrile Download PDFInfo
- Publication number
- CN103319368A CN103319368A CN2013102902320A CN201310290232A CN103319368A CN 103319368 A CN103319368 A CN 103319368A CN 2013102902320 A CN2013102902320 A CN 2013102902320A CN 201310290232 A CN201310290232 A CN 201310290232A CN 103319368 A CN103319368 A CN 103319368A
- Authority
- CN
- China
- Prior art keywords
- synthetic method
- solvent
- reaction
- preferred
- vinyl cyanide
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a synthesis method of 2-methylene glutaronitrile. According to the method, tricyclohexylphosphine is taken as a catalyst; an acrylonitrile dimer is chemically catalyzed under the condition with a solvent or not; the dosage of the catalyst is 0.1-5.0 wt%; the reaction temperature is 50-90 DEG C; and the initial concentration of the acrylonitrile is 3.0-15.2 mol/L. Furthermore, the reaction product is purified in a distilling manner. The method is available in materials, mild in reaction condition, high in yield, good in selectivity, strong in atom economy, friendly to the environment and applicable to industrial production.
Description
Technical field
The present invention relates to a kind of synthetic method of 2-methylene glutaronitrile, more specifically, relate to take vinyl cyanide as catalytic material two methods that aggregate into the 2-methylene glutaronitrile.
Background technology
The 2-methylene glutaronitrile is the intermediate of preparation sterilant bromothalonil, and it has important using value.Vinyl cyanide is cheap and easy to get, and two to aggregate into the 2-methylene glutaronitrile be an effective method take vinyl cyanide as catalytic material.The method Atom economy is high, raw material is cheap, environmentally friendly.
Yet, existing vinyl cyanide dimerization prepares the method for 2-methylene glutaronitrile, often need severe condition (the Tetrahedron Lett.2000 such as High Temperature High Pressure, 41,3091-3094), and exist the defectives such as selectivity is low, productive rate is low, reaction density is low, particularly need to use expensive and poisonous ruthenium catalyst, to environment, and cost high (J.Chem.Res.1995,267; J.Mol.Cat.1992,73, L15-19; J.Chem.Soc.Perkin Trans.12002,1318-1323; Tetrahedron Lett.1987,28,4591-4592; J.Org.Chem.1970,35,3045-3048).
Summary of the invention
The object of the present invention is to provide a kind of vinyl cyanide highly selective to be converted into the synthetic method of 2-methylene glutaronitrile.
We find recently, and vinyl cyanide can be converted into the 2-methylene glutaronitrile by highly selective under the thricyclohexyl phosphine catalyst.Compare with traditional method, the method has the series of advantages such as reactive component is simple, concentration is high, productive rate is high, selectivity is good, reaction conditions is gentle.
Technical scheme of the present invention is as follows:
A kind of synthetic method of 2-methylene glutaronitrile, take vinyl cyanide as raw material, the vinyl cyanide dimerization generates the 2-methylene glutaronitrile under the thricyclohexyl phosphine catalyst.
In the present invention, based on the quality of vinyl cyanide, tricyclohexyl phosphine is the preferred 0.1～5.0wt% of consumption of catalyzer, more preferably 1.0～5.0wt%.
In the present invention, preferred 50～90 ℃ of dimerization reaction temperature, more preferably 60～80 ℃.
In the present invention, reaction can be carried out under solvent-free or solvent condition; Wherein solvent can also can be acetonitrile, ethyl acetate, ethanol, Virahol, trimethyl carbinol isopolarity solvent for non-polar solvents such as benzene, toluene, hexanaphthene, sherwood oils, preferred tertiary butanols or Virahol.The starting point concentration of vinyl cyanide can be 3.0～15.2mol/L, preferred 3.0～5.0mol/L in the reaction; The starting point concentration of vinyl cyanide is 15.2mol/L when solvent-free.
Further, come purified product with distillation after reaction finishes.Preferably, distillation temperature is 115～128 ℃, and pressure is 5～25mmHg.
The present invention utilizes tricyclohexyl phosphine catalyzing propone nitrile dimerization to prepare the 2-methylene glutaronitrile, and raw material is easy to get, and productive rate is high, and Atom economy is strong, does not produce harmful waste, and is environmentally friendly.
Embodiment
The following examples are set forth in more detail to the present invention, rather than limitation of the invention further.Wherein, the catalyzer tricyclohexyl phosphine is commercially available product, purity〉98%.Except as otherwise noted, wherein " % " is " quality % ".
Embodiment 1
Add successively vinyl cyanide, the trimethyl carbinol, tricyclohexyl phosphine (charging capacity is as shown in table 1) in a 50mL round-bottomed flask, connect reflux condensing tube, be heated to 70 ℃ and stirred 10 hours under nitrogen protection, reaction solution is flavescence gradually.Connect the water distilling apparatus distillation, at first steam solvent tertiary butanol (80～83 ℃).Raffinate is transferred to (20mL round-bottomed flask) underpressure distillation in the smaller container, and 115～128 ℃/10mmHg steams product 2-methylene glutaronitrile.Obtain the 7.0g cyanobenzene, productive rate 86%.
The charging capacity of table 1 reaction raw materials, solvent and catalyzer
| Material | Molecular weight | Amount of substance/mmol | Quality/g | Volume/mL |
| Vinyl cyanide | 53 | 153 | 8.1 | 10 |
| The trimethyl carbinol | 74 | 213 | 15.7 | 20 |
| Tricyclohexyl phosphine | 280 | 0.8 | 0.224 | - |
Embodiment 2
Other conditions change the consumption of thricyclohexyl phosphine catalyst with embodiment 1, and reaction result is as shown in table 2.
Table 2 catalyst levels is on the impact of reaction
| Numbering | Catalyst levels/wt% | Productive rate/% |
| 1 | 0.5 | 62 |
| 2 | 1.0 | 73 |
| 3 | 2.0 | 78 |
| 4 (embodiment 1) | 2.8 | 86 |
| 5 | 4.0 | 72 |
| 6 | 5.0 | 70 |
Embodiment 3
Substitute the trimethyl carbinol with other solvents, solvent load is 20mL, and other conditions are with embodiment 1, and experimental result sees Table 3.
Table 3 different solvents is on the impact of reaction
| Numbering | Solvent | Productive rate/% |
| 1 | Benzene | 43 |
| 2 | Hexanaphthene | 36 |
| 3 | Virahol | 54 |
| 4 (embodiment 1) | The trimethyl carbinol | 86 |
Embodiment 4
Other conditions change the starting point concentration of acrylonitrile reactor thing with embodiment 1, and except embodiment 6, solvent for use is the trimethyl carbinol, and experimental result sees Table 3.
Table 4 vinyl cyanide starting point concentration is on the impact of reaction
| Numbering | Acrylonitrile concentration/mol/L) | Productive rate/% |
| 1 | 3.0 | 78 |
| 2 | 4.0 | 80 |
| 3(embodiment 1) | 5.0 | 86 |
| 4 | 6.0 | 76 |
| 5 | 10.0 | 53 |
| 6 | 15.2 | 51 |
Embodiment 5
Other conditions change temperature of reaction with embodiment 1, and experimental result sees Table 5.
Table 5 temperature of reaction is on the impact of reaction
| Numbering | Temperature/℃ | Productive rate/% |
| 1 | 50 | 66 |
| 2 | 60 | 78 |
| 3 | 70(embodiment 1) | 86 |
| 4 | 80 | 72 |
| 5 | The 90(tube sealing) | 57 |
Annotate: tube sealing refers to carry out in an airtight Glass tubing, and when temperature of reaction surpassed the boiling point of solvent in the reaction, solvent can not volatilize like this.
Claims (10)
1. the synthetic method of a 2-methylene glutaronitrile take vinyl cyanide as raw material, is characterized in that, the vinyl cyanide dimerization generates the 2-methylene glutaronitrile under the thricyclohexyl phosphine catalyst.
2. synthetic method according to claim 1 is characterized in that, based on the vinyl cyanide quality, described tricyclohexyl phosphine catalyst levels is 0.1～5.0wt%, preferred 1.0～5.0wt%.
3. synthetic method according to claim 1 is characterized in that, described temperature of reaction is 50～90 ℃, preferred 60～80 ℃.
4. synthetic method according to claim 1 is characterized in that, the starting point concentration of vinyl cyanide described in the reaction is 3.0～15.2mol/L, preferred 3～5mol/L.
5. synthetic method according to claim 1 is characterized in that, described dimerization reaction carries out under condition of no solvent.
6. synthetic method according to claim 1 is characterized in that, described dimerization reaction carries out having under the solvent condition.
7. synthetic method according to claim 6 is characterized in that, described solvent is non-polar solvent, preferred benzene, toluene, hexanaphthene or sherwood oil.
8. synthetic method according to claim 6 is characterized in that, described solvent is polar solvent, preferred acetonitrile, ethyl acetate, ethanol, Virahol or the trimethyl carbinol.
9. synthetic method according to claim 8 is characterized in that, described solvent is the trimethyl carbinol or Virahol.
10. synthetic method according to claim 1 is characterized in that, further, reaction product is by distilation, and preferred distillation temperature is that 115～128 ℃, pressure are 5～25mmHg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013102902320A CN103319368A (en) | 2013-07-11 | 2013-07-11 | Synthesis method of 2-methylene glutaronitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013102902320A CN103319368A (en) | 2013-07-11 | 2013-07-11 | Synthesis method of 2-methylene glutaronitrile |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103319368A true CN103319368A (en) | 2013-09-25 |
Family
ID=49188463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013102902320A Pending CN103319368A (en) | 2013-07-11 | 2013-07-11 | Synthesis method of 2-methylene glutaronitrile |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103319368A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105837470A (en) * | 2015-01-12 | 2016-08-10 | 华东理工大学 | Method for preparing 2-methyleneglutaronitrile (MGN) through dimerization of acrylonitrile |
| CN115702140A (en) * | 2020-10-12 | 2023-02-14 | 株式会社Lg化学 | Process for producing acrylonitrile dimer |
| CN117384065A (en) * | 2023-12-13 | 2024-01-12 | 潍坊裕凯化工有限公司 | Preparation method of 2-methyleneglutaronitrile |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3499922A (en) * | 1965-03-02 | 1970-03-10 | Nat Distillers Chem Corp | Dimerization process |
-
2013
- 2013-07-11 CN CN2013102902320A patent/CN103319368A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3499922A (en) * | 1965-03-02 | 1970-03-10 | Nat Distillers Chem Corp | Dimerization process |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105837470A (en) * | 2015-01-12 | 2016-08-10 | 华东理工大学 | Method for preparing 2-methyleneglutaronitrile (MGN) through dimerization of acrylonitrile |
| CN115702140A (en) * | 2020-10-12 | 2023-02-14 | 株式会社Lg化学 | Process for producing acrylonitrile dimer |
| CN117384065A (en) * | 2023-12-13 | 2024-01-12 | 潍坊裕凯化工有限公司 | Preparation method of 2-methyleneglutaronitrile |
| CN117384065B (en) * | 2023-12-13 | 2024-02-20 | 潍坊裕凯化工有限公司 | Preparation method of 2-methyleneglutaronitrile |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cheng et al. | Effect of hydrogen bond of hydroxyl-functionalized ammonium ionic liquids on cycloaddition of CO2 | |
| MY153255A (en) | Low-energy extractive distillation process for dehydration of aqueous ethanol | |
| CN103319368A (en) | Synthesis method of 2-methylene glutaronitrile | |
| CN103420918A (en) | Simple and convenient preparation method of key intermediate (2-methyl-4-amino-5-amino methyl pyrimidine) for vitamin B1 | |
| Song et al. | Efficient conversion of glucose and cellulose to 5-hydroxymethylfurfural in DBU-based ionic liquids | |
| CN105837470A (en) | Method for preparing 2-methyleneglutaronitrile (MGN) through dimerization of acrylonitrile | |
| Jastrzebski et al. | Sustainable production of dimethyl adipate by non-heme iron (III) catalysed oxidative cleavage of catechol | |
| CN102367230B (en) | Method for synthesizing nitrile from aldoxime | |
| CN103694136A (en) | One-step method for synthesizing adiponitrile by using butadiene | |
| CN107522585B (en) | Hydrogenation resolution method of quinoline axial chiral compound | |
| EP2882709B1 (en) | Transesterification process of retinol esters | |
| CN110845415B (en) | Environment-friendly synthesis method of 2-ethyl-4-methylimidazole | |
| CN104292113A (en) | Preparation method of 3-chloro-4-fluoroaniline | |
| CN103145559A (en) | Preparation method of N-allyl arylamine | |
| SG178864A1 (en) | Method for producing a compound with a double bond | |
| CN109438237B (en) | Preparation method of 3-ethoxy ethyl acrylate | |
| CN103641741B (en) | Preparation method of pesticide intermediate malononitrile | |
| CN103420939B (en) | Method for synthesizing azacycloheptane | |
| JP5911468B2 (en) | Process for producing asymmetric secondary tert-butylamine in gas phase | |
| CN104230879A (en) | Simple and convenient preparation method of 2-((4R,6S)-6-formyl-2,2-disubstituted-1,3-dioxane-4-yl)acetate | |
| CN109824483B (en) | New method for preparing nopol | |
| CN104058930A (en) | Method for synthesizing sorbic acid through real-time splitting decomposition of acetic acid | |
| CN106278790B (en) | A method of preparing isoprene | |
| JP6301481B2 (en) | Process for producing alkanol | |
| JP5609041B2 (en) | Process for producing hydroxy (alkyl) piperazines |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130925 |