CN112624922A - Method for alkylation reaction by phase transfer catalysis - Google Patents
Method for alkylation reaction by phase transfer catalysis Download PDFInfo
- Publication number
- CN112624922A CN112624922A CN202011349962.XA CN202011349962A CN112624922A CN 112624922 A CN112624922 A CN 112624922A CN 202011349962 A CN202011349962 A CN 202011349962A CN 112624922 A CN112624922 A CN 112624922A
- Authority
- CN
- China
- Prior art keywords
- phase transfer
- reaction
- alkylation
- alkylation reaction
- transfer catalyst
- 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.)
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 23
- 238000003408 phase transfer catalysis Methods 0.000 title claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 12
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 4
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims abstract description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 8
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- RZWGTXHSYZGXKF-UHFFFAOYSA-N 2-(2-methylphenyl)acetic acid Chemical compound CC1=CC=CC=C1CC(O)=O RZWGTXHSYZGXKF-UHFFFAOYSA-N 0.000 claims description 3
- -1 bromo-phenylacrylic acid methyl ester Chemical compound 0.000 claims description 2
- 230000029936 alkylation Effects 0.000 claims 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003442 catalytic alkylation reaction Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012022 methylating agents Substances 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
Abstract
The invention discloses a method for catalyzing alkylation reaction by using phase transfer, which comprises the alkylation reaction, wherein the alkylation reaction is carried out in a nonpolar solvent, and in the process of the alkylation reaction, a phase transfer catalyst and concentrated alkali are added, dimethyl sulfate is added dropwise, the phase transfer catalyst is quaternary ammonium salt or polyethylene glycol, the addition amount of the phase transfer catalyst is 1% -10% of the mass of a reaction substance, the concentration of added liquid alkali is 30% -50%, and the concentrated alkali is KOH or NaOH. In the implementation process of the invention, the reaction yield can be improved, the reaction temperature is reduced, the reaction time is shortened, and the post-treatment process is simplified.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a method for alkylation reaction by phase transfer catalysis.
Background
Dimethyl sulfate is a common methylating agent in chemical production and is mainly used for alkylation reaction in chemical products such as pharmacy, pesticides, dyes and the like.
Although dimethyl sulfate is highly toxic, it is still the first choice for methylating agents because of its high reactivity and low cost.
In the reaction process, a polar solvent is adopted, and strong base (KOH and NaOH) is added dropwise into dimethyl sulfate for reaction. However, post-treatment after reaction requires the steps of desolventizing, extracting, layering and the like, and separation difficulty is increased due to the fact that most of polar solvents (such as acetone, DMF and the like) after desolventizing are subjected to azeotropy with water. Moreover, the reaction time is long, the temperature is high, and the yield is low.
Disclosure of Invention
In view of the above situation, the present invention provides a method for alkylation reaction using phase transfer catalysis, which effectively solves the problems in the background art.
In order to achieve the purpose, the invention provides the following technical scheme: a process for phase transfer catalytic alkylation reaction includes alkylation reaction in non-polar solvent, adding phase transfer catalyst, concentrated alkali and dimethyl sulfate drop by drop.
Preferably, the phase transfer catalyst is quaternary ammonium salts or polyethylene glycols.
Preferably, the addition amount of the phase transfer catalyst is 1-10% of the mass of the reactants.
Preferably, the concentration of the added liquid alkali is 30% -50%, and the concentrated alkali is KOH or NaOH.
Preferably, the chemical reaction equation for preparing the methyl bromophenacrylate from o-methylphenylacetic acid is shown as follows,
in the reaction equation, the acylate is dissolved in acetone, added with metered dimethyl sulfate and potassium carbonate (or KOH), stirred, heated, refluxed, reacted for 3 hours, cooled, filtered, desolventized, extracted by dichloromethane, washed with an organic phase, dried, filtered, and dichloromethane-removed to obtain yellow liquid,
directly adding a phase transfer catalyst with the mass ratio of 1-2% into the reacted acylate dichloromethane solution, then dropwise adding a KOH aqueous solution, dropwise adding dimethyl sulfate in a water bath after the dropwise adding is finished, then heating to room temperature, dropwise adding the reactants within 0.5-1h until the reactants are subjected to point tracking, after the reaction is finished, supplementing a certain amount of water, standing for layering, extracting a water layer with dichloromethane, combining organic phases, and desolventizing to obtain a light yellow liquid.
Preferably, the concentration of the KOH aqueous solution is 40-50%.
Compared with the prior art, the invention has the beneficial effects that:
when the scheme disclosed by the invention is implemented, the reaction yield is improved, the reaction temperature is reduced, the reaction time is shortened, and the post-treatment process is simplified.
Detailed Description
The technical solution of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments; all other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention discloses a method for catalyzing alkylation reaction by using phase transfer, which comprises the alkylation reaction, wherein the alkylation reaction is carried out in a nonpolar solvent, and when the alkylation reaction is carried out, a phase transfer catalyst and concentrated alkali are added, dimethyl sulfate is dropwise added, the phase transfer catalyst is quaternary ammonium salt or polyethylene glycol, the addition amount of the phase transfer catalyst is 1% -10% of the mass of a reaction substance, the concentration of added liquid alkali is 30% -50%, and the concentrated alkali is KOH or NaOH.
Examples
The chemical reaction equation for preparing the bromo-phenylacrylic acid methyl ester by the o-methylphenylacetic acid is shown as follows,
the methylation reaction comprises the following one-step original process:
dissolving acylate in acetone, adding metered dimethyl sulfate and potassium carbonate (or KOH), stirring, heating, refluxing, reacting for 3h, cooling, filtering, desolventizing, extracting with dichloromethane, washing an organic phase, drying, filtering, and removing dichloromethane to obtain yellow liquid, wherein the yield is about 85%.
The process provided by the invention comprises the following steps:
directly adding a phase transfer catalyst with the mass ratio of 1-2% into the reacted acylate dichloromethane solution, then dropwise adding 40-50% KOH aqueous solution, dropwise adding dimethyl sulfate in a water bath after the dropwise adding is finished, then heating to room temperature, dropwise tracking the reactant within 0.5-1h until the reactant is completely reacted, adding a certain amount of water, standing for layering, extracting a water layer with dichloromethane, combining organic phases, and desolventizing to obtain a light yellow liquid, wherein the yield is about 95%.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. A method of alkylation using phase transfer catalysis, characterized by: the method comprises an alkylation reaction, wherein the alkylation reaction is carried out in a nonpolar solvent, and when the alkylation reaction is carried out, a phase transfer catalyst, concentrated alkali and dimethyl sulfate are added dropwise.
2. A process for alkylation using phase transfer catalysis according to claim 1, wherein: the phase transfer catalyst is quaternary ammonium salt or polyethylene glycol.
3. A process for alkylation using phase transfer catalysis according to claim 2, wherein: the addition amount of the phase transfer catalyst is 1-10% of the mass of the reactant.
4. A process for alkylation using phase transfer catalysis according to claim 3, wherein: the concentration of the added liquid alkali is 30-50%, and the concentrated alkali is KOH or NaOH.
5. A process according to claim 4 using a phase transfer catalyzed alkylation reaction, wherein: the chemical reaction equation for preparing the bromo-phenylacrylic acid methyl ester by the o-methylphenylacetic acid is shown as follows,
directly adding a phase transfer catalyst with the mass ratio of 1-2% into the reacted acylate dichloromethane solution, then dropwise adding a KOH aqueous solution, dropwise adding dimethyl sulfate under a water bath after the dropwise adding is finished, then heating to room temperature, dropwise tracking the reactant within 0.5-1h until the reactant is completely reacted, adding a certain amount of water, standing for layering, extracting a water layer with dichloromethane, combining organic phases, and desolventizing to obtain a light yellow liquid.
6. A process according to claim 5 using a phase transfer catalyzed alkylation reaction, wherein: the concentration of the KOH aqueous solution is 40-50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011349962.XA CN112624922A (en) | 2020-11-26 | 2020-11-26 | Method for alkylation reaction by phase transfer catalysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011349962.XA CN112624922A (en) | 2020-11-26 | 2020-11-26 | Method for alkylation reaction by phase transfer catalysis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112624922A true CN112624922A (en) | 2021-04-09 |
Family
ID=75304067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011349962.XA Pending CN112624922A (en) | 2020-11-26 | 2020-11-26 | Method for alkylation reaction by phase transfer catalysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112624922A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114014829A (en) * | 2021-11-11 | 2022-02-08 | 河北维达康生物科技有限公司 | Method for synthesizing 7, 4' -dimethylnaringenin |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000191554A (en) * | 1998-12-29 | 2000-07-11 | Nippon Soda Co Ltd | Production of acrylic acid derivative having functional group having high reaction activity |
| CN101234955A (en) * | 2008-03-10 | 2008-08-06 | 孔繁昇 | Method for preparing 3-methoxyl-4-t-butyltoluene |
| CN101269076A (en) * | 2007-03-22 | 2008-09-24 | 中国人民解放军军事医学科学院放射与辐射医学研究所 | Medicine use of beta-methoxy acrylic ester compounds as novel STAT3 restrainer |
| CN101268780A (en) * | 2008-05-08 | 2008-09-24 | 华中师范大学 | Methoxy group acrylic ester fungicide, preparation method and uses thereof |
| CN101381305A (en) * | 2008-10-21 | 2009-03-11 | 江苏耕耘化学有限公司 | Bactericidal agent intermediate (E)-2-(2'-bromomethyl)phenyl-3-methoxylacrylate preparation method |
| CN107629004A (en) * | 2017-10-25 | 2018-01-26 | 贾明宏 | 13The pyraoxystrobin and its synthetic method of C flag |
| CN107674027A (en) * | 2017-10-25 | 2018-02-09 | 河南衡谱分析检测技术有限公司 | 13The pyraoxystrobin and its synthetic method of C flag |
-
2020
- 2020-11-26 CN CN202011349962.XA patent/CN112624922A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000191554A (en) * | 1998-12-29 | 2000-07-11 | Nippon Soda Co Ltd | Production of acrylic acid derivative having functional group having high reaction activity |
| CN101269076A (en) * | 2007-03-22 | 2008-09-24 | 中国人民解放军军事医学科学院放射与辐射医学研究所 | Medicine use of beta-methoxy acrylic ester compounds as novel STAT3 restrainer |
| CN101234955A (en) * | 2008-03-10 | 2008-08-06 | 孔繁昇 | Method for preparing 3-methoxyl-4-t-butyltoluene |
| CN101268780A (en) * | 2008-05-08 | 2008-09-24 | 华中师范大学 | Methoxy group acrylic ester fungicide, preparation method and uses thereof |
| CN101381305A (en) * | 2008-10-21 | 2009-03-11 | 江苏耕耘化学有限公司 | Bactericidal agent intermediate (E)-2-(2'-bromomethyl)phenyl-3-methoxylacrylate preparation method |
| CN107629004A (en) * | 2017-10-25 | 2018-01-26 | 贾明宏 | 13The pyraoxystrobin and its synthetic method of C flag |
| CN107674027A (en) * | 2017-10-25 | 2018-02-09 | 河南衡谱分析检测技术有限公司 | 13The pyraoxystrobin and its synthetic method of C flag |
Non-Patent Citations (1)
| Title |
|---|
| PREETI M CHAUDHARY ET AL: "Synthesis and antifungal potential of 1,2,3-triazole and 1,2,4-triazole thiol substituted strobilurin derivatives", 《INDIAN JOURNAL OF CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114014829A (en) * | 2021-11-11 | 2022-02-08 | 河北维达康生物科技有限公司 | Method for synthesizing 7, 4' -dimethylnaringenin |
| CN114014829B (en) * | 2021-11-11 | 2023-03-07 | 河北维达康生物科技有限公司 | Method for synthesizing 7,4' -dimethylnaringenin |
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Application publication date: 20210409 |
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