CN1314653C - Method of producing carboxylate - Google Patents
Method of producing carboxylate Download PDFInfo
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- CN1314653C CN1314653C CNB2004100043094A CN200410004309A CN1314653C CN 1314653 C CN1314653 C CN 1314653C CN B2004100043094 A CNB2004100043094 A CN B2004100043094A CN 200410004309 A CN200410004309 A CN 200410004309A CN 1314653 C CN1314653 C CN 1314653C
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- general formula
- ether
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- alkyl
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Abstract
The present invention discloses a method for preparing carboxylate shown in a general formula (III). The method comprises reaction steps of a Grignard reagent shown in a general formula (I) and carbonate shown in a general formula (II) in an organic solvent, wherein R and R; are substituent groups or aromatic substituent groups of a fatty group, and X is halogen atoms. The present invention realizes the preparation of carboxylate with one more carbon atom in a one-step process.
Description
Technical field
The present invention relates to the preparation method of carboxylicesters, particularly utilize Grignard reagent and carbonate reaction to prepare the method for carboxylicesters.
Background technology
Grignard reagent (Grinard reagent) is a reagent commonly used in the organic synthesis, and it can play addition reaction with carbonyl, for example with aldehyde, ketone, ester in the carbonyl addition after, through hydrolysis can obtain primary, the second month in a season and the tertiary alcohol.
Yet, in the report that Grignard reagent is used, do not see that it is directly used in the preparation carboxylicesters.In all documents that carbonic ether is used, do not see that it is used for synthesizing carboxylate.In all documents of carboxylicesters synthetic, do not see carboxylicesters with the many carbon atoms of Grignard reagent one-step synthesis.
The present invention is directed to the existing not enough method that proposes to utilize the Grignard reagent synthesizing carboxylate.
Summary of the invention
The purpose of this invention is to provide a kind of method that is prepared as follows the carboxylicesters shown in the general formula (III), this method comprises the step that the carbonic ether shown in Grignard reagent shown in the following general formula (I) and the following general formula (II) is reacted in organic solvent:
RMgX (I)
RCOOR′ (III)
Wherein, R, R ' are aliphatics substituting group or aromatic substituents, and X is a halogen atom.
Aliphatics substituting group in the inventive method is meant alkyl, aminoalkyl group, hydroxyalkyl or cycloalkyl.Preferably methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-or the tertiary butyl.
Aromatic substituents in the inventive method is meant and replaces or unsubstituted phenyl or replacement or unsubstituted benzyl.The benzyl or the fluoro benzyl that replace of the phenyl, fluoro phenyl, benzyl, the alkyl that replace of phenyl, alkyl preferably.
X in the inventive method is bromine or chlorine preferably.
The used organic solvent of the present invention is the anhydrous solvent that contains ethers.The mixture of ether, mixed ether or ether and other non-ether solvents preferably.It most preferably is tetrahydrofuran (THF).
Compared with prior art, the present invention utilizes Grignard reagent and carbonate reaction to synthesize carboxylicesters, has realized the preparation of the carboxylicesters of the many carbon atoms of one-step synthesis.
Embodiment
The present invention will be described in more detail below in conjunction with embodiment.
Embodiment 1
Get 3,4-bromofluorobenzene 100g (0.518mol), magnesium powder 13g (0.54mol), tetrahydrofuran (THF) 140ml, after making Grignard reagent with the method for routine, in 35-40 ℃ of mixed solution that in Grignard reagent, drips methylcarbonate 47g (0.522mol) and 60ml tetrahydrofuran (THF), about 1 hour of dropping time, do not make reaction too fierce.Continuing reaction after 1 hour, is that 16.5% aqueous ammonium chloride solution 180ml splashes in the reaction solution degradation production with concentration.To be decomposed fully after, tell the tetrahydrofuran (THF) layer, with tetrahydrofuran (THF) 120ml aqueous layer extracted twice, merge the tetrahydrofuran (THF) layer, add anhydrous sodium sulphate 10g dried overnight, tetrahydrofuran (THF) 150ml is removed in distillation after the elimination anhydrous sodium sulphate, be cooled to 0 ℃ again, filtration, dry product 3, the 4-difluoro-benzoic acid methyl esters 52g of getting, purity 98% (GC, area normalization method).
Embodiment 2
With 3,5-difluoro bromobenzene 100g (0.518mol) replaces 3, and the 4-difluoro bromobenzene repeats the operation of embodiment 1, gets product 3,5-difluoro-benzoic acid methyl esters 49g, purity 97%.
Embodiment 3
Replace 3 with monobromethane 11g (0.10mol), the 4-difluoro bromobenzene replaces methylcarbonate with diethyl carbonate 13g (0.11mol), repeats the operation of embodiment 1, and the tetrahydrofuran (THF) layer records and contains ethyl propionate 5.8g in the solution after anhydrous sodium sulfate drying, filtration.
Should be appreciated that embodiments of the invention only are for understanding the indefiniteness explanation that the present invention makes the present invention better.Those skilled in the art are not departing from the spirit and scope of the present invention and can make various modifications, replacement and change to the present invention, and these modifications, replacement and change still belong to protection scope of the present invention.
Claims (8)
1. method that is prepared as follows the carboxylicesters shown in the general formula (III), described method comprises the step that the carbonic ether shown in Grignard reagent shown in the following general formula (I) and the following general formula (II) is reacted in organic solvent:
RMgX (I)
RCOOR′ (III)
Wherein, R, R ' are aliphatics substituting group or aromatic substituents, and X is a halogen atom.
2. the method for claim 1, wherein said aliphatics substituting group is meant alkyl, aminoalkyl group, hydroxyalkyl or cycloalkyl.
3. method as claimed in claim 2, wherein said aliphatics substituting group is methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-or the tertiary butyl.
4. the method for claim 1, wherein said aromatic substituents are benzyl or the fluoro benzyls that phenyl, fluoro phenyl, benzyl, alkyl that phenyl, alkyl replace replace.
5. the method for claim 1, wherein said halogen atom is bromine or chlorine.
6. the method for claim 1, wherein said organic solvent is the anhydrous solvent that contains ethers.
7. method as claimed in claim 6, wherein said organic solvent are the mixtures of ether, mixed ether or ether and other non-ether solvents.
8. method as claimed in claim 7, wherein said organic solvent is a tetrahydrofuran (THF).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100043094A CN1314653C (en) | 2004-02-13 | 2004-02-13 | Method of producing carboxylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100043094A CN1314653C (en) | 2004-02-13 | 2004-02-13 | Method of producing carboxylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1654452A CN1654452A (en) | 2005-08-17 |
| CN1314653C true CN1314653C (en) | 2007-05-09 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100043094A Expired - Fee Related CN1314653C (en) | 2004-02-13 | 2004-02-13 | Method of producing carboxylate |
Country Status (1)
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| CN (1) | CN1314653C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100430346C (en) * | 2006-03-20 | 2008-11-05 | 兰州大学 | Selective alkylation reaction of acid anhydride or ester |
| WO2007137799A1 (en) * | 2006-05-31 | 2007-12-06 | Schwarz Pharma Ltd. | New synthesis of substituted hydroxymethyl phenols |
| IES20060424A2 (en) * | 2006-06-08 | 2007-10-31 | Schwarz Pharma Ltd | Accelerated synthesis of (3-Diisopropylamino-1-phenylpropyl)-4-(hydroxymethyl)phenol and its phenolic monoesters |
| CN103539666B (en) * | 2013-09-27 | 2015-06-03 | 上虞新和成生物化工有限公司 | Preparation method of 2-methyl-3-butenoic acid ester |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1357547A (en) * | 2001-09-29 | 2002-07-10 | 昆山双鹤药业有限责任公司 | Prepn. of levo-ofloxacin |
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2004
- 2004-02-13 CN CNB2004100043094A patent/CN1314653C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1357547A (en) * | 2001-09-29 | 2002-07-10 | 昆山双鹤药业有限责任公司 | Prepn. of levo-ofloxacin |
Non-Patent Citations (1)
| Title |
|---|
| 高等教育出版社 刑其毅等，基础有机化学，第2期 * |
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| Publication number | Publication date |
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| CN1654452A (en) | 2005-08-17 |
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Granted publication date: 20070509 |