CN110804034A - Synthetic method of furalaxyl-M - Google Patents
Synthetic method of furalaxyl-M Download PDFInfo
- Publication number
- CN110804034A CN110804034A CN201911198436.5A CN201911198436A CN110804034A CN 110804034 A CN110804034 A CN 110804034A CN 201911198436 A CN201911198436 A CN 201911198436A CN 110804034 A CN110804034 A CN 110804034A
- Authority
- CN
- China
- Prior art keywords
- furalaxyl
- reaction
- tsm
- methyl
- dimethylphenylamino
- 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
- CIEXPHRYOLIQQD-CYBMUJFWSA-N (R)-furalaxyl Chemical compound CC=1C=CC=C(C)C=1N([C@H](C)C(=O)OC)C(=O)C1=CC=CO1 CIEXPHRYOLIQQD-CYBMUJFWSA-N 0.000 title claims abstract description 13
- 238000010189 synthetic method Methods 0.000 title claims abstract description 9
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 10
- 229940101629 l- methyl lactate Drugs 0.000 claims abstract description 8
- LPEKGGXMPWTOCB-VKHMYHEASA-N methyl (S)-lactate Chemical compound COC(=O)[C@H](C)O LPEKGGXMPWTOCB-VKHMYHEASA-N 0.000 claims abstract description 8
- 229940017219 methyl propionate Drugs 0.000 claims abstract description 7
- OFTKFKYVSBNYEC-UHFFFAOYSA-N 2-furoyl chloride Chemical compound ClC(=O)C1=CC=CO1 OFTKFKYVSBNYEC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005576 amination reaction Methods 0.000 claims abstract description 5
- 238000006482 condensation reaction Methods 0.000 claims abstract description 5
- 238000005886 esterification reaction Methods 0.000 claims abstract description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- NEOYGRJJOGVQPO-UHFFFAOYSA-N alpha-(2,6-dimethylanilino)-propionic acid methyl ester Natural products COC(=O)C(C)NC1=C(C)C=CC=C1C NEOYGRJJOGVQPO-UHFFFAOYSA-N 0.000 claims description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical group CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000007529 inorganic bases Chemical class 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims 2
- 238000003786 synthesis reaction Methods 0.000 claims 2
- 230000002194 synthesizing effect Effects 0.000 claims 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- CIEXPHRYOLIQQD-UHFFFAOYSA-N methyl N-(2,6-dimethylphenyl)-N-2-furoylalaninate Chemical compound CC=1C=CC=C(C)C=1N(C(C)C(=O)OC)C(=O)C1=CC=CO1 CIEXPHRYOLIQQD-UHFFFAOYSA-N 0.000 description 3
- -1 2, 6-dimethylphenyl Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000549404 Hyaloperonospora parasitica Species 0.000 description 1
- 241000233614 Phytophthora Species 0.000 description 1
- 241000233639 Pythium Species 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000000817 effect on oomycetes Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- DWKPPFQULDPWHX-UHFFFAOYSA-N methyl 2-aminopropanoate Chemical compound COC(=O)C(C)N DWKPPFQULDPWHX-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthetic method of furalaxyl-M, which comprises the following steps: (1) carrying out esterification reaction on L-methyl lactate and R-benzene sulfonyl chloride to prepare TSM; (2) carrying out amination reaction on TSM and 2, 6-dimethylaniline to generate 2- (2, 6-dimethylphenylamino) methyl propionate; (3)2- (2, 6-dimethylphenylamino) methyl propionate and furoyl chloride are subjected to condensation reaction to obtain the furalaxyl-M. The method is convenient to operate, the content of the produced furalaxyl-m is 90-92%, and the yield is over 90%.
Description
Technical Field
The invention relates to a synthetic method of furalaxyl-M.
Background
Furalaxyl (furalaxyl) is a heterocyclic fungicide with the chemical name: n- (2, 6-dimethylphenyl) -N- (2-furylcarbonyl) -racemic methyl aminopropionate. Furalaxyl-M is a high-efficiency isomer of furalaxyl, and has good control effect on oomycete diseases caused by pythium, phytophthora and peronospora parasitica on various crops. The existing synthetic method of the furalaxyl-M has defects in yield, content and the like, and needs to be further improved.
Disclosure of Invention
The invention aims to provide a synthetic method of furalaxyl-m, which has high yield, high content and easy operation.
The technical solution of the invention is as follows:
a synthetic method of furalaxyl-M is characterized by comprising the following steps: comprises the following steps:
(1) carrying out esterification reaction on L-methyl lactate and R-benzene sulfonyl chloride to prepare TSM;
(2) carrying out amination reaction on TSM and 2, 6-dimethylaniline to generate 2- (2, 6-dimethylphenylamino) methyl propionate;
(3)2- (2, 6-dimethylphenylamino) methyl propionate and furoyl chloride are subjected to condensation reaction to obtain the furalaxyl-M.
R in the R-benzene sulfonyl chloride is alkyl.
And (2) adding an acid binding agent during the reaction in the step (1).
The acid-binding agent is DIEA, pyridine, triethylamine or inorganic base.
The feeding molar ratio in the step (1) is as follows: r-benzenesulfonyl chloride, L-methyl lactate is 1: 1-1.5; the feeding molar ratio in the step (2) is as follows: TSM 2, 6-dimethylaniline 1: 2-7; the feeding molar ratio in the step (3) is as follows: methyl 2- (2, 6-dimethylphenylamino) propionate furoyl chloride 1: 1-1.5.
The reaction formula is as follows:
esterification reaction
Amination reaction
Condensation reaction
The method is convenient to operate, the content of the produced furalaxyl-m is 90-92%, and the yield is over 90%.
Drawings
The invention is further illustrated by the following figures and examples.
FIG. 1 is a process flow diagram of one embodiment of the present invention.
Detailed Description
A synthetic method of furalaxyl-M comprises the following steps:
(1) carrying out esterification reaction on L-methyl lactate and R-benzene sulfonyl chloride to prepare TSM; r in R-benzenesulfonyl chloride is alkyl (e.g., H, methyl, ethyl, etc.)
Feeding molar ratio: r-benzenesulfonyl chloride, L-methyl lactate ═ 1:1 to 1.5 (examples 1:1, 1:1.2, 1: 1.5);
the specific method comprises the following steps:
adding toluene, R-benzene sulfonyl chloride (alkyl substituted benzene sulfonyl chloride) and acid-binding agent (DIEA, pyridine, triethylamine or inorganic base can be adopted), cooling to below 10 ℃, and dropwise adding L-methyl lactate. After the addition, the reaction was incubated at room temperature for 5 hours. After the reaction, toluene and water are added for standing and layering. And (4) desolventizing the oil phase to obtain TSM, and recovering toluene.
(2) Carrying out amination reaction on TSM and 2, 6-dimethylaniline to generate methyl 2- (2, 6-dimethylphenylamino) propionate (DMA);
feeding molar ratio: TSM 2, 6-dimethylaniline 1: 2-7 (examples 1:2, 1:5, 1: 7);
the specific method comprises the following steps:
adding TSM and 2, 6-dimethylaniline into a kettle, carrying out reflux reaction for 5 hours, cooling, adjusting the pH to 9-10 with 5% NaOH, washing with water, standing for layering, rectifying an oil phase to obtain DMA, and recovering the 2, 6-dimethylaniline.
(3)2- (2, 6-dimethylphenylamino) methyl propionate and furoyl chloride are subjected to condensation reaction to obtain furalaxyl-M;
feeding molar ratio: methyl 2- (2, 6-dimethylphenylamino) propionate furoyl chloride 1: 1-1.5;
the specific method comprises the following steps:
adding toluene and furoyl chloride as solvent into the kettle, and dripping DMA. After the addition, the temperature is raised to reflux, the reaction is kept for 5 hours, and then the finished product is obtained by washing and removing the solvent toluene.
The content of the produced benfuralaxyl-m is 90-92%, and the yield is more than 90%.
Claims (5)
1. A synthetic method of furalaxyl-M is characterized by comprising the following steps: comprises the following steps:
(1) carrying out esterification reaction on L-methyl lactate and R-benzene sulfonyl chloride to prepare TSM;
(2) carrying out amination reaction on TSM and 2, 6-dimethylaniline to generate 2- (2, 6-dimethylphenylamino) methyl propionate;
(3)2- (2, 6-dimethylphenylamino) methyl propionate and furoyl chloride are subjected to condensation reaction to obtain the furalaxyl-M.
2. The method for synthesizing furalaxyl-m according to claim 1, which comprises the following steps: r in the R-benzene sulfonyl chloride is alkyl.
3. Method for the synthesis of furalaxyl-m according to claim 1 or 2, characterized in that: and (2) adding an acid binding agent during the reaction in the step (1).
4. A method of synthesizing furalaxyl-m according to claim 3, which comprises: the acid-binding agent is DIEA, pyridine, triethylamine or inorganic base.
5. Method for the synthesis of furalaxyl-m according to claim 1 or 2, characterized in that: the feeding molar ratio in the step (1) is as follows: r-benzene sulfonyl chloride is L-methyl lactate =1: 1-1.5; the feeding molar ratio in the step (2) is as follows: TSM 2, 6-dimethylaniline =1: 2-7; the feeding molar ratio in the step (3) is as follows: methyl 2- (2, 6-dimethylphenylamino) propionate furoyl chloride =1: 1-1.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911198436.5A CN110804034A (en) | 2019-11-29 | 2019-11-29 | Synthetic method of furalaxyl-M |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911198436.5A CN110804034A (en) | 2019-11-29 | 2019-11-29 | Synthetic method of furalaxyl-M |
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| Publication Number | Publication Date |
|---|---|
| CN110804034A true CN110804034A (en) | 2020-02-18 |
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|---|---|---|---|
| CN201911198436.5A Pending CN110804034A (en) | 2019-11-29 | 2019-11-29 | Synthetic method of furalaxyl-M |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111747859A (en) * | 2020-06-16 | 2020-10-09 | 浙江禾本科技股份有限公司 | Method for synthesizing N- (2, 6-xylyl) methyl aminopropionate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000076960A1 (en) * | 1999-06-15 | 2000-12-21 | Isagro S.P.A. | Process for the preparation of optically active n-acyl derivatives of methyl n-(2,6-dimethylphenyl)-d-alaninate |
| CN109180514A (en) * | 2018-07-03 | 2019-01-11 | 浙江禾本科技有限公司 | A kind of synthetic method of optical activity metalaxyl |
-
2019
- 2019-11-29 CN CN201911198436.5A patent/CN110804034A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000076960A1 (en) * | 1999-06-15 | 2000-12-21 | Isagro S.P.A. | Process for the preparation of optically active n-acyl derivatives of methyl n-(2,6-dimethylphenyl)-d-alaninate |
| CN109180514A (en) * | 2018-07-03 | 2019-01-11 | 浙江禾本科技有限公司 | A kind of synthetic method of optical activity metalaxyl |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111747859A (en) * | 2020-06-16 | 2020-10-09 | 浙江禾本科技股份有限公司 | Method for synthesizing N- (2, 6-xylyl) methyl aminopropionate |
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