CN109134321A - A kind of preparation method of mesotrione intermediate - Google Patents
A kind of preparation method of mesotrione intermediate Download PDFInfo
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- CN109134321A CN109134321A CN201811232647.1A CN201811232647A CN109134321A CN 109134321 A CN109134321 A CN 109134321A CN 201811232647 A CN201811232647 A CN 201811232647A CN 109134321 A CN109134321 A CN 109134321A
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- mesotrione
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
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Abstract
The present invention relates to a kind of preparation methods of mesotrione intermediate; to mesyl bromobenzene as starting material; nitration reaction occurs with nitric acid first, the ethyl acetate of system after reaction and saturated sodium bicarbonate aqueous solution are subjected to extraction processing, organic phase of going out obtains product；Then cyanogenation occurs at high temperature with cuprous cyanide using DMF as solvent, solvent in removing system passes through column chromatography for separation product；Acidification is hydrolyzed in product and obtains final product mesotrione intermediate 2- nitro -4-(methyl sulphonyl) benzoic acid.By this method compared to traditional synthetic method, reduce the use of strong oxidizer, reaction condition is more mild, increases operational safety, while each step reaction treatment is easy, and is conducive to the progress of reaction, yield with higher.
Description
Technical field
The present invention relates to the synthesis of organic compound, and in particular to a kind of preparation method of mesotrione.
Background technique
Mesotrione (mesotrion) also known as mesotrione, Meath lead to, and chemical name is 2- (4- methylsulfonyl -2- nitre
Base-benzoyl) hexamethylene -1,3- diketone is a kind of inhibition p-hydroxybenzene pyruvic acid (HPP) dioxygen developed by Syngenta Co., Ltd
The herbicide patented product for changing enzyme (HPPD) promotes the use of a large area Europe is multinational, works well, initially enter in recent years
State market.Mesotrione is mainly action of contace poison, after susceptible weeds touch mesotrione, in plant xylem and bast
Portion's conduction, generates alphosis, slowly dead thereafter.Mesotrione can effectively prevent and kill off corn field annual broadleaf weed and one
A little gramineae weeds, the weeds effect for especially fighting sulfonylurea herbicide is obvious, to corn and its succession crop safety, to ring
Border is friendly.Mesotrione to the preventive effect of broadleaf weeds and gramineae weed respectively up to 90% and 80% or more, biological activity ratio
Similar medicament sulphur humulone is higher by 1 times.
2- nitro -4-(methyl sulphonyl) benzoic acid be synthesizing methyl sulphur humulone key intermediate, it is reported at present
Synthetic method about the intermediate is that adjacent nitro mesyl toluene is obtained through oxidation, is needed in the process using strong oxidizer,
Reaction condition is violent, is unfavorable for controlling, and pollutes larger.
Summary of the invention
The present invention is in view of the foregoing drawbacks, it is therefore intended that find it is a kind of without using strong oxidizer and reaction condition it is more mild
Route, while can be improved reaction yield.
Thus the technical solution adopted by the present invention is that: select to mesyl bromobenzene replace to mesyl toluene as
Beginning raw material.
A kind of preparation method of mesotrione intermediate, comprising the following steps:
(1), as starting material, to react with nitric acid, reaction equation is as follows to bromine mesyl benzene:
；
(2) then obtained compound 2 is reacted with cuprous cyanide again, reaction equation is as follows:
；
(3) acidification reaction then is hydrolyzed in obtained compound 3 again, reaction equation is as follows:
。
Acid is excessive in step (1), and reactant can just be added after need to two kinds of acid being uniformly mixed and be cooled down, wherein nitration mixture
Also it is used as reaction dissolvent.
Nitration reaction temperature is 0 ~ 10 DEG C in step (1), and the reaction time is 1 hour.
Cuprous cyanide needs excess in step (2), and the ratio between compound 2 and the amount of cuprous cyanide substance are 1 ~ 1.2.
In step (2), reaction temperature is 130 ~ 140 DEG C, and the reaction time is 6 hours.
In step (3), for acid using sulfuric acid and acetic acid nitration mixture, sulfuric acid acid and acetic acid equivalent proportion are 1 ~ 1, reaction temperature is 100 ~
105 DEG C, the reaction time is 6 hours.
The technical effect that the present invention generates: the oxidation that this method will will use when preparing mesotrione key intermediate
The step of acidification, is replaced by hydrolysis acidification, and reaction condition is mildly easily-controllable, is more advantageous to the progress of reaction, improves reaction yield.
Specific embodiment
In order to which the present invention is furture elucidated, a series of embodiments are given below, these embodiments be entirely it is illustrative, it
Only be used to the present invention specifically describe, be not construed as limitation of the present invention.
Embodiment 1
100 ml concentrated nitric acids (65 %) is added in reaction flask, is placed in ice bath and stirs, the 50 ml concentrated sulfuric acids (98 are added dropwise at 0 DEG C
%), it is added dropwise after 0.5 hour.23.5 g are added into reaction flask to mesyl bromobenzene (0.1 mol), 0 ~ 10 DEG C
Lower open mouth reacts 0.5 hour.After reaction, then with 500 ml saturated sodium bicarbonate aqueous solutions and 1000 ml acetic acid
Ethyl ester extracts reaction solution in batches, and organic phase is collected after extraction, and vacuum distillation obtains adjacent nitro to mesyl bromobenzene 24.7
G, yield are 88.5 %.
Embodiment 2
60 ml concentrated nitric acids (65 %) is added in reaction flask, is placed in ice bath and stirs, the 50 ml concentrated sulfuric acids (98 are added dropwise at 0 DEG C
%), it is added dropwise after 0.5 hour.23.5 g are added into reaction flask to mesyl bromobenzene (0.1 mol), 0 ~ 10 DEG C
Lower open mouth reacts 0.5 hour.After reaction, then with 500 ml saturated sodium bicarbonate aqueous solutions and 1000 ml acetic acid
Ethyl ester extracts reaction solution in batches, and organic phase is collected after extraction, and vacuum distillation obtains adjacent nitro to mesyl bromobenzene 23.1
G, yield 82.6%.
Embodiment 3
120 ml concentrated nitric acids (65 %) is added in reaction flask, is placed in ice bath and stirs, the 50 ml concentrated sulfuric acids (98 are added dropwise at 0 DEG C
%), it is added dropwise after 0.5 hour.23.5 g are added into reaction flask to mesyl bromobenzene (0.1 mol), 0 ~ 10 DEG C
Lower open mouth reacts 0.5 hour.After reaction, then with 500 ml saturated sodium bicarbonate aqueous solutions and 1000 ml acetic acid
Ethyl ester extracts reaction solution in batches, and organic phase is collected after extraction, and vacuum distillation obtains adjacent nitro to mesyl bromobenzene 25.3
G, yield 90.5%.
Embodiment 4
14.0 g adjacent nitros are added in reaction flask to mesyl bromobenzene (0.05 mol) and 7.16 g cuprous cyanides
50 ml DMF, 6 hours of back flow reaction at 140 DEG C are added in (0.08 mol).Vacuum distillation removes DMF after reaction,
Residual reaction liquid ethyl acetate and water extract, and extraction finishes collection organic phase, are evaporated under reduced pressure to adjacent nitro to mesyl benzene
10.5 g of formonitrile HCN, yield 93.1%.
Embodiment 5
14.0 g adjacent nitros are added in reaction flask to mesyl bromobenzene (0.05 mol) and 5.37 g cuprous cyanides
50 ml DMF, 6 hours of back flow reaction at 140 DEG C are added in (0.06 mol).Vacuum distillation removes DMF after reaction,
Residual reaction liquid ethyl acetate and water extract, and extraction finishes collection organic phase, are evaporated under reduced pressure to adjacent nitro to mesyl benzene
10.2 g of formonitrile HCN, yield 90.1%.
Embodiment 6
14.0 g adjacent nitros are added in reaction flask to mesyl bromobenzene (0.05 mol) and 5.37 g cuprous cyanides
50 ml DMF, 6 hours of back flow reaction at 140 DEG C are added in (0.04 mol).Vacuum distillation removes DMF after reaction,
Residual reaction liquid ethyl acetate and water extract, and extraction finishes collection organic phase, are evaporated under reduced pressure to adjacent nitro to mesyl benzene
9.8 g of formonitrile HCN, yield 86.4%.
Embodiment 7
11.3 g adjacent nitros are added in reaction flask to mesyl benzonitrile (0.05 mol) and 50 ml distilled water, then
10 ml glacial acetic acid are added into system, then the 10 ml concentrated sulfuric acids are added dropwise into reaction solution, after being added dropwise, reaction flask is placed in
6 hours are reacted at 100 DEG C.After reaction, it is extracted, has been extracted in batches with ethyl acetate with saturated sodium bicarbonate aqueous solution
Organic phase is collected after finishing, is evaporated under reduced pressure to mesotrione intermediate adjacent nitro to 11.4 g of methyl sulfonylbenzoic acid, yield is
93%。
Embodiment 8
11.3 g adjacent nitros are added in reaction flask to mesyl benzonitrile (0.05 mol) and 50 ml distilled water, then
5 ml glacial acetic acid are added into system, then the 5 ml concentrated sulfuric acids are added dropwise into reaction solution, after being added dropwise, reaction flask is placed in
6 hours are reacted at 100 DEG C.After reaction, it is extracted, has been extracted in batches with ethyl acetate with saturated sodium bicarbonate aqueous solution
Organic phase is collected after finishing, is evaporated under reduced pressure to mesotrione intermediate adjacent nitro to 10.9 g of methyl sulfonylbenzoic acid, yield is
89%。
Claims (6)
1. a kind of preparation method of mesotrione intermediate, which comprises the following steps:
(1), as starting material, to react with nitric acid, reaction equation is as follows to bromine mesyl benzene:
；
(2) then obtained compound 2 is reacted with cuprous cyanide again, reaction equation is as follows:
；
(3) acidification reaction then is hydrolyzed in obtained compound 3 again, reaction equation is as follows:
。
2. the preparation method of mesotrione intermediate according to claim 1, which is characterized in that acid was wanted in step (1)
Amount, and reactant can just be added after need to two kinds of acid being uniformly mixed and be cooled down, wherein nitration mixture is also used as reaction dissolvent.
3. the preparation method of mesotrione intermediate according to claim 1, which is characterized in that nitrification is anti-in step (1)
Answering temperature is 0 ~ 10 DEG C, and the reaction time is 1 hour.
4. the preparation method of mesotrione intermediate according to claim 1, which is characterized in that cyaniding is sub- in step (2)
Copper needs excess, and the ratio between compound 2 and the amount of cuprous cyanide substance are 1 ~ 1.2.
5. the preparation method of mesotrione intermediate according to claim 1, which is characterized in that in step (2), reaction temperature
Degree is 130 ~ 140 DEG C, and the reaction time is 6 hours.
6. the preparation method of mesotrione intermediate according to claim 1, which is characterized in that in step (3), acid is used
Sulfuric acid and acetic acid nitration mixture, sulfuric acid acid and acetic acid equivalent proportion are 1 ~ 1, and reaction temperature is 100 ~ 105 DEG C, and the reaction time is 6 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922367A (en) * | 2019-10-31 | 2020-03-27 | 江苏中旗科技股份有限公司 | Intermediate of topramezone and preparation method of topramezone |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4801717A (en) * | 1983-02-23 | 1989-01-31 | Roussel Uclaf | Hydroxylamine derivative of 5-nitro-8-hydroxy quinoline |
| CN1800160A (en) * | 2005-10-08 | 2006-07-12 | 浙江大学 | 3-amido-4-alkylamino lauseto neu preparation method |
| US20070213349A1 (en) * | 2006-03-08 | 2007-09-13 | Zacharia Cheruvallath | Glucokinase activators |
| CN101628885A (en) * | 2009-08-21 | 2010-01-20 | 北京颖泰嘉和科技股份有限公司 | Preparation method of 2-nitryl-4-thiamphenicol benzoic acid |
-
2018
- 2018-10-22 CN CN201811232647.1A patent/CN109134321A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4801717A (en) * | 1983-02-23 | 1989-01-31 | Roussel Uclaf | Hydroxylamine derivative of 5-nitro-8-hydroxy quinoline |
| CN1800160A (en) * | 2005-10-08 | 2006-07-12 | 浙江大学 | 3-amido-4-alkylamino lauseto neu preparation method |
| US20070213349A1 (en) * | 2006-03-08 | 2007-09-13 | Zacharia Cheruvallath | Glucokinase activators |
| CN101628885A (en) * | 2009-08-21 | 2010-01-20 | 北京颖泰嘉和科技股份有限公司 | Preparation method of 2-nitryl-4-thiamphenicol benzoic acid |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922367A (en) * | 2019-10-31 | 2020-03-27 | 江苏中旗科技股份有限公司 | Intermediate of topramezone and preparation method of topramezone |
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