CN106317042A - Synthesis method of 7-fluorine-6-amino-4-(2-propargyl)-1,4-benzoxazine-3(4H)-ketone derivative - Google Patents
Synthesis method of 7-fluorine-6-amino-4-(2-propargyl)-1,4-benzoxazine-3(4H)-ketone derivative Download PDFInfo
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- CN106317042A CN106317042A CN201610682770.8A CN201610682770A CN106317042A CN 106317042 A CN106317042 A CN 106317042A CN 201610682770 A CN201610682770 A CN 201610682770A CN 106317042 A CN106317042 A CN 106317042A
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- C07—ORGANIC CHEMISTRY
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- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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Abstract
The invention relates to the field of organic synthesis, in particular to a synthesis method of a 7-fluorine-6-amino-4-(2-propargyl)-1,4-benzoxazine-3(4H)-ketone derivative. The method includes the step of conducting reaction under the catalysis effect of organic acid and salt with 6-amino-7-fluorine-4-propinyl-1,4-benzoxazine-3(4H)-ketone and 3,4,5,6-tetrahydrophthalic anhydride as the raw materials to obtain the 7-fluorine-6-amino-4-(2-propargyl)-1,4-benzoxazine-3(4H)-ketone derivative, wherein acetic acid and potassium acetate are optimally selected as catalysts, and potassium acetate is low in price. Compared with an existing catalytic reaction method with piperidine as the catalyst, the method has the outstanding advantage of being low in production cost with acetic acid and potassium acetate as the catalysts; the reaction yield can reach 91% or above, the purity can reach 99.5% or above, and the product purity and impurity specification meet related standards.
Description
Technical field
The present invention relates to technical field of organic synthesis, particularly relate to a kind of 7-fluoro-6-amino-4-(2-propargyl)-Isosorbide-5-Nitrae-
The synthetic method of benzimidazole dihydrochloride-3 (4H)-one derivant.
Background technology
7-fluoro-6-amino-4-(2-propargyl)-Isosorbide-5-Nitrae-benzimidazole dihydrochloride-3 (4H)-one derivant, also known as flumioxazin
(speed receive), is IV-phenylphthalimide class herbicide of absorbing for plumelet and blade of a class, can effectively prevent and kill off 1 year
Raw broad leaved weed and grassy weed.Meanwhile, this herbicide because having efficiently, low toxicity, high selectivity be strong and low environment pollutes
Feature, market prospect is quite varied.
There are main a few class methods in the at present synthesis of flumioxazin:
US4640707 discloses a kind of method preparing flumioxazin, and the method includes with acetic acid as solvent, is not added with urging
Agent, 6-amino-7-fluoro-4-propinyl-Isosorbide-5-Nitrae-benzoxazine-3 (4H)-one and 3,4,5,6-THPA reactions, thus
To product flumioxazin, according to this patent prepare product purity is the highest, it is impossible to meet existing market to product purity
Requirement more than 99.2%；CN105061416A discloses a kind of method preparing flumioxazin, and the method includes with first
Benzene, dichloroethanes or methyl iso-butyl ketone (MIBK) are solvent, add the mixed of alkalescence itrogenous organic substance or organic acid and itrogenous organic substance
Compound is catalyst, 6-amino-7-fluoro-4-propinyl-Isosorbide-5-Nitrae-benzoxazine-3 (4H)-one and 3,4,5,6-THPA dehydrations
Product flumioxazin is prepared in reaction.The catalyst of this patent report, especially preferably piperidines is control chemicals, uses not
Convenience and price are high.
In sum: existing method has the disadvantage that 1. product purities are low, falls short of specifications.2. the catalysis used
Agent particularly piperidines belongs to easily toxogen material processed, and industrial applications is restricted and expensive.
In consideration of it, provide a kind of raw material to be easy to get, the reaction of cheap catalyst, and ensure that product quality meets rule
The synthetic method of fixed flumioxazin is necessary.
Summary of the invention
It is an object of the invention to provide a kind of 7-fluoro-6-amino-4-(2-propargyl)-1,4-benzimidazole dihydrochloride-3 (4H)-one
The synthetic method of derivant, particularly as follows: with 6-amino-7-fluoro-4-propinyl-Isosorbide-5-Nitrae-benzoxazine-3 (4H)-one and 3,4,5,
6-THPA is raw material, reacts, to obtain final product under the catalytic action of organic acid and salt.
The reaction mechanism mechanism of reaction is as follows:
Preferably, described salt is organic salt, and described organic salt is acetate or ammonium acetate；It is further preferred that described vinegar
At least one in potassium acetate, cesium acetate, sodium acetate of hydrochlorate；Most preferably, described acetate is potassium acetate.
Or, described salt is inorganic salt；Preferably, described inorganic salt is selected from potassium carbonate, cesium carbonate, potassium chloride, phosphoric acid hydrogen
One or more in dipotassium, potassium dihydrogen phosphate, potassium sulfate, potassium acid sulfate.
Preferably, one or more in acetic acid, propanoic acid, butanoic acid, trifluoroacetic acid of described organic acid, further preferably
For acetic acid.
As the most preferred scheme of the present invention, in said method, described organic acid is acetic acid, and described salt is potassium acetate.
Preferably, in said method, the mol ratio of organic acid and salt is 1:(0.01-5), more preferably 1:(0.05-
3)。
Preferably, in said method, 6-amino-7-fluoro-4-propinyl-Isosorbide-5-Nitrae-benzoxazine-3 (4H)-one, 3,4,5,6-
THPA, the mol ratio of organic acid are 1:(0.95-1.3): (0.05-2).
Preferably, described reaction is carried out in a solvent, described solvent selected from acetic acid, toluene, chloroform, hexamethylene, 1,2-bis-
One or more in ethyl chloride, methyl iso-butyl ketone (MIBK).
It is further preferred that the reaction of the present invention is with toluene as solvent.
Preferably, described reaction is carried out under the conditions of reflux dewatering.
As the technical scheme that the present invention is optimal, the operation of above-mentioned reaction is particularly as follows: according to 6-amino-7-fluoro-4-propine
Base-1,4-benzoxazine-3 (4H)-one, 3,4,5,6-THPA, the mol ratio of acetic acid are 1:(0.95-1.3): (0.05-
2), the mol ratio of acetic acid and potassium acetate is 1:(0.05-3) ratio, with toluene as solvent, under the conditions of reflux dewatering react,
Obtain.
The synthetic method of the present invention also includes the step that reacted system carries out post processing, and described post processing is concrete
For: after completion of the reaction, remove solvent, gained solid is used organic solvent making beating, after filtration, be dried, obtain product.
Preferably, one or more in ethyl acetate, ethanol, dichloromethane of the solvent that described making beating uses.?
It is preferably ethyl acetate.
The by-product that the reaction of the present invention generates is water, it is therefore desirable in course of reaction, constantly remove the water generated thus
Promote that reaction is carried out towards positive reaction direction.But due to 6-amino-7-fluoro-4-propinyl-1,4-benzoxazine-3 (4H)-one with
The particularity of 3,4,5,6-THPA raw materials, under conditions of without catalyst, even if at conventional point of aqueous solvent such as toluene, dichloro
Carrying out in methane, response speed is very slow, greatly have impact on industrial production efficiency.Present inventors have unexpectedly found that with organic acid and salt
Reaction efficiency can be greatly improved as catalyst, shorten the response time, and in reaction, side reaction is suppressed well, impurity is raw
Become less.Probe into its reaction mechanism further, it may be possible to because by acid and the combination of salt, the PH of reaction environment can be regulated
Value, promotes reaction to carry out towards primary response.
The method of synthesis flumioxazin is optimized by the present invention, and the method after optimization has the advantage that
(1) inorganic salt catalyst used is cheap, and the price used in about 2000 yuan/ton, with prior art is about
The piperidines of 50000 yuan/ton compares (piperidines is controlled drug), has low cost, the advantage that raw material is easy to get；
(2) this reaction yield is up to more than 91%, the purity of flumioxazin up to more than 99.5%, product purity and miscellaneous
Matter specification meets the requirements.
On the basis of meeting common sense in the field, above-mentioned each optimum condition, can be mutually combined, obtain the present invention each preferably
Embodiment.
Detailed description of the invention
Following example are used for illustrating the present invention, but are not limited to the scope of the present invention.The reagent mentioned in embodiment
Or raw material is known product, commercially available acquisition；The operation related to if no special instructions, is this area routine techniques behaviour
Make.
Embodiment 1
A kind of synthetic method of 7-fluoro-6-amino-4-(2-propargyl)-Isosorbide-5-Nitrae-benzimidazole dihydrochloride-3 (4H)-one derivant, tool
Gymnastics conduct:
By 6-amino-7-fluoro-4-propinyl-Isosorbide-5-Nitrae-benzoxazine-3 (4H)-one of 23.2g 95%, 15.9g 3,4,5,
6-THPA, 0.6g acetic acid, 1.96g potassium acetate adds in 100mL toluene solvant, reacts 6h, HPLC at 110 DEG C of reflux dewaterings
Monitoring reaction process, after having reacted, solvent is sloughed in decompression, gained filter cake uses ethyl acetate making beating, is dried after filtration,
Flumioxazin 32.1g, purity 99.5%, yield 91%.Product confirms through NMR and LC-MS.
Embodiment 2
The synthetic method of a kind of 7-fluoro-6-amino-4-(2-propargyl)-Isosorbide-5-Nitrae-benzimidazole dihydrochloride-3 (4H)-one derivant, should
The operation of embodiment, with embodiment 1, differs only in: potassium acetate is replaced with sodium acetate.Reaction terminates, and obtains flumioxazin
31.8g, purity 99.2%, yield 90%.
Embodiment 3
The synthetic method of a kind of 7-fluoro-6-amino-4-(2-propargyl)-Isosorbide-5-Nitrae-benzimidazole dihydrochloride-3 (4H)-one derivant, should
The operation of embodiment, with embodiment 1, differs only in: potassium acetate is replaced with potassium carbonate.Reaction terminates, and obtains flumioxazin
31.7g, purity 99.5%, yield 90%.
Embodiment 4
The synthetic method of a kind of 7-fluoro-6-amino-4-(2-propargyl)-Isosorbide-5-Nitrae-benzimidazole dihydrochloride-3 (4H)-one derivant, should
The operation of embodiment, with embodiment 1, differs only in: potassium acetate is replaced with ammonium acetate.Reaction terminates, and obtains flumioxazin
31.6g, purity 99.5%, yield 89%.
Embodiment 5
The synthetic method of a kind of 7-fluoro-6-amino-4-(2-propargyl)-Isosorbide-5-Nitrae-benzimidazole dihydrochloride-3 (4H)-one derivant, should
The operation of embodiment, with embodiment 1, differs only in: acetic acid is replaced with propanoic acid.Reaction terminates, and obtains flumioxazin 32.3g,
Purity 99.4%, yield 92%.
Embodiment 6
The synthetic method of a kind of 7-fluoro-6-amino-4-(2-propargyl)-Isosorbide-5-Nitrae-benzimidazole dihydrochloride-3 (4H)-one derivant, should
The operation of embodiment, with embodiment 1, differs only in: toluene replaces with 1, and 2-dichloroethanes, reflux dewatering reacts, reaction knot
Bundle, obtains flumioxazin 32.0g, purity 99.7%, yield 91%.
Embodiment 7
The synthetic method of a kind of 7-fluoro-6-amino-4-(2-propargyl)-Isosorbide-5-Nitrae-benzimidazole dihydrochloride-3 (4H)-one derivant, should
The operation of embodiment, with embodiment 1, differs only in: the consumption of potassium acetate is 2.9g, and reaction terminates, and obtains flumioxazin
31.7g, purity 99.5%, yield 90%.
Embodiment 8
The synthetic method of a kind of 7-fluoro-6-amino-4-(2-propargyl)-Isosorbide-5-Nitrae-benzimidazole dihydrochloride-3 (4H)-one derivant, should
The operation of embodiment, with embodiment 1, differs only in: the consumption of potassium acetate is 0.05g, and reaction terminates, and obtains flumioxazin
31.8g, purity 99.4%, yield 90%.
Comparative example 1
The operation of this comparative example, with embodiment 1, differs only in: the consumption of potassium acetate is 3.5g, and reaction terminates, and obtains propine
Benfluralin 27.1g, purity 98.5%, yield 76%.
Comparative example 2
The operation of this comparative example, with embodiment 1, differs only in: the consumption of acetic acid is 0.02g, and the consumption of potassium acetate is
0.098g, reaction terminates, and obtains flumioxazin 19.9g, purity 97%, yield 55%.
Although, used general explanation, detailed description of the invention and test, the present invention made detailed retouching
Stating, but on the basis of the present invention, can make some modifications or improvements it, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Scope.
Claims (10)
1. a synthetic method for 7-fluoro-6-amino-4-(2-propargyl)-Isosorbide-5-Nitrae-benzimidazole dihydrochloride-3 (4H)-one derivant, it is special
Levy and be: with 6-amino-7-fluoro-4-propinyl-Isosorbide-5-Nitrae-benzoxazine-3 (4H)-one and 3,4,5,6-THPAs are raw material,
React under the catalytic action of organic acid and salt, to obtain final product.
Synthetic method the most according to claim 1, it is characterised in that: described salt is organic salt, and described organic salt is acetic acid
Salt or ammonium acetate；Or, described salt is inorganic salt, described inorganic salt selected from potassium carbonate, cesium carbonate, potassium chloride, dipotassium hydrogen phosphate,
One or more in potassium dihydrogen phosphate, potassium sulfate, potassium acid sulfate.
Synthetic method the most according to claim 2, it is characterised in that: described acetate is selected from potassium acetate, cesium acetate, acetic acid
At least one in sodium, preferably potassium acetate.
4. according to the synthetic method described in any one of claim 1-3, it is characterised in that: described organic acid selected from acetic acid, propanoic acid,
One or more in butanoic acid, trifluoroacetic acid.
Synthetic method the most according to claim 1, it is characterised in that: described organic acid is acetic acid, and described salt is potassium acetate.
Synthetic method the most according to claim 1 or 5, it is characterised in that: the mol ratio of described organic acid and salt is 1:
(0.01-5), preferably 1:(0.05-3).
Synthetic method the most according to claim 1, it is characterised in that: 6-amino-7-fluoro-4-propinyl-Isosorbide-5-Nitrae-benzo is disliked
Piperazine-3 (4H)-one, 3,4,5,6-THPA, the mol ratio of organic acid are 1:(0.95-1.3): (0.05-2).
8. according to the synthetic method described in any one of claim 1-3 or 5 or 7, it is characterised in that: described reaction is entered in a solvent
OK, described solvent selected from acetic acid, toluene, chloroform, hexamethylene, 1,2-dichloroethanes, methyl iso-butyl ketone (MIBK) one or more；Excellent
Elect toluene as.
Synthetic method the most according to claim 1, it is characterised in that: according to 6-amino-7-fluoro-4-propinyl-Isosorbide-5-Nitrae-benzene
And oxazines-3 (4H)-one, 3,4,5,6-THPAs, the mol ratio of acetic acid are 1:(0.95-1.3): (0.05-2), acetic acid and vinegar
Acid potassium mol ratio be 1:(0.05-3) ratio, with toluene as solvent, under the conditions of reflux dewatering react, to obtain final product.
10. according to the synthetic method described in claim 1 or 9, it is characterised in that: after described reaction also includes carrying out reactant liquor
The step processed, described post processing particularly as follows: after completion of the reaction, is sloughed solvent, gained filter cake is used organic solvent making beating, mistake
Product it is dried to obtain after filter；
Preferably, one or more in ethanol, ethyl acetate, dichloromethane of described organic solvent.
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| CN201610682770.8A CN106317042B (en) | 2016-08-17 | 2016-08-17 | A kind of synthetic method of the fluoro- 6- amino -4- of 7- (2- propargyls) -1,4- benzoxazines -3 (4H) -one derivative |
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| CN201610682770.8A CN106317042B (en) | 2016-08-17 | 2016-08-17 | A kind of synthetic method of the fluoro- 6- amino -4- of 7- (2- propargyls) -1,4- benzoxazines -3 (4H) -one derivative |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503506A (en) * | 2018-11-21 | 2019-03-22 | 内蒙古世杰化工有限公司 | A kind of intermediate production method of flumioxazin |
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| EP0170191A2 (en) * | 1984-07-23 | 1986-02-05 | Sumitomo Chemical Company, Limited | Tetrahydrophtalimides, and their production and use |
| CN103965181A (en) * | 2014-05-22 | 2014-08-06 | 黑龙江大学 | Preparation method of flumioxazin |
| WO2014122674A1 (en) * | 2013-02-08 | 2014-08-14 | Rallis India Limited | Process for preparation of derivatives of tetrahydrophthalimide |
| CN105061416A (en) * | 2015-07-16 | 2015-11-18 | 北京颖泰嘉和生物科技股份有限公司 | Method for preparing flumioxazin |
| CN105837563A (en) * | 2016-04-25 | 2016-08-10 | 四川义结科技有限责任公司 | Production method of flumioxazin |
-
2016
- 2016-08-17 CN CN201610682770.8A patent/CN106317042B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0170191A2 (en) * | 1984-07-23 | 1986-02-05 | Sumitomo Chemical Company, Limited | Tetrahydrophtalimides, and their production and use |
| WO2014122674A1 (en) * | 2013-02-08 | 2014-08-14 | Rallis India Limited | Process for preparation of derivatives of tetrahydrophthalimide |
| CN103965181A (en) * | 2014-05-22 | 2014-08-06 | 黑龙江大学 | Preparation method of flumioxazin |
| CN105061416A (en) * | 2015-07-16 | 2015-11-18 | 北京颖泰嘉和生物科技股份有限公司 | Method for preparing flumioxazin |
| CN105837563A (en) * | 2016-04-25 | 2016-08-10 | 四川义结科技有限责任公司 | Production method of flumioxazin |
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| Title |
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| TOSHIYUKI KATAGI: "Hydrolysis of N-phenylimide herbicide flumioxazin and its anilic acid derivative in aqueous solutions", 《JOURNAL OF PESTICIDE SCIENCE》 * |
| 刘安昌，等: "新型除草剂丙炔氟草胺的合成研究", 《世界农药》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109503506A (en) * | 2018-11-21 | 2019-03-22 | 内蒙古世杰化工有限公司 | A kind of intermediate production method of flumioxazin |
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Denomination of invention: A synthetic method of 7-fluoro-6-amino-4 - (2-propargyl) - 1,4-benzoxazine-3 (4h) - one derivative Effective date of registration: 20210702 Granted publication date: 20181113 Pledgee: Agricultural Development Bank of China Baiyin branch business department Pledgor: Purpana (Beijing) Technologies Co.,Ltd. Registration number: Y2021990000573 |
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