CN108997254A - The synthetic method of indeno oxadiazines compound - Google Patents
The synthetic method of indeno oxadiazines compound Download PDFInfo
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- CN108997254A CN108997254A CN201810981748.2A CN201810981748A CN108997254A CN 108997254 A CN108997254 A CN 108997254A CN 201810981748 A CN201810981748 A CN 201810981748A CN 108997254 A CN108997254 A CN 108997254A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D273/00—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00
- C07D273/02—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00 having two nitrogen atoms and only one oxygen atom
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Abstract
This application involves a kind of synthetic methods of indeno oxadiazines compound, the following steps are included: by toluene, 5- chloro- 2,3- dihydro -2- hydroxyl -1- benzofuran -2- carboxylate methyl ester, hydrazino benzyl formate and toluenesulfonic acid mixing, at 60 DEG C~70 DEG C, it is reacted under vacuum condition, water is removed while reaction, obtains the first reaction solution；Toluene and diethoxymethane are mixed, are added dropwise the first reaction solution, reaction while removes ethyl alcohol, obtains the second reaction solution；Second reaction solution is isolated and purified, chloro- 2,3,4a, 5- tetrahydro -2- (benzyloxy) carbonyl indeno (1,3, the 4) oxadiazines -4a- carboxylate methyl ester of high-purity 7- is obtained, reaction yield is also higher.
Description
Technical field
The present invention relates to chemosynthesis technical fields, more particularly to a kind of synthetic method of indeno oxadiazines compound.
Background technique
Indoxacarb is that DuPont Corporation kills in a kind of carbamates containing oxadiazines structure of exploitation in 1992
Worm agent, chemical name are chloro- 2,3,4a, the 5- tetrahydro -2- of (4aS) -7- { methoxycarbonyl [(4- trifluoromethoxy) phenyl] amino
Formoxyl } indeno [1,2-e] [1,3,4] oxadiazines -4a- carboxylate methyl ester.It is a chiral molecules, because it is efficient, less toxic, low
Wide and the characteristics of without carcinogenic teratogenesis mutagenesis by global pesticide industry the attention of residual, insecticidal spectrum.Its mechanism of action
It is the sodium-ion channel blocked in pest nerve cell, leads to target pest ataxia, paralysis, final death cannot be fed,
To protect Target crops well.
The chloro- 2,3,4a of 7-, 5- tetrahydro -2- (benzyloxy) carbonyl indeno (1,3,4) oxadiazines -4a- carboxylate methyl ester are to close
At one of the key intermediate of indoxacarb.Traditional production technology is main are as follows: the first step is solvent, chloro- 2, the 3- bis- of 5- with methanol
Hydrogen -2- hydroxyl -1- benzofuran -2- carboxylate methyl ester and hydrazino benzyl formate condensation generate (the chloro- 2,3- dihydro -2- hydroxyl -2- methoxy of 5-
Base carbonyl indenes -1- subunit) hydrazine carboxylic acid's benzyl esters, it crystallizes, be filtered, washed and dried；Second step makees solvent with dichloroethanes, in
Between product again with diethoxymethane closed loop generate the chloro- 2,3,4a of 7-, 5- tetrahydro -2- (benzyloxy) carbonyl indeno (1,3,4)
Oxadiazines -4a- carboxylate methyl ester, sloughs dichloroethanes, with recrystallizing methanol, is filtered, washed and dried to obtain target product.
The drawbacks such as that there are product yields is low for above-mentioned traditional technology, purity is low.
Summary of the invention
Based on this, it is necessary to provide a kind of synthetic method of the indeno oxadiazines compound of high yield, high-purity.
A kind of synthetic method of indeno oxadiazines compound, comprising the following steps:
By toluene, the chloro- 2,3- dihydro -2- hydroxyl -1- benzofuran -2- carboxylate methyl ester of 5-, hydrazino benzyl formate and methylbenzene sulphur
Acid-mixed is closed, and is reacted under 60 DEG C~70 DEG C, vacuum condition, and reaction while removes water, obtains the first reaction solution；
Toluene and diethoxymethane are mixed, are added dropwise first reaction solution, reaction while removes ethyl alcohol, obtains the
Two reaction solutions；
Second reaction solution is isolated and purified, chloro- 2,3,4a, 5- tetrahydro -2- (benzyloxy) the carbonyl indeno of 7- is obtained
(1,3,4) oxadiazines -4a- carboxylate methyl ester.
Chloro- 2, the 3- dihydro -2- hydroxyl -1- benzofuran -2- carboxylate methyl ester of the 5-, diazanyl first in one of the embodiments,
The molar ratio of acid benzyl ester and toluenesulfonic acid is 1:(1.2~1.5): (0.1~0.3).
The diethoxymethane and chloro- 2, the 3- dihydro -2- hydroxyl -1- benzofuran -2- carboxylic of 5- in one of the embodiments,
The molar ratio of sour methyl esters is (2.5~3.5): 1.
The vacuum degree reacted under the vacuum condition in one of the embodiments, is 0.085MPa~0.095MPa.
The reaction time reacted under the vacuum condition in one of the embodiments, is 4~8 hours.
The water is removed using the method for reflux water-dividing in one of the embodiments,.
The ethyl alcohol is removed using rectifying column in one of the embodiments,.
The tower top temperature of the rectifying column is 70 DEG C~80 DEG C in one of the embodiments, the tower reactor of the rectifying column
Temperature is 100 DEG C~120 DEG C.
The method isolated and purified in one of the embodiments, are as follows: filtering removes solvent, takes residue that first is added
Alcohol is clarified in 50 DEG C~60 DEG C dissolutions, filtering, drying after freezing and crystallizing.
The synthetic method of above-mentioned indeno oxadiazines compound, first step condensation reaction is using toluene as solvent, toluenesulfonic acid
For catalyst, chloro- 2, the 3- dihydro -2- hydroxyl -1- benzofuran -2- carboxylate methyl ester of 5- and hydrazino benzyl formate are raw material, 60 DEG C~
It 70 DEG C, reacts under vacuum condition, reaction while removes water, is conducive to the progress of reaction and reduces the generation of side reaction；Second
Ring-closure reaction is walked by mixing toluene and diethoxymethane, is removed while the reaction solution reaction of above-mentioned first step reaction is added dropwise
Ethyl alcohol is removed, the progress of reaction is further promoted, improves yield and purity.
In addition, the reaction solution of above-mentioned first step reaction can directly be added dropwise without processing, for anti-with diethoxymethane
It answers, simplifies operating procedure, facilitate industrialized production.
Specific embodiment
To facilitate the understanding of the present invention, below will to invention is more fully described, and give it is of the invention compared with
Good embodiment.But the invention can be realized in many different forms, however it is not limited to embodiment described herein.Phase
Instead, purpose of providing these embodiments is makes the disclosure of the present invention more thorough and comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
Any and all combinations of the listed item of pass.
It should be noted that the indeno oxadiazines compound of the application is chloro- 2,3,4a, 5- tetrahydro -2- (the benzene methoxy of 7-
Base) carbonyl indeno (1,3,4) oxadiazines -4a- carboxylate methyl ester.
The chloro- 2,3,4a of the 7- of one embodiment, 5- tetrahydro -2- (benzyloxy) carbonyl indeno (1,3,4) oxadiazines -4a-
The synthetic method of carboxylate methyl ester, comprising the following steps:
S110, by toluene, the chloro- 2,3- dihydro -2- hydroxyl -1- benzofuran -2- carboxylate methyl ester of 5-, hydrazino benzyl formate and methyl
Benzene sulfonic acid mixing, reacts under 60 DEG C~70 DEG C, vacuum condition, and reaction while removes water, obtains the first reaction solution；
Wherein, chloro- 2, the 3- dihydro -2- hydroxyl -1- benzofuran -2- carboxylate methyl ester of 5-, hydrazino benzyl formate and toluenesulfonic acid
Molar ratio be 1:(1.2~1.5): (0.1~0.3).
Further, chloro- 2, the 3- dihydro -2- hydroxyl -1- benzofuran -2- carboxylate methyl ester of 5-, hydrazino benzyl formate and methylbenzene
The molar ratio of sulfonic acid is 1:1.2:0.1.
Further, the vacuum degree reacted under vacuum condition is 0.085MPa~0.095MPa.
Further, the reaction time reacted under vacuum condition is 4~8 hours.
Further, the water for reacting generation is removed using the method for reflux water-dividing.
It is appreciated that toluene and water form azeotropic mixture, the density ratio water of toluene is small, and by condensation, toluene and water are in Fen Shui
It is layered in device, water product is removed in water segregator lower part, and solvent then backflows into reaction system.
Further, the reaction equation of step S110 are as follows:
Above-mentioned steps S110 can form azeotropic mixture with the water generated is reacted, reaction while passes through back using toluene as solvent
Flow point water promotes reaction to carry out, and controls reaction and carry out under 60 DEG C~70 DEG C, vacuum condition, can be further reduced side reaction
Generation, improve reaction yield and product purity.
S120, toluene and diethoxymethane being mixed, is added dropwise above-mentioned first reaction solution, reaction while, removes ethyl alcohol,
Obtain the second reaction solution.
Wherein, the molar ratio of diethoxymethane and chloro- 2, the 3- dihydro -2- hydroxyl -1- benzofuran -2- carboxylate methyl ester of 5- is
(2.5~3.5): 1.
Further, the molar ratio of diethoxymethane and chloro- 2, the 3- dihydro -2- hydroxyl -1- benzofuran -2- carboxylate methyl ester of 5-
For 3:1.
Further, the ethyl alcohol for reacting generation is removed using rectifying column.
Further, the tower top temperature of rectifying column is 70 DEG C~80 DEG C, and the bottom temperature of rectifying column is 100 DEG C~120 DEG C.
Further, the reaction equation of step S120 is as follows:
Above-mentioned steps S120 mixes toluene and diethoxymethane, and above-mentioned first reaction solution can be direct without processing
It is added dropwise for reacting, simplifies operating procedure, reaction while removes ethyl alcohol, further promotes the progress of reaction, improves product
Yield and purity.
S130, above-mentioned second reaction solution is isolated and purified, obtains chloro- 2,3,4a, 5- tetrahydro -2- (benzyloxy) carbonyl of 7-
Indeno (1,3,4) oxadiazines -4a- carboxylate methyl ester.
Further, the method isolated and purified are as follows: filtering removes solvent, takes residue that methanol is added, at 50 DEG C~60 DEG C
Dissolution is clarified, filtering, drying after freezing and crystallizing.
The above-mentioned chloro- 2,3,4a of 7-, 5- tetrahydro -2- (benzyloxy) carbonyl indeno (1,3,4) oxadiazines -4a- carboxylate methyl ester
Synthetic method, do not need separation and Extraction intermediate product after the completion of first step condensation reaction, second step directly carried out in one pot
Ring-closure reaction simplifies operating procedure, more conducively industrialized production, while also improving product yield and purity.
The above-mentioned chloro- 2,3,4a of 7-, 5- tetrahydro -2- (benzyloxy) carbonyl indeno (1,3,4) oxadiazines -4a- carboxylate methyl ester
Synthetic method, product purity >=97%, yield >=93%.
The following are specific embodiments
Embodiment 1
The chloro- 2,3- dihydro -2- of 5- is added into the 500mL four-hole boiling flask equipped with blender, thermometer and reflux water-dividing device
Hydroxyl -1- benzofuran -2- carboxylate methyl ester 50g (96%, 0.20mol), hydrazino benzyl formate 40g (0.24mol), toluene 250g and nothing
Water toluenesulfonic acid 3.5g (0.02mol), heating, vacuumizes, reflux water-dividing, insulation reaction 8 hours at 60 DEG C, and it is anti-to obtain first
Answer liquid spare.
Diethoxymethane 63g is added into the 1000mL four-hole boiling flask equipped with blender, thermometer and rectifying column
(0.60mol) and toluene 150g, the first reaction solution is gradually added drop-wise in flask, removes dereaction by rectifying column while reaction
The ethyl alcohol of generation, kettle temperature are controlled at 120 DEG C, and rectifying tower top temperature control system obtains the second reaction solution at 70 DEG C.
After second reaction solution is removed toluenesulfonic acid and a small amount of impurity by filter, vacuum sloughs toluene and excessive two
Ethoxy methane；Methanol is added, is warming up to 55 DEG C of stirring dissolved clarifications, freezing and crystallizing, filtering, drying obtain product 77g.
Through detecting, chloro- 2,3,4a, 5- tetrahydro -2- (benzyloxy) carbonyl indeno (1,3, the 4) oxadiazines -4a- of 7- in product
The purity of carboxylate methyl ester is 97%, yield 93.2%.
Embodiment 2
The chloro- 2,3- dihydro -2- of 5- is added into the 500mL four-hole boiling flask equipped with blender, thermometer and reflux water-dividing device
Hydroxyl -1- benzofuran -2- carboxylate methyl ester 50g (96%, 0.20mol), hydrazino benzyl formate 50g (0.3mol), toluene 250g and nothing
Water toluenesulfonic acid 10.5g (0.06mol), heating, vacuumizes, reflux water-dividing at 70 DEG C, insulation reaction 4 hours, obtains first
Reaction solution is spare.
Diethoxymethane 105g is added into the 1000mL four-hole boiling flask equipped with blender, thermometer and rectifying column
(1mol) and toluene 150g, the first reaction solution is gradually added drop-wise in flask, by rectifying column except dereaction is given birth to while reaction
At ethyl alcohol, kettle temperature control at 100 DEG C, rectifying tower top temperature control system obtains the second reaction solution at 80 DEG C.
After second reaction solution is removed toluenesulfonic acid and a small amount of impurity by filter, vacuum sloughs toluene and excessive two
Ethoxy methane；Methanol is added, is warming up to 60 DEG C of stirring dissolved clarifications, freezing and crystallizing, filtering, drying obtain product 77g.
Through detecting, chloro- 2,3,4a, 5- tetrahydro -2- (benzyloxy) carbonyl indeno (1,3, the 4) oxadiazines -4a- of 7- in product
The purity of carboxylate methyl ester is 97%, yield 93.2%.
Comparative example 1
The chloro- 2,3- dihydro -2- of 5- is added into the 500mL four-hole boiling flask equipped with blender, thermometer and reflux condenser
Hydroxyl -1- benzofuran -2- carboxylate methyl ester 50g (96%, 0.20mol), hydrazino benzyl formate 40g (0.24mol), methanol 250g and nothing
Water toluenesulfonic acid 3.5g (0.02mol), heating, back flow reaction 4h~8h, freezing and crystallizing, filtering, drying obtain intermediate product
70g。
Dichloroethanes 300g, diethyl are added into the 500mL four-hole boiling flask equipped with blender, thermometer and reflux condenser
Oxygroup methane 63g (0.60mol) and phosphorus pentoxide (0.24mol) 34g, heating, is added portionwise intermediate product into flask, returns
Fully reacting is flowed, reaction solution is obtained.
After above-mentioned reaction solution is removed phosphorus pentoxide and a small amount of impurity by filter, vacuum sloughs dichloroethanes and mistake
Measure diethoxymethane；Methanol is added, is warming up to 55 DEG C of stirring dissolved clarifications, freezing and crystallizing, filtering, drying obtain product 60.5g.
Through detecting, chloro- 2,3,4a, 5- tetrahydro -2- (benzyloxy) carbonyl indeno (1,3, the 4) oxadiazines -4a- of 7- in product
The purity of carboxylate methyl ester is 96%, yield 72.5%.
Comparative example 2
Comparative example 2 is substantially the same manner as Example 1, unlike, comparative example 2 is the reflux water-dividing at 110 DEG C.
Through detecting, chloro- 2,3,4a, 5- tetrahydro -2- (benzyloxy) the carbonyl indeno of 7- in the product that comparative example 2 obtains (1,
3,4) purity of oxadiazines -4a- carboxylate methyl ester is 96.6%, yield 89.2%.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (9)
1. a kind of synthetic method of indeno oxadiazines compound, which comprises the following steps:
Toluene, the chloro- 2,3- dihydro -2- hydroxyl -1- benzofuran -2- carboxylate methyl ester of 5-, hydrazino benzyl formate and toluenesulfonic acid are mixed
It closes, is reacted under 60 DEG C~70 DEG C, vacuum condition, except the water that dereaction generates while reaction, obtain the first reaction solution；
Toluene and diethoxymethane are mixed, are added dropwise first reaction solution, except the ethyl alcohol that dereaction generates while reaction,
Obtain the second reaction solution；
Second reaction solution is isolated and purified, obtain chloro- 2,3,4a, 5- tetrahydro -2- (benzyloxy) the carbonyl indeno of 7- (1,3,
4) oxadiazines -4a- carboxylate methyl ester.
2. the synthetic method of indeno oxadiazines compound according to claim 1, which is characterized in that the 5- chloro- 2,3-
The molar ratio of dihydro -2- hydroxyl -1- benzofuran -2- carboxylate methyl ester, hydrazino benzyl formate and toluenesulfonic acid is 1:(1.2~1.5):
(0.1~0.3).
3. the synthetic method of indeno oxadiazines compound according to claim 2, which is characterized in that the diethoxy first
The molar ratio of alkane and the chloro- 2,3- dihydro -2- hydroxyl -1- benzofuran -2- carboxylate methyl ester of 5- is (2.5~3.5): 1.
4. the synthetic method of indeno oxadiazines compound according to claim 1, which is characterized in that under the vacuum condition
The vacuum degree of reaction is 0.085MPa~0.095MPa.
5. the synthetic method of indeno oxadiazines compound according to claim 1, which is characterized in that under the vacuum condition
The reaction time of reaction is 4~8 hours.
6. the synthetic method of described in any item indeno oxadiazines compounds according to claim 1~5, which is characterized in that described
Water is removed using the method for reflux water-dividing.
7. the synthetic method of described in any item indeno oxadiazines compounds according to claim 1~5, which is characterized in that described
Ethyl alcohol is removed using rectifying column.
8. the synthetic method of indeno oxadiazines compound according to claim 7, which is characterized in that the tower of the rectifying column
Pushing up temperature is 70 DEG C~80 DEG C, and the bottom temperature of the rectifying column is 100 DEG C~120 DEG C.
9. the synthetic method of described in any item indeno oxadiazines compounds according to claim 1~5, which is characterized in that described
The method isolated and purified are as follows: filtering removes solvent, takes residue that methanol is added, and clarifies in 50 DEG C~60 DEG C dissolutions, freezing and crystallizing
It filters afterwards, is dry.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651288A (en) * | 2018-12-29 | 2019-04-19 | 京博农化科技有限公司 | A kind of preparation method of indoxacarb intermediate |
| CN111269194A (en) * | 2020-03-18 | 2020-06-12 | 京博农化科技有限公司 | Preparation method of indoxacarb key intermediate |
| CN114957158A (en) * | 2022-05-31 | 2022-08-30 | 浙江禾本科技股份有限公司 | Method for preparing indoxacarb intermediate |
| CN115974808A (en) * | 2022-12-21 | 2023-04-18 | 大连奇凯医药科技有限公司 | Preparation method of 2-benzyl-7-chlorine [1,2-e ] indeno [1,3,4] oxadiazine methyl diformate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998005656A1 (en) * | 1996-08-05 | 1998-02-12 | E.I. Du Pont De Nemours And Company | Processes for preparing indeno[1,2-e][1,3,4]oxadiazine-dicarboxylates |
| US5869657A (en) * | 1994-04-20 | 1999-02-09 | E. I. Du Pont De Nemours And Company | Preparation of arthropodicidal oxadiazines |
| CN106397351A (en) * | 2016-08-31 | 2017-02-15 | 京博农化科技股份有限公司 | Preparation method of indoxacarb intermediate |
| CN107235926A (en) * | 2017-06-21 | 2017-10-10 | 南通施壮化工有限公司 | A kind of preparation method of the female medicine of indoxacarb |
| CN107915692A (en) * | 2017-10-30 | 2018-04-17 | 安徽富田农化有限公司 | A kind of preparation method of indoxacarb |
-
2018
- 2018-08-27 CN CN201810981748.2A patent/CN108997254A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5869657A (en) * | 1994-04-20 | 1999-02-09 | E. I. Du Pont De Nemours And Company | Preparation of arthropodicidal oxadiazines |
| WO1998005656A1 (en) * | 1996-08-05 | 1998-02-12 | E.I. Du Pont De Nemours And Company | Processes for preparing indeno[1,2-e][1,3,4]oxadiazine-dicarboxylates |
| CN106397351A (en) * | 2016-08-31 | 2017-02-15 | 京博农化科技股份有限公司 | Preparation method of indoxacarb intermediate |
| CN107235926A (en) * | 2017-06-21 | 2017-10-10 | 南通施壮化工有限公司 | A kind of preparation method of the female medicine of indoxacarb |
| CN107915692A (en) * | 2017-10-30 | 2018-04-17 | 安徽富田农化有限公司 | A kind of preparation method of indoxacarb |
Non-Patent Citations (1)
| Title |
|---|
| 贾鹏飞等: "7-氯-2，5-二氢茚并［1，2-e］［1，3，4］噁二嗪-4a-(3H)-羧酸甲酯的合成研究", 《安徽农业科学》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651288A (en) * | 2018-12-29 | 2019-04-19 | 京博农化科技有限公司 | A kind of preparation method of indoxacarb intermediate |
| CN111269194A (en) * | 2020-03-18 | 2020-06-12 | 京博农化科技有限公司 | Preparation method of indoxacarb key intermediate |
| CN111269194B (en) * | 2020-03-18 | 2023-05-05 | 山东京博农化科技股份有限公司 | Preparation method of indoxacarb key intermediate |
| CN114957158A (en) * | 2022-05-31 | 2022-08-30 | 浙江禾本科技股份有限公司 | Method for preparing indoxacarb intermediate |
| CN115974808A (en) * | 2022-12-21 | 2023-04-18 | 大连奇凯医药科技有限公司 | Preparation method of 2-benzyl-7-chlorine [1,2-e ] indeno [1,3,4] oxadiazine methyl diformate |
| CN115974808B (en) * | 2022-12-21 | 2024-03-12 | 大连奇凯医药科技有限公司 | Preparation method of 2-benzyl-7-chloro [1,2-e ] indeno [1,3,4] oxadiazine dimethyl ester |
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Application publication date: 20181214 |