CN107216316A - The method of synthesis dinotefuran intermediate is reacted by Mannish - Google Patents
The method of synthesis dinotefuran intermediate is reacted by Mannish Download PDFInfo
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- CN107216316A CN107216316A CN201710506557.6A CN201710506557A CN107216316A CN 107216316 A CN107216316 A CN 107216316A CN 201710506557 A CN201710506557 A CN 201710506557A CN 107216316 A CN107216316 A CN 107216316A
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- Prior art keywords
- dinotefuran
- mannish
- synthesizing
- react
- aldehyde
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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- 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
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/14—Radicals substituted by nitrogen atoms not forming part of a nitro radical
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses the method for synthesizing dinotefuran intermediate is reacted by Mannish, the problem of solving complicated preparation method of the prior art, high cost and relatively low yield rate.Present invention resides in add 2 in solvent, 3 dihydrofuran, aldehyde, the nitroimino 1,3 of 1,5 dimethyl 2,5 Hexahydrotriazines, the Hexahydrotriazine of 1 (3 tetrahydrofuran methyl) 2 nitroimino 1,3,5 for hydrolyzing generation MTI-446 in acid condition is synthesized by catalyst.Present invention process is simple, and cost is relatively low, is adapted to industrialized production.
Description
Technical field
The present invention relates to a kind of method for synthesizing dinotefuran intermediate, and in particular to passes through Mannish reaction synthesis furan worms
The method of amine intermediate.
Background technology
In the prior art, the synthesis MTI-446 technique at present compared with main flow is：
And the synthesis technique of its intermediate A has：
Method one, concrete technology flow process are as follows：
Method two, concrete technology flow process are as follows：
Complex process is caused by the method for prior art, cost is high and yield is relatively low.
The content of the invention
The technical problems to be solved by the invention are：Preparation method of the prior art is complicated, cost is high and yield rate compared with
Low the problem of, it is therefore intended that provide and the method for synthesizing dinotefuran intermediate is reacted by Mannish, pass through the optimization energy of this method
Simplify preparation process, reduce cost, and improve yield.
The present invention is achieved through the following technical solutions：
The method of synthesis dinotefuran intermediate is reacted by Mannish, including：
2,3 dihydrofuran are added in a solvent, and aldehyde, 1,5- dimethyl -2- nitroiminos -1,3,5- Hexahydrotriazines lead to
Cross catalyst and synthesize 1- (3- tetrahydrofuran methyls) -2- nitro imido that MTI-446 is generated for hydrolyzing in acid condition
Base -1,3,5- Hexahydrotriazines.
Further, the temperature that catalyzes and synthesizes is 20~120 DEG C.Preferably, the temperature that catalyzes and synthesizes is 60~80 DEG C.
Further, the solvent is water, ethanol, acetic acid or ethyl acetate.
Further, in a solvent, 2,3 dihydrofuran, aldehyde, 1,5- dimethyl -2- nitroiminos -1,3 are sequentially added into,
5- Hexahydrotriazines, catalyst.
Further, in a solvent, it is sequentially added into aldehyde, 1,5- dimethyl -2- nitroiminos -1,3,5- Hexahydrotriazines,
Catalyst and 2,3 dihydrofuran.
Further, the aldehyde is formaldehyde.
Further, the catalyst is lewis acid, lewis base, bronsted acid, organic catalyst or praline.
Further, the catalyst is hydrochloric acid, sulfuric acid, ZnCl2、NiCl2、FeCl3In one kind.
The present invention compared with prior art, has the following advantages and advantages：
The cost of present invention reduction synthesis MTI-446, simplifies reactions steps, with the low feature of simple to operate, cost, fits
Close industrialized production.
Embodiment
For the object, technical solutions and advantages of the present invention are more clearly understood, with reference to embodiment, to present invention work
Further to describe in detail, exemplary embodiment and its explanation of the invention is only used for explaining the present invention, is not intended as to this
The restriction of invention.
Embodiment 1
The method of synthesis dinotefuran intermediate is reacted by Mannish, specific preparation method is as follows：
25mL absolute ethyl alcohols and 25mL concentrated hydrochloric acids are mixed to form solution, the dihydrofuran of 7.0g 2,3 is dissolved, pours into three mouthfuls
Flask, by 15.7g 1,5- dimethyl -2- nitroiminos -1,3,5- Hexahydrotriazines from dropping funel instills three-necked flask,
80 DEG C of stirrings of heating, after one hour of backflow, 75mL 37% formalin are slowly dropped into flask, then back flow reaction 1
Individual hour, colourless transparent solution is obtained, the solution is the dinotefuran intermediate of the present invention, then added plus watery hydrochloric acid hydrolysis,
Obtain MTI-446 product.Concrete technology route is as follows：
The amount of the MTI-446 product obtained by the present embodiment mode is 16.4g.
Embodiment 2
The method of synthesis dinotefuran intermediate is reacted by Mannish, specific preparation method is as follows：
25mL acetic acid and 25mL concentrated hydrochloric acids are mixed to form solution, the dihydrofuran of 7.0g 2,3 is dissolved, pours into three-necked flask,
By 15.7g 1,5- dimethyl -2- nitroiminos -1,3,5- Hexahydrotriazines are from dropping funel instills three-necked flask, heating 80
DEG C stirring, after one hour of backflow, 75mL 37% formalin is slowly dropped into flask, then 1 hour of back flow reaction,
Colourless transparent solution is obtained, then adds plus watery hydrochloric acid hydrolysis, obtains 18.1g MTI-446 products.
Embodiment 3
The method of synthesis dinotefuran intermediate is reacted by Mannish, specific preparation method is as follows：
25mL dimethylformamides and 25mL concentrated hydrochloric acids are mixed to form solution, the dihydrofuran of 7.0g 2,3 is dissolved, pours into
Three-necked flask, by 15.7g 1,5- dimethyl -2- nitroiminos -1,3,5- Hexahydrotriazines instill three-necked flask from dropping funel
In, 80 DEG C of stirrings are heated, after one hour of backflow, 75mL 37% formalin is slowly dropped into flask, then are flowed back anti-
1 hour is answered, colourless transparent solution is obtained, then adds plus watery hydrochloric acid hydrolysis, obtains 19.3g MTI-446 products.
Embodiment 4
The method of synthesis dinotefuran intermediate is reacted by Mannish, specific preparation method is as follows：
25mL water and 25mL concentrated hydrochloric acids are mixed to form solution, the dihydrofuran of 7.0g 2,3 is dissolved, pours into three-necked flask, will
15.7g 1,5- dimethyl -2- nitroiminos -1,3,5- Hexahydrotriazines heat 80 DEG C from dropping funel instills three-necked flask
Stirring, after one hour of backflow, 9.0g metaformaldehydes is added in flask, then 1 hour of back flow reaction, obtains water white transparency molten
Liquid, then adds plus watery hydrochloric acid hydrolysis, obtains 18.5g MTI-446 products.
Above-described embodiment, has been carried out further to the purpose of the present invention, technical scheme and beneficial effect
Describe in detail, should be understood that the embodiment that the foregoing is only the present invention, be not intended to limit the present invention
Protection domain, within the spirit and principles of the invention, any modification, equivalent substitution and improvements done etc. all should be included
Within protection scope of the present invention.
Claims (9)
1. the method for synthesizing dinotefuran intermediate is reacted by Mannish, it is characterised in that including：
2,3 dihydrofuran, aldehyde, 1,5- dimethyl -2- nitroiminos -1,3,5- Hexahydrotriazines, by urging are added in a solvent
Agent catalyze and synthesize for hydrolyze in acid condition generation MTI-446 1- (3- tetrahydrofuran methyls) -2- nitroiminos -
1,3,5- Hexahydrotriazine.
2. according to claim 1 react the method for synthesizing dinotefuran intermediate by Mannish, it is characterised in that institute
State and catalyze and synthesize temperature for 20~120 DEG C.
3. according to claim 1 react the method for synthesizing dinotefuran intermediate by Mannish, it is characterised in that institute
State and catalyze and synthesize temperature for 60~80 DEG C.
4. according to claim 1 react the method for synthesizing dinotefuran intermediate by Mannish, it is characterised in that institute
Solvent is stated for water, ethanol, acetic acid, ethyl acetate or dimethylformamide.
5. according to claim 1 react the method for synthesizing dinotefuran intermediate by Mannish, it is characterised in that
In solvent, 2,3 dihydrofuran, aldehyde, 1,5- dimethyl -2- nitroiminos -1,3,5- Hexahydrotriazines, catalysis are sequentially added into
Agent.
6. according to claim 1 react the method for synthesizing dinotefuran intermediate by Mannish, it is characterised in that
In solvent, aldehyde, 1,5- dimethyl -2- nitroiminos -1,3,5- Hexahydrotriazines, catalyst and 2,3 dihydro furans are sequentially added into
Mutter.
7. according to claim 1 react the method for synthesizing dinotefuran intermediate by Mannish, it is characterised in that institute
Aldehyde is stated for formaldehyde.
8. according to claim 1 react the method for synthesizing dinotefuran intermediate by Mannish, it is characterised in that institute
It is lewis acid, lewis base, bronsted acid, organic catalyst or praline to state catalyst.
9. according to claim 8 react the method for synthesizing dinotefuran intermediate by Mannish, it is characterised in that institute
Catalyst is stated for hydrochloric acid, sulfuric acid, ZnCl2、NiCl2、FeCl3In one kind.
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| CN201710506557.6A CN107216316A (en) | 2017-06-27 | 2017-06-27 | The method of synthesis dinotefuran intermediate is reacted by Mannish |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112556A (en) * | 1993-10-26 | 1995-11-29 | 三井东压化学株式会社 | Furanyl insecticide |
| JP3258502B2 (en) * | 1993-10-26 | 2002-02-18 | 三井化学株式会社 | Insecticidal tetrahydrofuran derivative |
-
2017
- 2017-06-27 CN CN201710506557.6A patent/CN107216316A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112556A (en) * | 1993-10-26 | 1995-11-29 | 三井东压化学株式会社 | Furanyl insecticide |
| JP3258502B2 (en) * | 1993-10-26 | 2002-02-18 | 三井化学株式会社 | Insecticidal tetrahydrofuran derivative |
Non-Patent Citations (4)
| Title |
|---|
| ASHRAF H. ABADI，等: "Phenylpiperazinylmethylheterocycle Derivatives: Synthesis and Dopamine Receptor Binding Profiles", 《ARCH. PHARM. PHARM. MED. CHEM.》 * |
| JI-TAI LI，等: "Improved synthesis of 3-(dialkylaminomethyl)-indole in acetic acid aqueous solution under ultrasound irradiation", 《ULTRASONICS SONOCHEMISTRY》 * |
| MATTHIEU JEANTY，等: "Design and synthesis of 1-(2-alkanamidoethyl)-6-methoxy-7-azaindole derivatives as potent melatonin agonists", 《BIOORGANIC & MEDICINAL CHEMISTRY LETTERS 》 * |
| 戴炜锷，等: "第三代烟碱类杀虫剂呋虫胺的合成", 《现代农药》 * |
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Application publication date: 20170929 |