CN106946772B - A kind of synthetic method of 2,2 '-bipyridyls -4,4 '-methyl formate - Google Patents
A kind of synthetic method of 2,2 '-bipyridyls -4,4 '-methyl formate Download PDFInfo
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- CN106946772B CN106946772B CN201610944888.3A CN201610944888A CN106946772B CN 106946772 B CN106946772 B CN 106946772B CN 201610944888 A CN201610944888 A CN 201610944888A CN 106946772 B CN106946772 B CN 106946772B
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- methyl formate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
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Abstract
The synthetic method of one kind 2,2'- bipyridyl -4,4'- methyl formate, comprising the following steps: 1) by 2,2 '-bipyridyls, methylchloroformate, acid binding agent, solvent and catalyst mixing, be passed through protection gas, 5~9h is reacted under 90~120 DEG C, 3~4MPa；2) it cools down after reaction, separating-purifying is up to product 2,2'- bipyridyl -4,4'- methyl formate.With 2,2'- bipyridyl for initial feed, raw material is easy to get and cheap the present invention；Reaction step is shorter, is single step reaction, operates simpler；It can avoid using the strong corrosive materials such as dichromic acid and sulfuric acid, it is safe operation, simple；Yield is high, reaches 98% or more, and process costs are low；Post-processing is simple, and pollution is few.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to the conjunction of one kind 2,2'- bipyridyl -4,4'- methyl formate
At method.
Background technique
2,2'- bipyridyl -4,4'- methyl formates are off-white color crystal powder, are mainly used as medicine intermediate and photosensitive dye
Expect ligand intermediate.2,2'- bipyridyl -4,4'- methyl formates can be used as ligand, and being formed with various metals such as rutheniums has conjugation electricity
The complex of subsystem has significant photoelectric conversion effect.
In the prior art, synthesize 2,2'- bipyridyl -4,4'- methyl formate basic skills be with dimethyl -2 4,4'-,
2'- bipyridyl is raw material, under the effect of the strong oxidizers such as potassium bichromate, first carries out oxidative synthesis 2,2'- bipyridyl -4,4'- bis-
Then formic acid is esterified to obtain 2,2'- bipyridyl -4,4'- methyl formate with methanol.As CN105294773,
PCT2016025742、Angewandte Chemie, International Edition, 52(38), 9956-9960;
2013、Chemical Communications (Cambridge, United Kingdom), (45), 6949-6951;
2009 etc..
This method needs two steps that could complete, and yield is lower, and needs to be related to using deep-etchings such as dichromic acid, sulfuric acid
Property substance, operation is more dangerous, is easy to produce equipment corrosion and water pollution, gross production rate be not high.
Summary of the invention
It is an object of that present invention to provide a kind of synthetic methods of 2,2'- bipyridyl -4,4'- methyl formate.
Based on above-mentioned purpose, this invention takes following technical solutions: one kind 2,2'- bipyridyl -4,4'- methyl formate
Synthetic method, comprising the following steps: 1) by 2,2 '-bipyridyls, methylchloroformate, acid binding agent, solvent and catalyst mixing, be passed through
Gas is protected, 5~9h is reacted under 90~120 DEG C, 3~4MPa；2) it cools down after reaction, separating-purifying is up to product 2,2'-
Bipyridyl -4,4'- methyl formate.
The catalyst is prepared by the following method: phosphotungstic acid and sodium tungstate is soluble in water, it is incorporated as phosphotungstic acid weight
6~8 times of nano-titanium dioxide and nano zircite mixture, 30~40h is stirred at 45~60 DEG C, vacuum drains water
Point, 120~160 DEG C of 2~5h of drying to obtain the final product；The mass ratio of the phosphotungstic acid, sodium tungstate and water three is 1:0.15~0.26:5
~8.
The concrete operations of separating-purifying are as follows: be first filtered to remove insoluble matter (catalyst and the 2,2 '-connection that may do not react precipitation
Pyridine), filtrate adds water concentration through separation and Extraction, concentration, drying to get 2,2'- bipyridyl -4,4'- methyl formate.
2,2 ' described in step 1)-bipyridyl, methylchloroformate, acid binding agent molar ratio 1:(2~3.6): (5~
5.15)；2,2 '-bipyridyls, solvent, catalyst amount ratio be 1mol:(500~800) ml:(0.3~0.8) g.
The acid binding agent is one of triethylamine, diethylamine and ethylenediamine.
Solvent in step 1) is one of methanol, tetrahydrofuran, methylene chloride and chloroform.
The protection gas is nitrogen or argon gas.
In the present invention, two kinds of 2,2 '-bipyridyls of primary raw material, methylchloroformates are in pressurization, catalyst and acid binding agent
Under collective effect, 2,2'- bipyridyl -4,4'- methyl formate is directly synthesized；Its reaction mechanism is that catalyst makes methylchloroformate
Electrophilic reaction similar with the generation of 2,2 '-bipyridyls；A molecule hydrogen chloride is taken off, then acid binding agent can combine rapidly hydrogen chloride,
So that reaction is continued, yield can be effectively increased using the reaction；And in entire reaction process, pollutant row is not generated
It puts.Meanwhile in the present invention, since raw material (especially methylchloroformate and acid binding agent) boiling point is lower, pressurization can be such that reactant connects
Touching is more abundant, is conducive to reaction and carries out；Protection gas is added simultaneously can avoid the nitrogen for forming 2,2 '-bipyridyls under the reaction conditions
Oxide reduces side reaction.
Therefore, compared with prior art, the present invention has following technical effect that
1) with 2,2'- bipyridyl for initial feed, raw material is easy to get and cheap；
2) reaction step is shorter, is single step reaction, operates simpler；
3) it avoids using strong corrosive materials such as dichromic acid and sulfuric acid, it is safe operation, simple；
4) yield is high, reaches 98% or more (the yield highest only up to 88% of the prior art), and process costs are low；
5) post-processing is simple, and pollution is few.
Detailed description of the invention
Fig. 1 is the H of embodiment 11NMR figure.
Specific embodiment
Combined with specific embodiments below, the present invention is further illustrated.
Embodiment 1
The synthetic method of one kind 2,2'- bipyridyl -4,4'- methyl formate, comprising the following steps:
1) by 2,2 '-bipyridyls, methylchloroformate, diethylamine, methanol and catalyst mixing, it is passed through nitrogen, in 90 DEG C, 3
5h is reacted under MPa；In step 1), 2,2 '-bipyridyls, methylchloroformate, diethylamine molar ratio 1:2:5；2,2 '-bipyridyls,
Methanol, catalyst amount ratio be 1mol:500ml:0.3g；
The catalyst is prepared by the following method: phosphotungstic acid and sodium tungstate is soluble in water, it is incorporated as phosphotungstic acid weight
6 times of nano-titanium dioxide and nano zircite the mixture titanium dioxide of 70% weight (mixture contain), at 60 DEG C
Stir 30h, vacuum drains moisture, and 160 DEG C of drying 2h to obtain the final product；The mass ratio of the phosphotungstic acid, sodium tungstate and water three is 1:
0.15:5；
2) it cools down after reaction, is first filtered to remove insoluble matter, be added to the water, then extracted with ethyl acetate, passed through
Up to white solid 2,2'- bipyridyl -4,4'- methyl formate, yield 98.2% after concentration.
Embodiment 2
The synthetic method of one kind 2,2'- bipyridyl -4,4'- methyl formate, comprising the following steps:
1) by 2,2 '-bipyridyls, methylchloroformate, triethylamine, tetrahydrofuran and catalyst mixing, it is passed through argon gas, in 120
DEG C, react 8 h under 4 MPa；In step 1), 2,2 '-bipyridyls, methylchloroformate, triethylamine molar ratio 1:3.6:5.15；2,
2 '-bipyridyls, tetrahydrofuran, catalyst amount ratio be 1mol:700ml:0.6g；
The catalyst is prepared by the following method: phosphotungstic acid and sodium tungstate is soluble in water, phosphotungstic acid, sodium tungstate and water
The mass ratio of three is 1:0.20:6；Then 7 times of the nano-titanium dioxide and nano zircite of phosphotungstic acid weight are incorporated as
Mixture (titanium dioxide that the mixture contains 66% weight), stirs 28 h at 55 DEG C, and vacuum drains moisture, 160 DEG C of drying
2h obtains catalyst；
2) it cools down after reaction, is first filtered to remove insoluble matter, be added to the water, then extracted with chloroform, it is concentrated
Afterwards up to white solid 2,2'- bipyridyl -4,4'- methyl formate, 99.5 % of yield.
Embodiment 3
The synthetic method of one kind 2,2'- bipyridyl -4,4'- methyl formate, comprising the following steps:
1) by 2,2 '-bipyridyls, methylchloroformate, ethylenediamine, chloroform and catalyst mixing be passed through nitrogen, in 100 DEG C,
9 h are reacted under 3.5 MPa；In step 1), 2,2 '-bipyridyls, methylchloroformate, ethylenediamine molar ratio 1:3:5.1；2,2'-
Bipyridyl, tetrahydrofuran, catalyst amount ratio be 1mol:800ml:0.8g；
The catalyst is prepared by the following method: phosphotungstic acid and sodium tungstate is soluble in water, phosphotungstic acid, sodium tungstate and water
The mass ratio of three is 1:0.26:8；Then 8 times of the nano-titanium dioxide and nano zircite of phosphotungstic acid weight are incorporated as
Mixture (titanium dioxide that the mixture contains 60% weight), stirs 40h, vacuum drains moisture, 120 DEG C of drying 5h at 45 DEG C
Obtain catalyst；
2) it cools down after reaction, is first filtered to remove insoluble matter, be added to the water, then extracted with chloroform, it is concentrated
Afterwards up to white solid 2,2'- bipyridyl -4,4'- methyl formate, 99.0 % of yield.
Product confirmation
The product that embodiment 1-3 is obtained is white solid, while carrying out fusing point test, HNMR test and mass spectrum to each product
Analysis, being analyzed to identify products therefrom really is target product 2,2'- bipyridyl -4,4'- methyl formate, product H1NMR is shown in Fig. 1
Shown product fusing point: 211.1~211.9 DEG C of fusing point；Mass spectral analysis: molecular ion peak m/z=272, corresponding molecular weight of product.
Claims (6)
1. one kind 2, the synthetic method of 2'- bipyridyl -4,4'- methyl formate, which comprises the following steps: 1) by 2,
2 '-bipyridyls, methylchloroformate, acid binding agent, solvent and catalyst mixing, are passed through protection gas, under 90~120 DEG C, 3~4MPa
React 5~9h；2) it cools down after reaction, separating-purifying is up to product 2,2'- bipyridyl -4,4'- methyl formate；
The catalyst is prepared by the following method: phosphotungstic acid and sodium tungstate is soluble in water, the 6~8 of phosphotungstic acid weight are added
Times nano-titanium dioxide and nano zircite mixture, 30~40h is stirred at 45~60 DEG C, vacuum drains moisture, 120
DEG C~160 DEG C of 2~5h of drying；The mass ratio of the phosphotungstic acid, sodium tungstate and water three is 1:0.15~0.26:5~8.
2. the synthetic method of 2,2'- bipyridyl -4,4'- methyl formate as described in claim 1, which is characterized in that separation mentions
Pure concrete operations are as follows: be first filtered to remove insoluble matter, filtrate through separation and Extraction, concentration, dry to get bipyridyl -4 2,2'-,
4'- methyl formate.
3. the synthetic method of 2,2'- bipyridyl -4,4'- methyl formate as described in claim 1-2 is any, which is characterized in that
2,2 ' described in step 1)-bipyridyl, methylchloroformate, acid binding agent molar ratio 1:(2~3.6): (5~5.15)；2,2 '-connection
Pyridine, solvent, catalyst amount ratio be 1mol:(500~800) ml:(0.3~0.8) g.
4. the synthetic method of 2,2'- bipyridyl -4,4'- methyl formate as claimed in claim 3, which is characterized in that described to tie up
Sour agent is one of triethylamine, diethylamine and ethylenediamine.
5. the synthetic method of 2,2'- bipyridyl -4,4'- methyl formate as claimed in claim 3, which is characterized in that step 1)
In solvent be one of methanol, tetrahydrofuran, methylene chloride and chloroform.
6. the synthetic method of 2,2'- bipyridyl -4,4'- methyl formate as claimed in claim 3, which is characterized in that the guarantor
Protecting gas is nitrogen or argon gas.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010132999A1 (en) * | 2009-05-21 | 2010-11-25 | Chlorion Pharma, Inc. | Methyl sulfanyl pyrmidmes useful as antiinflammatories, analgesics, and antiepileptics |
| CN105503738A (en) * | 2015-12-21 | 2016-04-20 | 哈尔滨工业大学 | Method for synthesizing bionic redox couple 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzimidazole-5-carboxylic acid |
| WO2016090317A1 (en) * | 2014-12-05 | 2016-06-09 | Aquinnah Pharmaceuticals, Inc. | Sulfonamide derivatives, compositions and methods of use in the treatment of neurodegenerative diseases |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010132999A1 (en) * | 2009-05-21 | 2010-11-25 | Chlorion Pharma, Inc. | Methyl sulfanyl pyrmidmes useful as antiinflammatories, analgesics, and antiepileptics |
| WO2016090317A1 (en) * | 2014-12-05 | 2016-06-09 | Aquinnah Pharmaceuticals, Inc. | Sulfonamide derivatives, compositions and methods of use in the treatment of neurodegenerative diseases |
| CN105503738A (en) * | 2015-12-21 | 2016-04-20 | 哈尔滨工业大学 | Method for synthesizing bionic redox couple 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzimidazole-5-carboxylic acid |
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