CN106946772A - A kind of synthetic method of 2,2` bipyridyls 4,4` methyl formates - Google Patents
A kind of synthetic method of 2,2` bipyridyls 4,4` methyl formates Download PDFInfo
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- CN106946772A CN106946772A CN201610944888.3A CN201610944888A CN106946772A CN 106946772 A CN106946772 A CN 106946772A CN 201610944888 A CN201610944888 A CN 201610944888A CN 106946772 A CN106946772 A CN 106946772A
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- bipyridyls
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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
2,2' of one kind bipyridyls 4, the synthetic method of 4' methyl formates comprises the following steps：1）By 2,2 ' bipyridyls, methylchloroformate, acid binding agent, solvent and catalyst mixing, protection gas is passed through, in 5~9h of reaction under 90~120 DEG C, 3~4MPa；2）Reaction is cooled down after terminating, and separating-purifying produces product 2,2' bipyridyls 4,4' methyl formates.The present invention is with 2,2' bipyridyls for initial feed, and raw material is easy to get and cheap；Reactions steps are shorter, are single step reaction, operate simpler；It can avoid using the strong corrosive material such as dichromic acid and sulfuric acid, it is safe operation, simple；Yield is high, reaches more than 98%, 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 formates
Into method.
Background technology
2,2'- bipyridyl -4,4'- methyl formates are off-white color crystal powder, are mainly used as medicine intermediate and photosensitive dye
Expect part intermediate.2,2'- bipyridyl -4,4'- methyl formates can have conjugation electricity as part with the various metals formation such as ruthenium
The complex of subsystem, with significant opto-electronic conversion effect.
In the prior art, synthesis 2,2'- bipyridyl -4,4'- methyl formates basic skills be with 4,4'- dimethyl -2,
2'- bipyridyls are raw material, under the effect of the strong oxidizers such as potassium bichromate, first carry out oxidative synthesis 2,2'- bipyridyls -4,4'- bis-
Formic acid, then with methanol be esterified obtaining 2,2'- bipyridyl -4,4'- methyl formates.Such as CN105294773,
PCT2016025742、Angewandte Chemie, International Edition, 52(38), 9956-9960;
2013、Chemical Communications (Cambridge, United Kingdom), (45), 6949-6951;
2009 etc..
This method two steps of needs could be completed, and yield is relatively low, and need to be directed to use with the deep-etchings such as dichromic acid, sulfuric acid
Property material, operation is more dangerous, easily produces equipment corrosion and water pollution, gross production rate is not high.
The content of the invention
Present invention aims at there is provided a kind of synthetic method of 2,2'- bipyridyls -4,4'- methyl formates.
Based on above-mentioned purpose, this invention takes following technical scheme：A kind of 2,2'- bipyridyls -4,4'- methyl formates
Synthetic method, comprises the following steps：1）By 2,2 '-bipyridyl, methylchloroformate, acid binding agent, solvent and catalyst mixing, it is passed through
Gas is protected, in 5~9h of reaction under 90~120 DEG C, 3~4MPa；2）Reaction is cooled down after terminating, and separating-purifying produces product 2,2'-
Bipyridyl -4,4'- methyl formates.
The catalyst is made using following methods：Phosphotungstic acid and sodium tungstate is soluble in water, it is incorporated as phosphotungstic acid weight
6~8 times of nano titanium oxide and the mixture of nano zircite, in stirring 30~40h at 45~60 DEG C, vacuum drains water
Point, 120~160 DEG C of 2~5h of drying are produced；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：First it is filtered to remove insoluble matter（Catalyst and the 2,2 '-connection that may not react precipitation
Pyridine）, filtrate through separation and Extraction, concentration, dry, produce, add water concentration, produce 2,2'- bipyridyl -4,4'- methyl formates.
Step 1）Described in 2,2 '-bipyridyl, methylchloroformate, the mol ratio 1 of acid binding agent:（2~3.6）:（5~
5.15）；2,2 '-bipyridyl, solvent, the amount ratio of catalyst are 1mol:（500~800）ml:（0.3~0.8）g.
The acid binding agent is one kind in triethylamine, diethylamine and ethylenediamine.
Step 1）In solvent be methanol, tetrahydrofuran, dichloromethane and chloroform in one kind.
The protection gas is nitrogen or argon gas.
In the present invention, two kinds of primary raw materials 2,2 '-bipyridyl, methylchloroformate are in pressurization, catalyst and acid binding agent
Under collective effect, 2,2'- bipyridyl -4,4'- methyl formates are directly synthesized；Its reaction mechanism is that catalyst makes methylchloroformate
With the similar electrophilic reaction of 2,2 '-bipyridyl generation；A molecule hydrogen chloride is taken off, then acid binding agent can combine hydrogen chloride rapidly,
So that reaction is proceeded, yield can be effectively increased using the reaction；And in whole course of reaction, pollutant row is not produced
Put.Meanwhile, in the present invention, due to raw material（Especially methylchloroformate and acid binding agent）Boiling point is relatively low, and pressurization can connect reactant
Touch more fully, carried out beneficial to reaction；Adding protection gas simultaneously can avoid being formed the nitrogen of 2,2 '-bipyridyl under the reaction conditions
Oxide, reduces side reaction.
Therefore, compared with prior art, the present invention has following technique effect：
1）With 2,2'- bipyridyls for initial feed, raw material is easy to get and cheap；
2）Reactions steps are shorter, are single step reaction, operate simpler；
3）Avoid using the strong corrosive material such as dichromic acid and sulfuric acid, it is safe operation, simple；
4）Yield is high, reaches more than 98%（The yield highest only up to 88% of prior art）, and process costs are low；
5）Post processing is simple, and pollution is few.
Brief description of the drawings
Fig. 1 is the H of embodiment 11NMR schemes.
Embodiment
With reference to specific embodiment, the present invention is further illustrated.
Embodiment 1
The synthetic method of one kind 2,2'- bipyridyl -4,4'- methyl formates, comprises the following steps：
1）By 2,2 '-bipyridyl, methylchloroformate, diethylamine, methanol and catalyst mixing, nitrogen is passed through, in 90 DEG C, 3 MPa
Lower reaction 5h；Step 1）In, 2,2 '-bipyridyl, methylchloroformate, the mol ratio 1 of triethylamine:2:5；2,2 '-bipyridyl, first
Alcohol, the amount ratio of catalyst are 1mol:500ml:0.3g；
The catalyst is made using following methods：Phosphotungstic acid and sodium tungstate is soluble in water, it is incorporated as 6 times of phosphotungstic acid weight
Nano titanium oxide and nano zircite mixture（The mixture contains the titanium dioxide of 70% weight）, in stirring at 60 DEG C
30h, vacuum drains moisture, and 160 DEG C of drying 2h are produced；The mass ratio of the phosphotungstic acid, sodium tungstate and water three is 1:0.15:
5；
2）Reaction is cooled down after terminating, and is first filtered to remove insoluble matter, is added to the water, is then extracted with ethyl acetate, concentrated
After produce white solid 2,2'- bipyridyl -4,4'- methyl formates, yield 98.2%.
Embodiment 2
The synthetic method of one kind 2,2'- bipyridyl -4,4'- methyl formates, comprises the following steps：
1）By 2,2 '-bipyridyl, methylchloroformate, triethylamine, catalyst described in tetrahydrofuran and embodiment 3 is mixed, and is passed through argon
Gas, in reacting 8 h under 120 DEG C, 4 MPa；Step 1）In, 2,2 '-bipyridyl, methylchloroformate, the mol ratio 1 of triethylamine:
3.6:5.15；2,2 '-bipyridyl, tetrahydrofuran, the amount ratio of catalyst are 1mol:700ml:0.6g；
The catalyst is made using following methods：Phosphotungstic acid and sodium tungstate is soluble in water, phosphotungstic acid, sodium tungstate and water three
Mass ratio be 1:0.20:6；Then it is incorporated as the mixing of 7 times of nano titanium oxide and nano zircite of phosphotungstic acid weight
Thing（The mixture contains the titanium dioxide of 66% weight）, in stirring 28 h at 55 DEG C, vacuum drains moisture, and 160 DEG C of drying 2h are obtained
To catalyst；
2）Reaction is cooled down after terminating, and is first filtered to remove insoluble matter, is added to the water, is then extracted with chloroform, concentrated to be afterwards
Obtain white solid 2,2'- bipyridyl -4,4'- methyl formates, the % of yield 99.5.
Embodiment 3
The synthetic method of one kind 2,2'- bipyridyl -4,4'- methyl formates, comprises the following steps：
1）By 2,2 '-bipyridyl, methylchloroformate, ethylenediamine, catalyst described in chloroform and embodiment 2 is mixed, and is passed through nitrogen, in
100 DEG C, react 9 h under 3.5 MPa；Step 1）In, 2,2 '-bipyridyl, methylchloroformate, the mol ratio 1 of triethylamine:3:5.1；
2,2 '-bipyridyl, tetrahydrofuran, the amount ratio of catalyst are 1mol:800ml:0.8g；
The catalyst is made using following methods：Phosphotungstic acid and sodium tungstate is soluble in water, phosphotungstic acid, sodium tungstate and water three
Mass ratio be 1:0.26:8；Then it is incorporated as the mixing of 8 times of nano titanium oxide and nano zircite of phosphotungstic acid weight
Thing（The mixture contains the titanium dioxide of 60% weight）, in stirring 40h at 45 DEG C, vacuum drains moisture, and 120 DEG C of drying 5h are obtained
Catalyst；
2）Reaction is cooled down after terminating, and is first filtered to remove insoluble matter, is added to the water, is then extracted with chloroform, concentrated to be afterwards
Obtain white solid 2,2'- bipyridyl -4,4'- methyl formates, the % of yield 99.0.
Product confirms
The product that embodiment 1-3 is obtained is white solid, while carrying out fusing point test, HNMR tests and mass spectrum point to each product
Analysis, is really target product 4,4'- dihydroxy -2,2'- bipyridyls, its product H through being analyzed to identify products therefrom1NMR is as shown in Figure 1
Product fusing point：211.1~211.9 DEG C of fusing point；Mass spectral analysis：Molecular ion peak m/z=272, correspondence molecular weight of product.
Claims (7)
1. one kind 2, the synthetic method of 2'- bipyridyl -4,4'- methyl formates, it is characterised in that comprise the following steps：1）By 2,
2 '-bipyridyl, methylchloroformate, acid binding agent, solvent and catalyst mixing, are passed through protection gas, under 90~120 DEG C, 3~4MPa
React 5~9h；2）Reaction is cooled down after terminating, and separating-purifying produces product 2,2'- bipyridyl -4,4'- methyl formates.
2. the synthetic method of 2,2'- bipyridyls -4,4'- methyl formate as claimed in claim 1, it is characterised in that described to urge
Agent is made using following methods：Phosphotungstic acid and sodium tungstate is soluble in water, add 6~8 times of nanometer two of phosphotungstic acid weight
The mixture of titanium oxide and nano zircite, in stirring 30~40h at 45~60 DEG C, vacuum drains moisture, 120 DEG C~160 DEG C
Dry 2~5h；The mass ratio of the phosphotungstic acid, sodium tungstate and water three is 1:0.15~0.26:5~8.
3. the synthetic method of 2,2'- bipyridyls -4,4'- methyl formate as claimed in claim 2, it is characterised in that separation is carried
Pure concrete operations are：Insoluble matter is first filtered to remove, filtrate produces 2,2'- bipyridyl -4 through separation and Extraction, concentration, drying,
4'- methyl formates.
4. the synthetic method of 2,2'- bipyridyl -4,4'- methyl formates as described in claim 1-3 is any, it is characterised in that
Step 1）Described in 2,2 '-bipyridyl, methylchloroformate, the mol ratio 1 of acid binding agent:（2~3.6）:（5~5.15）；2,2 '-connection
Pyridine, solvent, the amount ratio of catalyst are 1mol:（500~800）ml:（0.3~0.8）g.
5. the synthetic method of 2,2'- bipyridyls -4,4'- methyl formate as claimed in claim 4, it is characterised in that described to tie up
Sour agent is one kind in triethylamine, diethylamine and ethylenediamine.
6. the synthetic method of 2,2'- bipyridyls -4,4'- methyl formate as claimed in claim 4, it is characterised in that step 1）
In solvent be methanol, tetrahydrofuran, dichloromethane and chloroform in one kind.
7. the synthetic method of 2,2'- bipyridyls -4,4'- methyl formate as claimed in claim 4, it is characterised in that the guarantor
It is nitrogen or argon gas to protect gas.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116396213A (en) * | 2023-04-14 | 2023-07-07 | 济南大学 | Preparation method of 2-methyl picolinate |
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| 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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Patent 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 |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116396213A (en) * | 2023-04-14 | 2023-07-07 | 济南大学 | Preparation method of 2-methyl picolinate |
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