CN101787018A - 2,6-dimethyl 3,5-bis-[4,4'-(2-amino-3-cyano-thiophene)] pyridine and synthetic method thereof - Google Patents

2,6-dimethyl 3,5-bis-[4,4'-(2-amino-3-cyano-thiophene)] pyridine and synthetic method thereof Download PDF

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CN101787018A
CN101787018A CN 201010126491 CN201010126491A CN101787018A CN 101787018 A CN101787018 A CN 101787018A CN 201010126491 CN201010126491 CN 201010126491 CN 201010126491 A CN201010126491 A CN 201010126491A CN 101787018 A CN101787018 A CN 101787018A
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pyridine
dimethyl
thiophene
cyano
methyl
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CN101787018B (en
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张敏
谈霁雯
张军
汪霞云
朱逸雯
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University of Shanghai for Science and Technology
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Abstract

The invention relates to a 2,6-dimethyl 3,5-bis-[4, 4'-(2-amino-3-cyano-thiophene)] pyridine and a synthetic method thereof. The compound has a structural formula described in the specification. The invention has the advantages of simple operation, mild conditions, high yield, and the like.

Description

2,6-dimethyl-3,5-pair-[4,4 '-(2-amido-3-cyano-thiophene)] pyridine and synthetic method thereof
Technical field
The present invention relates to a kind of thiophene and synthetic method thereof that contains pyridine ring, particularly a kind of 2,6-dimethyl-3,5-is two-[4,4 '-(2-amido-3-cyano-thiophene)] pyridine and synthetic method thereof.
Background technology
Pyridine is common and crucial heterogeneous ring compound in the organic synthesis, of many usesly can reduce 4 aspects, i.e. medicine and intermediate, agricultural chemicals and intermediate, chemical intermediate, dyestuff.For example medicine and intermediate have Norxin, vitamin A, antitumor drug dexamethasone, acetylspiramycin, nicotinic acid/niacinamide, Yi Yansuan, bromination pentadecyl pyridine, 2-vinyl pyridine; Chemical industry and intermediate have oxo pyridine, Perchloropyridine; Dyestuff has N-ethylpyridine ketone series.Particularly Application Areass all in the agricultural chemicals and various structure type have been spreaded all over as agricultural chemicals and intermediate pyridine thereof, particularly the pyridines sterilant--after nicotine nitro alkene class was developed, the patent that contains the pyridines novel pesticide increased sharply, is worth coming into the picture.See from structure type that from structure type except that individually comparatively the uniqueness, the overwhelming majority has formed series.To sulfonylurea, imidazolone type agricultural chemicals the compound that contains pyridine is arranged all from organophosphorus, amino formate.Wherein the organic phosphates agricultural chemicals that contains pyridine has
Figure GSA00000052936100011
The carbamate chemicals for agriculture that contains pyridine has
Figure GSA00000052936100012
The agricultural chemicals that contains the pyridine pyrethroid has
Figure GSA00000052936100021
The five member ring heterocyclic compound thiophene has 6 П electronics, meets Huckel's rule, has aromaticity.The cloud density height of thiophene has unique optical property and electron transport ability, is widely used in electrochemical energy and stores, advanced electrochemical sensor, the preparation and the research of organic film field-effect transistor(FET) (OFLET) and Organic Light Emitting Diode (OLED).
Along with going deep into of conjugated polymer research, the research of electron deficiency heterocyclic polymkeric substance has been caused electron rich groups such as great concern and thiophene are opposite, the polymkeric substance that the short of electricity subring constitutes generally has the reduction characteristics that (n-doping) back electric conductivity significantly improves of mixing.Consider from application point, utilize the charge transfer between electron deficiency unit and the electron rich unit, can reduce ground state and excited energy is poor, improve the conjugated degree of polymkeric substance.If electron deficiency unit and the copolymerization of electron rich unit because intramolecularly is realized charge transfer, can generate charge transfer type (CT-type) polymkeric substance, improve the not specific conductivity of dopant states.Thiphene ring is a class electron rich type aromatic nucleus, so " charge transfer " type multipolymer of thiophene and the copolymerization of electron deficiency pyridine ring is as a class photoelectric material, and its research also will cause great concern.
Summary of the invention
One of purpose of the present invention is to provide a kind of thiophene-based photoelectric material 2 that contains pyridine, 6-dimethyl-3,5-pair-[4,4 '-(2-amido-3-cyano-thiophene)] pyridine.
Two of purpose of the present invention is to provide the synthetic method of this compounds.
For achieving the above object, the reaction mechanism that the inventive method has adopted is:
Figure GSA00000052936100022
According to above-mentioned reaction mechanism, the present invention adopts following technical scheme:
A kind of 2,6-dimethyl-3,5-is two-[4,4 '-(2-amido-3-cyano-thiophene)] pyridine, it is characterized in that the structure of this compound is:
Figure GSA00000052936100031
The physical parameter of this compound:
Molecular formula: C 17H 13N 5S 2
Chinese named: 2,6-dimethyl-3,5-pair-[4,4 '-(2-amido-3-cyano-thiophene)] pyridine
English name:
4，4’-(2，6-dimethylpyridine-3，5-diyl)bis(2-aminothiophene-3-carbonitrile)
Molecular weight: 351.45
Fusing point (adopting WRS-1B numeral fusing point instrument): 257.5-257.8 ℃
Outward appearance: white solid
Infrared spectra (adopting the Perkin-Elmer983G infrared spectrometer, the KBr compressing tablet):
υmax(cm -1)：3446.75，3229.41，1656.27，1605.45，1534.97，1489.49，1277.21，1131.61，708.82。
Proton nmr spectra (500MHz, CDCl 3, interior mark: TMS): 10.816 (NH, 2H), 7.897～7.417 (11H, ArH and pyridine ring H), 2.562～2.294 (12H, CH 3).
A kind of synthetic above-mentioned 2,6-dimethyl-3,5-is two-method of [4,4 '-(2-amido-3-cyano-thiophene)] pyridine, it is characterized in that this method has following steps:
A. with 2,6-dimethyl-3,5-diacetyl pyridine, propane dinitrile and ammonium acetate are dissolved in the acetate by 1: 2.1～2.8: 2.2～3.2 mol ratio, react 6～7 hours under 70 ℃～85 ℃ conditions; Reaction is left standstill cooling after finishing, and the conditioned reaction system pH is 7.0～7.2, has a large amount of solids to generate; Through suction filtration, washing, drying, get white powder solid 2,6-dimethyl-3,5-pair-(1-methyl-2,2-dinitrile vinyl) pyridine, its structural formula is:
Figure GSA00000052936100032
B. with step a gained 2,6-dimethyl-3,5-pair-(1-methyl-2,2-dinitrile vinyl) pyridine and sulphur are dissolved in the ethanol by 2.2～2.6 mol ratio, the triethylamine that adds catalyst levels, 65～80 ℃ of reactions to 2,6-dimethyl-3,5-pair-(1-methyl-2,2-dinitrile vinyl) pyridine complete reaction; Reaction is left standstill cooling after finishing, and remove and desolvate, suction filtration, washing, drying, purifying gets orange solids 2,6-dimethyl-3,5-pair-[4,4 '-(2-amido-3-cyano-thiophene)] pyridine.
Through the OTFT performance test, 2,6-dimethyl-3,5-pair-[4,4 '-(2-amido-3-cyano-thiophene)] pyridine is cavity type (p type) structure, electron transfer rate I D(A) 1/2=2.2 * 10 -4, have photoelectric properties.
That the present invention has is simple to operate, mild condition, productive rate advantages of higher.
Embodiment:
Embodiment one: concrete steps are as follows:
A.50 in Hao Sheng the flask, adding 1.01 grams 2,6-dimethyl-3,5-diacetyl pyridine, 0.72 restrain propane dinitrile, 0.88 gram ammonium acetate, 1mL Glacial acetic acid, and 80 ℃ were reacted 7 hours down.Cooling adds 10%NaOH solution while stirring, and the conditioned reaction system pH is 7.0, has a large amount of solids to generate, suction filtration washes twice with water, with a small amount of 95% washing with alcohol, gets 2,6-dimethyl-3,5-pair-(1-methyl-2,2-dinitrile vinyl) pyridine 1.41 grams, productive rate 93.7%.
B. do system with ethanol, triethylamine is an alkali, and 65～80 ℃ were reacted about 1 hour, 2, and 6-dimethyl-3, the mol ratio of 5-pair-(1-methyl-2,2-dinitrile vinyl) pyridine and sulphur is 1: 2.2.Reaction is left standstill cooling after finishing, etoh solvent is spin-dried for, and suction filtration, washing, drying gets orange solids with (EtOH: H2O: THF=1: 2: 1) recrystallization, is 2,6-dimethyl-3,5-pair-[4,4 '-(2-amido-3-cyano-thiophene)] pyridine.
Embodiment two: concrete steps are as follows:
A.250 in Hao Sheng the flask, adding 8 grams 2,6-dimethyl-3,5-diacetyl pyridine, 5.76 restrain propane dinitrile, 7.05 gram ammonium acetates, 8mL Glacial acetic acid, and 80 ℃ were reacted 8 hours down.Cooling adds 10%NaOH solution while stirring, and the conditioned reaction system pH is 7.2, has a large amount of solids to generate, suction filtration washes twice with water, with a small amount of 95% washing with alcohol, gets 2,6-dimethyl-3,5-pair-(1-methyl-2,2-dinitrile vinyl) pyridine 11.30 grams, productive rate 94.1%.
B.25 in Hao Sheng the flask, add 1.00 grams 2,6-dimethyl-3,5-pair-(1-methyl-2,2-dinitrile vinyl) pyridine, 0.25 restrains sulphur powder, THF 2mL, is heated to 35 ℃.Under 35 ℃, slow Dropwise 5 mL 10%NaHCO 3Solution (about one hour), after adding finished, mixture continued to stir 30 minutes.Cooling, system respectively with 12.5%, 25%NaCl solution 5mL washs once, suction filtration goes out solid, wash twice with water, drying, head product gets orange solids 2 with (EtOH: H2O: THF=1: 2: 1) recrystallization, 6-dimethyl-3,5-pair-[4,4 '-(2-amido-3-cyano-thiophene)] pyridine 1.04 grams, productive rate 85.2%.

Claims (2)

1. one kind 2,6-dimethyl-3, is characterized in that the structural formula of this compound is by 5-pair-[4,4 '-(2-amido-3-cyano-thiophene)] pyridine:
One kind synthetic according to claim 12,6-dimethyl-3,5-is two-method of (1-methyl-2,2-dinitrile vinyl) pyridine, it is characterized in that the concrete steps of this method are:
A. with 2,6-dimethyl-3,5-diacetyl pyridine, propane dinitrile and ammonium acetate are dissolved in the acetate by 1: 2.1～2.8: 2.2～3.2 mol ratio,
Figure FSA00000052936000012
Reacted under the condition 6～7 hours; Reaction is left standstill cooling after finishing, and the conditioned reaction system pH is
Figure FSA00000052936000013
There are a large amount of solids to generate; Through suction filtration, washing, drying, get white powder solid 2,6-dimethyl-3,5-pair-(1-methyl-2,2-dinitrile vinyl) pyridine, its structural formula is:
Figure FSA00000052936000014
B. with step a gained 2,6-dimethyl-3,5-is two-and (1-methyl-2,2-dinitrile vinyl) pyridine and sulphur presses
Figure FSA00000052936000015
Mol ratio be dissolved in the ethanol, add the triethylamine of catalyst levels, 65～80 ℃ of reactions to 2,6-dimethyl-3,5-is two-(1-methyl-2,2-dinitrile vinyl) pyridine complete reaction; Reaction is left standstill cooling after finishing, and remove and desolvate, suction filtration, washing, drying, purifying gets orange solids 2,6-dimethyl-3,5-pair-[4,4 '-(2-amido-3-cyano-thiophene)] pyridine.
CN2010101264916A 2010-03-17 2010-03-17 2,6-dimethyl 3,5-bis-[4,4'-(2-amino-3-cyano-thiophene)] pyridine and synthetic method thereof Expired - Fee Related CN101787018B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102225933A (en) * 2011-04-26 2011-10-26 上海大学 2,6-dimethyl-3,5-bis[3-(5- trifluoromethyl)-1H- pyrazole] pyridine and synthesis method thereof
CN108912044A (en) * 2018-08-23 2018-11-30 山东师范大学 A kind of method of copper catalysis alkenyl azide synthesis polysubstituted pyridine

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1948287A (en) * 2006-11-09 2007-04-18 上海大学 Acetyl-2,6-dimethyl pyridine-3,5-diethyl ketone hydrazone and its synthesis method
CN1966503A (en) * 2006-11-09 2007-05-23 上海大学 2,6-dimethyl-3,5-bi-(2-methyl-3-N-acetyl-5-phenyl-[1,3,4] oxadiazoles) pyridine and its synthesis method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1948287A (en) * 2006-11-09 2007-04-18 上海大学 Acetyl-2,6-dimethyl pyridine-3,5-diethyl ketone hydrazone and its synthesis method
CN1966503A (en) * 2006-11-09 2007-05-23 上海大学 2,6-dimethyl-3,5-bi-(2-methyl-3-N-acetyl-5-phenyl-[1,3,4] oxadiazoles) pyridine and its synthesis method

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Title
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102225933A (en) * 2011-04-26 2011-10-26 上海大学 2,6-dimethyl-3,5-bis[3-(5- trifluoromethyl)-1H- pyrazole] pyridine and synthesis method thereof
CN108912044A (en) * 2018-08-23 2018-11-30 山东师范大学 A kind of method of copper catalysis alkenyl azide synthesis polysubstituted pyridine

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