CN102993085B - Synthesis method of 2, 2'-(2, 2'-dipyridyl-4, 4'-dimethyl) di-malononitrile and substitute for 2, 2'-(2, 2'-dipyridyl-4, 4'-dimethyl) di-malononitrile - Google Patents
Synthesis method of 2, 2'-(2, 2'-dipyridyl-4, 4'-dimethyl) di-malononitrile and substitute for 2, 2'-(2, 2'-dipyridyl-4, 4'-dimethyl) di-malononitrile Download PDFInfo
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- CN102993085B CN102993085B CN201210490817.2A CN201210490817A CN102993085B CN 102993085 B CN102993085 B CN 102993085B CN 201210490817 A CN201210490817 A CN 201210490817A CN 102993085 B CN102993085 B CN 102993085B
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Abstract
The invention belongs to the field of organic synthesis technology, and particularly relates to a synthesis method of 2, 2'-(2, 2'-dipyridyl-4, 4'-dimethyl) di-malononitrile and a substitute for 2, 2'-(2, 2'-dipyridyl-4, 4'-dimethyl) di-malononitrile. The synthesis method comprises the following steps: with malononitrile and bipyridyl dialdehyde compound shown by formula (II) as raw materials, stirring for reaction for 1-6h at the temperature of 45-160 DEG C, and after the reaction, carrying out aftertreatment on reaction liquid to obtain the target product shown by formula (I), wherein the molar ratio of bipyridyl dialdehyde compound to malononitrile is 1: 2.5-8. The formula (II) and (I) are shown in the specification, wherein R1 is H, CH3 or C2H5, and R2 is H, CH3 or C2H5. According to the method, the bipyridyl dialdehyde compound and malononitrile are taken as raw materials, and the method is carried out under the condition that solvent and catalyst are not available, so that the operation is simple and convenient, and the product yield is high.
Description
Technical field
The invention belongs to technical field of organic synthesis, be specifically related to the synthetic method of a kind of 2,2'-(2,2'-dipyridyl-4,4'-bis-methynes) two propane dinitrile and substituent thereof.
Background technology
Bipyridyliums derivative is the important medicine of a class, agricultural chemicals and dyestuff intermediate, recently finds that this class material and various metals complexing form the title complex with conjugated electrons system, have significant opto-electronic conversion effect.Be presented at structure composition upper, the conjugated system size of ligand molecular can affect this specific character significantly.
The condensation reaction occurring between carbonyl compound and active methylene group is that Knoevenagel reacts, and is the important method that forms carbon-carbon double bond in organic synthesis, is paid much attention to for a long time and broad research, has become the classics reaction in organic synthesis.Taking piperidines catalysis as representative, catalysis Knoevenagel repercussion study has obtained larger development; Also there is report few in number without catalysis Knoevenagel reaction.Ren Zhongjiao etc. (organic chemistry), have studied phenyl aldehyde and the propane dinitrile Knoevenagel under catalyst-free, and conclusion is in the solvent-free situation of catalyst-free, and phenyl aldehyde with propane dinitrile, Knoevenagel does not occur and reacts.
The application is based on without the solvent-free object of catalysis, through research, find surprisingly 2,2'-dipyridyl-4,4'-dicarbaldehyde and substituent thereof, under at catalyst-free, without external solvent condition, successfully carry out Knoevenagel reaction, and obtained very high yield, thereby find a kind of synthetic 2, the simple and effective method of 2'-(2,2'-dipyridyl-4,4'-bis-methynes) two propane dinitrile and substituent thereof.
Summary of the invention
The object of the invention is to provide a kind of 2,2'-(2,2'-dipyridyl-4,4'-bis-methynes) synthetic method of two propane dinitrile and substituent thereof, the method is taking dipyridyl twain-aldehyde compound compound and propane dinitrile as raw material, under the condition of solvent-free, catalyst-free, carry out, easy and simple to handle, product yield is higher.
For achieving the above object, the present invention adopts following technical scheme:
A kind of 2,2'-(2,2'-dipyridyl-4,4'-bis-methynes) synthetic method of two propane dinitrile and substituent thereof, it comprises the steps: taking the dipyridyl twain-aldehyde compound compound shown in propane dinitrile and lower formula II as raw material, stirring reaction 1-6h under 45-160 DEG C of temperature condition, after reaction finishes, reaction solution obtains the target product shown in lower formula I through aftertreatment; Described dipyridyl twain-aldehyde compound compound is 1:2.5～8 with the amount of substance ratio of propane dinitrile;
, wherein R
1for H, CH
3or C
2h
5, R
2for H, CH
3or C
2h
5.R
1and R
2can be identical, also can be different.
Preferably, described dipyridyl twain-aldehyde compound compound reacts 4h than 1:5 by amount of substance with propane dinitrile under 80 DEG C of conditions.
Described aftertreatment is specially: reaction solution adds water and mixes, and filters, and filter residue is through washing, dry, organic solvent recrystallization and get final product.
In post-processing step, the addition of water is preferably 2-5 times of reaction solution volume; Filter residue preferably washs with the aqueous ethanolic solution of volumetric concentration 10-50%, also can before aqueous ethanolic solution washing, first wash with water for several times.
Recrystallization organic solvent used is preferably dimethyl formamide (DMF) or methyl-sulphoxide (DMSO).
The synthetic route of the inventive method is as shown below.In reaction process, 1) dipyridyl twain-aldehyde compound compound is 1:2 with the amount ratio of the theoretical reactive material of propane dinitrile, but because dipyridyl twain-aldehyde compound compound is solid, fusing point is higher, therefore needs to add the actual solvent that serves as of propane dinitrile.The very few homogeneous reaction that is unfavorable for of propane dinitrile consumption; Too much can cause waste.More suitable ratio range is 1:2.5～8, best results in the time of 1:5.2) 30.5 DEG C of propane dinitrile fusing points, 220 DEG C of boiling points.Under the reflux temperature of propane dinitrile, rising temperature all can improve speed of response in theory, but propane dinitrile is toxic substance, and excess Temperature is volatile, and later stage product can be precipitated out after forming, and system temperature is little to reaction contribution.So temperature range of choice should be 45-160 DEG C (when 100 DEG C of left and right, effect be better), in this temperature range, dipyridyl twain-aldehyde compound compound initial reaction stage can be dissolved formation solution.
The inventive method is taking dipyridyl twain-aldehyde compound compound and propane dinitrile as reaction raw materials, under the condition of solvent-free, catalyst-free, synthesized corresponding 2,2'-(2,2'-dipyridyl-4,4'-bis-methynes) two propane dinitrile and substituent thereof.In reaction, avoid using solvent and catalyzer, be a kind of simple to operate, cheaply, comparatively green synthetic method.The method is easy and simple to handle, and product yield is higher.
Brief description of the drawings
Fig. 1 is the synthetic gained 2 of embodiment 1, the mass spectrum of 2'-(2,2'-dipyridyl-4,4'-bis-methynes) two propane dinitrile, and its molecular weight is 308 as can be seen from Figure, mass spectrograph model QP-5000, Japanese Shimadzu company produces;
Fig. 2 is the synthetic gained 2 of embodiment 1,2'-(2,2'-dipyridyl-4,4'-bis-methynes) the nucleus magnetic hydrogen spectrum figure of two propane dinitrile, always have as can be seen from Figure 4 kinds of hydrogen, and ratio is 1:1:1:1, split the known hydrogen atom in chemical shift 7.8,8.8 and 9.0 of mark by chemical shiftsum and be positioned on pyridine ring, the hydrogen atom of chemical shift 8.7 is positioned on two keys; Nuclear magnetic resonance analyser model Mercury Plus 400, VARIAN Oncology Systems produces.
embodiment
By the following examples the inventive method is described further, but protection scope of the present invention is not limited to this.
embodiment 1
A kind of 2,2'-(2,2'-dipyridyl-4,4'-bis-methynes) synthetic method of two propane dinitrile, it comprises the steps: 2.00 g(9.42mmol) 2,2'-dipyridyl-4,4'-dicarbaldehyde joins and fills 3.11g(47.1mmol) in the flask of propane dinitrile, under agitation condition, be heated to 100 DEG C, maintain this thermotonus 4h(system and become turbid, thin-layer chromatographic analysis reaction finishes).Reaction finishes, in water that rear reaction solution proceeds to approximately 4 times of amounts of its volume, to mix, decompress filter, and a small amount of water washing of filter cake, then, with the aqueous ethanolic solution washing of volumetric concentration 40%, is dried and obtains crude product.Gained crude product DMF recrystallization, obtains the micro-yellow solid of 2.86g, yield 98.3%.
embodiment 2
A kind of 2,2'-(2,2'-dipyridyl-4,4'-bis-methynes) synthetic method of two propane dinitrile substituents, it comprises the steps: 2.00 g(8.32mmol) 6,6'-dimethyl-2,2'-dipyridyl-4,4'-dicarbaldehyde joins and fills 3.30g(49.95mmol) in the flask of propane dinitrile, under agitation condition, be heated to 150 DEG C, maintain this thermotonus 2h.Reaction finishes, in water that rear reaction solution proceeds to approximately 3 times of amounts of its volume, to mix, decompress filter, and a small amount of water washing of filter cake, then, with the aqueous ethanolic solution washing of volumetric concentration 30%, is dried and obtains crude product.Gained crude product DMF recrystallization, obtains 2.72g faint yellow solid, yield 97.1%.
embodiment 3
A kind of 2,2'-(2,2'-dipyridyl-4,4'-bis-methynes) synthetic method of two propane dinitrile substituents, it comprises the steps: 2.00 g(7.45mmol) 6,6'-diethyl-2,2'-dipyridyl-4,4'-dicarbaldehyde joins and fills 3.94g(59.64mmol) in the flask of propane dinitrile, under agitation condition, be heated to 60 DEG C, maintain this thermotonus 5h.Reaction finishes, in water that rear reaction solution proceeds to approximately 5 times of amounts of its volume, to mix, decompress filter, and a small amount of water washing of filter cake, then, with the aqueous ethanolic solution washing of volumetric concentration 20%, is dried and obtains crude product.Gained crude product DMF recrystallization, obtains 2.60g gray solid, yield 95.72%.
embodiment 4
A kind of 2,2'-(2,2'-dipyridyl-4,4'-bis-methynes) synthetic method of two propane dinitrile substituents, it comprises the steps: 2.00 g(7.86mmol) 6-methyl-6'-ethyl-2,2'-dipyridyl-4,4'-dicarbaldehyde joins and fills 2.08g(31.34mmol) in the flask of propane dinitrile, under agitation condition, be heated to 45 DEG C, maintain this thermotonus 6h.Reaction finishes, in water that rear reaction solution proceeds to approximately 3 times of amounts of its volume, to mix, decompress filter, and a small amount of water washing of filter cake, then, with the aqueous ethanolic solution washing of volumetric concentration 40%, is dried and obtains crude product.Gained crude product DMF recrystallization, obtains 2.63g gray solid, yield 95.43%.
Claims (3)
1. one kind 2,2'-(2,2'-dipyridyl-4,4'-bis-methynes) synthetic method of two propane dinitrile and substituent thereof, it is characterized in that, comprise the steps: taking the dipyridyl twain-aldehyde compound compound shown in propane dinitrile and lower formula II as raw material stirring reaction 1-6h under 45-160 DEG C of temperature condition, after reaction finishes, reaction solution obtains the target product shown in lower formula I through aftertreatment; Described dipyridyl twain-aldehyde compound compound is 1:2.5～8 with the amount of substance ratio of propane dinitrile; Wherein R
1for H, CH
3or C
2h
5, R
2for H, CH
3or C
2h
5;
Described aftertreatment is specially: reaction solution adds water and mixes, and filters, and filter residue is through washing, dry, organic solvent recrystallization and get final product;
?；
Recrystallization organic solvent used is dimethyl formamide.
2. as claimed in claim 12, the synthetic method of 2'-(2,2'-dipyridyl-4,4'-bis-methynes) two propane dinitrile and substituent thereof, it is characterized in that, described dipyridyl twain-aldehyde compound compound reacts 4h than 1:5 by amount of substance with propane dinitrile under 80 DEG C of conditions.
3. as claimed in claim 12, the synthetic method of 2'-(2,2'-dipyridyl-4,4'-bis-methynes) two propane dinitrile and substituent thereof, is characterized in that, in aftertreatment the addition of water be reaction solution volume 2-5 doubly; Filter residue washs with the aqueous ethanolic solution of volumetric concentration 10-50%.
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| CN106000386B (en) * | 2016-05-31 | 2018-08-14 | 河南省商业科学研究所有限责任公司 | A kind of catalyst and the method using catalyst preparation 2,2 '-bipyridyl-the 4,4 '-diacrylate |
| CN105906555B (en) * | 2016-05-31 | 2018-04-24 | 河南省商业科学研究所有限责任公司 | The method that one kind prepares 2,2 '-bipyridyl -4,4 '-diacrylate |
| CN108727147A (en) * | 2018-05-14 | 2018-11-02 | 南京林业大学 | A kind of aldehyde Knoevenagel condensation reaction methods under the conditions of no catalyst or solvent |
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