CN105330566A - Synthetic method of dicyano compound - Google Patents
Synthetic method of dicyano compound Download PDFInfo
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- CN105330566A CN105330566A CN201510718528.7A CN201510718528A CN105330566A CN 105330566 A CN105330566 A CN 105330566A CN 201510718528 A CN201510718528 A CN 201510718528A CN 105330566 A CN105330566 A CN 105330566A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/16—Preparation of carboxylic acid nitriles by reaction of cyanides with lactones or compounds containing hydroxy groups or etherified or esterified hydroxy groups
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Abstract
The invention relates to a synthetic method of a dicyano compound shown in the following formula (III). The method comprises the steps that a compound shown in the following formula (I) and a compound shown in the following formula (II) react in an organic solvent under the effects of a catalyst, an oxidizing agent, a reaction promoter and an activator; after the reaction is over, aftertreatment is conducted, and then the compound shown in the following formula (III) is obtained, wherein R1 refers to C1-C6 alkyl, and R2 refers to phenyl or benzyl. According to the technical scheme, a proper substrate and cyaniding agent as well as the catalyst, the oxidizing agent, the reaction promoter and the activator are adopted, and the organic solvent is selected properly, so that conversion of materials is promoted efficiently, and a high-yield reaction effect is achieved; moreover, reaction conditions are mild, and the method has a broad prospect and scientific research value in industrial application.
Description
Technical field
The present invention relates to a kind of synthetic method of dicyano compound, belong to organic chemical synthesis field.
Background technology
In organic chemistry, cyano compound can be widely used in the building process of bioactive molecules, is also the important synthetic intermediate in organic synthesis simultaneously.
In cyano compound, dicyano compounds causes the concern of numerous scientific research personnel, this is such as, owing to comprising two cyano group in its structure thus being convenient to follow-up functionalized, can react formation third dithio acid amides further, or cyclisation, alpha-carbon alkylation or photoinduction rearrangement etc. occur.
Up to the present, about the synthetic method of dicyano compound has report more in prior art, such as:
FrankStansfiled etc. (" ReactionsofS-AIkyl-NN-disubstitutedThioamideSalts.Part3. ThiocarbamoylCyanideDerivatives ", J.Chem.Soc., PerkinTrans.1,1979,2708 – 2710) report a kind of method preparing dialkyl amido malononitrile derivative with S-alkyl-propane dinitrile class raw material, its reaction formula is as follows:
AlbertPadwa etc. (" SyntheticApplicationofCyanoaminosilanesasAzomethineYlide Equivalents ", J.Org.Chem., 1985,50,4006-4014) report a kind of novel method by silicane Material synthesis propane dinitrile analog derivative, its reaction formula is as follows:
As mentioned above, the multiple synthetic method of cyano group substitutional amine-group compound is disclosed in prior art.But the step that these methods existing often have reaction yield that is tediously long, that have reaction conditions that is not high enough, that have is comparatively harsh, and these problems seriously govern application in the industrial production.
Therefore, for the synthetic method of dicyano compound, still there is the necessity proceeding to study, this is the power place that is accomplished of the present invention just also.
Summary of the invention
In order to overcome above-mentioned pointed many defects and the novel method for synthesizing seeking dicyano compound, present inventor has performed deep research and exploration, after having paid enough creative works, thus completing the present invention.
It should be noted that the applicant have submitted another section patent application on the same day, present patent application is the further improvement to another section patent application.
Specifically, technical scheme of the present invention and content relate to the synthetic method of dicyano compound shown in a kind of following formula (III), described method comprises: in organic solvent, under the existence of catalyzer, oxygenant, reaction promoter and activator, under (I) compound and following formula (II) compound react, after reaction terminates, through aftertreatment, thus obtain described formula (III) compound
Wherein, R
1for C
1-C
6alkyl;
R
2for phenyl or benzyl.
In described synthetic method of the present invention, described C
1-C
6the implication of alkyl refers to the straight or branched alkyl with 1-6 carbon atom, such as can be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl or n-hexyl etc. in non-limiting manner.
In described synthetic method of the present invention, described catalyzer is ferric acetyl acetonade (Fe (acac)
3), any one in ferrocene, Aminoferrocene or cyclooctatetraene iron tricarbonyl, most preferably be Aminoferrocene.
In described synthetic method of the present invention, described oxygenant is iodobenzene diacetate (PhI (OAc)
2), DDQ (DDQ), tertbutyl peroxide (TBHP), ammonium persulphate or two (trifluoroacetic acid) iodobenzene (PhI (TFA)
2) in any one, most preferably be PhI (TFA)
2.
In described synthetic method of the present invention, described reaction promoter is the mixture of tetramethyl ethylene ketone borine and triethanolamine borate, and wherein, the mol ratio of tetramethyl ethylene ketone borine and triethanolamine borate is 1:1-2, such as, can be 1:1,1:1.5 or 1:2.
In described synthetic method of the present invention, described activator is ten dicarbapentaborane three ruthenium (Ru
3(CO)
12).
In described synthetic method of the present invention, described organic solvent is the DMF (DMF) of volume ratio 1:2 and the mixture of Macrogol 200 (PEG-200).
Wherein, the consumption of described organic solvent strict restriction, and those skilled in the art can carry out suitable selection according to practical situation and determine, such as its consumption size is carried out and aftertreatment to facilitate reaction, is no longer described in detail at this.
In described synthetic method of the present invention, the mol ratio of described formula (I) compound and formula (II) compound is 1:2.5-3.5, such as, can be 1:2.5,1:3 or 1:3.5.
In described synthetic method of the present invention, the mol ratio of described formula (I) compound and catalyzer is 1:0.1-0.16, such as, can be 1:0.1,1:0.13 or 1:0.16.
In described synthetic method of the present invention, the mol ratio of described formula (I) compound and oxygenant is 1:1-2, such as, can be 1:1,1:1.5 or 1:2.
In described synthetic method of the present invention, the mol ratio of described formula (I) compound and reaction promoter is 1:0.12-0.2, namely the mole dosage of described formula (I) compound is 1:0.12-0.2 with forming the tetramethyl ethylene ketone borine of reaction promoter with the ratio of total mole dosage of triethanolamine borate, such as, can be 1:0.12,1:0.14,1:0.16,1:0.18 or 1:0.2.
In described synthetic method of the present invention, the mol ratio of described formula (I) compound and activator is 1:0.06-0.1, such as, can be 1:0.06,1:0.08 or 1:0.1.
In described synthetic method of the present invention, temperature of reaction is 50-70 DEG C, such as, can be 50 DEG C, 60 DEG C or 70 DEG C.
In described synthetic method of the present invention, the reaction times is 4-7 hour, such as, can be 4 hours, 5 hours, 6 hours or 7 hours.
In described synthetic method of the present invention, aftertreatment after reaction terminates is specific as follows: after reaction terminates, reaction system is chilled to room temperature naturally, and adjust ph is neutral, then filter, add saturated aqueous common salt in filtrate fully to wash, use ethyl acetate oscillation extraction 2-3 time again, merge organic phase, anhydrous magnesium sulfate drying, vacuum concentration, residue is crossed 300-400 order silica gel column chromatography and is separated, with the ethyl acetate of equal-volume ratio and chloroform mixture for elutriant, thus obtain described formula (III) compound.
In sum, the invention provides a kind of synthetic method of dicyano compound, this technical scheme adopts suitable substrate, cyanidization agent and catalyzer, oxygenant, reaction promoter and activator, and pass through the suitable selection of organic solvent, thus efficiently facilitate the conversion of material, show the reaction effect of high yield, and reaction conditions is gentle, industrial application has broad prospects and scientific research value.
Embodiment
Below by specific embodiment, the present invention is described in detail; but the purposes of these exemplary embodiments and object are only used for exemplifying the present invention; not any type of any restriction is formed to real protection scope of the present invention, more non-protection scope of the present invention is confined to this.
Embodiment 1
Under room temperature, (be the DMF (N of volume ratio 1:2 to appropriate organic solvent, dinethylformamide) with the mixture of Macrogol 200 (PEG-200)) in, add 100mmol above formula (I) compound, 300mmol above formula (II) compound, 13mmol catalyzer Aminoferrocene, 150mmol oxygenant PhI (TFA)
2, 6mmol activator Ru
3(CO)
12with 15mmol reaction promoter (mixture for 6mmol tetramethyl ethylene ketone borine and 9mmol triethanolamine borate), be then warming up to 60 DEG C, and stirring reaction 5 hours at such a temperature;
After reaction terminates, reaction system is chilled to room temperature naturally, and adjust ph is neutral, then filter, add saturated aqueous common salt in filtrate fully to wash, then use ethyl acetate oscillation extraction 2-3 time, merge organic phase, anhydrous magnesium sulfate drying, vacuum concentration, residue is crossed 300-400 order silica gel column chromatography and is separated, with the ethyl acetate of equal-volume ratio and chloroform mixture for elutriant, thus obtaining above formula (III) compound, productive rate is 92.8%.
1HNMR(CDCl
3,400MHz):δ7.38-7.27(m,2H),7.06(t,J＝7.4Hz,1H),7.01-6.91(m,2H),5.37(s,1H),3.03(s,3H)。
Embodiment 2
Under room temperature, (be the DMF (N of volume ratio 1:2 to appropriate organic solvent, dinethylformamide) with the mixture of Macrogol 200 (PEG-200)) in, add 100mmol above formula (I) compound, 300mmol above formula (II) compound, 13mmol catalyzer Aminoferrocene, 150mmol oxygenant PhI (TFA)
2, 8mmol activator Ru
3(CO)
12with 15mmol reaction promoter (mixture for 6mmol tetramethyl ethylene ketone borine and 9mmol triethanolamine borate), be then warming up to 60 DEG C, and stirring reaction 5 hours at such a temperature;
After reaction terminates, reaction system is chilled to room temperature naturally, and adjust ph is neutral, then filter, add saturated aqueous common salt in filtrate fully to wash, then use ethyl acetate oscillation extraction 2-3 time, merge organic phase, anhydrous magnesium sulfate drying, vacuum concentration, residue is crossed 300-400 order silica gel column chromatography and is separated, with the ethyl acetate of equal-volume ratio and chloroform mixture for elutriant, thus obtaining above formula (III) compound, productive rate is 93.2%.
1HNMR(CDCl
3,400MHz):δ7.33-7.17(m,5H),4.49(s,1H),3.56(s,2H),2.47(s,3H)。
Embodiment 3
Reaction formula is with embodiment 1, and concrete reaction process is as follows:
Under room temperature, (be the DMF (N of volume ratio 1:2 to appropriate organic solvent, dinethylformamide) with the mixture of Macrogol 200 (PEG-200)) in, add 100mmol above formula (I) compound, 350mmol above formula (II) compound, 10mmol catalyzer Aminoferrocene, 200mmol oxygenant PhI (TFA)
2, 6mmol activator Ru
3(CO)
12with 12mmol reaction promoter (mixture for 6mmol tetramethyl ethylene ketone borine and 6mmol triethanolamine borate), be then warming up to 50 DEG C, and stirring reaction 7 hours at such a temperature;
After reaction terminates, reaction system is chilled to room temperature naturally, and adjust ph is neutral, then filter, add saturated aqueous common salt in filtrate fully to wash, then use ethyl acetate oscillation extraction 2-3 time, merge organic phase, anhydrous magnesium sulfate drying, vacuum concentration, residue is crossed 300-400 order silica gel column chromatography and is separated, with the ethyl acetate of equal-volume ratio and chloroform mixture for elutriant, thus obtaining above formula (III) compound, productive rate is 92.9%.
Characterization data is with embodiment 1.
Embodiment 4
Reaction formula is with embodiment 2, and concrete reaction process is as follows:
Under room temperature, (be the DMF (N of volume ratio 1:2 to appropriate organic solvent, dinethylformamide) with the mixture of Macrogol 200 (PEG-200)) in, add 100mmol above formula (I) compound, 250mmol above formula (II) compound, 16mmol catalyzer Aminoferrocene, 100mmol oxygenant PhI (TFA)
2, 10mmol activator Ru
3(CO)
12with 20mmol reaction promoter (mixture for 6.5mmol tetramethyl ethylene ketone borine and 13.5mmol triethanolamine borate), be then warming up to 70 DEG C, and stirring reaction 4 hours at such a temperature;
After reaction terminates, reaction system is chilled to room temperature naturally, and adjust ph is neutral, then filter, add saturated aqueous common salt in filtrate fully to wash, then use ethyl acetate oscillation extraction 2-3 time, merge organic phase, anhydrous magnesium sulfate drying, vacuum concentration, residue is crossed 300-400 order silica gel column chromatography and is separated, with the ethyl acetate of equal-volume ratio and chloroform mixture for elutriant, thus obtaining above formula (III) compound, productive rate is 92.7%.
Characterization data is with embodiment 2.
From above-described embodiment 1-4, according to synthetic method of the present invention, object product can be obtained with high yield.
Embodiment 5-16
Embodiment 5-8: replace with except ferric acetyl acetonade except by catalyzer, other operation is all constant, thus repeats to implement embodiment 1-4, obtains embodiment 5-8 in turn.
Embodiment 9-12: replace with except ferrocene except by catalyzer, other operation is all constant, thus repeats to implement embodiment 1-4, obtains embodiment 9-12 in turn.
Embodiment 13-16: except being replaced with by catalyzer except cyclooctatetraene iron tricarbonyl, other operation is all constant, thus repeats to implement embodiment 1-4, obtains embodiment 13-16 in turn.
The results are shown in following table 1.
Table 1
As can be seen here, in all catalyzer, Aminoferrocene has best catalytic effect, even if ferrocene, its productive rate also has significant reduction.Ferric acetyl acetonade or cyclooctatetraene iron tricarbonyl then have and reduce more significantly.
Embodiment 17-32
Embodiment 17-20: except oxygenant is replaced with PhI (OAc)
2outward, other operation is all constant, thus repeats to implement embodiment 1-4, obtains embodiment 17-20 in turn.
Embodiment 21-24: replace with except DDQ except by oxygenant, other operation is all constant, thus repeats to implement embodiment 1-4, obtains embodiment 21-24 in turn.
Embodiment 25-28: replace with except TBHP except by oxygenant, other operation is all constant, thus repeats to implement embodiment 1-4, obtains embodiment 25-28 in turn.
Embodiment 29-32: replace with except ammonium persulphate except by oxygenant, other operation is all constant, thus repeats to implement embodiment 1-4, obtains embodiment 29-32 in turn.
The results are shown in following table 2.
Table 2
As can be seen here, in all oxygenants, PhI (TFA)
2there is best effect, even if with its very similar PhI (OAc)
2, its productive rate also has the reduction of 6-7 percentage point.Other oxygenant then reduces more obvious.
Embodiment 33-44
Embodiment 33-36: except reaction promoter being replaced with one-component tetramethyl ethylene ketone borine that consumption is the total consumption sum of original two kinds of components, other operation is all constant, thus repeats to implement embodiment 1-4, obtains embodiment 33-36 in turn.
Embodiment 37-40: except reaction promoter being replaced with one-component triethanolamine borate that consumption is the total consumption sum of original two kinds of components, other operation is all constant, thus repeats to implement embodiment 1-4, obtains embodiment 37-40 in turn.
Embodiment 41-44: except being omitted by reaction promoter, other operation is all constant, thus repeats to implement embodiment 1-4, obtains embodiment 41-44 in turn.
The results are shown in following table 3.
Table 3
As can be seen here, when using one-component as reaction promoter, productive rate all has significant reduction; And when not using any auxiliary agent, its productive rate is with only using the productive rate of triethanolamine borate to be more or less the same, this proves that triethanolamine borate does not play facilitation effect.Also prove to only have to use this two kinds of components simultaneously, could synergy be produced, obtain good yield of the present invention.
Embodiment 45-48
Except being omitted by the activator in embodiment 1-4, other operation is all constant, thus repeats to implement embodiment 1-4, obtains embodiment 45-52 in turn, the results are shown in following table 4.
Table 4
As can be seen here, when dispensing activator, products collection efficiency has and significantly reduces, and this proves the existence of activator, and significantly can improve the productive rate of product, this is unexpected.
Embodiment 49-56
Embodiment 49-52: except being replaced with by organic solvent except single solvent DMF, other operation is all constant, thus repeats to implement embodiment 1-4, obtains embodiment 49-52 in turn.
Embodiment 53-56: except being replaced with by organic solvent except single solvent PEG-200, other operation is all constant, thus repeats to implement embodiment 1-4, obtains embodiment 53-56 in turn.
The results are shown in following table 5.
Table 5
As can be seen here, when using single solvent component, the equal decrease to some degree of productive rate, reduces more obvious when being especially used alone PEG-200, when this proves the mixture when both uses, beyond thoughtly achieves best solvent effect.
The invention provides a kind of synthetic method of dicyano compound, this technical scheme adopts suitable substrate, cyanidization agent and catalyzer, oxygenant, reaction promoter and activator, and pass through the suitable selection of organic solvent, thus efficiently facilitate the conversion of material, show the reaction effect of high yield, and reaction conditions is gentle, industrial application has broad prospects and scientific research value.
Should be appreciated that the purposes of these embodiments is only not intended to for illustration of the present invention limit the scope of the invention.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can make various change, amendment and/or modification to the present invention, and these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.
Claims (10)
1. the synthetic method of dicyano compound shown in a following formula (III), described method comprises: in organic solvent, under the existence of catalyzer, oxygenant, reaction promoter and activator, under (I) compound and following formula (II) compound react, after reaction terminates, through aftertreatment, thus obtain described formula (III) compound
Wherein, R
1for C
1-C
6alkyl;
R
2for phenyl or benzyl.
2. synthetic method as claimed in claim 1, is characterized in that: described catalyzer is ferric acetyl acetonade (Fe (acac)
3), any one in ferrocene, Aminoferrocene or cyclooctatetraene iron tricarbonyl, most preferably be Aminoferrocene.
3. synthetic method as claimed in claim 1 or 2, is characterized in that: described oxygenant is iodobenzene diacetate (PhI (OAc)
2), DDQ (DDQ), tertbutyl peroxide (TBHP), ammonium persulphate or two (trifluoroacetic acid) iodobenzene (PhI (TFA)
2) in any one, most preferably be PhI (TFA)
2.
4. the synthetic method as described in any one of claim 1-3, is characterized in that: described reaction promoter is the mixture of tetramethyl ethylene ketone borine and triethanolamine borate, and wherein, the mol ratio of tetramethyl ethylene ketone borine and triethanolamine borate is 1:1-2.
5. the synthetic method as described in any one of claim 1-4, is characterized in that: described activator is ten dicarbapentaborane three ruthenium (Ru
3(CO)
12).
6. the synthetic method as described in any one of claim 1-5, is characterized in that: the mol ratio of described formula (I) compound and formula (II) compound is 1:2.5-3.5.
7. the synthetic method as described in any one of claim 1-6, is characterized in that: the mol ratio of described formula (I) compound and catalyzer is 1:0.1-0.16.
8. the synthetic method as described in any one of claim 1-7, is characterized in that: the mol ratio of described formula (I) compound and oxygenant is 1:1-2.
9. the synthetic method as described in any one of claim 1-8, is characterized in that: the mol ratio of described formula (I) compound and reaction promoter is 1:0.12-0.2.
10. the synthetic method as described in any one of claim 1-9, is characterized in that: the mol ratio of described formula (I) compound and activator is 1:0.06-0.1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134338A (en) * | 2018-10-16 | 2019-01-04 | 求秋平 | Pyrrolidines tertiary amine is the alpha-aminonitriles compounds process for production thereof of substrate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070100149A1 (en) * | 2005-11-02 | 2007-05-03 | Palle Venkata Raghavendra A | Process for preparing letrozole |
| CN103288845A (en) * | 2013-05-24 | 2013-09-11 | 武汉工程大学 | Spiro-compound 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5] hendecane and synthetic method thereof |
-
2015
- 2015-10-29 CN CN201510718528.7A patent/CN105330566A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070100149A1 (en) * | 2005-11-02 | 2007-05-03 | Palle Venkata Raghavendra A | Process for preparing letrozole |
| CN103288845A (en) * | 2013-05-24 | 2013-09-11 | 武汉工程大学 | Spiro-compound 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5] hendecane and synthetic method thereof |
Non-Patent Citations (1)
| Title |
|---|
| CHAO YANG ET AL: "Copper-catalyzed dicyanation of N,N-disubstituted formamide", 《TETRAHEDRON LETTERS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134338A (en) * | 2018-10-16 | 2019-01-04 | 求秋平 | Pyrrolidines tertiary amine is the alpha-aminonitriles compounds process for production thereof of substrate |
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