CN113861069B - Preparation method of nitrile compound - Google Patents
Preparation method of nitrile compound Download PDFInfo
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- CN113861069B CN113861069B CN202111254803.6A CN202111254803A CN113861069B CN 113861069 B CN113861069 B CN 113861069B CN 202111254803 A CN202111254803 A CN 202111254803A CN 113861069 B CN113861069 B CN 113861069B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
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- 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
- C07D213/84—Nitriles
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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Abstract
The invention belongs to the technical field of organic synthesis, and in particular relates to a preparation method of a nitrile compound, which takes an aldoxime derivative as a raw material, adds DPPA and DBU, reacts in an organic solvent, and prepares the nitrile compound in one step, wherein the synthesis route is as follows:
wherein R is aryl, alkyl or alkenyl. The nitrile compound prepared by the method has the advantages of low-cost and easily-obtained raw materials, short synthetic route, simple reaction operation, short reaction time, high yield, easy post-treatment, small environmental pollution, objective economic and practical values, and wide application prospect in the field of medicine synthesis.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of a nitrile compound.
Background
Nitriles are a very important class of organic synthetic intermediates. As an important raw material and an intermediate commonly used in the production of fine chemicals, the nitrile compound has wide application in the fields of medicine, materials, agriculture, chemical industry and the like. In recent years, with rapid development of technology, nitrile compounds are more widely used in various fields. Therefore, research on a method for synthesizing nitrile compounds and development of variety diversity of nitrile compounds have become one of hot problems in the field of organic chemistry.
At present, a large number of methods for synthesizing nitrile compounds are reported, and the methods are mainly divided into: the method comprises the steps of preparing by a halohydrocarbon cyanide method, preparing by oxidative dehydrogenation of amine, preparing by C-H or C-C bond rupture of aromatic alkane, preparing by C=C bond rupture of aromatic alkene, preparing by C-C bond rupture of aromatic alkyne, preparing by C-O bond rupture of aromatic alcohol, preparing by C=O bond rupture of aromatic aldehyde ketone and amide, preparing by C=N bond rupture of aldoxime and the like. Among them, the preparation of nitrile compounds by cleavage of aldoxime c=n is an important direction, and dehydration is mainly used in the process of preparing nitrile c≡n from aldoxime c=n, and conventional dehydration agents include strong acidity (acetic anhydride, trifluoromethanesulfonic anhydride, phthalic anhydride, thionyl chloride, sulfonic acid, etc.), strong basicity (sodium hydroxide, potassium hydroxide, etc.), and metal compounds (pyridinium chlorochromate, scandium trifluoroacetate, etc.), however, the above methods have limitations such as the use of metal (heavy metal or transition metal) dehydration agents, severe reaction conditions (high temperature, anhydrous environment, long reaction time), limited substrate applicability, etc. Therefore, the exploration of a new method for synthesizing the nitrile compound is of great importance.
Disclosure of Invention
In order to solve the problems, the invention provides the preparation method of the nitrile compound, which has the advantages of low-cost and easily-obtained raw materials, short synthetic route, simple reaction operation, high reaction speed, easy post-treatment, high yield and small environmental pollution, is suitable for industrial production, and has objective economic and practical values.
The invention aims to provide a preparation method of a nitrile compound, which takes an aldoxime derivative as a raw material, adds DPPA and DBU, reacts in an organic solvent to prepare the nitrile compound in one step, and 1, the synthetic route is as follows:
wherein R is aryl, alkyl or alkenyl.
Preferably, the aryl is a benzene aromatic ring, pyridine, imidazole, thiophene, thiazole, pyrimidine or indole.
Preferably, the molar ratio of diphenyl azide phosphate DPPA, 1, 8-diazabicyclo undec-7-ene DBU and aldoxime derivative is 1.2:1.1:1.
Preferably, the organic solvent is one of acetonitrile, dichloromethane and chloroform.
Preferably, the reaction time is 0.5 to 2 hours.
Preferably, the temperature of the reaction is 25-80 ℃.
Preferably, the nitrile compound is prepared by the steps of: adding an organic solvent into a reaction bottle, sequentially adding an aldoxime derivative and 1, 8-diazabicyclo undec-7-ene DBU, uniformly stirring, slowly adding diphenyl azide phosphate DPPA, reacting at room temperature, concentrating under reduced pressure to obtain a nitrile compound crude product, and performing chromatographic separation.
Preferably, thin layer chromatography is used to detect whether the reaction is complete and the reaction is stopped after completion.
Preferably, the eluent for chromatographic separation is petroleum ether and ethyl acetate, and the volume ratio of petroleum ether to ethyl acetate is 2-10:1.
Compared with the prior art, the invention has the following beneficial effects:
the process has the advantages of cheap and easily obtained raw materials, short synthetic route, simple reaction operation, short reaction time, high yield, easy post-treatment, small environmental pollution, objective economic and practical values, and wide application prospect in the field of medicine synthesis.
Drawings
FIG. 1 is a synthetic route for the preparation of nitrile compounds according to the present invention;
FIG. 2 is a schematic diagram of a 2-nitronitrile compound prepared in example 2 of the present invention 1 H-NMR chart;
FIG. 3 is a schematic diagram of a 4-bromoxynil compound prepared according to example 3 of the present invention 1 H-NMR chart;
FIG. 4 is a photograph of a methyl 4-cyanobenzoate compound prepared in example 4 of the present invention 1 H-NMR chart;
FIG. 5 is a schematic diagram of a 4-propoxybenzonitrile compound prepared in example 5 of the present invention 1 H-NMR chart;
FIG. 6 is a preparation of example 6 of the present invention4-Butoxybenzonitrile compound (B) 1 H-NMR chart;
FIG. 7 is a schematic diagram of a 4-benzyloxybenzonitrile compound prepared in example 7 of the present invention 1 H-NMR chart;
FIG. 8 is a schematic diagram of a 2, 2-dimethoxybenzonitrile compound prepared in example 8 of the present invention 1 H-NMR chart;
FIG. 9 is a schematic representation of a 2-cyanopyridine compound prepared in accordance with example 9 of the present invention 1 H-NMR chart;
FIG. 10 is a drawing of (E) -cinnamonitrile compound prepared in example 10 of the invention 1 H-NMR chart;
FIG. 11 is a schematic diagram of a (E) -4-chlorocinnamonitrile compound prepared in example 11 of the invention 1 H-NMR chart;
FIG. 12 is a schematic diagram of a (E) -2-benzylideneceptanoid compound prepared in example 12 of the present invention 1 H-NMR chart;
FIG. 13 is a drawing of (E) -3- (furan-2-yl) acrylonitrile compound produced in example 13 of the present invention 1 H-NMR chart;
FIG. 14 is a single crystal structure diagram of (E) -3- (furan-2-yl) acrylonitrile compound produced in example 13 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that the technical terms used in the present invention are only for describing specific examples, and are not intended to limit the scope of the present invention, and various raw materials, reagents, instruments and equipment used in the following examples of the present invention are commercially available or prepared by the existing method, wherein DPPA is diphenyl azide phosphate and DBU is 1, 8-diazabicyclo undec-7-ene unless otherwise specifically indicated.
Example 1
A preparation method of nitrile compound takes aldoxime derivative as raw material, DPPA and DBU are added, and the nitrile compound is prepared by reacting in organic solvent, and the synthetic route is as follows:
wherein R is aryl, alkyl, alkenyl or pyridine. The synthetic route diagram of the nitrile compound is shown in figure 1, and a possible reaction mechanism is as follows:
example 2 2 Synthesis of Nitrophonitrile
498mg (3.0 mmol) of 2-nitrobenzaldehyde oxime and 548mg (3.6 mmol) of DBU are added into a reaction bottle of acetonitrile (4 mL), after being stirred uniformly, 908mg (3.3 mmol) of DPPA is slowly added, the reaction is carried out at room temperature of 25 ℃ for 30min, after TLC monitoring, the reaction is carried out, the pressure is reduced, the obtained crude product is separated by column chromatography (eluent V) Petroleum ether :V Acetic acid ethyl ester =10:1) to give a tan solid in 68.5% yield. 1 H NMR(400MHz,DMSO-d 6 ) Delta 8.39 (d, j=8.8 hz,2 h), 8.19 (d, j=8.8 hz,2 h). See in particular figure 2.
Example 34 Synthesis of bromoxynil
597mg (3.0 mmol) of 4-bromobenzaldehyde oxime and 548mg (3.6 mmol) of DBU are added into a reaction bottle of acetonitrile (4 mL), after being stirred uniformly, 908mg (3.3 mmol) of DPPA is slowly added, the reaction is carried out for 1h at room temperature of 25 ℃, after TLC monitoring is finished, the reaction solution is concentrated under reduced pressure, and the obtained crude product is separated by column chromatography (eluent V) Petroleum ether :V Acetic acid ethyl ester =10:1) to give a white solid in 71.0% yield. 1 H NMR(400MHz,CDCl 3 ) Delta 7.66 (d, j=7.6 hz,2 h), 7.55 (d, j=7.6 hz,2 h). See in particular figure 3.
Example 44 Synthesis of methyl cyanobenzoate
537mg (3.0 mmol) of methyl 4- (hydroxyimino) methylbenzoate and 548mg (3.6 mmol) of DBU are added into a reaction bottle of acetonitrile (4 mL), after being stirred uniformly, 908mg (3.3 mmol) of DPPA is slowly added, the mixture is reacted for 2h at room temperature of 25 ℃, after TLC monitoring the reaction, the obtained crude product is concentrated under reduced pressure, and the obtained crude product is separated by column chromatography (eluent V) Petroleum ether :V Acetic acid ethyl ester =10:1) to give a pale yellow solid in 66.2% yield. 1 H NMR(400MHz,CDCl 3 ) Delta 8.16 (d, j=7.5 hz, 2H), 7.77 (d, j=7.5 hz, 2H), 3.98 (s, 3H). See in particular figure 4.
Example 54 Synthesis of propoxybenzonitrile
537mg (3.0 mmol) of 4-propoxybenzaldehyde oxime and 548mg (3.6 mmol) of DBU are added into a reaction bottle of chloroform (4 mL), after being stirred uniformly, 908mg (3.3 mmol) of DPPA is slowly added, the reaction is carried out at room temperature of 25 ℃ for 30min, after TLC monitoring, the reaction is finished, the obtained crude product is concentrated under reduced pressure, and the crude product is separated by column chromatography (eluent V) Petroleum ether :V Acetic acid ethyl ester =10:1) to give a pale yellow liquid, yield 80.7%. 1 H NMR(400MHz,DMSO-d 6 ) Delta 7.75 (dd, j=9.2, 2.2hz, 2H), 7.12-7.06 (m, 2H), 4.01 (t, j=6.5 hz, 2H), 1.78-1.66 (m, 2H), 0.97 (t, j=7.4 hz, 3H). See in particular figure 5.
Example 64 Synthesis of Butoxybenzonitrile
579mg (3.0 mmol) of 4-butoxybenzaldoxime and 548mg (3.6 mmol) of DBU are added into a reaction bottle of methylene dichloride (4 mL), after stirring uniformly, 908mg (3.3 mmol) of DPPA is slowly added, the reaction is carried out at room temperature of 25 ℃ for 45min, after TLC monitoring, the reaction is finished, the solution is concentrated under reduced pressure, and the obtained crude product is separated by column chromatography (eluent V) Petroleum ether :V Acetic acid ethyl ester =10:1) to give a pale yellow liquid, yield 78.3%. 1 H NMR(400MHz,DMSO-d 6 ) Delta 7.81-7.68 (m, 2H), 7.76-7.70 (m, 2H), 7.14-7.02 (m, 2H), 7.10-7.04 (m, 2H), 4.03 (t, J=6.5 Hz, 2H), 1.69 (dt, J=14.4, 6.5Hz, 2H), 1.47-1.34 (m, 2H), 0.91 (t, J=7.4 Hz, 3H). See in particular figure 6.
Example 7 4 Synthesis of Benzyloxybenzonitrile
681mg (3.0 mmol) of 4-benzyloxy-benzaldehyde oxime and 548mg (3.6 mmol) of DBU are added into a reaction bottle of acetonitrile (4 mL), after being stirred uniformly, 908mg (3.3 mmol) of DPPA is slowly added, the reaction is carried out for 30min at 50 ℃, after TLC monitoring, the reaction is finished, the pressure is reduced, and the obtained crude product is separated by column chromatography (eluent V) Petroleum ether :V Acetic acid ethyl ester =10:1) to give a white solid in 82.2% yield. 1 H NMR(400MHz,DMSO-d 6 ) Delta 7.83-7.75 (m, 2H), 7.49-7.44 (m, 2H), 7.44-7.38 (m, 2H), 7.37 (dd, J=6.4, 2.0Hz, 1H), 7.23-7.15 (m, 2H), 5.21 (s, 2H). See in particular fig. 7.
EXAMPLE 8 Synthesis of 2, 4-Dimethoxybenzonitrile
543mg (3.0 mmol) of 2, 4-dimethoxy benzaldehyde oxime and 548mg (3.6 mmol) of DBU are added into a reaction bottle of acetonitrile (4 mL), after being stirred uniformly, 908mg (3.3 mmol) of DPPA is slowly added, the reaction is carried out for 30min at room temperature of 25 ℃, after TLC monitoring, the reaction is finished, the decompression concentration is carried out, and the obtained crude product is separated by column chromatography (eluent V) Petroleum ether :V Acetic acid ethyl ester =10:1) to give a pale yellow liquid in 81.4% yield. 1H NMR (400 MHz, DMSO-d) 6 ) Delta 7.50 (d, j=8.4 hz, 1H), 6.54 (d, j=8.5 hz, 1H), 6.48 (s, 1H), 3.93 (s, 3H), 3.88 (s, 3H). See in particular figure 8.
EXAMPLE 9 2 Synthesis of cyanopyridine
366mg (3.0 mmol) of pyridine-2-formaldoxime and 548mg (3.6 mmol) of DBU are added into a reaction bottle of acetonitrile (4 mL), after being stirred uniformly, 908mg (3.3 mmol) of DPPA is slowly added, the mixture is reacted for 1.5min at 80 ℃, after TLC monitoring the reaction is finished, the obtained crude product is concentrated under reduced pressure, and the obtained crude product is separated by column chromatography (eluent V) Petroleum ether :V Acetic acid ethyl ester =5:1) to give a reddish brown liquid in 64.2% yield. 1 HNMR(400MHz,DMSO-d 6 ) Delta 4.87 (s, 2H), 4.54 (s, 2H), 4.38 (s, 5H). See in particular figure 9.
EXAMPLE 10 Synthesis of (E) -cinnamonitrile
441mg (3.0 mmol) of cinnamaldehyde oxime and 548mg (3.6 mmol) of DBU are added into a reaction bottle of acetonitrile (4 mL), after being stirred uniformly, 908mg (3.3 mmol) of DPPA is slowly added, the reaction is carried out for 1h at 50 ℃, after the TLC monitoring is finished, the pressure is reduced, and the obtained crude product is separated by column chromatography (eluent V) Petroleum ether :V Acetic acid ethyl ester =10:1) to give a pale yellow liquid with a yield of 66.4%. 1 H NMR(400MHz,DMSO-d 6 ) Delta 7.7-7.62 (m, 3H), 7.50-7.41 (m, 3H), 6.49 (d, j=16.8 hz, 1H). See in particular fig. 10.
EXAMPLE 11 Synthesis of (E) -4-chlorocinnamonitrile
543mg of3.0 mmol) of 4-chlorocinnamaldehyde oxime and 548mg (3.6 mmol) of DBU are added into a reaction bottle of acetonitrile (4 mL), 908mg (3.3 mmol) of DPPA is slowly added after being stirred uniformly, the reaction is carried out for 1.5h at the temperature of 60 ℃, after the TLC monitoring is finished, the pressure is reduced, and the obtained crude product is separated by column chromatography (eluent V) Petroleum ether :V Acetic acid ethyl ester =10:1) to give a pale yellow liquid, yield 62.8%. 1 H NMR(400MHz,DMSO-d 6 ) Delta 7.40 (s, 1H), 7.29 (t, j=3.8 hz, 4H), 5.89 (d, j=16.7 hz, 1H). See in particular figure 11.
EXAMPLE 12 Synthesis of (E) -2-benzylidene heptanenitrile
651mg (3.0 mmol) of alpha-amyl cinnamaldehyde oxime and 548mg (3.6 mmol) of DBU are added into acetonitrile (4 mL), after being stirred uniformly, 908mg (3.3 mmol) of DPPA is slowly added, the reaction is carried out for 1.5h at 50 ℃, after the TLC monitoring reaction is finished, the pressure is reduced, the obtained crude product is separated by column chromatography (eluent V) Petroleum ether :V Acetic acid ethyl ester =5:1) to give a colorless liquid with a yield of 58.4%. 1 H NMR(400MHz,DMSO-d 6 ) Delta 7.49-7.38 (m, 6H), 2.46 (t, J=7.7 Hz, 2H), 1.61-1.52 (m, 2H), 1.31-1.24 (m, 4H), 0.84 (t, J=6.8 Hz, 3H). See in particular fig. 12.
EXAMPLE 13 Synthesis of (E) -3- (furan-2-yl) acrylonitrile
411mg (3.0 mmol) of 3- (2-furyl) acrolein oxime, 548mg (3.6 mmol) of DBU are added into acetonitrile (4 mL), after stirring uniformly, 908mg (3.3 mmol) of DPPA are slowly added, the reaction is carried out at 50 ℃ for 2h, after TLC monitoring, the reaction is finished, the pressure is reduced, the crude product is concentrated under reduced pressure, and the crude product is separated by column chromatography (eluent V) Petroleum ether :V Acetic acid ethyl ester =5:1) to give a tan solid in 63.6% yield. 1 HNMR(400MHz,CDCl 3 )δ:7.52(s,1H),7.14(d,J＝16.3Hz,1H),6.65(s,1H),6.53(s,1H),5.79(d,J＝16.2Hz,1H). See in particular fig. 13.
Dissolving (E) -3- (furan-2-yl) acrylonitrile in mixed solvent of dichloromethane and methanol, volatilizing naturally at room temperature for about 5 days to obtain colorless crystals, selecting 0.15X10.12X10.08 mm 3 Is subjected to single crystal of (2), and MoK alpha rays which are obtained by adopting graphite monochromatization are collected through an APEX II CCD type X-ray single crystal diffractometer
Diffraction points are collected by using an omega-2 theta scanning mode, and the crystal structure is directly solved by adopting a SHELXL-97 program in data processing.
The crystal structure of the product (E) -3- (furan-2-yl) acrylonitrile (1 q) belongs to monoclinic system, as shown in Table 1, P2 1 N space group, unit cell parameters
ɑ＝γ＝90.00°，β＝102.59(4)°，/>
Z＝4，T＝170.0K，Dc＝1.314g/cm3，μ＝0.09mm -1 F (000) =248. The steric structure of the product 1q can be seen by X-ray single crystal diffraction, see in particular FIG. 14.
TABLE 1 Crystal data and structure refinement of the product (E) -3- (furan-2-yl) acrylonitrile (1 q)
It should be noted that, when numerical ranges are referred to in the present invention, it should be understood that two endpoints of each numerical range and any numerical value between the two endpoints are optional, and because the adopted step method is the same as the embodiment, in order to prevent redundancy, the present invention describes a preferred embodiment. While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (4)
1. A preparation method of nitrile compound is characterized in that an aldoxime derivative is taken as a raw material, diphenyl azide phosphate and 1, 8-diazabicyclo undec-7-ene are added for reaction in an organic solvent, and the nitrile compound is prepared in one step, and the synthetic route is as follows:
the nitrile compound is 2-nitronitrile, 4-bromoxynil, methyl 4-cyanobenzoate, 4-propoxybenzonitrile, 4-butoxybenzonitrile, 4-benzyloxy-benzonitrile, 2, 4-dimethoxy-benzonitrile, 2-cyanopyridine, (E) -cinnamonitrile, (E) -4-chlorocinnamonitrile, (E) -2-benzylidene-heptonitrile and (E) -3- (furan-2-yl) acrylonitrile;
the molar ratio of the diphenyl azide phosphate to the 1, 8-diazabicyclo undec-7-ene to the aldoxime derivative is 1.2:1.1:1;
the reaction time is 0.5-2h;
the temperature of the reaction is 25-80 ℃;
the organic solvent is one of acetonitrile, dichloromethane and chloroform.
2. The method for producing a nitrile compound according to claim 1, wherein the nitrile compound is produced by: adding an organic solvent into a reaction bottle, sequentially adding an aldoxime derivative and diphenyl azide phosphate, uniformly stirring, slowly adding 1, 8-diazabicyclo undec-7-ene, performing a reaction at room temperature, concentrating under reduced pressure to obtain a nitrile compound crude product, and performing chromatographic separation.
3. The method for producing nitrile compounds according to claim 2, wherein the completion of the reaction is detected by thin layer chromatography, and the reaction is stopped after the completion of the reaction.
4. The method for producing nitrile compounds according to claim 3, wherein the eluent for chromatographic separation is petroleum ether and ethyl acetate in a volume ratio of 2-10:1.
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