CN114539097B - Polysubstituted alkenyl cyanide and synthetic method thereof - Google Patents
Polysubstituted alkenyl cyanide and synthetic method thereof Download PDFInfo
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- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/34—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring with cyano groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by unsaturated carbon chains
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- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/35—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms, or by nitro or nitroso groups
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Abstract
The invention discloses a polysubstituted alkenyl cyanide and a synthesis method thereof. Under the nitrogen or inert atmosphere, the sulfonium salt which is easy to prepare, has structural diversity and multiple reaction centers is used as a raw material, the ketene cyanide is used as a synthon, and the polysubstituted alkenyl cyanide is synthesized under the alkaline condition. Compared with the reported method for synthesizing the alkenyl cyano compound, the method has the advantages of cheap and easily obtained raw materials, simple and convenient operation, mild synthesis reaction conditions, good stereoselectivity of products, high reaction efficiency and diversity of functional groups.
Description
Technical Field
The invention belongs to the technical field of chemical organic synthesis, and particularly relates to polysubstituted alkenyl cyanide and a synthesis method thereof.
Background
Polysubstituted alkenyl cyanides are ubiquitous in many natural products, pharmaceuticals and agrochemicals, molecular materials, and can also serve as universal precursors for a range of amine, amide, aldehyde, ketone, and carboxylic acid functional groups. The synthesis of polysubstituted alkenyl cyanides has received constant attention from chemists due to their remarkable biological activity, unique plasticity, broad use.
At present, few methods are used for preparing alkenyl cyanide, and 4 synthetic documents are reported. The preparation method comprises the following steps: 1) Reaction of allyl halides with potassium cyanide (J.Am.chem.Soc.1982, 104, 1560-1568); 2) Conjugate addition of alkynonitrile to organic grignard reagents (org. Lett.2002,4, 659-661); 3) Nickel and cobalt co-catalyzed alkyne hydrocyanation (ACS Catal.2019,9, 3360-3365); 4) Copper trifluoroacetate catalyzed condensation of pyridine-directed olefins with α -iminonitriles (Synlett 2019,30, 203-206). However, the above method is often limited in application to synthesis to a certain extent because the reaction conditions are harsh, the raw material stability is poor, long-term storage is difficult, and the substrate application range is narrow.
In view of the fact that the synthesis method of the polysubstituted alkenyl cyanide is few, the polysubstituted alkenyl sulfonium salt which is easy to prepare and has structure diversity and multiple reaction centers is used as a raw material to carry out the cyaniding reaction, and a series of polysubstituted alkenyl cyano compounds with different structures are synthesized.
Disclosure of Invention
The invention aims to provide a method for synthesizing a polysubstituted alkenyl cyano compound, which has the advantages of easily obtained raw materials, mild reaction conditions, wide substrate application range and simplicity and convenience.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a polysubstituted alkenyl cyanide having the following molecular structure:
R 1 selected from methyl, ethyl or aryl; r is 2 Selected from methyl, ethyl, aryl, naphthalene ring, furan ring, thiophene ring or pyridine ring; r is 3 Selected from hydrogen, methyl, ethyl, benzyl, aryl, naphthalene ring, furan ring, thiophene ring or pyridine ring; wherein the aryl is selected from phenyl, the phenyl ring has substituent groups, the substituent groups on the phenyl ring are selected from 1-5 of methyl, methoxy, fluorine, chlorine, bromine, iodine, trifluoromethyl and nitro, and the number of the substituent groups is 1-5.
The synthesis method of the polysubstituted alkenyl cyanide takes polysubstituted alkenyl sulfonium salt II which is easy to prepare and has structural diversity and multiple reaction centers as a starting material, palladium (Pd) salt as a catalyst and an organic phosphorus compound as a ligand, and reacts with cuprous cyanide in a common solvent under the alkaline condition to generate polysubstituted alkenyl cyanide I;
the molecular structural formula of the polysubstituted alkenyl sulfonium salt II is as follows:
R 1 selected from methyl, ethyl or aryl; r 2 Selected from methyl, ethyl, aryl, naphthalene ring, furan ring, thiophene ring or pyridine ring; r 3 Selected from hydrogen, methyl, ethyl, benzyl, aryl, naphthalene ring, furan ring, thiophene ring or pyridine ring; wherein, the aryl is selected from phenyl and the substituent group on the benzene ring, the substituent group on the benzene ring is selected from 1 to 5 of methyl, methoxy, fluorine, chlorine, bromine, iodine, trifluoromethyl and nitro, and the number of the substituent groups is 1 to 5; n is an integer from 0 to 3;
the reaction formula of the synthetic route is as follows:
further, in the above technical scheme, the molar ratio of the polysubstituted alkenylsulfonium salt II to cuprous cyanide is 1;
the palladium salt is palladium chloride, palladium trifluoroacetate, palladium acetate (Pd (OAc) 2 ) The reaction takes palladium acetate as a catalyst, and the molar ratio of the polysubstituted alkenyl sulfonium salt II to the palladium salt is 1;
the base is lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, potassium phosphate, sodium acetate, potassium acetate, cesium acetate, potassium hydroxide, or potassium tert-butoxide (KO) t Bu), lithium tert-butoxide and sodium hydride (NaH), wherein potassium tert-butoxide is the most effective in the reaction, and the molar ratio of the polysubstituted alkenylsulfonium salt II to the base is 1;
the ligand is triphenylphosphine, 2-dicyclohexyl phosphorus-2, 4, 6-triisopropyl biphenyl, 2-dicyclohexyl phosphorus-2 ',6' -dimethoxy biphenyl (X-PHOS), tricyclohexyl phosphine or tri- (4-methylphenyl) phosphine, wherein the reaction takes 2-dicyclohexyl phosphorus-2, 4, 6-triisopropyl biphenyl as a catalyst, the molar ratio of the polysubstituted alkenyl sulfonium salt II to the ligand is 1.1-1;
the reaction solvent is one or a mixture of more than two of N, N-Dimethylformamide (DMF), dimethyl sulfoxide, acetonitrile, toluene, 1, 4-dioxane, dichloromethane (DCM), ethyl acetate and methanol, wherein the N, N-dimethylformamide is the best solvent for the reaction, and the molar concentration of the polysubstituted alkenyl sulfonium salt II in the reaction solvent is 0.5-1.5M, preferably 1-1.5M.
Further, in the above technical scheme, the reaction time is 8-24 hours, wherein the optimal reaction time is 12-24 hours.
Further, in the technical scheme, the reaction temperature is 0-120 ℃, wherein the optimal reaction temperature is 30-100 ℃.
Further, in the above technical solution, the reaction atmosphere is nitrogen or an inert atmosphere, such as helium or argon.
Further, in the above technical scheme, after the reaction is finished, the product is separated according to a conventional separation and purification method to obtain the polysubstituted alkenyl cyanide I.
Under the nitrogen or inert atmosphere, the sulfonium salt which is easy to prepare, has structural diversity and multiple reaction centers is used as a raw material, the ketene cyanide is used as a synthon, and the polysubstituted alkenyl cyanide is synthesized under the alkaline condition. Compared with the reported synthesis method of the alkenyl cyano compound, the method has the advantages of cheap and easily obtained raw materials, simple and convenient operation, mild synthesis reaction conditions, good product stereoselectivity, high reaction efficiency and diversity of functional groups.
The invention has the following advantages:
1) The polysubstituted alkenyl sulfonium salt II as the reaction material has diverse structure and may be used in synthesizing different types of polysubstituted alkenyl cyanide I.
2) The synthesized cuprous cyanide is cheap and easy to obtain.
3) The synthesis reaction condition of the polysubstituted alkenyl sulfonium salt II is mild, the product yield is high and the application range is wide.
In a word, the invention utilizes the type and the structural diversity of the polysubstituted alkenyl sulfonium salt II to efficiently synthesize the polysubstituted alkenyl cyanide I of different types, and has the advantages of cheap and easily obtained raw materials, simple and convenient operation, high yield of target products and wide application range of substrates.
Detailed Description
In the present invention, the following technical scheme can be used for operation, but the invention is not limited in scope, olefin compound A, sulfoxide compound B and trifluoromethanesulfonic anhydride Tf 2 O, in the presence of dichloromethane DCM as a solvent to generate polysubstituted alkenyl sulfonium salt II (reaction formula 1, R in formula A) 1 、R 2 、R 3 Wherein n is as defined in formula II, and wherein n is as defined in formula II). Then II is used as raw material, palladium salt such as palladium acetate Pd (OAc) 2 As catalyst, in the presence of a base such as potassium tert-butoxide KO t Bu in an organic solvent such as N, N-dimethylformamide DMF under heating (reaction formula 2). And after the reaction is finished, performing product separation and characterization by a conventional column chromatography or thin-layer chromatography separation and purification method to obtain the polysubstituted alkenyl cyanide I.
The specific process is as follows: displacing nitrogen gas for 3 times in a 50mL round-bottomed bottle, sequentially adding olefin A (5.0 mmol), sulfoxide compound B (5.5 mmol) and DCM in the nitrogen atmosphere, and slowly dropwise adding TfO at-30 deg.C 2 (5.5 mmol) and reacted for 5 hours. After the reaction was completed, the solvent was removed under reduced pressure, and then separated by silica gel column chromatography (eluent dichloromethane/methanol, v/v = 10. The target product was confirmed by nuclear magnetic resonance spectroscopy, high resolution mass spectrometry and reference to literature references (Angew. Chem. Int. Ed.2018,57, 9785-9789).
The specific process is as follows: to a 10mL stoppered tube were added successively alkenylsulfonium salt II (0.3 mmol), cuCN (40.3mg, 0.45mmol), pd acetate (OAc) 2 (13.5mg, 0.06mmol), potassium tert-butoxide KO t Bu or sodium hydride NaH (101.0mg, 0.9mmol) and 2-dicyclohexylphosphonium-2, 4, 6-triisopropylbiphenyl X-PHOS or triphenylphosphine (43.0mg, 0.09 mmol)mmol), then the nitrogen is replaced 3 times, then 3mL of N, N-dimethylformamide DMF or toluene or dimethyl sulfoxide are added, and stirring is carried out at 80 ℃ for 18 hours. After cooling to room temperature, insoluble matter was removed by celite filtration, volatile components were removed under reduced pressure, and then separated by silica gel column chromatography (eluent petroleum ether (60-90 ℃)/ethyl acetate, v/v = 4). The target product is confirmed by nuclear magnetic resonance spectrometry, high-resolution mass spectrometry and reference documents.
The following examples are provided to aid in the further understanding of the present invention, but the invention is not limited thereto.
Example 1
To a 10mL stoppered tube, 1- (2, 2-diphenylvinyl) tetrahydro-1H-thiophene-1-triflate 2a (124.9mg, 0.3mmol), cuCN (40.3mg, 0.45mmol), pd acetate (OAc) 2 (13.5mg, 0.06mmol), potassium tert-butoxide KO t Bu (101.0mg, 0.9mmol) and 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl X-PHOS (43.0mg, 0.09mmol), followed by 3 times replacement of nitrogen gas, 3mL of N, N-dimethylformamide DMF was further added, and the mixture was stirred at 80 ℃ for 18 hours. After cooling to room temperature, insoluble matter was removed by filtration through celite, volatile components were removed under reduced pressure, and then the residue was separated by silica gel column chromatography (eluent petroleum ether (60-90 ℃)/ethyl acetate, v/v =4: 1) to obtain the target product 1a (59.2 mg, yield 96%), which was confirmed by nmr spectroscopy.
Typical compound characterization data
3, 3-Diphenylacrylonitrile (1 a), a pale yellow oily liquid. 1 H NMR(400MHz,CDCl 3 )δ7.51-7.48(m,6H,aromatic CH),7.41-7.37(m,2H,aromatic CH),7.33-7.30(m,2H,aromatic CH),5.75(s,1H,CH). 13 CNMR(100MHz,CDCl 3 )δ163.2,139.0,137.1,130.5,130.1,129.6,128.7,128.6,128.5,118.0(CN),94.9(CH).C 15 H 11 HRMS theoretical value of N ([ M + H ]] + ) 206.2675; found 206.2677.
Comparative example 1
The procedure of the reaction was the same as in example 1, except that palladium acetate was not added as in example 1. The reaction is stopped, and the target product 1a is not obtained after the post-treatment. Indicating that palladium acetate is essential in the reaction.
Example 2
The reaction procedure and operation were the same as in example 1, except that the ligand was triphenylphosphine, as in example 1. The reaction was stopped and worked up to give the desired product 1a (27.7 mg, yield 45%). It is stated that triphenylphosphine may also act as a ligand for the reaction, but is not the optimal ligand.
Example 3
The procedure is as in example 1, except that the base is sodium hydride NaH. The reaction was stopped and worked up to give the desired product 1a (3.2 mg, yield 5%). Indicating that strong base is not favorable for the reaction.
Example 4
The procedure and operation were the same as in example 1 except that the solvent used in the reaction was toluene, which was different from example 1. The reaction was terminated, and the desired product 1a (6.5 mg, yield 10%) was obtained by post-treatment. Which indicates that toluene is not favorable for the reaction.
Example 5
The reaction procedure and operation were the same as in example 1, except that dimethyl sulfoxide was used as the solvent in the reaction, in contrast to example 1. The reaction was stopped and worked up to give the desired product 1a (48.1 mg, yield 78%). It is stated that dimethyl sulfoxide can be used as a solvent for the reaction, but is not the optimal solvent for the reaction.
Example 6
The reaction procedure and operation were the same as in example 1, except that the reaction time was shortened to 8 hours from example 1. The reaction was stopped and worked up to give the desired product 1a (32.7 mg, yield 53%). It is shown that the reaction time is shortened, which is disadvantageous for the reaction.
Example 7
The procedure and operation were the same as in example 1, except that the reaction temperature was 50 ℃ in example 1. The reaction was terminated, and the desired product 1a (18.6 mg, yield 30%) was obtained by workup. It is shown that lowering the reaction temperature is disadvantageous for the reaction.
Example 8
The reaction procedure and operation were identical to example 1, except that the alkenylsulfonium salt added to the reaction system was 2b (133.4 mg, 0.3mmol). The reaction was stopped and worked up to give the desired product 1b (53.2 mg, 76% yield) as a colorless waxy solid. The target product is confirmed by nuclear magnetic resonance spectrum and high-resolution mass spectrometry.
Typical compound characterization data
3, 3-di-p-tolylacrylonitrile (1 b) as a colorless waxy solid having a melting point of 45-47 ℃. 1 H NMR(400MHz,CDCl 3 )δ7.36-7.38(m,2H,aromatic CH),7.29-7.27(m,2H,aromatic CH),7.24-7.19(m,3H,aromatic CH),5.69(s,1H,CH),2.45(s,3H,CH 3 ),2.42(s,3H,CH 3 ). 13 C NMR(100MHz,CDCl 3 )δ163.2,140.8,140.2,136.4,134.4,129.6,129.4,129.2,128.5,118.4(CN),93.4(CH),21.5(CH 3 )and21.4(CH 3 ).C 17 H 15 HRMS theoretical value of N ([ M + H ]] + ) 234.3215; the measured value is 234.3218.
Example 9
The reaction procedure was the same as that in example 1 except that the alkenylsulfonium salt added to the reaction system was 2c (135.6 mg,0.3 mmol) in example 1. The reaction was stopped and worked up to give the desired product 1c as a white solid (72 mg, 99% yield). The target product is confirmed by the measurement of nuclear magnetic resonance spectrum and high-resolution mass spectrum.
Typical Compound characterization data
3, 3-di-p-fluorophenyl acrylonitrile (1 c) as a white solid, mp 59-62 ℃. 1 H NMR(400MHz,CDCl 3 )δ7.45(t,J＝6.0Hz,2H,aromatic CH),7.31(t,J＝6.0Hz,2H,aromatic CH),7.17(t,J＝8.0Hz,2H,aromatic CH),7.10(t,J＝8.0Hz,2H,aromatic CH),5.71(s,1H,CH). 13 C NMR(100MHz,CDCl 3 )δ165.4,165.0,162.9,162.5,160.9,134.9(d,J＝4.0Hz),132.9(d,J＝3.0Hz),131.7(d,J＝9.0Hz),130.5(d,J＝9.0Hz),117.7(CH),116.0(d,J＝6.0Hz),115.8(d,J＝6.0Hz),94.92(CH).C 15 H 9 F 2 HRMS theoretical value of N ([ M + H ]] + ) 242.2483; found 242.2482.
Example 10
The procedure and operation were identical to those of example 1, except that the alkenylsulfonium salt added to the reaction system was 2d (129.2 mg,0.3 mmol). The reaction was stopped, and the desired product 1d (47.4 mg, yield 72%) was obtained as a colorless oily liquid by post-treatment. The target product is confirmed by nuclear magnetic resonance spectrum and high-resolution mass spectrometry.
Typical Compound characterization data
3-phenyl-3- (p-tolyl) acrylonitrile (1 d), a colorless oily liquid. 1 H NMR(400MHz,CDCl 3 )δ7.47-7.43(m,3H,aromatic CH),7.40-7.30(m,4H,aromatic CH),7.22-7.17(m,2H,aromatic CH),5.72(s,1H,CH),2.42(s,3H,CH 3 ). 13 C NMR(100MHz,CDCl 3 )δ162.4,139.9,137.5,137.0,134.4,128.8,128.5,128.2,127.8,116.8(CN),4.18(CH),21.3(CH 3 ).C 16 H 13 HRMS theoretical value of N ([ M + H ]] + ) 220.1048; the measurement value was 220.1045.
Example 11
The reaction procedure was as in example 1 except that the alkenylsulfonium salt added to the reaction system was 2e (124.9mg, 0.3mmol). The reaction was stopped, and the desired product 1e was obtained as a colorless oily liquid by post-treatment (46.1 mg, yield 75%). The target product is confirmed by the measurement of nuclear magnetic resonance spectrum and high-resolution mass spectrum.
Typical compound characterization data
3, 3-Diphenylacrylonitrile (1 e), a colorless oily liquid. 1 H NMR(400MHz,CDCl 3 )δ7.43-7.34(m,6H,aromatic CH and vinyl CH),7.34-7.30(m,1H,aromatic CH),7.28-7.24(m,2H,aromatic CH),7.21-7.19(m,2H,aromatic CH). 13 CNMR(100MHz,CDCl 3 )δ147.4,135.1,134.2,128.9,128.5,128.4,127.8,127.5,126.3,118.8(CN),99.4(CH).C 15 H 11 HRMS theoretical value of N ([ M + H ]] + ) 206.2647; found 206.2649.
Claims (8)
1. A method for synthesizing polysubstituted alkenyl cyanide is characterized in that: taking a polysubstituted alkenyl sulfonium salt II as an initial raw material, palladium salt as a catalyst and an organophosphorus compound as a ligand, and reacting with cuprous cyanide under an alkaline condition to generate a polysubstituted alkenyl cyanide I;
the reaction formula of the synthetic route is as follows:
R 1 selected from methyl, ethyl or aryl;
R 2 selected from methyl, ethyl, aryl, naphthalene ring, furan ring, thiophene ring or pyridine ring;
R 3 selected from hydrogen, methyl, ethyl, benzyl, aryl, naphthalene rings, furan rings, thiophene rings or pyridine rings;
wherein, the aryl is selected from phenyl, the benzene ring has substituent groups, the substituent groups on the benzene ring are selected from 1 to 5 of methyl, methoxy, fluorine, chlorine, bromine, iodine, trifluoromethyl and nitro, and the number of the substituent groups is 1 to 5;
n is an integer from 0 to 3;
the palladium salt is one or more of palladium chloride, palladium trifluoroacetate, palladium acetate, palladium hydroxide, tetraacetonitrile palladium tetrafluoroborate, bis (acetonitrile) palladium chloride and palladium acetylacetonate;
the base is selected from one of lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, potassium phosphate, sodium acetate, potassium acetate, cesium acetate, potassium hydroxide, potassium tert-butoxide, lithium tert-butoxide and sodium hydride;
the ligand is one or more than two of triphenylphosphine, 2-dicyclohexyl phosphine-2, 4, 6-triisopropyl biphenyl, 2-dicyclohexyl phosphine-2 ',6' -dimethoxy biphenyl, tricyclohexyl phosphine and tri- (4-methylphenyl) phosphine;
the reaction solvent is one or a mixture of more than two of N, N-dimethylformamide, dimethyl sulfoxide, acetonitrile, toluene, 1, 4-dioxane, dichloromethane, ethyl acetate or methanol.
2. The method of synthesis according to claim 1, characterized in that:
the molar ratio of the polysubstituted alkenyl sulfonium salt II to the cuprous cyanide is 1-1;
the molar ratio of the polysubstituted alkenyl sulfonium salt II to the palladium salt is 1;
the molar ratio of the polysubstituted alkenyl sulfonium salt II to the alkali is 1;
the molar ratio of the polysubstituted alkenyl sulfonium salt II to the ligand is 1.1-1;
the reaction solvent is one or a mixture of more than two of N, N-dimethylformamide, dimethyl sulfoxide, acetonitrile, toluene, 1, 4-dioxane, dichloromethane, ethyl acetate or methanol, and the molar concentration of the polysubstituted alkenyl sulfonium salt II in the reaction solvent is 0.5-1.5M.
3. The method of synthesis according to claim 2, characterized in that: the reaction time is 8-24 hours; the reaction temperature is 0-120 ℃; the reaction atmosphere is nitrogen or inert atmosphere.
4. The method of synthesis according to claim 2, characterized in that: and after the reaction is finished, separating the product according to a conventional separation and purification method to obtain the polysubstituted alkenyl cyanide I.
5. The method of synthesis according to claim 2, characterized in that: the molar ratio of the polysubstituted alkenyl sulfonium salt II to the palladium salt is 1.
6. The method of synthesis according to claim 2, characterized in that: the molar ratio of the polysubstituted alkenylsulfonium salt II to the base is 1 to 1.
7. The method of synthesis according to claim 2, characterized in that: the molar concentration of the polysubstituted alkenyl sulfonium salt II in the reaction solvent is 1-1.5M.
8. The method of synthesis according to claim 2, characterized in that: the reaction time is 12-24 hours; the reaction temperature is 30-100 ℃.
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| GB1068133A (en) * | 1965-02-04 | 1967-05-10 | Lubrizol Corp | Nitrogen-containing derivatives of substituted succinic acids |
| CN111253293A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Cyanoalkyl substituted tetra-substituted olefin derivatives and synthesis thereof |
| CN111302990A (en) * | 2018-12-11 | 2020-06-19 | 中国科学院大连化学物理研究所 | Conjugated diene compound and synthetic method thereof |
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| GB1068133A (en) * | 1965-02-04 | 1967-05-10 | Lubrizol Corp | Nitrogen-containing derivatives of substituted succinic acids |
| CN111253293A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Cyanoalkyl substituted tetra-substituted olefin derivatives and synthesis thereof |
| CN111302990A (en) * | 2018-12-11 | 2020-06-19 | 中国科学院大连化学物理研究所 | Conjugated diene compound and synthetic method thereof |
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| 2-(4-溴苯基)-3,3-二苯基丙烯腈的合成及光物理性质;何刚 等;《合成化学》;20181231;第26卷(第8期);第607-610页 * |
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