CN112321449A - Method for preparing primary and secondary amide compound - Google Patents

Method for preparing primary and secondary amide compound Download PDF

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CN112321449A
CN112321449A CN202011254931.6A CN202011254931A CN112321449A CN 112321449 A CN112321449 A CN 112321449A CN 202011254931 A CN202011254931 A CN 202011254931A CN 112321449 A CN112321449 A CN 112321449A
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amide compound
primary
secondary amide
substituted
dichloro
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夏远志
尤婷杰
陈建辉
陈佳佳
罗燕书
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Wenzhou University
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Abstract

The invention belongs to the field of organic chemical synthesis, and particularly relates to a method for preparing primary and secondary amide compounds. A process for preparing the primary and secondary amide compounds includes such steps as catalytic reduction of N-substituted amide compound in the presence of protonic solvent as reducing reagent and dichloro (p-methyl isopropylbenzene) ruthenium (II) dimer as catalyst at 30-130 deg.C to obtain reaction liquid, and post-treating. The method for preparing the primary and secondary amide compounds disclosed by the invention realizes the transfer hydrogenation reaction of nitrogen-oxygen and nitrogen-carbon bonds, has mild and simple reaction conditions, wide substrate application range, convenient operation, high efficiency and high selectivity, and obtains the corresponding primary amide compound or secondary amide compound.

Description

Method for preparing primary and secondary amide compound
Technical Field
The invention belongs to the field of organic chemical synthesis, and particularly relates to a method for preparing primary and secondary amide compounds.
Background
The reduction reaction is one of the most important reaction types in organic synthesis, and has very important application in the industrial mass production of medicines, pesticides, fine chemicals and the like. Among them, the transfer hydrogenation reaction using a protic solvent such as alcohol, water and acid as a reducing agent is a simple and safe reduction method, and is a powerful supplement to the hydrogenation reaction directly using hydrogen as a hydrogen source. At present, the field of transfer hydrogenation has been mainly focused on reduction reactions of unsaturated bonds such as ketones, imines, and olefins, but research on reduction reactions of nitrogen-oxygen bonds, nitrogen-carbon bonds, and the like has not been advanced.
However, amine compounds containing nitrogen-hydrogen bonds are one of important synthetic transformants in organic chemistry, and if the nitrogen-oxygen bonds, nitrogen-carbon bonds and the like can be reduced by a transfer hydrogenation method to obtain corresponding primary or secondary amine compounds, the amine compounds have important value and significance for synthetic chemistry and industrial application. Based on the method, the invention provides a method for reducing the N-substituted amide compound in a transfer hydrogenation mode, and the corresponding primary or secondary amide is synthesized mildly and efficiently.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims at the problems existing in the prior art to improve, namely the invention discloses a method for preparing primary and secondary amide compounds, which takes dichloro (p-methyl isopropylbenzene) ruthenium (II) dimer complex as a catalyst and a protic solvent as a hydrogen source to catalyze, transfer, hydrogenate and reduce nitrogen-oxygen bonds or nitrogen-carbon bonds of N-substituted amide, and obtain the corresponding primary amide compounds or secondary amide compounds with high efficiency and high selectivity.
The technical scheme is as follows: a method for preparing primary and secondary amide compounds comprises the steps of using a protic solvent as a reduction reagent, using dichloro (p-methyl isopropyl benzene) ruthenium (II) dimer complex as a catalyst, carrying out catalytic reduction on an N-substituted amide compound at the temperature of 30-130 ℃, obtaining a reaction liquid after the reduction reaction is finished, and carrying out post-treatment on the reaction liquid to obtain the corresponding primary amide compound or secondary amide compound, wherein:
the molar ratio of the N-substituted amide compound to the dichloro (p-methyl cumyl) ruthenium (II) dimer complex is 1: (0.0001 to 0.1);
the molar ratio of the N-substituted amide compound to the protic solvent is 1: (5-1000).
Further, the structural formula of the N-substituted amide compound is shown in the specification
Figure BDA0002772818060000021
Wherein:
R1is phenyl, benzyl, heteroaryl, C1～C10Is one of a hydrocarbon group, a hydrocarbon sulfonyl group and a substituted phenyl group, the substituent of the substituted phenyl group being C1～C6A hydrocarbon group of1～C6At least one of a hydrocarbyloxy group and a halogen substituent of (a);
R2is C1～C10A hydrocarbon group of1～C10Hydrocarbyloxy group of (C)1～C10The substituent of the substituted phenyl group is C1～C6A hydrocarbon group of1～C6At least one of a hydrocarbyloxy group and a halogen substituent of (a);
R3is hydrogen or C1～C10A hydrocarbon group of (1).
Further, the protic solvent is any one or more of water, formic acid, acetic acid, methanol, ethanol, propanol, butanol and triethylamine.
Furthermore, the protic solvent is prepared by mixing water, formic acid and triethylamine according to the volume ratio of 2: 1: 1, preparing the mixture.
Further, the molar ratio of the N-substituted amide compound to the dichloro (p-methylisopropylene) ruthenium (II) dimer complex was 1: (0.001 to 0.05);
further, the reaction temperature of the reduction reaction is 80-110 ℃, and the reaction time is 1-24 hours.
Further, the reaction temperature of the reduction reaction was 100 ℃ and the reaction time was 12 hours.
Further, the post-treatment is one of recrystallization, thin layer chromatography, column chromatography, or distillation under reduced pressure.
Has the advantages that: the method for preparing the primary and secondary amide compounds disclosed by the invention realizes the transfer hydrogenation reaction of nitrogen-oxygen and nitrogen-carbon bonds, has mild and simple reaction conditions, wide substrate application range, convenient operation, high efficiency and high selectivity, and obtains the corresponding primary amide compound or secondary amide compound.
The specific implementation mode is as follows:
the following describes in detail specific embodiments of the present invention.
The invention relates to a method for reducing nitrogen-oxygen bond or nitrogen-carbon bond of N-substituted amide compound with high efficiency and mildness and obtaining corresponding primary or secondary amide compound with high selectivity, wherein the general formula of the product molecule is as follows:
Figure BDA0002772818060000031
wherein the content of the first and second substances,
R1is phenyl or substituted phenyl (substituent is C)1～C6A hydrocarbon group of1～C6Alkoxy and halogen atom of (1-5), benzyl, heteroaryl, C1～C10Hydrocarbyl and hydrocarbyl sulfonyl of (a);
R3is hydrogen or C1～C10A hydrocarbon group of (1).
The invention discloses a method for preparing primary and secondary amide compounds, which takes a protic solvent as a reducing reagent and adopts dichloro (p-methyl isopropyl benzene) ruthenium (II) dimer as a ligandCompound ({ [ RuCl)2(p-cymene))]2And) is a catalyst, the N-substituted amide compound is catalytically reduced at the temperature of 30-130 ℃, reaction liquid is obtained after the reduction reaction is finished, and the reaction liquid is subjected to post-treatment to obtain a corresponding primary amide compound or a corresponding secondary amide compound, which can be represented by the following formula:
Figure BDA0002772818060000041
the molar ratio of the N-substituted amide compound to the dichloro (p-methyl cumyl) ruthenium (II) dimer complex is 1: 0.0001-0.1;
further, the molar ratio of the N-substituted amide compound to the dichloro (p-methylisopropylene) ruthenium (II) dimer complex is 1: 0.001-0.05;
particularly preferred molar ratios of the N-substituted amide compound to the dichloro (p-methylisoprene) ruthenium (II) dimer complex are 1: 0.025.
the protic solvent is any one or a mixture of water, formic acid, acetic acid, methanol, ethanol, propanol, butanol, triethylamine and the like;
preferably recommending a mixed solution of water, formic acid and triethylamine, wherein the volume ratio is 2: 1: 1.
the reaction temperature is preferably from 30 ℃ to 130 ℃, more preferably from 80 ℃ to 110 ℃, particularly preferably 100 ℃.
As the hydrocarbon group, a group having 1 to 10 carbon atoms is preferable, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl and the like.
The heteroaryl mentioned in the invention refers to naphthyl and heteroaryl containing N, O and S.
The invention provides a method for synthesizing a corresponding primary or secondary amide compound by reducing an N-substituted amide compound in a transfer hydrogenation mode.
The technical scheme of the invention is further specifically explained by the following specific examples:
concrete implementExample 1
Figure BDA0002772818060000051
Preparation of
A process for preparing the primary and secondary amide compounds includes catalytic reduction of N-substituted amide compound in the presence of protonic solvent as reducing reagent and dichloro (p-methyl isopropylbenzene) ruthenium (II) dimer as catalyst at 100 deg.C for 12 hr to obtain reaction liquid, post-treating to obtain white solid in 95% yield
Figure BDA0002772818060000052
Wherein:
the molar ratio of the N-substituted amide compound to the dichloro (p-methyl cumyl) ruthenium (II) dimer complex is 1: 0.025;
the molar ratio of the N-substituted amide compound to the protic solvent is 1: 100.
further, the structural formula of the N-substituted amide compound is shown in the specification
Figure BDA0002772818060000053
Wherein:
R1is phenyl;
R2is methoxy;
R3is hydrogen.
Further, the protic solvent is prepared by mixing water, formic acid and triethylamine according to the volume ratio of 2: 1: 1, preparing the mixture.
Further, the post-treatment is recrystallization.
The nuclear magnetic detection was performed on the product of specific example 1, and the detection results were as follows:1H NMR(500MHz；CDCl3)δ7.82(d,J＝7.2Hz,2H),7.52(t,J＝7.4Hz,1H),7.44(t,J＝7.6Hz,2H),6.29(bs,2H)；13C NMR(125MHz；CDCl3)δ169.7,133.5,132.0,128.6,127.4.
specific example 2
Figure BDA0002772818060000061
Preparation of
A process for preparing the primary and secondary amide compounds includes catalytic reduction of N-substituted amide compound in the presence of protonic solvent as reducing reagent and dichloro (p-methyl isopropylbenzene) ruthenium (II) dimer as catalyst at 30 deg.C for 24 hr to obtain reaction liquid, post-treating to obtain white solid in 58% yield
Figure BDA0002772818060000062
Wherein:
the molar ratio of the N-substituted amide compound to the dichloro (p-methyl cumyl) ruthenium (II) dimer complex is 1: 0.1;
the molar ratio of the N-substituted amide compound to the protic solvent is 1: 1000.
further, the structural formula of the N-substituted amide compound is shown in the specification
Figure BDA0002772818060000063
Wherein:
R1is chlorophenyl;
R2is methoxy;
R3is hydrogen.
Further, the protic solvent is prepared by mixing water, formic acid and triethylamine according to the volume ratio of 2: 1: 1, preparing the mixture.
Further, the post-treatment is thin layer chromatography.
The nuclear magnetic detection of the product of the specific example 2 showed the following results:1H NMR(500MHz；CDCl3)δ7.82(t,J＝1.8Hz,1H),7.68(dt,J＝7.8Hz,1.3Hz 1H),7.50(dq,J＝8.0,1.0Hz,1H).,7.39(t,J＝7.9Hz,1H),6.18(bs,2H)；13C NMR(125MHz；CDCl3)δ168.2,135.2,134.9,132.09,123.0,127.8,125.5.
specific example 3
Figure BDA0002772818060000071
Preparation of
A process for preparing the primary and secondary amide compounds includes catalytic reduction of N-substituted amide compound in the presence of protonic solvent as reducing reagent and dichloro (p-methyl isopropylbenzene) ruthenium (II) dimer as catalyst at 130 deg.C for 1 hr to obtain reaction liquid, post-treating to obtain white solid, and obtaining the primary amide compound as the white solid in 45% yield
Figure BDA0002772818060000072
Wherein:
the molar ratio of the N-substituted amide compound to the dichloro (p-methyl cumyl) ruthenium (II) dimer complex is 1: 0.0001;
the molar ratio of the N-substituted amide compound to the protic solvent is 1: 5.
further, the structural formula of the N-substituted amide compound is shown in the specification
Figure BDA0002772818060000081
Wherein:
R1is phenyl containing substituent which is methoxyl;
R2is methoxy;
R3is hydrogen.
Further, the protic solvent is prepared by mixing water, formic acid and triethylamine according to the volume ratio of 2: 1: 1, preparing the mixture.
Further, the post-treatment is column chromatography.
The nuclear magnetic assay of the product of the specific example 3 showed the following results:1H NMR(300MHz；CDCl3)δ7.82–7.78(m,2H),6.97–6.94(m,2H),5.90(bs,2H),3.87(s,3H).
specific example 4
Figure BDA0002772818060000082
Preparation of
A process for preparing the primary and secondary amide compounds by dimerization of dichloro (p-methyl isopropylbenzene) ruthenium (II) with protonic solvent as reducing reagentThe bulk complex is used as a catalyst, the N-substituted amide compound is catalytically reduced at the temperature of 80 ℃, the reduction reaction is carried out for 24 hours, reaction liquid is obtained after the reaction is finished, and the reaction liquid is post-treated to obtain the corresponding primary amide compound
Figure BDA0002772818060000083
It was a white solid with a yield of 60%, where:
the molar ratio of the N-substituted amide compound to the dichloro (p-methyl cumyl) ruthenium (II) dimer complex is 1: 0.005;
the molar ratio of the N-substituted amide compound to the protic solvent is 1: 10.
further, the structural formula of the N-substituted amide compound is shown in the specification
Figure BDA0002772818060000091
Wherein:
R1is phenyl containing substituent, and the substituent in the phenyl containing substituent is ethoxy;
R2is methoxy;
R3is hydrogen.
Further, the protic solvent is water.
Further, the post-treatment is one of vacuum distillation.
The nuclear magnetic assay of the product of the specific example 4 showed the following results:1H NMR(500MHz；CDCl3)δ8.22(dd,J＝7.8,1.8Hz,1H),7.88(bs,1H),7.45(td,J＝8.4,1.8Hz,1H),7.06(t,J＝7.5Hz,1H),6.96(d,J＝8.3Hz,1H),6.49(bs,1H),4.20(q,J＝7.0Hz,2H),1.51(t,J＝7.0Hz,3H)；13C NMR(125MHz；CDCl3)δ167.4,157.3,133.3,132.5,121.1,120.9,112.3,64.7,14.8.
specific example 5
Figure BDA0002772818060000092
Preparation of
A process for preparing the primary and secondary amide compounds from the protonic solvent as reducing agent and dichloro (p-methyl)Cumene) ruthenium (II) dimer complex is used as catalyst, N-substituted amide compound is catalytically reduced at the temperature of 110 ℃, reduction reaction is carried out for 1 hour, reaction liquid is obtained after the reaction is finished, and the reaction liquid is post-treated to obtain corresponding primary amide compound
Figure BDA0002772818060000101
It was a white solid with a yield of 80%, where:
the molar ratio of the N-substituted amide compound to the dichloro (p-methyl cumyl) ruthenium (II) dimer complex is 1: 0.03;
the molar ratio of the N-substituted amide compound to the protic solvent is 1: 200.
further, the structural formula of the N-substituted amide compound is shown in the specification
Figure BDA0002772818060000102
Wherein:
R1is one of phenyl containing substituent groups, and the substituent groups in the phenyl containing substituent groups are two adjacent methyl groups;
R2is methoxy;
R3is hydrogen.
Further, the protic solvent is formic acid.
Further, the post-treatment is recrystallization.
The nuclear magnetic assay of the product of the specific example 5 showed the following results:1H NMR(500MHz；CDCl3)δ7.42(s,2H),7.15(s,1H),6.24(bs,2H),2.35(s,6H)；13C NMR(125MHz；CDCl3)δ170.1,138.3,133.5,125.1,125.1,21.2.
specific example 6
Figure BDA0002772818060000103
Preparation of
A process for preparing the primary and secondary amide compounds features that the N-substituted amidation is carried out by catalytic reduction at 100 deg.C in the presence of protonic solvent as reducing reagent and dichloro (p-methyl isopropylbenzene) ruthenium (II) dimer as catalystThe compound is reduced for 6 hours to obtain reaction liquid after the reaction is finished, and the reaction liquid is post-treated to obtain the corresponding primary amide compound
Figure BDA0002772818060000111
It was a white solid with a yield of 90%, where:
the molar ratio of the N-substituted amide compound to the dichloro (p-methyl cumyl) ruthenium (II) dimer complex is 1: 0.01;
the molar ratio of the N-substituted amide compound to the protic solvent is 1: 60.
further, the structural formula of the N-substituted amide compound is shown in the specification
Figure BDA0002772818060000112
Wherein:
R1is benzyl;
R2is methoxy;
R3is hydrogen.
Further, the protic solvent is acetic acid.
Further, the post-treatment is distillation under reduced pressure.
The nuclear magnetic assay of the product of specific example 6 showed the following results:1H NMR(500MHz；CDCl3)δ7.37-7.34(m,2H),7.31-7.26(m,3H),5.90(bs,1H),5.44(bs,1H),3.57(s,2H)；13C NMR(125MHz；CDCl3)δ173.7,134.9,129.4,129.1,127.4,43.3.
specific example 7
Figure BDA0002772818060000113
Preparation of
A process for preparing the primary and secondary amide compounds includes catalytic reduction of N-substituted amide compound in the presence of protonic solvent as reducing reagent and dichloro (p-methyl isopropylbenzene) ruthenium (II) dimer as catalyst at 120 deg.C for 10 hr to obtain reaction liquid, and post-treating to obtain the primary amide compound
Figure BDA0002772818060000121
It was a white solid with a yield of 85%, where:
the molar ratio of the N-substituted amide compound to the dichloro (p-methyl cumyl) ruthenium (II) dimer complex is 1: 0.01;
the molar ratio of the N-substituted amide compound to the protic solvent is 1: 100.
further, the structural formula of the N-substituted amide compound is shown in the specification
Figure BDA0002772818060000122
Wherein:
R1is heteroaryl;
R2is methoxy;
R3is hydrogen.
Further, the protic solvent is methanol.
Further, the post-treatment is column chromatography.
The nuclear magnetic assay of the product of the specific example 7 showed the following results:1H NMR(500MHz；d6-DMSO)δ8.23(d,J＝0.8Hz,1H),8.19(bs,1H),7.80(bs,1H),7.52(d,J＝3.4Hz,1H),7.02(dd,J＝3.4,1.7Hz,1H)；13C NMR(125MHz,d6-DMSO)δ160.3,148.9,145.9,114.5,112.6.
specific example 8
Figure BDA0002772818060000123
Preparation of
A process for preparing the primary and secondary amide compounds includes catalytic reduction of N-substituted amide compound in the presence of protonic solvent as reducing reagent and dichloro (p-methyl isopropylbenzene) ruthenium (II) dimer as catalyst at 40 deg.C for 24 hr to obtain reaction liquid, and post-treating to obtain the primary amide compound
Figure BDA0002772818060000131
It was a white solid with a yield of 60%, where:
the molar ratio of the N-substituted amide compound to the dichloro (p-methyl cumyl) ruthenium (II) dimer complex is 1: 0.008;
the molar ratio of the N-substituted amide compound to the protic solvent is 1: 100.
further, the structural formula of the N-substituted amide compound is shown in the specification
Figure BDA0002772818060000132
Wherein:
R1is heteroaryl;
R2is methoxy;
R3is hydrogen.
Further, the protic solvent is ethanol.
Further, the post-treatment is thin layer chromatography.
The nuclear magnetic assay of the product of the specific example 8 showed the following results:1H NMR(500MHz；d6-DMSO)δ7.95(bs,1H),7.74(dd,J＝9.7,4.2Hz,2H),7.36(bs,1H),7.13(t,J＝4.2Hz,1H)；13C NMR(125MHz；d6-DMSO)δ162.9,140.3,130.9,128.6,127.8.
specific example 9
Figure BDA0002772818060000133
Preparation of
A process for preparing the primary and secondary amide compounds includes catalytic reduction of N-substituted amide compound in the presence of protonic solvent as reducing reagent and dichloro (p-methyl isopropylbenzene) ruthenium (II) dimer as catalyst at 110 deg.C for 12 hr to obtain reaction liquid, and post-treating to obtain the primary amide compound
Figure BDA0002772818060000141
It was a white solid with a yield of 88%, where:
the molar ratio of the N-substituted amide compound to the dichloro (p-methyl cumyl) ruthenium (II) dimer complex is 1: 0.0025;
the molar ratio of the N-substituted amide compound to the protic solvent is 1: 10.
further, the structural formula of the N-substituted amide compound is shown in the specification
Figure BDA0002772818060000142
Wherein:
R1is heteroaryl;
R2is methoxy;
R3is hydrogen.
Further, the protic solvent is propanol.
Further, the post-treatment is column chromatography.
The nuclear magnetic assay of the product of the specific example 9 showed the following results:1H NMR(500MHz；CDCl3)δ5.79(bs,1H),5.64(bs,1H),2.05(d,J＝2.5Hz,3H),1.88(t,J＝4.4Hz,6H),1.73(q,J＝12.3Hz,6H)；13C NMR(125MHz；CDCl3)δ181.0,40.6,39.3,36.5,28.1.
specific example 10: reduction of N-acetoxybenzamide
A process for preparing the primary and secondary amide compounds includes catalytic reduction of N-substituted amide compound in the presence of protonic solvent as reducing reagent and dichloro (p-methyl isopropylbenzene) ruthenium (II) dimer as catalyst at 110 deg.C to obtain reaction liquid, and post-treating to obtain the primary amide compound
Figure BDA0002772818060000151
The yield was 90%, wherein:
the molar ratio of the N-substituted amide compound to the dichloro (p-methyl cumyl) ruthenium (II) dimer complex is 1: 0.01;
the molar ratio of the N-substituted amide compound to the protic solvent is 1: 10.
Figure BDA0002772818060000152
further, the structural formula of the N-substituted amide compound is shown in the specification
Figure BDA0002772818060000153
Wherein:
R1is phenyl;
R2is C1A hydrocarbon acyloxy group of (a);
R3is hydrogen.
The protic solvent is prepared from water, formic acid and triethylamine according to the volume ratio of 2: 1: 1, preparing the mixture.
Further, the post-treatment is recrystallization.
Specific example 11: reduction reaction of N-benzyloxy benzamide
A process for preparing the primary and secondary amide compounds includes catalytic reduction of N-substituted amide compound in the presence of protonic solvent as reducing reagent and dichloro (p-methyl isopropylbenzene) ruthenium (II) dimer as catalyst at 110 deg.C for 12 hr to obtain reaction liquid, and post-treating to obtain the primary amide compound
Figure BDA0002772818060000161
The yield was 90%, wherein:
the molar ratio of the N-substituted amide compound to the dichloro (p-methyl cumyl) ruthenium (II) dimer complex is 1: 0.01;
the molar ratio of the N-substituted amide compound to the protic solvent is 1: 10.
Figure BDA0002772818060000162
further, the structural formula of the N-substituted amide compound is shown in the specification
Figure BDA0002772818060000163
Wherein:
R1is phenyl;
R2is C2A hydrocarbon acyloxy group of (a);
R3is hydrogen.
Further, the protic solvent is prepared by mixing water, formic acid and triethylamine according to the volume ratio of 2: 1: 1, preparing the mixture.
Further, the post-treatment is thin layer chromatography.
Specific example 12: reduction of N-tert-valeryloxy-N-methylbenzamide
A method for preparing primary and secondary amide compounds comprises the steps of using a protic solvent as a reduction reagent, using dichloro (p-methyl isopropyl benzene) ruthenium (II) dimer complex as a catalyst, carrying out catalytic reduction on an N-substituted amide compound at the temperature of 110 ℃, carrying out reduction reaction for 12 hours, obtaining reaction liquid after the reaction is finished, and carrying out post-treatment on the reaction liquid to obtain the corresponding primary amide compound, wherein the yield is 82%, and the method comprises the following steps:
the molar ratio of the N-substituted amide compound to the dichloro (p-methyl cumyl) ruthenium (II) dimer complex is 1: 0.01;
the molar ratio of the N-substituted amide compound to the protic solvent is 1: 5.
Figure BDA0002772818060000171
further, the structural formula of the N-substituted amide compound is shown in the specification
Figure BDA0002772818060000172
Wherein:
R1is phenyl;
R2is methyl;
R3is hydrogen.
Further, the protic solvent is prepared by mixing water, formic acid and triethylamine according to the volume ratio of 2: 1: 1, preparing the mixture.
Further, the post-treatment is recrystallization.
Specific example 13: hydrogen transfer reaction using ethanol as reducing reagent
A method for preparing primary and secondary amide compounds comprises the steps of using a protic solvent as a reduction reagent, using dichloro (p-methyl isopropyl benzene) ruthenium (II) dimer complex as a catalyst, carrying out catalytic reduction on an N-substituted amide compound at the temperature of 110 ℃, carrying out reduction reaction for 12 hours, obtaining reaction liquid after the reaction is finished, and carrying out post-treatment on the reaction liquid to obtain the corresponding primary amide compound, wherein the yield is 40%, and the method comprises the following steps:
the molar ratio of the N-substituted amide compound to the dichloro (p-methyl cumyl) ruthenium (II) dimer complex is 1: 0.025;
the molar ratio of the N-substituted amide compound to the protic solvent is 1: 5.
Figure BDA0002772818060000181
further, the structural formula of the N-substituted amide compound is shown in the specification
Figure BDA0002772818060000182
Wherein:
R1is phenyl;
R2is a hydrocarbyloxy group;
R3is hydrogen.
Further, the protic solvent is ethanol.
Further, the post-treatment is thin layer chromatography.
EXAMPLES example 14
A method for preparing primary and secondary amide compounds comprises the steps of using a protic solvent as a reduction reagent, using dichloro (p-methyl isopropyl benzene) ruthenium (II) dimer complex as a catalyst, carrying out catalytic reduction on an N-substituted amide compound at the temperature of 100 ℃, carrying out reduction reaction for 15 hours, obtaining reaction liquid after the reaction is finished, and carrying out post-treatment on the reaction liquid to obtain the corresponding secondary amide compound, wherein:
the molar ratio of the N-substituted amide compound to the dichloro (p-methyl cumyl) ruthenium (II) dimer complex is 1: 0.01;
the molar ratio of the N-substituted amide compound to the protic solvent is 1: 100.
further, the structural formula of the N-substituted amide compound is shown in the specification
Figure BDA0002772818060000191
Wherein:
R1is methyl;
R2is n-decyl;
R3is n-decyl.
Further, the protic solvent is butanol.
Further, the post-treatment is recrystallization.
Specific example 15
A method for preparing primary and secondary amide compounds comprises the steps of using a protic solvent as a reduction reagent, using dichloro (p-methyl isopropyl benzene) ruthenium (II) dimer complex as a catalyst, carrying out catalytic reduction on an N-substituted amide compound at the temperature of 120 ℃, carrying out reduction reaction for 10 hours, obtaining reaction liquid after the reaction is finished, and carrying out post-treatment on the reaction liquid to obtain the corresponding primary amide compound or secondary amide compound, wherein:
the molar ratio of the N-substituted amide compound to the dichloro (p-methyl cumyl) ruthenium (II) dimer complex is 1: 0.0025;
the molar ratio of the N-substituted amide compound to the protic solvent is 1: 50.
further, the structural formula of the N-substituted amide compound is shown in the specification
Figure BDA0002772818060000192
Wherein:
R1is n-decyl;
R2is methyl;
R3is methyl.
Further, the protic solvent is butanol.
Further, the post-treatment is distillation under reduced pressure.
EXAMPLE 16
A method for preparing primary and secondary amide compounds comprises the steps of using a protic solvent as a reduction reagent, using dichloro (p-methyl isopropyl benzene) ruthenium (II) dimer complex as a catalyst, carrying out catalytic reduction on an N-substituted amide compound at the temperature of 110 ℃, carrying out reduction reaction for 12 hours, obtaining reaction liquid after the reaction is finished, and carrying out post-treatment on the reaction liquid to obtain the corresponding secondary amide compound, wherein:
the molar ratio of the N-substituted amide compound to the dichloro (p-methyl cumyl) ruthenium (II) dimer complex is 1: 0.025;
the molar ratio of the N-substituted amide compound to the protic solvent is 1: 20.
further, the structural formula of the N-substituted amide compound is shown in the specification
Figure BDA0002772818060000201
Wherein:
R1is a hydrocarbon sulfonyl group;
R2is benzyl;
R3is n-butyl.
Further, the protic solvent is butanol.
Further, the post-treatment is recrystallization.
Specific example 17
A method for preparing primary and secondary amide compounds comprises the steps of using a protic solvent as a reduction reagent, using dichloro (p-methyl isopropyl benzene) ruthenium (II) dimer complex as a catalyst, carrying out catalytic reduction on an N-substituted amide compound at the temperature of 110 ℃, carrying out reduction reaction for 12 hours, obtaining reaction liquid after the reaction is finished, and carrying out post-treatment on the reaction liquid to obtain the corresponding secondary amide compound, wherein:
the molar ratio of the N-substituted amide compound to the dichloro (p-methyl cumyl) ruthenium (II) dimer complex is 1: 0.002;
the molar ratio of the N-substituted amide compound to the protic solvent is 1: 10.
further, the structural formula of the N-substituted amide compound is shown in the specification
Figure BDA0002772818060000211
Wherein:
R1is one of phenyl containing substituent groups, and the substituent group in the phenyl containing the substituent groups is n-hexyl;
R2is heteroaryl
Figure BDA0002772818060000212
R3Is ethyl.
Further, the protic solvent is a mixed solution of water, formic acid, acetic acid, methanol, ethanol, propanol, butanol, and triethylamine in equal volume.
Further, the post-treatment is column chromatography.
Detailed description of example 18
A method for preparing primary and secondary amide compounds comprises the steps of using a protic solvent as a reduction reagent, using dichloro (p-methyl isopropyl benzene) ruthenium (II) dimer complex as a catalyst, carrying out catalytic reduction on an N-substituted amide compound at the temperature of 110 ℃, carrying out reduction reaction for 10 hours, obtaining reaction liquid after the reaction is finished, and carrying out post-treatment on the reaction liquid to obtain the corresponding secondary amide compound, wherein:
the molar ratio of the N-substituted amide compound to the dichloro (p-methyl cumyl) ruthenium (II) dimer complex is 1: 0.03;
the molar ratio of the N-substituted amide compound to the protic solvent is 1: 10.
further, the structural formula of the N-substituted amide compound is shown in the specification
Figure BDA0002772818060000221
Wherein:
R1is one of phenyl containing substituent, and the substituent in the phenyl containing substituent is C6Hydrocarbyloxy groups of (a);
R2is one of phenyl containing substituent groups, and the substituent group in the phenyl containing the substituent groups is n-hexyl;
R3is n-hexyl.
Further, the protic solvent is prepared by mixing water, formic acid and triethylamine according to the volume ratio of 2: 1: 1, preparing the mixture.
Further, the post-treatment is recrystallization.
Specific example 19
A method for preparing primary and secondary amide compounds comprises the steps of using a protic solvent as a reduction reagent, using dichloro (p-methyl isopropyl benzene) ruthenium (II) dimer complex as a catalyst, carrying out catalytic reduction on an N-substituted amide compound at the temperature of 80 ℃, carrying out reduction reaction for 24 hours, obtaining reaction liquid after the reaction is finished, and carrying out post-treatment on the reaction liquid to obtain the corresponding secondary amide compound, wherein:
the molar ratio of the N-substituted amide compound to the dichloro (p-methyl cumyl) ruthenium (II) dimer complex is 1: 0.02;
the molar ratio of the N-substituted amide compound to the protic solvent is 1: 10.
further, the structural formula of the N-substituted amide compound is shown in the specification
Figure BDA0002772818060000231
Wherein:
R1is phenyl containing substituent, and the substituent in the phenyl containing substituent is C3Hydrocarbyloxy groups of (a);
R2is phenyl containing substituent, and the substituent in the phenyl containing substituent is Br in halogen substituent;
R3is n-butyl.
Further, the protic solvent is prepared by mixing water, formic acid and triethylamine according to the volume ratio of 2: 1: 1, preparing the mixture.
Further, the post-treatment is recrystallization.
The embodiments of the present invention have been described in detail. However, the present invention is not limited to the above-described embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.

Claims (8)

1. A method for preparing primary and secondary amide compounds is characterized in that a protonic solvent is used as a reduction reagent, dichloro (p-methyl isopropyl benzene) ruthenium (II) dimer complex is used as a catalyst, N-substituted amide compounds are catalytically reduced at the temperature of 30-130 ℃, reaction liquid is obtained after the reduction reaction is finished, and the reaction liquid is subjected to post-treatment to obtain the corresponding primary amide compounds or secondary amide compounds, wherein:
the molar ratio of the N-substituted amide compound to the dichloro (p-methyl cumyl) ruthenium (II) dimer complex is 1: (0.0001 to 0.1);
the molar ratio of the N-substituted amide compound to the protic solvent is 1: (5-1000).
2. The method of claim 1, wherein the N-substituted amide compound has the formula
Figure FDA0002772818050000011
Wherein:
R1is phenyl, benzyl, heteroaryl, C1～C10Is one of a hydrocarbon group, a hydrocarbon sulfonyl group and a substituted phenyl group, the substituent of the substituted phenyl group being C1～C6A hydrocarbon group of1～C6At least one of a hydrocarbyloxy group and a halogen substituent of (a);
R2is C1～C10A hydrocarbon group of1～C10Hydrocarbyloxy group of (C)1～C10The substituent of the substituted phenyl group is C1～C6A hydrocarbon group of1～C6At least one of a hydrocarbyloxy group and a halogen substituent of (a);
R3is hydrogen or C1～C10A hydrocarbon group of (1).
3. The method for producing primary and secondary amide compounds according to claim 1, wherein the protic solvent is any one or more of water, formic acid, acetic acid, methanol, ethanol, propanol, butanol and triethylamine.
4. The process for producing primary and secondary amide compounds according to claim 3, wherein the protic solvent is a mixture of water, formic acid and triethylamine in a volume ratio of 2: 1: 1, preparing the mixture.
5. The process for preparing a primary and secondary amide compound of claim 1, wherein the molar ratio of N-substituted amide compound to dichloro (p-cymene) ruthenium (II) dimer complex is 1: (0.001-0.05).
6. The method for producing primary and secondary amide compounds according to claim 1, wherein the reduction reaction is carried out at a reaction temperature of 80 ℃ to 110 ℃ for 1 to 24 hours.
7. The process for producing primary and secondary amide compounds according to claim 6, wherein the reduction reaction is carried out at a reaction temperature of 100 ℃ for 12 hours.
8. The process for producing a primary and secondary amide compound according to claim 1, wherein the post-treatment is one of recrystallization, thin layer chromatography, column chromatography or distillation under reduced pressure.
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