CN112961093A - Method for reducing C = C double bond of nitroolefin with high selectivity - Google Patents

Method for reducing C = C double bond of nitroolefin with high selectivity Download PDF

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CN112961093A
CN112961093A CN202110196671.XA CN202110196671A CN112961093A CN 112961093 A CN112961093 A CN 112961093A CN 202110196671 A CN202110196671 A CN 202110196671A CN 112961093 A CN112961093 A CN 112961093A
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methyl
furyl
thienyl
pyridyl
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杨占会
徐冬
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Beijing University of Chemical Technology
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
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    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
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Abstract

The invention provides a method for reducing C ═ C double bonds of nitroalkene with high selectivity. The method uses bidentate nitrogen ligand- [ Cp IrCl2]The complex is a catalyst, can conveniently convert nitroolefin into nitroalkane, and has extremely high catalytic efficiency and substrate conversion rate of more than 99 percent. The high-purity nitroalkane can be obtained by simple extraction, liquid separation and solvent removal under reduced pressure. The solvent is selected from water or a mixture of water and a hydrophilic solvent. The method is green and environment-friendly, and has high reaction efficiency. The nitroalkane compound prepared by the invention is a very important organic intermediate, and has wide application in the fields of national defense, pesticides, biology, medicine, fine chemical industry and the like.

Description

Method for reducing C ═ C double bond of nitroolefin with high selectivity
Technical Field
The invention belongs to the field of transition metal catalysis and organic synthesis, and particularly relates to a method for preparing nitroalkane through high-selectivity reduction of paranitroalkene.
Background
Nitroalkanes are a very important class of Organic intermediates, which can be processed into useful intermediates in fine synthetic chemistry such as amines, oximes, aldehydes or acids, and have important applications in The fields of defense, pesticides, biology, medicine, etc. (n.ono, The Nitro Group in Organic Synthesis, John Wiley & Sons, inc., New York, USA: 2002). Small-molecule nitro compounds such as nitromethane are widely used in rocket fuels (Shaozhi, Natural gas chemical (C1 chemical and chemical, 1992(02): 45-49)), short-chain nitro compounds can inhibit the generation of methane by rumen fermentation (Zhang Zhewei, Wang Yan Lu, Zhao Yu Qin, Yang Jiang, Li Sheng Li, animal nutrition research progress 2016, 186-. Nitroalkanes can be prepared by selective reduction of nitroalkenes.
The nitroalkenes have two functional groups, i.e., a C ═ C double bond and a nitro group, and when two or more functional groups are present in one molecule, it is a very challenging goal to selectively convert one of the functional groups into a target functional group. Conventional reduction methods, such as borane reduction, borohydride reduction or other metal hydride reduction, produce byproducts such as hydroxylamine, oximes or dimers (j.c. sircar et al, j.org.chem.,1967,32, 4134; r.s.var et al, Tetrahedron,1990,46, 7443; a.shrinidhi, gene chem.,2015,1: 1061412). Currently, new methods such as biocatalytic reduction, transition metal catalytic hydrogenation, transfer hydrogenation, etc. have been developed to address the problem of chemoselectivity and even enantioselectivity (K.Ozaki et al, J.org.chem.,1989,54, 1802; P.R.Schreiner et al, Synthesis,2007,16, 2559; H.
Figure BDA0002947042750000011
et al,Angew.CheInt.ed.,2013,52, 9323; x.zhang et al, angelw.chem.int.ed., 2012,51, 8573; q.zhou et al, chem.commun.,2016,52, 4812; r.gilmour et al, org.lett.,2019,21, 10164). A great deal of research shows that the transfer hydrogenation reaction is an excellent first-choice experimental method in the aspects of experimental operation, reaction conditions, reaction safety and the like, and has great breakthrough in the aspect of selective reducibility of nitroolefin: hantzsch esters can act as excellent hydrogen donors in the presence of transition metals or organic catalysts, and can selectively reduce nitroalkenes to nitroalkanes (e.meggers, j.am.chem.soc.,2016,138,8774); benzimidazolines and hydrosilanes have also been used as hydrogen donors for reduction reactions (k. itoh et al, synth. commun.,1985,15, 527; e.m. carreira et al, angle. chem. int.ed.,2003,42, 4793; e.m. carreira, org. lett.,2004,6, 4575). Although these hydrogen donors effect the reduction of part of the nitroolefin to nitroalkane, by-products such as pyridine-3, 5-dicarboxyl, benzimidazole, silane are formed in the reaction, which is not favorable for product separation.
In addition, the above methods of reducing nitroolefins in which these catalysts or reagents participate have strict requirements on the structure of the nitroolefin substrate, and generally only one structure of nitroolefin can be selectively reduced. For nitroolefins with different structures, different reduction products are obtained by using the same catalyst, and the catalyst has the disadvantages of large dosage, long reaction time, low catalytic efficiency and insufficient specificity. The production of organic by-products results in poor atom economy and requires column separation after the reaction is complete.
In view of the above problems, the present invention aims to provide a high-efficiency catalytic reduction method, which uses the same catalyst to reduce the C ═ C double bonds of nitroalkenes with different structures with high selectivity. The hydrogen source is formic acid or formate, and the byproduct is carbon dioxide or carbonate, so that the separation of organic products is not influenced. The method has the advantages of specific selectivity, high reduction efficiency, high conversion rate and simple product purification. The nitroalkane compound prepared by the invention is a very important organic intermediate, and has wide application in the fields of national defense, pesticides, biology, medicine, fine chemical industry and the like
Disclosure of Invention
The invention provides a high-efficiency reduction method for reducing a plurality of nitroolefin C ═ C double bonds with different structures in a high-selectivity manner. The reduction product nitroalkane is a very important organic intermediate and has important function in the field of fine chemical engineering. The invention uses specific bidentate nitrogen ligands and Cp IrCl2The complex is used as a catalyst (Cp is a pentamethyl cyclopentadiene ligand), water or a mixture of water and a hydrophilic solvent is used as a solvent, and formic acid or sodium formate is used as a proton source. The method can be used for reaction in the air without using protective gas, and has the advantages of simple operation, small catalyst consumption, high catalytic efficiency, specific selectivity and simple product separation.
The technical scheme of the invention is as follows:
the nitroalkane (formula 2) is prepared by using a nitroolefin substrate (formula 1) and formic acid or formate as a hydrogen source under the catalysis of a [ Cp x Ir ] -bidentate nitrogen ligand complex (shown as a formula 3, and the specific structure is C1-C13) and under a specific solvent and temperature.
Figure BDA0002947042750000021
In the above reaction formula:
R3、R4、R5both represent short-chain alkyl and cycloalkyl with 1-6 carbon atoms, phenyl or substituted aryl with 6-15 carbon atoms and heterocyclic substituent. Short chain alkyl groups include methyl, ethyl, isopropyl, butyl, pentyl, hexyl and their isomers; cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl; the aryl group with substituent groups is various, and the substituent groups on the aryl group can be in ortho position, para position and meta position, can be one (single substituent group), two (double substituent groups) or three (triple substituent groups), and can be the same or different. Heterocyclic substituents include cyclic substituents containing O, S, N elements.
The aryl containing the substituent refers to aryl with 6-15 carbon atoms, and comprises phenyl and naphthyl; wherein monosubstituted include three major classes: mono-substituted aryl groups at the ortho position including o-methylphenyl, o-ethylphenyl, o-methoxyphenyl, o-methylthiophenyl, o-mercaptophenyl, o-aminophenyl, o-fluorophenyl, o-chlorophenyl, o-bromophenyl, o-trifluoromethylphenyl, o-methoxycarbonyl, o-ethoxycarbonylphenyl, o-nitrophenyl, o-cyanophenyl, o-hydroxyphenyl and the like; mono-substituted aryl in the meta position including m-methylphenyl, m-ethylphenyl, m-methoxyphenyl, m-methylthiophenyl, m-mercaptophenyl, m-aminophenyl, m-fluorophenyl, m-chlorophenyl, m-bromophenyl, m-trifluoromethylphenyl, m-methoxycarbonyl, m-ethoxycarbonylphenyl, m-nitrophenyl, m-cyanophenyl, m-hydroxyphenyl and the like; mono-substituted nitroolefins in the para-position include p-dimethylaminophenyl, p-diethylaminophenyl, p-methylthiophenyl, p-mercaptophenyl, p-aminophenyl, p-methylphenyl, p-ethylphenyl, p-isopropylphenyl, p-tert-butylphenyl, p-methoxyphenyl, p-methylthiophenyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, p-trifluoromethylphenyl, p-methoxycarbonyl, p-ethoxycarbonylphenyl, p-nitrophenyl, p-cyanophenyl, p-hydroxyphenyl and the like. Disubstituted includes both ortho-disubstituted and meta-disubstituted aryl groups, the ortho-disubstituted aryl groups include, 3, 4-methylenedioxyphenyl, 3, 4-dimethylphenyl, 3, 4-dihydroxyphenyl, 3, 4-difluorophenyl, 3, 4-dichlorophenyl, 3, 4-dimethoxyphenyl, and the like; the m-disubstituted aryl group includes a 1, 6-difluorophenyl group, a 1, 6-dichlorophenyl group, a 1, 6-dimethylphenyl group, a 1, 6-dinitrophenyl group, a 2, 4-difluorophenyl group, a 2, 4-dichlorophenyl group, a 2, 4-dimethylphenyl group, a 2, 4-dinitrophenyl group and the like. Trisubstituted aryl groups include 2,4, 6-trimethylphenyl, 2,4, 6-trinitrophenyl, 2,4, 6-trichlorophenyl.
The heterocyclic substituent comprises O, S, N heterocyclic substituents respectively containing three elements, wherein the O-containing heterocyclic substituent comprises 2-furyl, 5-methyl-2-furyl, 5-fluoro-2-furyl, 5-chloro-2-furyl, 5-mercapto-2-furyl, 3-methyl-2-furyl, 3-fluoro-2-furyl, 3-chloro-2-furyl and 3-mercapto-2-furyl; the N-containing heterocyclic substituent includes 2-pyridyl, 6-methyl-2-pyridyl, 6-fluoro-2-pyridyl, 6-chloro-2-pyridyl, 6-mercapto-2-pyridyl, 4-methyl-2-pyridyl, 4-fluoro-2-pyridyl, 4-chloro-2-pyridyl, 4-mercapto-2-pyridyl, 3-indolyl, etc.; the S-containing heterocyclic substituent comprises 2-thienyl, 5-methyl-2-thienyl, 5-fluoro-2-thienyl, 5-chloro-2-thienyl, 5-mercapto-2-thienyl, 3-methyl-2-thienyl, 3-fluoro-2-thienyl, 3-chloro-2-thienyl and 3-mercapto-2-thienyl.
The various kinds of nitroalkane compounds prepared by reduction are 2a to 2l as follows, and the structures are as follows:
Figure BDA0002947042750000041
in the above-described reduction process for preparing nitroalkanes, a total of 13 [ Cp x Ir ] -bidentate nitrogen ligand complexes (C1-C13) of different structures were screened.
In the above reduction method, the preferred catalysts are C3, C4, and C5. Most preferred among these is the C3 catalyst.
In the above reduction method, the catalyst is used in an amount of 0.005 to 1 mol%, preferably 0.005, 0.01, 0.02, 0.04 mol%, based on the nitroolefin. The amount of catalyst used varies with the substrate structure.
In the above-mentioned reduction method, the reaction is usually carried out at room temperature to 120 ℃ with an optimum temperature of 80 ℃.
In the above-mentioned reduction method, the reaction time is determined depending on the structure of the substrate, and the reaction time is generally completed within 2 hours.
In the above reduction method, the solvent is usually water, and in some examples, water-miscible organic solutions including methanol, ethanol, propanol, isopropanol, butanol, isobutanol, ethylene glycol, tetrahydrofuran, DMF, DMSO, dioxane, and acetone are also used.
In the above reduction method, the hydrogen source used is different for the nitroolefins with different structures, formic acid is used as the hydrogen source for the β -mono-substituted nitroolefin and the β, β -di-substituted nitroolefin, and formate (for example, sodium formate, lithium formate, potassium formate, magnesium formate, ammonium formate, zinc formate, etc.) is used as the hydrogen source for the α, β -di-substituted nitroolefin.
In the reduction method, the molar equivalent of formic acid is 2-8 times of the molar equivalent of nitroolefin, and the molar equivalent of formate is 1-4 times of the molar equivalent of nitroolefin.
The invention has the advantages and positive effects that:
the nitroalkane compound prepared by the invention is a very important organic intermediate, and has wide application in the fields of national defense, pesticides, biology, medicine, fine chemical industry and the like.
The catalytic reduction method provided by the invention takes the nitrogen-containing bidentate ligand-Cp Ir complex as a catalyst, takes nitroolefin as a raw material, takes formic acid or formate as a hydrogen source, and reacts in a water phase to conveniently prepare the nitroalkane. The method is simple to operate, short in reaction time, high in conversion rate (> 99%), simple in product separation, and efficient and high-selectivity metal catalytic reduction. The method is green and environment-friendly, is simple to operate, and has a very good industrial application prospect.
Drawings
FIG. 1 is an abstract drawing
FIG. 2 is a scheme of beta-phenylnitroethane (2a)1H NMR Spectrum (CDCl)3As a solvent)
FIG. 3 is a scheme of beta-phenylnitroethane (2a)13C NMR Spectroscopy (CDCl)3As a solvent)
FIG. 4 shows the preparation of alpha-methyl-beta-phenylnitroethane (2b)1H NMR Spectrum (CDCl)3As a solvent)
FIG. 5 is a scheme of the preparation of alpha-methyl-beta phenylnitroethane (2b)13C NMR Spectroscopy (CDCl)3As a solvent)
FIG. 6 is a scheme of beta, beta-diphenylnitroethane (2c)1H NMR Spectrum (CDCl)3As a solvent)
FIG. 7 is a scheme of preparation of beta, beta-diphenylnitroethane (2c)13C NMR Spectroscopy (CDCl)3As a solvent)
FIG. 8 is a scheme showing that alpha-methyl-beta- (4-N-dimethylphenyl) nitroethane (2d)1H NMR Spectrum (CDCl)3As a solvent)
FIG. 9 is a scheme showing that alpha-methyl-beta- (4-N-dimethylphenyl) nitroethane (2d)13C NMR Spectroscopy (CDCl)3As a solvent)
FIG. 10 is a drawing of beta- (4-N-diethylphenyl) nitroethane (2e)1H NMR Spectrum (CDCl)3As a solvent)
FIG. 11 is a drawing of beta- (4-N-diethylphenyl) nitroethane (2e)13C NMR Spectroscopy (CDCl)3As a solvent)
FIG. 12 is a drawing showing a process for producing beta- (4-methylthiophenyl) nitroethane (2f)1H NMR Spectrum (CDCl)3As a solvent)
FIG. 13 is a drawing showing a process for producing beta- (4-methylthiophenyl) nitroethane (2f)13C NMR Spectroscopy (CDCl)3As a solvent)
FIG. 14 is a drawing showing a preparation method of beta- (4-tert-butylphenyl) nitroethane (2g)1H NMR Spectrum (CDCl)3As a solvent)
FIG. 15 is a drawing showing a preparation method of beta- (4-tert-butylphenyl) nitroethane (2g)13C NMR Spectroscopy (CDCl)3As a solvent)
FIG. 16 is a drawing showing the preparation of α -methyl- β - (4-methoxycarbonylphenyl) nitroethane (2h)1H NMR Spectrum (CDCl)3As a solvent)
FIG. 17 is a drawing showing a method for producing alpha-methyl-beta- (4-methoxycarbonylphenyl) nitroethane (2h)13C NMR Spectroscopy (CDCl)3As a solvent)
FIG. 18 is a scheme showing that alpha-methyl-beta- (4-methylsulfonylphenyl) nitroethane (2i)1H NMR Spectrum (CDCl)3As a solvent)
FIG. 19 is a scheme showing that alpha-methyl-beta- (4-methylsulfonylphenyl) nitroethane (2i)13C NMR Spectroscopy (CDCl)3As a solvent)
FIG. 20 is a drawing showing a process for preparing beta- (3, 4-dihydroxyphenyl) nitroethane (2j)1H NMR Spectrum (CDCl)3As a solvent)
FIG. 21 is a drawing showing a process for preparing beta- (3, 4-dihydroxyphenyl) nitroethane (2j)13C NMR Spectroscopy (CDCl)3As a solvent)
FIG. 22 is a drawing showing a method for producing alpha-methyl-beta- (3-indolyl) nitroethane (2k)1H NMR Spectrum (CDCl)3As a solvent)
FIG. 23 is a scheme showing that alpha-methyl-beta- (3-indolyl) nitroethane (2k)13C NMR Spectroscopy (CDCl)3As a solvent)
FIG. 24 is a scheme showing that (3, 4-methylenedioxyphenyl) nitroethane (2l)1H NMR Spectrum (CDCl)3As a solvent)
FIG. 25 is a photograph of (3, 4-methylenedioxyphenyl) nitroethane (2l)13C NMR Spectroscopy (CDCl)3As a solvent)
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the invention thereto.
Example one
Beta-phenylnitroethane 2a
11.92g (80 mmol) of beta-phenylnitroethylene was weighed into a 250mL single neck round bottom flask. 4.6mg (0.008mmol,0.01 mol%) of C3 catalyst (mol% indicates the molar ratio of the amount of catalyst to the amount of nitroolefin, the same applies hereinafter) was weighed into the flask. 160mL of tap water was measured and added to the flask. The flask was placed in an oil bath kettle preheated to 80 deg.C, stirred, connected to a reflux tube, and allowed to stand for 80 deg.C. The reflux tube was pulled off, formic acid (15g,320mmol) was added in two portions, about 2/3 was added for the first portion, and the remainder 1/3 was added five minutes later. After 1 hour of reaction, the reaction was stopped and cooled to room temperature. 150mL of tap water was added, and the mixture was extracted three times with 100mL of ethyl acetate. And combining the oil phases, adding anhydrous sodium sulfate, drying and performing suction filtration. And evaporating the solvent ethyl acetate by a rotary evaporator to obtain the target product beta-phenylnitroethane.
Orange oily liquid, yield: 11.91g, 98.6%; purity:>99％。1H NMR(400MHz,Chloroform-d)δ7.37-7.31(m,2H),7.30-7.26(m,1H),7.24-7.18(m,2H),4.61(t,J＝7.2Hz,2H),3.32(t,J＝7.2Hz,2H).13C NMR(101MHz,CDCl3) Delta 135.6,128.9,128.5,127.4,76.2,33.4, see figures 1 and 2 of the drawings.
Example two
Alpha-methyl-beta phenylnitroethane 2b
13.05g (80mmol,1 eq.) of alpha methyl-beta phenylnitroethylene was weighed into a 250mL single neck round bottom flask. 4.6mg (0.008mmol,0.01 mol%) of C3 catalyst was weighed out and charged into a flask. 16.5g (160mmol,2eq) of HCOONa was weighed into the flask. 160mL of tap water was measured and added to the flask. The flask was placed in an oil bath preheated to 80 ℃ and stirred, and a reflux tube was connected thereto. The timer was started when the temperature rose to 80 ℃ for about 5 minutes. After 1 hour of reaction, the reaction was stopped and cooled to room temperature. 150mL of tap water was added, and the mixture was extracted three times with 100mL of ethyl acetate. And combining the oil phases, adding anhydrous sodium sulfate, drying and performing suction filtration. And evaporating the solvent ethyl acetate by a rotary evaporator to obtain the target product alpha-methyl-beta phenyl nitroethane.
Orange oily liquid, yield: 12.90g, 97.7%; purity:>99％。1H NMR(400MHz,Chloroform-d)δ7.35–7.22(m,3H),7.19–7.12(m,2H),4.77(sex,J＝6.8Hz,1H),3.32(dd,J＝14.0,7.6Hz,1H),3.00(dd,J＝14.0,6.8Hz,1H),1.54(d,J＝7.2Hz,3H).13C NMR(101MHz,CDCl3) Delta 135.46,128.92,128.76,127.35,84.38,41.10 and 18.75, the spectra are shown in figure 3 and figure 4 of the accompanying drawings.
EXAMPLE III
Beta, beta-diphenylnitroethane 2c
Beta, beta-diphenylnitroethane was obtained as described in example one starting from beta, beta-diphenylnitroethylene (9.00g, 40mmol) in an amount of 9.2mg (0.016mmol,0.4 mol%) of catalyst. Light yellow oily liquid, yield: 8.81g, 97.0%; purity:>99％。1H NMR(400MHz,Chloroform-d)δ7.36–7.28(m,4H),7.28–7.19(m,6H),4.99–4.95(m,2H),4.90(dd,J＝9.2,6.8Hz,1H).13C NMR(101MHz,CDCl3) Delta 139.16,128.99,127.62,127.55,79.20,48.92, see fig. 5 and 6 of the drawings.
Example four
Alpha-methyl-beta- (4-N-dimethylphenyl) nitroethane 2d
Alpha-methyl-beta- (4-N-dimethylphenyl) nitroethane was obtained according to the method described in example two starting from alpha-methyl-beta- (4-N-dimethylphenyl) nitroethylene (2.06g, 10mmol) in an amount of 1.2mg (0.002mmol,0.02 mol%). Red oily liquid, yield: 2.05g, 98.5%; purity of>99％。1H NMR(400MHz,Chloroform-d)δ7.03(d,J＝8.8Hz,2H),6.68(d,J＝8.8Hz,2H),4.72(sex,J＝6.8Hz,1H),3.23(dd,J＝14.0,7.2Hz,1H),2.92(dd,J＝14.0,7.2Hz,1H),2.93(s,6H),1.52(d,J＝6.8Hz,3H).13C NMR(101MHz,CDCl3)δ149.81,129.62,123.00,112.70,84.75,40.46,40.42,18.51. The spectra are shown in figure 7 and figure 8 of the drawings.
EXAMPLE five
Beta- (4-N-diethylphenyl) nitroethane 2e
Beta- (4-N-dimethylphenyl) nitroethane was obtained from beta- (4-N-dimethylphenyl) nitroethylene (2.20g, 10mmol) in the amount of 1.2mg (0.002mmol,0.02 mol%) as described in example one. Red oily liquid, yield: 2.17g, 97.7%; purity:>99％。1H NMR(400MHz,Chloroform-d)δ7.04(d,J＝8.8Hz,2H),6.63(d,J＝8.8Hz,2H),4.54(t,J＝7.6Hz,2H),3.33(q,J＝7.2Hz,4H),3.21(t,J＝7.6Hz,2H),1.15(t,J＝7.2Hz,6H).13C NMR(101MHz,CDCl3) Delta 147.03,129.44,121.74,112.03,76.85,44.30,32.70 and 12.50, and the spectrograms are shown in figure 9 and figure 10 of the attached drawings.
EXAMPLE six
Beta- (4-methylthiophenyl) nitroethane 2f
Beta- (4-methylthiophenyl) nitroethane was obtained according to the method described in example one, starting from beta- (4-methylthiophenyl) nitroethylene (1.95g, 10mmol) and using 1.2mg (0.002mmol,0.02 mol%) of catalyst. Yellow oily liquid, yield: 1.93g, 98.0%; purity:>99％。1H NMR(400MHz,Chloroform-d)δ7.21(d,J＝8.0Hz,2H),7.12(d,J＝8.4Hz,2H),4.58(t,J＝7.2Hz,2H),3.27(t,J＝7.2Hz,2H),2.47(s,3H).13C NMR(101MHz,CDCl3) δ 137.71,132.32,129.00,127.05,76.17,32.86,15.79, see fig. 11 and 12 of the drawings.
EXAMPLE seven
Beta- (4-tert-butylphenyl) nitroethane 2g
Beta- (4-tert-butylphenyl) nitroethane was obtained in the same manner as in example one and using beta- (4-tert-butylphenyl) nitroethylene as a starting material (2.05g, 10mmol) and 1.2mg (0.002mmol,0.02 mol%) of a catalyst. Yellow oily liquid, yield: 1.99g, 96.1%; purity:>99％。1H NMR(400MHz,Chloroform-d)δ7.35(d,J＝8.4Hz,2H),7.15(d,J＝8.4Hz,2H),4.60(t,J＝7.6Hz,2H),3.30(t,J＝7.6Hz,2H),1.31(s,9H).13C NMR(101MHz,CDCl3)δ150.35132.50,128.22,125.83,76.27,34.47,32.92,31.28. the spectra are shown in figures 13 and 14 of the drawings.
Example eight
Alpha-methyl-beta- (4-methoxycarbonylphenyl) nitroethane 2h
By the method described in example two, α -methyl- β - (4-methoxycarbonylphenyl) nitroethylene was used as a starting material (2.21g, 10mmol) and the amount of the catalyst was 1.2mg (0.002mmol,0.02 mol%) to give α -methyl- β - (4-methoxycarbonylphenyl) nitroethane. Yellow oily liquid, yield: 2.18g, 97.7%; purity:>99％。1H NMR(400MHz,Chloroform-d)δ7.97(d,J＝8.4Hz,2H),7.23(d,J＝8.4Hz,2H),4.79(sex,J＝6.8Hz,1H),3.89(s,3H),3.35(dd,J＝14.0,8.0Hz,1H),3.06(dd,J＝14.0,6.4Hz,1H),1.55(d,J＝6.8Hz,3H).13C NMR(101MHz,CDCl3) Delta 166.59,140.61,130.02,129.34,128.96,83.90,52.06,40.84 and 18.85, which are shown in figure 15 and figure 16.
Example nine
Alpha-methyl-beta- (4-methylsulfonylphenyl) nitroethane 2i
Alpha-methyl-beta- (4-methylsulfonylphenyl) nitroethylene was obtained as the starting material (2.41g, 10mmol) and the catalyst in an amount of 1.2mg (0.002mmol,0.02 mol%) as described in example two, to give alpha-methyl-beta- (4-methylsulfonylphenyl) nitroethane. Yellow oily liquid, yield: 2.35g, 96.7%; purity:>99％。1H NMR(400MHz,Chloroform-d)δ7.88(d,J＝8.4Hz,2H),7.38(d,J＝8.4Hz,2H),4.87–4.76(m,1H),3.39(dd,J＝14.0,8.0Hz,1H),3.12(dd,J＝14.0,6.0Hz,1H),3.04(s,3H),1.59(d,J＝6.8Hz,3H).13C NMR(101MHz,CDCl3) δ 141.82,139.73,129.95,127.88,83.75,44.41,40.59,19.09, see figures 17 and 18 of the drawings.
Example ten
Beta- (3, 4-dihydroxyphenyl) nitroethane 2j
Beta- (3, 4-dihydroxyphenyl) nitroethane was obtained as described in example one starting from beta- (3, 4-dihydroxyphenyl) nitroethylene (1.81g, 10mmol) in an amount of 1.2mg (0.002mmol,0.02 mol%) of catalyst. Yellow oily liquid, yield: 1.79g, 97.8%, purity:>99％。1H NMR(400MHz,Chloroform-d)δ6.80(d,J＝8.0Hz,1H),6.72(d,J＝2.0Hz,1H),6.63(dd,J＝8.0,2.0Hz,1H),5.35(s,2H),4.55(t,J＝7.2Hz,2H),3.20(t,J＝7.2Hz,2H).13C NMR(101MHz,CDCl3) δ 143.85,142.77,128.59,121.08,115.76,115.66,76.53,32.84. the spectra are shown in fig. 19 and 20 of the drawings.
EXAMPLE eleven
Alpha-methyl-beta- (3-indolyl) nitroethane 2k
The procedure described in example two was followed using α -methyl- β - (3-indolyl) nitroethylene as starting material (2.02g, mmol) and 1.2mg (0.002mmol,0.02 mol%) of catalyst to give α -methyl- β - (3-indolyl) nitroethane. Brown oily liquid, yield: 1.96g, 96.1%, purity:>99％。1H NMR(400MHz,Chloroform-d)δ8.08(s,1H),7.59(d,J＝8.0Hz,1H),7.37(d,J＝8.0Hz,1H),7.23(t,J＝7.6Hz,1H),7.17(t,J＝7.6Hz,1H),7.02(s,1H),4.90(sex,J＝6.8Hz,1H),3.50(dd,J＝14.4,7.2Hz,1H),3.21(dd,J＝14.4,6.8Hz,1H),1.59(d,J＝7.2Hz,3H).13C NMR(101MHz,CDCl3) δ 136.11,126.91,122.97,122.35,119.79,118.21,111.37,109.86,83.80,31.20,18.94, see fig. 21 and 22 of the drawings.
Example twelve
(3, 4-methylenedioxyphenyl) nitroethane 2l
(3, 4-methylenedioxyphenyl) nitroethylene was obtained as described in example one starting from (3, 4-methylenedioxyphenyl) nitroethylene (1.93g, 10mmol) in the presence of 1.2mg (0.002mmol,0.02 mol%) of catalyst. Yellow oily liquid, yield: 1.91g, 97.9%, purity:>99％。1H NMR(400MHz,Chloroform-d)δ6.75(d,J＝8.0Hz,2H),6.70-6.62(m,2H),5.94(s,2H),4.56(t,J＝7.2Hz,2H),3.22(t,J＝7.2Hz,2H).13C NMR(101MHz,CDCl3) δ 148.00,146.89,129.18,121.68,108.86,108.60,101.10,76.49,33.18. the spectra are shown in fig. 23 and 24 of the drawings.

Claims (10)

1. A process for highly selective reduction of a nitroalkene C ═ C double bond, comprising the steps of:
reacting nitroolefin of formula 1 as a substrate, a bidentate nitrogen ligand-Cp Ir ligand of formula 3 as a catalyst, formic acid or formate as a hydrogen source, and water or a mixture of water and a hydrophilic solvent as a solvent at room temperature of-120 ℃ for a plurality of times;
obtaining corresponding nitro alkane in the formula 2 after the reaction is finished;
Figure FDA0002947042740000011
wherein R is3、R4And R5Independently selected from H, C1-6 short-chain alkyl, cycloalkyl with 3-6 ring atoms, aryl and heterocyclic substituent;
in formula 3
Figure FDA0002947042740000012
Representing a bidentate nitrogen ligand.
2. The method according to claim 1, wherein the short chain alkyl group having 1 to 6 carbon atoms includes methyl, ethyl, isopropyl, butyl, isobutyl, tert-butyl;
the cycloalkyl with 3-6 ring atoms comprises cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;
the aryl group is an aryl group having 6 to 15 carbon atoms;
the heterocyclic substituent includes a cyclic substituent containing O, S and one or more than two of N elements.
3. The method of claim 1, wherein the aryl group comprises phenyl, 1-and 2-naphthyl.
4. The method of claim 2, wherein the substituted aryl group is a mono-, di-or tri-substituted phenyl group when the substituted phenyl group is a substituted phenyl group.
5. The method according to claim 3, wherein said mono-substituted phenyl group comprises three main classes: mono-substituted phenyl at ortho position, including o-methylphenyl, o-ethylphenyl, o-methoxyphenyl, o-methylthiophenyl, o-mercaptophenyl, o-aminophenyl, o-fluorophenyl, o-chlorophenyl, o-bromophenyl, o-trifluoromethylphenyl, o-methoxycarbonylphenyl, o-ethoxycarbonylphenyl, o-nitrophenyl, o-cyanophenyl, o-hydroxyphenyl; mono-substituted phenyl in meta position, including m-methylphenyl, m-ethylphenyl, m-methoxyphenyl, m-methylthiophenyl, m-mercaptophenyl, m-aminophenyl, m-fluorophenyl, m-chlorophenyl, m-bromophenyl, m-trifluoromethylphenyl, m-methoxycarbonylphenyl, m-ethoxycarbonylphenyl, m-nitrophenyl, m-cyanophenyl, m-hydroxyphenyl; mono-substituted phenyl at para-position including p-dimethylaminophenyl, p-diethylaminophenyl, p-methylthiophenyl, p-mercaptophenyl, p-aminophenyl, p-methylphenyl, p-ethylphenyl, p-isopropylphenyl, p-tert-butylphenyl, p-methoxyphenyl, p-methylthiophenyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, p-trifluoromethylphenyl, p-methoxycarbonyl, p-ethoxycarbonylphenyl, p-nitrophenyl, p-cyanophenyl, p-hydroxyphenyl;
the disubstituted phenyl comprises two types of ortho-disubstituted phenyl and meta-disubstituted phenyl;
the ortho-disubstituted phenyl comprises 3, 4-methylenedioxyphenyl, 3, 4-dimethylphenyl, 3, 4-dihydroxyphenyl, 3, 4-difluorophenyl, 3, 4-dichlorophenyl and 3, 4-dimethoxyphenyl;
the m-disubstituted phenyl comprises 1, 6-difluorophenyl, 1, 6-dichlorophenyl, 1, 6-dimethylphenyl, 1, 6-dinitrophenyl, 2, 4-difluorophenyl, 2, 4-dichlorophenyl, 2, 4-dimethylphenyl and 2, 4-dinitrophenyl;
the trisubstituted phenyl group comprises 2,4, 6-trimethylphenyl, 2,4, 6-trinitrophenyl and 2,4, 6-trichlorophenyl.
6. The method of claim 1, wherein the heterocyclic substituent is an O-containing heterocyclic substituent comprising a cyclic substituent in the O element selected from the group consisting of 2-furyl, 5-methyl-2-furyl, 5-fluoro-2-furyl, 5-chloro-2-furyl, 5-mercapto-2-furyl, 3-methyl-2-furyl, 3-fluoro-2-furyl, 3-chloro-2-furyl, 3-mercapto-2-furyl; the N-containing heterocyclic substituent includes 2-pyridyl, 6-methyl-2-pyridyl, 6-fluoro-2-pyridyl, 6-chloro-2-pyridyl, 6-mercapto-2-pyridyl, 4-methyl-2-pyridyl, 4-fluoro-2-pyridyl, 4-chloro-2-pyridyl, 4-mercapto-2-pyridyl, 3-indolyl, etc.; the S-containing heterocyclic substituent comprises 2-thienyl, 5-methyl-2-thienyl, 5-fluoro-2-thienyl, 5-chloro-2-thienyl, 5-mercapto-2-thienyl, 3-methyl-2-thienyl, 3-fluoro-2-thienyl, 3-chloro-2-thienyl or 3-mercapto-2-thienyl.
7. The method of claim 1, wherein the bidentate nitrogen ligand-Cp Ir ligand species has a structure selected from the group consisting of C1-C13:
Figure FDA0002947042740000021
8. the process according to claim 1, wherein the reaction temperature is from room temperature to 120 ℃.
9. The method according to claim 1, wherein the formate is selected from one or a combination of two or more of sodium formate, potassium formate, lithium formate, ammonium formate, zinc formate and magnesium formate, and the formate is used in an amount of 1-16 molar equivalents of the nitroolefin.
10. The method according to claim 1, wherein the hydrophilic solvent is selected from one or a mixture of two or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, ethylene glycol, tetrahydrofuran, dioxane, acetone, trifluoroethanol, hexafluoroisopropanol, N-dimethylformamide, N-dimethylacetamide, hexamethylphosphoric triamide, and dimethyl sulfoxide; preferably, after the reaction is finished, ethyl acetate is extracted, dried and then distilled under reduced pressure to remove ethyl acetate, so that the corresponding nitroalkane of formula 2 is obtained.
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WO2018194537A1 (en) * 2017-04-17 2018-10-25 Tiger Instruments, Llc Iridium-based catalysts for highly efficient dehydrogenation and hydrogenation reactions in aqueous solution and applications thereof

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