CN111978349B - Method for synthesizing phosphonimide compound - Google Patents
Method for synthesizing phosphonimide compound Download PDFInfo
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- CN111978349B CN111978349B CN202011018730.6A CN202011018730A CN111978349B CN 111978349 B CN111978349 B CN 111978349B CN 202011018730 A CN202011018730 A CN 202011018730A CN 111978349 B CN111978349 B CN 111978349B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/535—Organo-phosphoranes
- C07F9/5355—Phosphoranes containing the structure P=N-
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/58—Pyridine rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
- C07F9/655345—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a five-membered ring
Abstract
The method relates to a method for synthesizing a phosphinimide compound, and belongs to the field of metal catalytic organic synthesis. A method for synthesizing phosphinimide compounds comprises the following steps: adding the N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting at room temperature in an air atmosphere, and performing post-treatment after the reaction is finished to obtain the phosphinimide compound. The method for synthesizing the phosphinimide compound disclosed by the invention has the following beneficial effects: (1) wide substrate range; (2) the catalyst is relatively low in price and less in dosage; (3) the reaction operation is simple; (4) The reaction yield is higher, and the higher yield can still be obtained when the reaction is amplified to gram level.
Description
Technical Field
The method relates to a method for synthesizing a phosphinimide compound, and belongs to the field of metal catalytic organic synthesis.
Background
The phosphonimide compound is an important organic synthesis intermediate, has a nitrogen-phosphine double bond structure, and has wide application in aza-Wittig (Wittig) reaction. Meanwhile, the phosphorus atom of the compound contains lone pair electrons, and can be coordinated with metal to be used as a guide group to realize the regioselective functionalization of C-H bond. Therefore, the synthesis of the compounds has very important significance, and a plurality of synthesis methods are continuously emerged.
In a classical Staudinger reaction, an azide compound and a tertiary phosphine (e.g., ph) 3 P) reacting to generate a phosphonyl imine intermediate which is unstable and is hydrolyzed to obtain the corresponding amine. When the N atom contains acyl, the stability of the compound is greatly enhanced, and the compound can be conveniently separated and used for subsequent reactions。
In 2005, calitzky et al disclosed a method of synthesizing N-acylphosphinimides (Helvetica Chimica Acta,2005,88 (7), 1664-1675) using an acyl azide compound and triphenylphosphine as reactants. The reaction formula is as follows:
froeyen et al, 1993, disclose a method for synthesizing phosphinimide compounds from benzoyl chloride, triphenylphosphine and sodium azide (phosphorous, sulfur and Silicon and the Related Elements,1993,78 (1-4), 161-71), wherein benzoyl chloride and sodium azide are used as starting materials to generate acyl azide in situ, and then the acyl azide reacts with triphenylphosphine to obtain phosphinimide. The reaction formula is as follows:
in 1988, cristau et al disclosed a method for synthesizing N-acylphosphinimide compounds from triphenylphosphine imide and ethyl benzoate (Tetrahedron Letters,1988,29 (32), 3931-3934). The reaction formula is as follows:
in 1984, laszlo et al disclosed a method for synthesizing phosphinimide compounds by using benzoyl hydrazine derivatives and triphenylphosphine as raw materials through multi-step reactions (Tetrahedron Letters,1984,25 (41), 4651-4654). In the method, benzoyl hydrazine is firstly generated into benzoyl azide under the action of Clayfen and then reacts with triphenylphosphine to generate phosphinimide. The reaction formula is as follows:
as described above, many reports have been made on the synthesis of phosphinimides. However, the disclosed methods usually require the use of explosive azide compounds as raw materials or intermediates, which has great safety hazards and limits the research and application of the phosphonimide.
Therefore, the need of continuous research for developing novel and efficient synthesis methods of the phosphonimide still exists, and therefore, the invention provides a method for synthesizing the phosphonimide compounds, which has the advantages that the raw materials for reaction are simple and easy to obtain, and a series of phosphonimide compounds are synthesized mildly and efficiently by using cheap metallic iron as a catalyst.
Disclosure of Invention
The invention aims to: in order to solve the defects of the prior art, the invention provides a simple and efficient method for synthesizing the phosphinimide compound, the method does not use the azide compound as the raw material, has simple reaction process, cheap catalyst and high yield, and can still obtain higher yield when the phosphinimide compound is amplified to gram-scale.
The technical scheme is as follows: a method for synthesizing a phosphinimide compound, comprising the steps of:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting in the air atmosphere at room temperature, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1 to 2:0.01 to 0.1;
the dosage of the organic solvent is 5 to 20ml/mmol based on the molar weight of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specification
Wherein:
R 1 is C1-C10 alkyl, phenyl, substituted phenyl, naphthyl or heterocycle, wherein:
the substituent group in the phenyl group containing the substituent group comprises one or more of C1-C10 alkyl, alkoxy, halogen, nitro and trifluoromethyl;
heterocycles include pyridine, furan, thiophene;
R 2 is one of methyl, ethyl, propyl, butyl, phenyl and benzyl;
the structural formula of the tertiary phosphine is shown in the specification
Wherein:
R 3 is one of phenyl, phenyl containing substituent groups and C1-C10 alkyl;
R 4 is one of phenyl, phenyl containing substituent groups and C1-C10 alkyl;
R 5 is one of phenyl, phenyl containing substituent groups and C1-C10 alkyl, wherein:
the substituent in the phenyl containing the substituent is one of C1-C6 alkyl, alkoxy, halogen, nitro and trifluoromethyl.
Further, the organic solvent is any one of methanol, ethanol, acetonitrile, dichloroethane, tetrahydrofuran, dichloromethane, petroleum ether and ethyl acetate.
Still further, the organic solvent is dichloroethane.
Further, the catalyst is any one of cuprous chloride, cuprous trifluoromethanesulfonate, ferrous chloride, ferrous acetate, ferrous sulfate heptahydrate and ferric chloride.
Further, the catalyst is ferrous chloride.
Further, the reaction time of the reaction is 0.5-12 h.
Further, the reaction time of the reaction was 1h.
Further, the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1.2:0.05.
the method for synthesizing the phosphinimide compound has the following advantages that:
(1) The range of the substrate is wide;
(2) The catalyst is relatively low in price and less in dosage;
(3) The reaction operation is simple;
(4) The reaction yield is high, and the yield can still be obtained when the reaction is amplified to gram level.
The specific implementation mode is as follows:
the following describes in detail specific embodiments of the present invention.
The invention discloses a method for synthesizing a phosphinimide compound, which comprises the following steps:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting in the air atmosphere at room temperature, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1 to 2:0.01 to 0.1;
the dosage of the organic solvent is 5 to 20ml/mmol based on the molar weight of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specification
Wherein:
R 1 is C1-C10 alkyl, phenyl, substituted phenyl, naphthyl and heterocycle, wherein:
the substituent group in the phenyl group containing the substituent group comprises one or more of C1-C10 alkyl, alkoxy, halogen, nitro and trifluoromethyl;
heterocycles include pyridine, furan, thiophene;
R 2 is one of methyl, ethyl, propyl, butyl, phenyl and benzyl;
the structural formula of the tertiary phosphine is shown in the specification
Wherein:
R 3 is one of phenyl, phenyl containing substituent groups and C1-C10 alkyl;
R 4 is phenyl, containing substituentsOne of phenyl and C1-C10 alkyl;
R 5 is one of phenyl, phenyl containing substituent groups and C1-C10 alkyl, wherein:
the substituent in the phenyl containing the substituent is one of C1-C6 alkyl, alkoxy, halogen, nitro and trifluoromethyl.
The reaction formula is as follows:
the organic solvent is any one of methanol, ethanol, acetonitrile, dichloroethane, tetrahydrofuran, dichloromethane, petroleum ether and ethyl acetate, and preferably dichloroethane.
The catalyst is any one of cuprous chloride, cuprous trifluoromethanesulfonate, ferrous chloride, ferrous acetate, ferrous sulfate heptahydrate and ferric chloride, and is preferably ferrous chloride.
Further, the reaction time of the reaction is 0.5 to 12 hours, and may be 1 hour, 3 hours, 5 hours, 8 hours, 10 hours, preferably 1 hour.
The room temperature range in this application is 0 to 35 ℃, and may be 0 ℃,5 ℃, 10 ℃, 15 ℃,20 ℃,25 ℃, 30 ℃, 35 ℃ and the like.
Example 1
A method for synthesizing phosphinimide compounds comprises the following steps:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting in an air atmosphere at room temperature, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound with the yield of 92 percent, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1.2:0.05;
the amount of the organic solvent is 10ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specification
Wherein:
R 1 is phenyl;
R 2 is tert-butyl;
the structural formula of the tertiary phosphine is
Wherein:
R 3 is phenyl;
R 4 is phenyl;
R 5 is phenyl.
Further, the organic solvent is dichloroethane.
Further, the catalyst is ferrous chloride.
Further, the reaction time of the reaction was 1h.
The product of this example was subjected to nuclear magnetic resonance, and the results were as follows:
1 H NMR(400MHz),8.41(d,J＝8.0Hz,2H),7.91-7.87(m,6H),7.60-7.57(m,3H),7.52-7.42(m,9H)pp。
example 2
A method for synthesizing a phosphinimide compound, comprising the steps of:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting at room temperature in an air atmosphere, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound with the yield of 86%, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:2:0.1;
the amount of the organic solvent is 5ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specification
Wherein:
R 1 is p-tolyl;
R 2 is a tertiary butyl group; (ii) a
The structural formula of the tertiary phosphine is
Wherein:
R 3 is phenyl;
R 4 is phenyl;
R 5 is phenyl.
Further, the organic solvent is methanol.
Further, the catalyst is cuprous chloride.
Further, the reaction time of the reaction was 12h.
The product of this example was subjected to nuclear magnetic resonance, and the results were as follows:
1H NMR(400MHz,CDCl 3 )δ8.24(d,J＝8.0Hz,2H),7.99–7.70(m,6H),7.66–7.51(m,3H),7.47(td,J＝7.4,3.0Hz,6H),7.20(d,J＝8.0Hz,2H),2.39(s,3H).
example 3
A method for synthesizing phosphinimide compounds comprises the following steps:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting in an air atmosphere at room temperature, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound with the yield of 70%, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1:0.01;
the amount of the organic solvent is 20ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specification
Wherein:
R 1 is p-chlorophenyl;
R 2 is a tertiary butyl group;
the structural formula of the tertiary phosphine is
Wherein:
R 3 is phenyl;
R 4 is phenyl;
R 5 is phenyl.
Further, the organic solvent is ethanol.
Further, the catalyst is cuprous trifluoromethanesulfonate.
Further, the reaction time of the reaction was 0.5h.
The product of this example was subjected to nuclear magnetic resonance, and the results were as follows:
1 H NMR(400MHz,CDCl 3 )δ8.27(d,J＝8.4Hz,2H),7.81(m,,6H),7.55(dd,J＝7.5,6.1Hz,3H),7.47(m,6H),7.34(d,J＝8.4Hz,2H).
example 4
A method for synthesizing a phosphinimide compound, comprising the steps of:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting at room temperature in an air atmosphere, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound with the yield of 85%, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1.5:0.8;
the amount of the organic solvent is 15ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specification
Wherein:
R 1 is naphthyl;
R 2 is tert-butyl;
the structural formula of the tertiary phosphine is
Wherein:
R 3 is phenyl;
R 4 is phenyl;
R 5 is phenyl.
Further, the organic solvent is acetonitrile.
Further, the catalyst is ferrous chloride.
Further, the reaction time of the reaction was 2h.
The product of this example was subjected to nuclear magnetic resonance, and the results of product detection were as follows:
1 H NMR(400MHz,CDCl 3 )δ8.87(s,1H),8.43(dd,J＝8.6,1.5Hz,1H),7.96(d,J＝7.4Hz,1H),7.93–7.77(m,8H),7.58(m,3H),7.54–7.42(m,8H).
example 5
A method for synthesizing a phosphinimide compound, comprising the steps of:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting in an air atmosphere at room temperature, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound with the yield of 78%, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1.2:0.02;
the amount of the organic solvent is 5ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specification
Wherein:
R 1 is p-bromophenyl;
R 2 is tert-butyl;
the structural formula of the tertiary phosphine is
Wherein:
R 3 is phenyl;
R 4 is phenyl;
R 5 is phenyl.
Further, the organic solvent is dichloroethane.
Further, the catalyst is ferrous acetate.
Further, the reaction time of the reaction was 3h.
The product of this example was subjected to nuclear magnetic resonance, and the results of product detection were as follows:
1 H NMR(400MHz,CDCl 3 )δ8.20(d,J＝8.4Hz,2H),7.82(m,6H),7.56(m,3H),7.49(m,8H).
example 6
A method for synthesizing a phosphinimide compound, comprising the steps of:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting at room temperature in an air atmosphere, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound with the yield of 85%, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:2:0.8;
the amount of the organic solvent is 8ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specification
Wherein:
R 1 is p-methoxyphenyl;
R 2 is a tertiary butyl group;
the structural formula of the tertiary phosphine is
Wherein:
R 3 is phenyl;
R 4 is phenyl;
R 5 is phenyl.
Further, the organic solvent is tetrahydrofuran.
Further, the catalyst is ferrous sulfate heptahydrate.
Further, the reaction time of the reaction was 10 hours.
The product of this example was subjected to nuclear magnetic resonance, and the results of product detection were as follows:
1 H NMR(400MHz,CDCl 3 )δ8.30(d,J＝8.8Hz,2H),7.91–7.72(m,6H),7.62–7.52(m,3H),7.47(m,6H),6.90(d,J＝8.8Hz,2H),3.84(s,3H).
example 7
A method for synthesizing a phosphinimide compound, comprising the steps of:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting in the air atmosphere at room temperature, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1:0.1;
the amount of the organic solvent is 16ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specification
Wherein:
R 1 is p-cyanophenyl;
R 2 is a tertiary butyl group;
the structural formula of the tertiary phosphine is
Wherein:
R 3 is phenyl;
R 4 is phenyl;
R 5 is phenyl.
Further, the organic solvent is dichloromethane.
Further, the catalyst is ferrous sulfate heptahydrate
Further, the reaction time of the reaction was 1h.
The product of this example was subjected to nuclear magnetic resonance, and the results of product detection were as follows:
1 H NMR(400MHz,CDCl 3 )δ8.40(s,2H),7.82(s,6H),7.73–7.41(m,11H).
example 8
A method for synthesizing a phosphinimide compound, comprising the steps of:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting in an air atmosphere at room temperature, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound with the yield of 85%, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1.6:0.5;
the amount of the organic solvent is 15ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specification
Wherein:
R 1 is m-fluorophenyl;
R 2 is tert-butyl;
the structural formula of the tertiary phosphine is shown in the specification
Wherein:
R 3 is phenyl;
R 4 is phenyl;
R 5 is phenyl.
Further, the organic solvent is petroleum ether.
Further, the catalyst is ferric chloride.
Further, the reaction time of the reaction was 0.75h.
The product of this example was subjected to nuclear magnetic resonance, and the results of product detection were as follows:
1 H NMR(400MHz,CDCl 3 )δ8.09(d,J＝7.7Hz,1H),8.07–7.99(m,1H),7.90–7.76(m,6H),7.58(td,J＝7.2,1.4Hz,3H),7.54–7.44(m,6H),7.35(td,J＝7.9,5.7Hz,1H),7.13(td,J＝8.3,2.3Hz,1H).
example 9
A method for synthesizing phosphinimide compounds comprises the following steps:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting in an air atmosphere at room temperature, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound with a yield of 65%, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1:0.01;
the amount of the organic solvent is 10ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specification
Wherein:
R 1 is m-chlorophenyl;
R 2 is tert-butyl;
the structural formula of the tertiary phosphine is
Wherein:
R 3 is phenyl;
R 4 is phenyl;
R 5 is phenyl.
Further, the organic solvent is ethyl acetate.
Further, the catalyst is ferric trichloride.
Further, the reaction time of the reaction was 2h.
The product of this example was subjected to nuclear magnetic resonance, and the results of product detection were as follows:
1 H NMR(400MHz,CDCl 3 )δ8.33(s,1H),8.18(d,J＝7.7Hz,1H),7.89–7.75(m,6H),7.57(dd,J＝7.6,5.9Hz,3H),7.49(td,J＝7.5,3.0Hz,6H),7.41(d,J＝7.9Hz,1H),7.32(t,J＝7.8Hz,1H).
example 10
A method for synthesizing phosphinimide compounds comprises the following steps:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting at room temperature in an air atmosphere, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound with the yield of 92%, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1.5:0.05;
the amount of the organic solvent is 10ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specification
Wherein:
R 1 is 3, 5-dimethylphenyl;
R 2 is tert-butyl;
the structural formula of the tertiary phosphine is
Wherein:
R 3 is phenyl;
R 4 is phenyl;
R 5 is phenyl.
Further, the organic solvent is dichloroethane.
Further, the catalyst is ferrous chloride.
Further, the reaction time of the reaction was 1h.
The product of this example was subjected to nuclear magnetic resonance, and the results of product detection were as follows: 1 H NMR(400MHz,CDCl 3 )δ7.96(s,2H),7.90–7.76(m,6H),7.55(m,3H),7.47(m,6H),7.08(s,1H),2.36(s,6H).
example 11
A method for synthesizing a phosphinimide compound, comprising the steps of:
adding the N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting at room temperature in an air atmosphere, and performing post-treatment after the reaction is finished to obtain the phosphinimide compound, wherein the yield is 87 percent:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1:0.06;
the amount of the organic solvent is 5ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specification
Wherein:
R 1 is m-tolyl;
R 2 is tert-butyl;
the structural formula of the tertiary phosphine is
Wherein:
R 3 is phenyl;
R 4 is phenyl;
R 5 is phenyl.
Further, the organic solvent is methanol.
Further, the catalyst is ferrous chloride.
Further, the reaction time of the reaction was 1h.
The product of this example was subjected to nuclear magnetic resonance, and the results of product detection were as follows:
1 H NMR(400MHz,CDCl 3 )δ8.16(d,J＝8.8Hz,2H),7.89–7.76(m,6H),7.55(td,J＝7.2,1.4Hz,3H),7.47(m,6H),7.33–7.26(m,2H),2.39(s,3H).
example 12
A method for synthesizing a phosphinimide compound, comprising the steps of:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting at room temperature in an air atmosphere, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound with the yield of 92%, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1.5:0.05;
the amount of the organic solvent is 15ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specification
Wherein:
R 1 is 2-thienyl;
R 2 is tert-butyl;
the structural formula of the tertiary phosphine is
Wherein:
R 3 is phenyl;
R 4 is phenyl;
R 5 is phenyl.
Further, the organic solvent is dichloroethane.
Further, the catalyst is ferrous chloride.
Further, the reaction time of the reaction was 1h.
The product of this example was subjected to nuclear magnetic resonance, and the results of product detection were as follows:
1 H NMR(400MHz,CDCl 3 )δ7.83(m,6H),7.77(d,J＝3.0Hz,1H),7.56(m,3H),7.48(m,6H),7.38(d,J＝4.9Hz,1H),7.08–6.99(m,1H).
examples 13 to 31
Is essentially the same as example 1, except that the substituent R 1 The following table specifically shows the differences:
examples 32 to 38
Is substantially the same as example 2, except that the substituent R 2 The following table specifically shows the differences:
| R 2 | |
| example 32 | Methyl radical |
| Example 33 | Ethyl radical |
| Example 34 | Isopropyl group |
| Example 35 | N-propyl radical |
| Example 36 | N-butyl |
| Example 37 | Phenyl radical |
| Example 38 | Benzyl radical |
Examples 39 to 56
Is essentially the same as example 3, except that the substituent R of the tertiary phosphine 3 The following table specifically shows the differences:
| R 3 | |
| example 39 | Phenyl having a substituent which is methyl |
| Example 40 | Phenyl having a substituent which is ethyl |
| EXAMPLE 41 | Phenyl having a substituent being n-heptyl |
| Example 42 | Phenyl containing a substituent being methoxy |
| Example 43 | Phenyl having a substituent of F |
| Example 44 | Phenyl containing a substituent, the substituent being Cl |
| Example 45 | Phenyl containing a substituent being nitro |
| Example 46 | Phenyl having a substituent which is trifluoromethyl |
| Example 47 | Methyl radical |
| Example 48 | Ethyl radical |
| Example 49 | Isopropyl group |
| Example 50 | Isobutyl radical |
| Example 51 | Isoamyl radical |
| Example 52 | N-hexyl radical |
| Example 53 | N-heptyl radical |
| Example 54 | N-octyl radical |
| Example 55 | N-nonyl radical |
| Example 56 | N-decyl radical |
Examples 57 to 74
Is essentially the same as example 4, except that the substituent R of the tertiary phosphine 4 The following table specifically shows the differences:
examples 75 to 92
Is essentially the same as example 5, except that the substituent R of the tertiary phosphine 5 The following table specifically shows the differences:
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 (7)
1. A method for synthesizing a phosphinimide compound is characterized by comprising the following steps:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting in the air atmosphere at room temperature, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound, wherein:
the reaction formula is as follows:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1 to 2:0.01 to 0.1;
the dosage of the organic solvent is 5 to 20ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specification
Wherein:
R 1 is C1-C10 alkyl, phenyl, substituted phenyl, naphthyl, heterocycle,
wherein:
the substituent in the phenyl containing the substituent is one or more of C1-C10 alkyl, alkoxy, halogen, nitro and trifluoromethyl;
the heterocyclic ring is pyridine, furan or thiophene;
R 2 is one of methyl, ethyl, propyl, butyl, phenyl and benzyl;
the structural formula of the tertiary phosphine is
Wherein:
R 3 is one of phenyl, phenyl containing substituent groups and C1-C10 alkyl;
R 4 is one of phenyl, phenyl containing substituent groups and C1-C10 alkyl;
R 5 is one of phenyl, phenyl containing substituent groups and C1-C10 alkyl, wherein:
the substituent group in the phenyl containing the substituent group is one of C1-C6 alkyl, alkoxy, halogen, nitro and trifluoromethyl, wherein:
the catalyst is any one of cuprous chloride, cuprous trifluoromethanesulfonate, ferrous chloride, ferrous acetate, ferrous sulfate heptahydrate and ferric chloride.
2. The method of claim 1, wherein the organic solvent is any one of methanol, ethanol, acetonitrile, dichloroethane, tetrahydrofuran, dichloromethane, petroleum ether, and ethyl acetate.
3. The method of claim 2, wherein the organic solvent is dichloroethane.
4. The method of claim 1, wherein the catalyst is ferrous chloride.
5. The method for synthesizing phosphinimide compounds according to claim 1, wherein the reaction time is 0.5 to 12 hours.
6. The method for synthesizing phosphinimide compounds according to claim 5, wherein the reaction time is 1h.
7. The method of claim 1, wherein the molar ratio of N-hydrocarbonacyloxy amide derivative, tertiary phosphine, catalyst is 1:1.2:0.05.
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| CN109762017A (en) * | 2019-01-17 | 2019-05-17 | 大连理工大学 | A kind of preparation method of the phosphorus nitrence compound of iron catalysis |
| CN109912603A (en) * | 2019-03-29 | 2019-06-21 | 苏州大学 | A kind of practical approach using N- methoxyamide as nitrogen source synthesizing new bioactive molecule |
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| CN109762017A (en) * | 2019-01-17 | 2019-05-17 | 大连理工大学 | A kind of preparation method of the phosphorus nitrence compound of iron catalysis |
| CN109912603A (en) * | 2019-03-29 | 2019-06-21 | 苏州大学 | A kind of practical approach using N- methoxyamide as nitrogen source synthesizing new bioactive molecule |
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| Title |
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| N-[(Trifluoromethanesulfonyl)oxy]carbamate: A New Reagent for the Synthesis of N-(Ethoxycarbonyl)sulfilimines;Yasumitsu Tamura et al.;《J. Org. Chem.》;19811231;第46卷;第1732-1734页 * |
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