CN108586527B - Aryl phosphonate compound and preparation method thereof - Google Patents

Aryl phosphonate compound and preparation method thereof Download PDF

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CN108586527B
CN108586527B CN201810554230.0A CN201810554230A CN108586527B CN 108586527 B CN108586527 B CN 108586527B CN 201810554230 A CN201810554230 A CN 201810554230A CN 108586527 B CN108586527 B CN 108586527B
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aryl phosphonate
phosphonate compound
aryl
photosensitizer
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陈晓岚
李�瑞
於兵
屈凌波
孙远强
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Zhengzhou University
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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
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4021—Esters of aromatic acids (P-C aromatic linkage)
    • 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
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/40—Esters thereof
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4075—Esters with hydroxyalkyl compounds

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Abstract

The invention discloses an aryl phosphonate compound and a preparation method thereof, wherein organic dye is used as photosensitizer, catalytic amount of alkali is added, aryl hydrazine and phosphite ester are used as reactants, acetonitrile is used as solvent, the temperature is controlled at 25-45 ℃, the reaction is carried out for 1-6h under the irradiation of visible light, and then the product aryl phosphonate compound is separated through column chromatography. The invention provides a novel method for synthesizing aryl phosphonate target compounds by using cheap and easily-obtained aryl hydrazine and phosphite compounds as starting raw materials for the first time. The method has the advantages of mild reaction conditions, simple operation and the like; in the drug synthesis, the residue of the metal catalyst brings great trouble to the production and application of the drug, so the metal-free catalytic system in the invention has great potential application value.

Description

Aryl phosphonate compound and preparation method thereof
Technical Field
The invention relates to the field of chemical synthesis, in particular to a preparation method of aryl phosphonate compounds.
Background
Phosphonate compounds are important organic phosphorus compounds and are widely applied to the fields of organic synthetic chemistry, material chemistry, pharmaceutical chemistry and the like due to unique biological activity and flame retardant property of the phosphonate compounds. Generally, phosphonates are synthesized by the Michaelis-Arbuzov reaction (e.g., org. Lett.2011,13, 1270) which uses halogenated hydrocarbons as starting materials to react with phosphites SN2, under heating, dialkyl alkylphosphonate and another molecule of alkyl halide are generated. Since aryl halides cannot react with phosphites to form SN2 substitution, so the Michaelis-Arbuzov reaction cannot be used to synthesize aryl phosphonate compounds. Furthermore, although coupling reactions of aryl bromides with hydrogen-phosphites can synthesize aryl phosphonate compounds (RSC Advances,2014,4,22808), such reactions typically require the use of expensive palladium catalysts, limiting their application to some extent. Recently, the literature reports the use of CuO as a catalyst with the addition of 3 equivalents of Cs2CO3Can realize the reaction of aromatic hydrazine and phosphite ester to generate aryl phosphonate compounds (J.org.chem.2014,79,1449); the process requires the participation of a metal catalyst and consumes an excess of inorganic base. The method for synthesizing the aryl phosphonate compound by using the aromatic hydrazine compound and the phosphite ester as raw materials under the irradiation of visible light disclosed by the invention has no related literature and patent report for a while.
Disclosure of Invention
The invention provides a preparation method of an aryl phosphonate compound, and provides a mild, cheap and metal-free visible light catalysis method for synthesizing aryl phosphonate. The synthesis method has mild reaction conditions, is simple, convenient and safe to operate in an open system in the air under the condition of visible light, has cheap and easily obtained raw materials and catalysts, and is an environment-friendly green synthesis method.
The technical scheme for realizing the invention is as follows: an aryl phosphonate compound having the structural formula:
Figure BDA0001681805430000021
wherein R is1Is trifluoromethyl, methyl, tert-butyl, methoxy, chlorine or nitro; r2Is ethyl, n-butyl, isopropyl or phenyl.
The preparation method of the aryl phosphonate compound comprises the following steps: adding aromatic hydrazine, phosphite ester and solvent into a reaction tube, then adding alkali and photosensitizer into the reaction tube, and reacting in the air under the irradiation of visible light and under the stirring condition to obtain the aryl phosphonate compound.
The structural formula of the aromatic hydrazine is as follows:
Figure BDA0001681805430000022
wherein R is1Is trifluoromethyl, methyl, tert-butyl, methoxy, chlorine or nitro.
The phosphite ester has the following structural formula:
Figure BDA0001681805430000023
wherein R is2Is ethyl, n-butyl, isopropyl or phenyl.
The solvent is any one of acetonitrile or N, N-dimethylformamide; the alkali is any one of triethylene diamine, triethylamine and 2, 6-dimethyl pyridine; the photosensitizer is any one of eosin Y and eosin B.
The molar ratio of the aromatic hydrazine to the phosphite ester to the alkali to the photosensitizer is 1 (1-2): 0.5:0.05.
The reaction temperature is 25-45 ℃ and the reaction time is 1-6 h.
The reaction general formula of the preparation method is as follows:
Figure BDA0001681805430000031
the invention has the beneficial effects that: the invention provides a preparation method of an aryl phosphonate compound, which is directly carried out in the air without adding an additional metal catalyst and uses a cheap and easily-obtained photosensitizer as a catalyst to efficiently synthesize the aryl phosphonate compound under the irradiation of visible light. The method has the advantages of simple and safe operation, mild reaction conditions, no metal, good economy and environmental friendliness.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The preparation method of the aryl phosphonate compound comprises the following steps:
adding photosensitizer eosin B (5 mol%), triethylene diamine (50 mol%), solvent acetonitrile 1.5mL, phenylhydrazine 0.5mmol and triethyl phosphite 1.0mmol into a 25mL reaction tube, stirring in air to control the reaction temperature to be 45 ℃, reacting for 6 hours under the irradiation of white light, and separating by silica gel column chromatography to obtain the final product, wherein the yield of the final product is 65% based on the molar weight of phenylhydrazine as 100%.
The specific results are as follows:
Figure BDA0001681805430000032
1HNMR(CDCl3,400MHz):δ＝7.70-7.83(m2H),7.50-7.56(m,1H),7.40-7.47(m,2H),4.00-4.20(m,4H),1.30-1.35(d,J＝14.1Hz)；13C NMR(CDCl3,100MHz):δ＝132.3(d,J ＝2.7Hz),131.7(d,J＝9.2Hz),128.44(d,J＝15.2Hz),128.41(d,J＝187.6Hz),62.0(d,J ＝5.9Hz),16.3(d,J＝6.5Hz)。
example 2
The preparation method of the aryl phosphonate compound comprises the following steps:
adding a photosensitizer eosin Y (5 mol%), triethylene diamine (50 mol%), a solvent acetonitrile 1.5mL, 4-methoxy phenylhydrazine 0.5mmol and triethyl phosphite 1.0mmol into a 25mL reaction tube, stirring in air to control the reaction temperature to be 25 ℃, reacting for 1 hour under the irradiation of white light, and separating by silica gel column chromatography to obtain the final product.
The specific results are as follows:
Figure BDA0001681805430000041
1H NMR(CDCl3,400MHz):δ＝7.64-7.70(m,2H),6.85-6.91(m,2H), 3.90-4.10(m,4H),3.77(s,1H),1.20-1.26(t,6H)；13C NMR(100MHz,CDCl3):δ＝ 162.8(d,J＝3.6Hz),133.7(d,J＝11.0Hz),119.5(d,J＝195.2Hz),113.9(d,J＝ 16.2Hz),61.8(d,J＝5.9Hz),55.3,16.3(d,J＝6.6Hz)。
example 3
The preparation method of the aryl phosphonate compound comprises the following steps:
a25 mL reaction tube was charged with the photosensitizer eosin B (5 mol%), triethylene diamine (50 mol%), the solvent N, N-dimethylformamide 1.5mL, 4-trifluoromethylphenylhydrazine 0.5mmol, and triethyl phosphite 1.0mmol, stirred in air at a reaction temperature of 35 ℃ and reacted for 2 hours under white light irradiation, and then separated by silica gel column chromatography to obtain the final product.
The specific results are as follows:
Figure BDA0001681805430000042
1H NMR(CDCl3,400MHz):δ＝7.92-7.98(m,2H),7.71-7.75(m,2H), 4.00-4.22(m,4H),1.32-1.36(t,6H)；13C NMR(CDCl3,100MHz):δ＝134.2(d,J＝ 3.13Hz),133.9(d,J＝3.2Hz),133.7(d,J＝186.2Hz),132.2(d,J＝10.15Hz), 125.4(dq,J＝11.2Hz),62.5(d,J＝5.6Hz),16.3(d,J＝6.2Hz)。
example 4
The preparation method of the aryl phosphonate compound comprises the following steps:
a25 mL reaction tube was charged with the photosensitizer eosin B (5 mol%), triethylamine (50 mol%), the solvent N, N-dimethylformamide 1.5mL, 2, 5-difluorophenylhydrazine 0.5mmol, and triethyl phosphite 0.5mmol, stirred in air at a reaction temperature of 35 ℃ and reacted for 2 hours under white light irradiation, and then separated by silica gel column chromatography to obtain the final product.
The specific results are as follows:
Figure BDA0001681805430000051
1H NMR(CDCl3,400MHz):δ＝7.43-7.51(m,1H),7.12-7.19(m,1H),7.00-7.07(m,1H),4.04-4.24(m,4H),1.26-1.30(t,6H)；13C NMR(CDCl3,100MHz):δ＝160.4(dd,J＝247Hz,2.2Hz),159.48(dd,J＝21.8Hz),157.0(dd,J＝19.2Hz),130.9(dd,J＝209 Hz),121.48(dd,J＝8.9Hz,2.5Hz),120.9(dd,J＝6.5Hz),117.8(dt,J＝25Hz), 62.8(d,J＝5.7Hz),16.3(d,J＝6.4Hz)。
example 5
The preparation method of the aryl phosphonate compound comprises the following steps:
the aromatic hydrazine is 2-trifluoromethyl phenylhydrazine, a photosensitizer eosin B (5mol percent), 2, 6-dimethyl pyridine (50mol percent), a solvent acetonitrile 1.5mL, 0.5mmol of 2-trifluoromethyl phenylhydrazine and 0.8mmol of triethyl phosphite are added into a 25mL reaction tube, the reaction temperature is controlled to be 45 ℃ by stirring in the air, and after the reaction is carried out for 5 hours under the irradiation of white light, the final product is obtained by silica gel column chromatography separation.
The specific results are as follows:
Figure BDA0001681805430000061
1H NMR(CDCl3,400MHz):δ＝8.20-8.28(m,1H),7.80-7.84(m,1H),7.64-7.68(m,2H),4.08-4.27(m,4H),1.32-1.37(t,6H)；13C NMR(CDCl3,100MHz):δ＝136.01(d,J ＝7.7Hz),132.37(d,J＝2.76Hz),131.4(d,J＝13.1Hz),127.9(dd,J＝185Hz),127.5(m),124.6(dd,J＝272Hz,4.8Hz),63.7(d,J＝5.9Hz),16.1(d,J＝6.6Hz)。
example 6
The aromatic hydrazine is 3, 5-dimethyl phenylhydrazine, other test methods and conditions are the same as example 1, and the specific results are as follows:
Figure BDA0001681805430000062
1H NMR(CDCl3,400MHz):δ＝7.37(s,1H),7.33(s,1H),3.94-4.12(m, 4H),2.28(s,6H),1.23-1.27(t,6H)；13C NMR(CDCl3,100MHz):δ＝138.2(d,J＝15.5 Hz),134.15(d,J＝3.2Hz),129.4(d,J＝9.8Hz),128.7(d,J＝184.8Hz),62.03(d,J＝5.4 Hz),21.19(s),16.38(d,J＝6.5Hz)。
example 7
The aromatic hydrazine is 4-chlorophenylhydrazine, other test methods and conditions are the same as those in example 1, and the specific results are as follows:
Figure BDA0001681805430000063
1HNMR(CDCl3,400MHz):δ＝7.65-7.70(dd,2H),7.37-7.39(dd,2H),3.96-4.01(m,4H),1.23-1.27(t,6H)；13CNMR(CDCl3,100MHz):δ＝138.98(s),133.2(d,J＝10.7Hz),128.9( d,J＝15.6Hz),62.3(d,J＝5.4Hz),16.3(d,J＝6.4Hz)。
example 8
The aromatic hydrazine is 2, 4-dichlorophenylhydrazine, other test methods and conditions are the same as those in example 1, and the specific results are as follows:
Figure BDA0001681805430000071
1HNMR(CDCl3,400MHz):δ＝7.84-7.90(dd,1H),7.40-7.42(dd,1H),7.25-7.30(dt,1 H),4.00-4.18(m,4H),1.26-1.30(t,6H)；13C NMR(CDCl3,100MHz):δ＝139.4(d,J＝3.6Hz),137.7(d,J＝3.7Hz),136.8(d,J＝8.6Hz),130.7(d,J＝10.8Hz),126.9(d,J＝14.4Hz),127.0(d,J＝192Hz),62.7(d,J＝1.6Hz),16.3(d,J＝6.4Hz)。
the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (3)

1. The preparation method of the aryl phosphonate compound is characterized by comprising the following steps: adding aromatic hydrazine, phosphite ester and a solvent into a reaction tube, then adding alkali and a photosensitizer, and reacting in the air under the irradiation of visible light and under the stirring condition to obtain an aryl phosphonate compound;
the structural formula of the aryl phosphonate compound is as follows:
Figure DEST_PATH_IMAGE001
；
wherein R is1Is trifluoromethyl, methyl, tert-butyl, methoxy, chlorine or nitro; r2Is ethyl, n-butyl, isopropyl, phenyl;
the structural formula of the aromatic hydrazine is as follows:
Figure 810208DEST_PATH_IMAGE002
wherein R is1Is trifluoromethyl, methyl, tert-butyl, methoxy, chlorine or nitro;
the phosphite ester has the following structural formula:
Figure DEST_PATH_IMAGE003
，
wherein R is2Is ethyl, n-butyl, isopropyl, phenyl;
the solvent is any one of acetonitrile or N, N-dimethylformamide; the alkali is any one of triethylene diamine, triethylamine and 2, 6-dimethyl pyridine; the photosensitizer is any one of eosin Y and eosin B.
2. The process for preparing arylphosphonate ester compounds according to claim 1, wherein: the molar ratio of the aromatic hydrazine to the phosphite ester to the alkali to the photosensitizer is 1 (1-2): 0.5:0.05.
3. The process for preparing arylphosphonate ester compounds according to claim 1, wherein: the reaction temperature is 25-45 ℃ and the reaction time is 1-6 h.
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CN109575071A (en) * 2018-10-06 2019-04-05 郑州大学 A kind of arylphosphonic acid ester type compound and preparation method thereof
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Copper-Catalyzed Coupling Reaction of Arylhydrazines and Trialkylphosphites;Sheng-Yan Chen et al.;《The Journal of Organic Chemistry》;20140127;第1449-1453页 *
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