CN114605466B - Synthesis method of acyl phosphate - Google Patents
Synthesis method of acyl phosphate Download PDFInfo
- Publication number
- CN114605466B CN114605466B CN202210156612.4A CN202210156612A CN114605466B CN 114605466 B CN114605466 B CN 114605466B CN 202210156612 A CN202210156612 A CN 202210156612A CN 114605466 B CN114605466 B CN 114605466B
- Authority
- CN
- China
- Prior art keywords
- formula
- catalyst
- represented
- substituted
- acyl phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- -1 acyl phosphate Chemical compound 0.000 title claims abstract description 51
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 40
- 239000010452 phosphate Substances 0.000 title claims abstract description 39
- 238000001308 synthesis method Methods 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 230000002194 synthesizing effect Effects 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 238000005917 acylation reaction Methods 0.000 claims description 13
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 12
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 235000009518 sodium iodide Nutrition 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 125000001544 thienyl group Chemical group 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims 2
- 125000001072 heteroaryl group Chemical group 0.000 abstract description 11
- 125000003118 aryl group Chemical group 0.000 abstract description 8
- 125000005843 halogen group Chemical group 0.000 abstract description 2
- 235000021317 phosphate Nutrition 0.000 description 36
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 239000012230 colorless oil Substances 0.000 description 6
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- BJMLLSSSTGHJJE-UHFFFAOYSA-N (4-methylbenzoyl) 4-methylbenzoate Chemical compound C1=CC(C)=CC=C1C(=O)OC(=O)C1=CC=C(C)C=C1 BJMLLSSSTGHJJE-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- YLBSXJWDERHYFY-UHFFFAOYSA-N (2-methylbenzoyl) 2-methylbenzoate Chemical compound CC1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C YLBSXJWDERHYFY-UHFFFAOYSA-N 0.000 description 2
- YGMHIBLUWGDWKP-UHFFFAOYSA-N (4-methoxybenzoyl) 4-methoxybenzoate Chemical compound C1=CC(OC)=CC=C1C(=O)OC(=O)C1=CC=C(OC)C=C1 YGMHIBLUWGDWKP-UHFFFAOYSA-N 0.000 description 2
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- OLENANGIJWDOPG-UHFFFAOYSA-N (2-chlorobenzoyl) 2-chlorobenzoate Chemical compound ClC1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1Cl OLENANGIJWDOPG-UHFFFAOYSA-N 0.000 description 1
- AGKBXKFWMQLFGZ-UHFFFAOYSA-N (4-methylbenzoyl) 4-methylbenzenecarboperoxoate Chemical compound C1=CC(C)=CC=C1C(=O)OOC(=O)C1=CC=C(C)C=C1 AGKBXKFWMQLFGZ-UHFFFAOYSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- WZPMZMCZAGFKOC-UHFFFAOYSA-N diisopropyl hydrogen phosphate Chemical compound CC(C)OP(O)(=O)OC(C)C WZPMZMCZAGFKOC-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/095—Compounds containing the structure P(=O)-O-acyl, P(=O)-O-heteroatom, P(=O)-O-CN
- C07F9/096—Compounds containing the structure P(=O)-O-C(=X)- (X = O, S, Se)
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Catalysts (AREA)
Abstract
The invention provides a synthesis method of acyl phosphate, which is a compound shown in a formula (3) and comprises the following steps: a step of acylating a peroxyaryl anhydride represented by the formula (1) with a phosphorous acid diester represented by the formula (2) in the presence of a catalyst, wherein R is represented by the formulae (1) to (3) 1 Is substituted or unsubstituted aryl or heteroaryl, R 2 And R 3 May be the same or different and are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl or heteroaryl group, and the catalyst is a halide, formula (1):formula (2):formula (3):
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a synthetic method of acyl phosphate.
Background
Organophosphates exist as building blocks in a variety of common natural products and pesticides, and have excellent biological properties. Meanwhile, acyl phosphate is one of the extremely important organic substances, and has been widely used in organic synthesis intermediates, drugs and functional materials. In addition, acyl phosphates are intermediates for many biochemical acylation reactions. Therefore, the synthesis of acyl phosphate ester has attracted continuous attention and has been studied extensively.
The synthesis method of acyl phosphate in the prior art mainly depends on factors such as acyl chloride, a low-temperature system, the use of a metal catalyst and the like, and has the problems of environmental unfriendliness, low economic efficiency of synthesis steps, limited reaction substrates and low operability. Therefore, it is necessary to develop an environmentally friendly and low-cost method for synthesizing acyl phosphate.
Disclosure of Invention
The inventors of the present application have found that by using a halide as a catalyst, it is possible to reduce the cost of synthesizing an acyl phosphate, reduce the environmental burden of the reaction, and synthesize an acyl phosphate in high yield. The purpose of the present application is to provide a method for synthesizing an acyl phosphate ester, which is efficient, environmentally friendly, and low-cost.
The purpose of the application is realized by adopting the following technical scheme:
the application provides a synthesis method of acyl phosphate, wherein the acyl phosphate is a compound shown as a formula (3) and comprises the following steps: a step of acylating a peroxyaryl anhydride represented by the formula (1) with a phosphorous acid diester represented by the formula (2) in the presence of a catalyst,
wherein, in the formulas (1) to (3), R 1 Is substituted or unsubstituted aryl or heteroaryl, R 2 And R 3 May be the same or different and are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl or heteroaryl group, and the catalyst is a halide.
According to the method for synthesizing acyl phosphate, the acyl phosphate can be synthesized efficiently at low cost and in an environment-friendly manner.
In some alternative embodiments, R 1 Aryl or heteroaryl substituted with an electron donating group.
According to the method for synthesizing acyl phosphate, acyl phosphate can be synthesized with higher yield.
In some alternative embodiments, R 1 Is unsubstituted phenyl, alkyl of 1 to 10 carbon atoms, halogen, alkoxy substituted phenyl, at least one of substituted or unsubstituted naphthyl and thienyl, and/or R 2 And R 3 Each being at least one of an unsubstituted alkyl group having 1 to 4 carbon atoms and a substituted or unsubstituted phenyl group.
According to the method for synthesizing acyl phosphate, acyl phosphate can be synthesized with higher yield.
In some alternative embodiments, the acyl phosphate ester is a compound of any one of formulas 3a to 3f,
in some optional embodiments, the catalyst is any one or combination of bromide, iodide, chloride, and/or the solvent for the acylation reaction is any one or combination of acetonitrile, dichloromethane, 1, 2-dichloroethane, and N, N-dimethylformamide.
In some optional embodiments, the catalyst is any one or combination of sodium bromide, lithium bromide, potassium bromide, ammonium bromide, tetrabutylammonium bromide, sodium iodide, and sodium chloride, and/or the solvent is acetonitrile.
According to the method for synthesizing acyl phosphate, the cost and the environmental burden of the reaction for synthesizing acyl phosphate can be further reduced.
In some alternative embodiments, the molar ratio of the phosphorous acid diester of formula (2), the peroxyaryl anhydride of formula (1), and the catalyst is 1: (1-3): (0.1-1.5).
According to the method for synthesizing an acyl phosphate of the present invention, the cost and the environmental burden of the reaction for synthesizing an acyl phosphate can be further reduced.
In some alternative embodiments, the molar ratio of the phosphorous acid diester of formula (2), the peroxyaryl anhydride of formula (1), and the catalyst is 1: (1.5-2): (0.2-1).
According to the method for synthesizing acyl phosphate, the cost of the reaction for synthesizing acyl phosphate can be further reduced.
In some alternative embodiments, the reaction temperature of the acylation reaction is 30 ℃ to 50 ℃, and/or the reaction atmosphere of the acylation reaction is air.
In some alternative embodiments, the reaction temperature for the acylation reaction is 40 ℃.
According to the method for synthesizing acyl phosphate, the cost and the environmental burden of synthesizing acyl phosphate can be further reduced.
Detailed Description
The present application is further described below with reference to specific embodiments, and it should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment.
The invention provides a synthesis method of acyl phosphate. Specifically disclosed is a method for synthesizing an acyl phosphate represented by the formula (3), which comprises: a step of acylating a peroxyaryl anhydride represented by the formula (1) with a phosphorous acid diester represented by the formula (2) in the presence of a catalyst,
wherein, in the formulae (1) to (3), R 1 Is substituted or unsubstitutedAryl or heteroaryl of, R 2 And R 3 May be the same or different and are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl or heteroaryl group, and the catalyst is a halide.
The acyl phosphate synthesis method of the invention not only reduces the synthesis cost of acyl phosphate, but also reduces the burden on the environment by replacing the metal catalyst (such as metal Na or Ag) in the prior art with halide.
The peroxyaryl anhydride represented by the formula (1) is not particularly limited, and for example, R in the formula (1) 1 And may be a substituted or unsubstituted aryl or heteroaryl group. Preferably, R 1 May be a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted thienyl group, or the like. The substituent of the substituted aryl and heteroaryl is not particularly limited, but is preferably an electron donating group, more preferably at least one of an alkyl group having 1 to 10 carbon atoms, a halogen and an alkoxy group, still more preferably at least one of a methyl group, cl, br and a methoxy group, and most preferably a methyl group.
The phosphorous diester represented by the formula (2) is not particularly limited, and for example, R in the formula (2) 2 And R 3 May be the same or different, and R 2 And R 3 Each independently represents an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group or a heteroaryl group. Preferably, R 2 And R 3 Each independently represents at least one of an alkyl group having 1 to 4 carbon atoms and a substituted or unsubstituted phenyl group. The substituent of the substituted aryl and heteroaryl is not particularly limited, but is preferably at least one of an alkyl group having 1 to 10 carbon atoms, a halogen group and an alkoxy group, more preferably at least one of a methyl group, cl, br and a methoxy group, and most preferably a methyl group.
Preferably, according to the method for synthesizing an acyl phosphate of the present invention, a compound represented by any one of the following formulas 3a to 3f can be synthesized.
The halide used as the catalyst in the present invention is not particularly limited, but is preferably any one or a combination of bromide, iodide and chloride, more preferably any one or a combination of sodium bromide, lithium bromide, potassium bromide, ammonium bromide, tetrabutylammonium bromide, sodium iodide and sodium chloride, and most preferably sodium bromide or tetrabutylammonium bromide (TBAB).
The amount of the catalyst to be used is not particularly limited, and for example, the molar ratio of the phosphorous diester represented by formula (2), the peroxyaryl anhydride represented by formula (1), and the catalyst is 1: (1-3): (0.1 to 1.5), preferably, the molar ratio of the phosphorous acid diester represented by the formula (2), the peroxyaryl anhydride represented by the formula (1) and the catalyst is 1: (1.5-2): (0.2-1). When the amount of the catalyst is excessively low, the acylation reaction does not proceed efficiently. On the other hand, excessive catalyst usage does not bring about further improvement of yield or selectivity, but causes catalyst waste, increasing cost and environmental burden.
The acylation reaction of the present invention needs to be carried out in a solvent. The solvent is preferably any one or a combination of acetonitrile, dichloromethane (DCM), dichloroethane (DCE) and N, N-Dimethylformamide (DMF), more preferably acetonitrile.
The reaction temperature of the acylation reaction of the present invention is not particularly limited, but is preferably 30 to 50 ℃, and more preferably 35 to 45 ℃. The reaction atmosphere for the acylation reaction of the present invention is not particularly limited, and may be carried out, for example, in an air atmosphere.
Examples
The present invention is further described below by way of specific examples, but the present invention is not limited to the following examples.
In the examples, use is made of 1 H-NMR、 13 C-NMR analysis and identification of the compounds were carried out.
< 1 H-NMR and 13 C-NMR analysis method>
In that 1 JNM-ECP400 manufactured by JEOL Datum Ltd. Was used for H-NMR analysis. The integral value of the NMR measurement value is a theoretical value. 1 H-NMR and 13 C-NMR in the cellCDCl at room temperature 3 TMS was used as an internal standard (400 MHz) 1 H,101MHz 13 C) In CDCl 3 The shifts (. Delta.) are reported in ppm and the J values in Hz.
Example 1
Bis (4-methylbenzoyl) peroxide (0.80 mmol), diethyl phosphite (0.4 mmol), naBr (20 mol%) and acetonitrile (4 mL) were added to a Schlenk tube (50 mL) with a stirring rod, and stirring was performed under air atmosphere at 40 ℃ for 12 hours under a closed condition. After the reaction is finished, the mixture is treated with CH 2 Cl 2 (3X 5 mL), dissolved, filtered and concentrated under reduced pressure. The residue was then purified by TLC technique (10: 1 (v/v) petroleum ether/ethyl acetate) to give the desired product (diethylphosphoric acid) 4-methylbenzoic anhydride (3 a).
Examples 2 to 6
Mixtures 3b to 3f shown below were synthesized under the same conditions as in example 1, with the compound of formula (1) and the compound of formula (2) being varied in kind, respectively, and the yields and the characterization results are as follows.
(diethylphosphoric acid) 4-methylbenzoic anhydride (3 a) a colorless oil. 1 H-NMR(400MHz,CDCl 3 )δ7.88(d,J=7.6Hz,2H),7.22(d,J=7.5Hz,2H),4.30(p,J=7.2Hz,4H),2.37(s,3H),1.36(t,J=7.1Hz,6H). 13 C NMR(101MHz,CDCl 3 )δ160.9(d,J=8.1Hz),145.6,130.6,129.4,125.3(d,J=9.1Hz),65.2(d,J=5.1Hz),21.7,16.0(d,J=7.1Hz)。
(diethylphosphoric acid) benzoic anhydride (3 b) colorless oil. 1 H NMR(400MHz,CDCl 3 )δ8.01(d,J=7.4Hz,2H),7.60(t,J=7.4Hz,1H),7.44(t,J=7.8Hz,2H),4.33(p,J=7.2Hz,4H),1.38(t,J=7.1Hz,6H). 13 C NMR(101MHz,CDCl3)δ161.0(d,J=8.1Hz),134.5,130.6,128.7,128.1(d,J=8.1Hz),65.3(d,J=6.1Hz),16.0(d,J=7.1Hz)。
(diethylphosphoric acid) 4-methoxybenzoic anhydride (3 c) as a colorless oil. 1 H NMR(400MHz,CDCl 3 )δ7.59(d,J=7.5Hz,1H),7.49(s,1H),7.33(t,J=8.1Hz,1H),7.13(dd,J=8.3,2.3Hz,1H),4.31(p,J=7.1Hz,4H),3.80(s,3H),1.37(t,J=7.2Hz,6H). 13 C NMR(101MHz,CDCl 3 )δ161.7(d,J=9.1Hz),160.5,130.5,121.8,115.7,66.1,56.2,16.9。
(diethylphosphoric acid) 2-methylbenzoic anhydride (3 d) as a colorless oil. 1 H NMR(400MHz,CDCl 3 )δ7.96(d,J=8.4Hz,1H),7.46(t,J=7.4Hz,1H),7.26(dd,J=8.7,5.5Hz,2H),4.34(p,J=7.1Hz,4H),2.62(s,3H),1.39(t,J=7.0Hz,6H). 13 C NMR(101MHz,CDCl 3 )δ161.1(d,J=8.1Hz),142.8,133.9,132.3,131.9,126.8(d,J=8.1Hz),126.2,65.3(d,J=6.1Hz),22.2,16.2(d,J=7.1Hz)。
(diethylphosphoric acid) 2-chlorobenzoic anhydride (3 e) a colorless oil. 1 H NMR(400MHz,CDCl 3 )δ7.95–7.90(m,1H),7.46(dd,J=5.8,2.8Hz,2H),7.32(ddd,J=8.3,5.6,3.2Hz,1H),4.33(p,J=7.1Hz,4H),1.36(t,J=6.6Hz,6H). 13 C NMR(101MHz,CDCl 3 )δ159.5(d,J=8.1Hz),135.5,134.5,133.0,131.9,131.3,127.1,65.8(d,J=6.1Hz),16.3(d,J=7.1Hz)。
(diisopropylphosphoric acid) 4-methylbenzoic anhydride (3 f) colorless oil. 1 H NMR(400MHz,CDCl 3 )δ7.89(d,J=8.2Hz,2H),7.24–7.21(m,2H),4.89(dq,J=12.5,6.2Hz,2H),2.38(s,3H),1.37(dd,J=9.0,6.2Hz,12H). 13 C NMR(101MHz,CDCl 3 )δ161.3(d,J=9.1Hz),145.7,130.8,129.7,125.9(d,J=8.1Hz),74.5(d,J=6.1Hz),23.8(dd,J=29.3Hz),22.0。
Examples 7 to 17 and comparative examples 1 to 3
Acyl phosphate 3a was synthesized from the same starting materials as in example 1 under the conditions shown in Table 1 below, with the number of equivalents of catalyst being based on diethyl phosphite. The specific yields are shown in table 1 below.
TABLE 1
As shown in Table 1, when NaI, naCl, NH were used 4 Br, liBr, TBAB and KBr as catalysts show better acyl phosphate yield. However, when I is used 2 When the catalyst was used or when no catalyst was used (comparative examples 1 and 2), the acyl phosphate could not be obtained. When NaBr was used as the catalyst, a yield of 71% was obtained even when used in a relatively low amount of 0.2 equivalents (example 1). On the other hand, when DCM, DCE and acetonitrile are used as solvents, higher yields can be obtained, whereas when DMF is used, only traces of the acyl phosphate are obtained. In terms of reaction temperature, when the reaction is carried out at 30-50 ℃, higher yield can be obtained, and when the reaction temperature is too high or too low, the yield is obviously reduced.
While the present application has been described in terms of various specific embodiments, examples, and applications thereof, it will be understood by those skilled in the art that various changes, substitutions, and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. A method for synthesizing an acyl phosphate, which is a compound represented by formula (3), comprising: a step of acylating a peroxyaryl acid anhydride represented by the formula (1) with a phosphorous acid diester represented by the formula (2) in the presence of a catalyst,
wherein, in the formulae (1) to (3), R 2 And R 3 The same or different;
R 1 is unsubstituted phenyl, alkyl of 1 to 10 carbon atoms, halogen, alkoxy substituted phenyl, at least one of substituted or unsubstituted naphthyl and thienyl, and/or R 2 And R 3 Each at least one of an unsubstituted alkyl group having 1 to 4 carbon atoms and a substituted or unsubstituted phenyl group;
the catalyst is any one or the combination of bromide, iodide and chloride, and the solvent for the acylation reaction is any one or the combination of acetonitrile, dichloromethane and 1, 2-dichloroethane;
the reaction temperature of the acylation reaction is 30-50 ℃.
3. the synthesis method according to claim 1, wherein the catalyst is any one or combination of sodium bromide, lithium bromide, potassium bromide, ammonium bromide, tetrabutylammonium bromide, sodium iodide and sodium chloride, and/or the solvent is acetonitrile.
4. The method according to claim 1, wherein the molar ratio of the phosphorous acid diester represented by formula (2), the peroxyaryl acid anhydride represented by formula (1), and the catalyst is 1: (1-3): (0.1-1.5).
5. The method according to claim 4, wherein the molar ratio of the phosphorous acid diester represented by formula (2) to the peroxyaryl anhydride represented by formula (1) to the catalyst is 1: (1.5-2): (0.2-1).
6. The synthesis method according to claim 1, wherein the reaction atmosphere of the acylation reaction is air.
7. The synthesis method according to claim 1, wherein the reaction temperature of the acylation reaction is 40 ℃.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210156612.4A CN114605466B (en) | 2022-02-21 | 2022-02-21 | Synthesis method of acyl phosphate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210156612.4A CN114605466B (en) | 2022-02-21 | 2022-02-21 | Synthesis method of acyl phosphate |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114605466A CN114605466A (en) | 2022-06-10 |
CN114605466B true CN114605466B (en) | 2022-12-23 |
Family
ID=81858692
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210156612.4A Active CN114605466B (en) | 2022-02-21 | 2022-02-21 | Synthesis method of acyl phosphate |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114605466B (en) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2648696A (en) * | 1951-06-19 | 1953-08-11 | Shell Dev | Mixed acid anhydrides and process for production of same |
US2939876A (en) * | 1958-10-28 | 1960-06-07 | Friedrich D Cramer | Preparation of acid anhydrides |
US3170943A (en) * | 1960-09-17 | 1965-02-23 | Shell Oil Co | Process for making phosphoric acid ester anhydrides |
CN106083917A (en) * | 2016-06-17 | 2016-11-09 | 刘志华 | A kind of improvement synthetic method of phosphate compounds |
CN106928273A (en) * | 2015-12-30 | 2017-07-07 | 北京化工大学 | A kind of method for synthesizing phosphorus-containing matter |
CN111621804A (en) * | 2020-05-13 | 2020-09-04 | 南昌大学 | Method for electrochemically synthesizing acyl phosphate |
CN114031639A (en) * | 2021-11-22 | 2022-02-11 | 烟台大学 | Preparation method of biphosphonate with P-O-C-P structure |
-
2022
- 2022-02-21 CN CN202210156612.4A patent/CN114605466B/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2648696A (en) * | 1951-06-19 | 1953-08-11 | Shell Dev | Mixed acid anhydrides and process for production of same |
US2939876A (en) * | 1958-10-28 | 1960-06-07 | Friedrich D Cramer | Preparation of acid anhydrides |
US3170943A (en) * | 1960-09-17 | 1965-02-23 | Shell Oil Co | Process for making phosphoric acid ester anhydrides |
CN106928273A (en) * | 2015-12-30 | 2017-07-07 | 北京化工大学 | A kind of method for synthesizing phosphorus-containing matter |
CN106083917A (en) * | 2016-06-17 | 2016-11-09 | 刘志华 | A kind of improvement synthetic method of phosphate compounds |
CN111621804A (en) * | 2020-05-13 | 2020-09-04 | 南昌大学 | Method for electrochemically synthesizing acyl phosphate |
CN114031639A (en) * | 2021-11-22 | 2022-02-11 | 烟台大学 | Preparation method of biphosphonate with P-O-C-P structure |
Non-Patent Citations (1)
Title |
---|
Preparation of alkyl- and arylmercury chlorides by the reaction of acyl peroxides with diethoxyphosphorylmercuric chloride;Hu, Hongwen等,;《Metalloorganicheskaya Khimiya》;19911231;全文 * |
Also Published As
Publication number | Publication date |
---|---|
CN114605466A (en) | 2022-06-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2011035532A1 (en) | Preparation method of aromatic borate ester compound | |
JP2009522210A (en) | 2,2 ', 6,6'-tetraoxazoline biphenyl ligand and method for preparing the same | |
CN114605466B (en) | Synthesis method of acyl phosphate | |
CN111925356A (en) | Synthesis method and application of chiral quinoline-imidazoline ligand | |
CN108558944B (en) | Preparation method of 4-phosphoryl-1, 4, 5-trisubstituted 1,2, 3-triazole | |
Zhou et al. | Methods, syntheses and characterization of diaryl, aryl benzyl, and dibenzyl sulfides | |
JP4677550B2 (en) | Cyclic ester compound | |
JP2010235453A (en) | Method for producing platinum complex | |
CN105130873A (en) | 3-difluoroalkyl substituted amino oxindole derivative and synthesis method thereof | |
CN107226829B (en) | Preparation method of ferrocenyl-group-containing phosphine oxide ligand | |
JP5280858B2 (en) | 1,1'-Biphenyls Axial Chirality Ligand Linked at 5,5 'Position and Method for Producing the Same | |
CN114773301B (en) | Method for synthesizing furan compounds from terminal alkyne and iodoylide | |
CN114539317B (en) | Catalytic preparation method of beta-amido-alpha, beta-unsaturated phosphine oxide | |
CN113861238B (en) | Method for synthesizing phosphine chiral center secondary/tertiary phosphine oxide compound through palladium/chiral ligand catalysis | |
CN101643450B (en) | Synthesis method for multi substituted 2, 3-dihydro-4(1H)-pyrimidin thionone | |
JP4887591B2 (en) | Method for producing alkene derivative | |
WO2005068481A2 (en) | Ferrocene derivatives | |
CN110885343A (en) | Mint-based dicarbo-phosphorus chiral tertiary phosphine derivative, and preparation method and application thereof | |
CN117402028A (en) | Method for synthesizing chiral alpha-amino phosphonic acid derivative by using cinchona alkaloid derivative as catalyst | |
JP2001089407A (en) | Diphenylacetylene compound and method of producing the same compound | |
CN116675639A (en) | Fluorescent luminous rare earth supermolecule complex and preparation method and application thereof | |
CN117050026A (en) | Synthesis method of fluoroalkyl substituted quinoxalinone derivative | |
CN117069755A (en) | Preparation method of benzofuran chiral disilicide compound | |
CN113620795A (en) | Method for synthesizing benzocycloheptenone compounds | |
CN118026807A (en) | Process for preparing 1, 1-difluoro substituted-1, 3-eneyne compounds |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |