CN108129512B - Preparation method of allyl thio or seleno phosphate and phosphonate - Google Patents
Preparation method of allyl thio or seleno phosphate and phosphonate Download PDFInfo
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- CN108129512B CN108129512B CN201810122738.3A CN201810122738A CN108129512B CN 108129512 B CN108129512 B CN 108129512B CN 201810122738 A CN201810122738 A CN 201810122738A CN 108129512 B CN108129512 B CN 108129512B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- JRPHGDYSKGJTKZ-UHFFFAOYSA-N selenophosphoric acid Chemical compound OP(O)([SeH])=O JRPHGDYSKGJTKZ-UHFFFAOYSA-N 0.000 title claims abstract description 9
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 title claims abstract description 7
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 18
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 10
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 9
- 239000011669 selenium Substances 0.000 claims abstract description 9
- 239000011593 sulfur Substances 0.000 claims abstract description 9
- 239000012043 crude product Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- 239000003208 petroleum Substances 0.000 claims description 9
- -1 phenoxy, substituted phenoxy, naphthoxy Chemical group 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 238000004440 column chromatography Methods 0.000 claims description 7
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 150000003582 thiophosphoric acids Chemical group 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 11
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000004679 31P NMR spectroscopy Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000005311 nuclear magnetism Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KIQBBFUDOVPDKE-UHFFFAOYSA-N OP(O)(O)=O.S.[SeH2] Chemical compound OP(O)(O)=O.S.[SeH2] KIQBBFUDOVPDKE-UHFFFAOYSA-N 0.000 description 1
- BEWOQXVDCFTBAQ-UHFFFAOYSA-N P(OC1=CC=CC=C1)(OC1=CC=CC=C1)=S Chemical compound P(OC1=CC=CC=C1)(OC1=CC=CC=C1)=S BEWOQXVDCFTBAQ-UHFFFAOYSA-N 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WYFVJPKJHDFWJB-UHFFFAOYSA-N hydroxy-phenyl-propan-2-yloxy-sulfanylidene-lambda5-phosphane Chemical compound CC(C)OP(O)(=S)c1ccccc1 WYFVJPKJHDFWJB-UHFFFAOYSA-N 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- FQUYBJOWNFKUJE-UHFFFAOYSA-N sulfo dihydrogen phosphate Chemical compound OP(O)(=O)OS(O)(=O)=O FQUYBJOWNFKUJE-UHFFFAOYSA-N 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- 238000005303 weighing Methods 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3229—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 Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/17—Esters of thiophosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or 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 Table
- 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 ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or 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
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657181—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention discloses a preparation method of allyl thio or seleno phosphate and phosphonate. The method comprises the following specific steps: 1) mixing cinnamyl alcohol and a sulfur reagent or a selenium reagent, and adding TsOH & H2O, reacting for 1-3 h at the temperature of 20-40 ℃ to obtain a crude product; the sulfur reagent is thiophosphoric acid or thiophosphinic acid; the selenium reagent is selenophosphoric acid or selenophosphoric acid; 2) separating and purifying the crude product obtained in the step 1) to obtain allyl sulfo-or selenophosphonate, or allyl sulfo-or selenophosphonate. The preparation method avoids the use of organic solvents and metal catalysts, and has the characteristics of rapid reaction, strong substrate adaptability, high atom economy and the like.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of allylthio or seleno phosphate and phosphonate.
Background
Allyl-containing compounds are widely present in a variety of compounds, are a wide variety of and widely present compounds in the natural world, are important building blocks in the skeleton of many biologically active natural and biological molecules, and have been proven to be important synthetic intermediates and play important roles in drug synthesis. Therefore, in such a background, synthesis of allyl compounds by avoiding unnecessary functionalization operations, guided by green chemistry principles, has become a focus of research. Allyl thio (seleno) phosphino (phospho) ates are a class of compounds that have been demonstrated to have good fungicidal and insecticidal activity and are of great pharmaceutical value. However, no efficient and green method for preparing allyl thio (seleno) phosphino (phospho) ate has been reported.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a high-efficiency preparation method of allylthio or seleno phosphate and phosphonate. The method has wide universality and is suitable for reaction of various substrates; the reaction condition is mild, and the reaction time is short.
In order to achieve the above object, the present invention adopts the following technical solutions.
The invention provides a preparation method of allyl thio-or seleno-phosphate and phosphonate, which relates to the following reaction general formula:
wherein: x is S or Se, R1、R2Independently selected from any one of aryl, aryloxy or alkoxy. The method comprises the following specific steps:
1) mixing cinnamyl alcohol and a sulfur reagent or a selenium reagent, and adding TsOH & H2O, reacting for 1-3 h at the temperature of 20-40 ℃ to obtain a crude product; wherein: the sulfur reagent or selenium reagent has a structure as shown in the formula
Wherein X is S or Se, R1、R2Independently selected from any one of aryl, aryloxy or alkoxy;
2) separating and purifying the crude product obtained in the step 1) to obtain allyl sulfo-or selenophosphonate, or allyl sulfo-or selenophosphonate.
In the invention, in the step 1), the aryl is phenyl, substituted phenyl, naphthyl or substituted naphthyl; aryloxy is phenoxy, substituted phenoxy, naphthoxy or substituted naphthoxy; alkoxy is C1-C30An alkoxy group.
In the invention, the substituted phenyl is mono-substituted or multi-substituted, and the substituent is selected from halogen and C1-C30Any one or more of alkyl and nitro; the substituted naphthyl is mono-substituted or multi-substituted, and the substituent is selected from halogen and C1-C30Any one or more of alkyl and nitro.
In the invention, in the step 1), cinnamyl alcohol, a sulfur reagent and TsOHH2The molar ratio of O is (1-2): 1: (1-2).
In the invention, in the step 1), cinnamyl alcohol, a selenium reagent and TsOH & H2The molar ratio of O is (1-2) 1: (1-2).
In the invention, in the step 1), the reaction temperature is 25-35 ℃, and the reaction time is 1-2 h.
In the invention, in the step 2), the crude product is separated and purified after being washed by saturated saline.
In the step 2), a column chromatography method is used for separation and purification, a developing agent is a mixture of ethyl acetate and petroleum ether, and the volume ratio of the ethyl acetate to the petroleum ether is 1/1-1/10.
Possible reaction mechanisms of the preparation process in the present invention are: p-TSA.H. taking cinnamyl alcohol as raw material2O is used for catalyzing cinnamyl alcohol to react with the cinnamyl alcohol to remove one molecule of water to form ether. Then sulfur (selenium) phosphate is induced to attack ether bond to obtain water and target compound.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts cinnamyl alcohol, a sulfur reagent or a selenium reagent and TsOH & H2And reacting the O at the temperature of 20-40 ℃ for 1-3 h to prepare the allyl sulfo (seleno) phosphoro (phosphono) sulfate. Avoids the use of organic solvent and metal catalyst, and has the characteristics of rapid reaction, strong substrate adaptability, economy, environmental protection and the like. The obtained target product allyl (selenium) phosphine (phosphate) can be applied to the fields of organic synthesis, medicine, photoelectric materials and the like.
Detailed Description
The present invention will be further described with reference to the following embodiments.
Example 1
The preparation method of S-allyl diphenyl thiophosphonate comprises the following steps:
0.33mmol of diphenylthiophosphonic acid and 0.3mmol of cinnamyl alcohol are weighed in a test tube, and then 0.3mmol of p-TSA is added.H2And O, sealing the test tube, and stirring and reacting for 1h at the temperature of 30 ℃ to obtain a reaction solution.
The obtained reaction solution was dissolved in ethyl acetate, washed with saturated brine, the organic phase was collected, dried and concentrated, and the concentrate was subjected to column chromatography using ethyl acetate/petroleum ether 1/3(v/v) as a developing solvent to obtain 81.9mg of the target product.
The target product yield of this example was 78%.
Performing nuclear magnetism characterization on a target product, wherein the results are as follows:1H NMR(500MHz,CDCl3):7.89(dd,J＝12.9,7.3Hz,4H),7.49-7.47(m,2H),7.46-7.41(m,4H),7.25-7.22(m,2H),7.20-7.17(m,3H),6.37(d,J＝15.6Hz,1H),6.07(dt,J＝15.3,7.5Hz,1H),3.67-3.64(m,2H)；13C NMR(125MHz,CDCl3):136.0,133.3,133.0(d,J＝106.4Hz),132.1(d,J＝3.0Hz),131.3(d,J＝10.4Hz),128.5(d,J＝12.9Hz),128.2,127.6,126.2,124.3(d,J＝4.2Hz),31.7(d,J＝2.2Hz)；31PNMR(500MHz,CDCl3):42.91.
example 2
The preparation method of the S-allyl O, O-diethyl thiophosphate comprises the following steps:
0.3mmol of O, O-diethyl S-hydrogen thiophosphoric acid and 0.33mmol of cinnamyl alcohol are weighed in a test tube, and then 0.3mmol of p-TSA is added.H2And O, sealing the test tube, and stirring and reacting for 1h at the temperature of 30 ℃ to obtain a reaction solution.
The obtained reaction solution is firstly added with ethyl acetate for dissolution, and then washed by saturated saline solution, an organic phase is collected, dried and concentrated, and then column chromatography separation is carried out on a concentrate by taking ethyl acetate/petroleum ether (1/3 (v/v)) as a developing agent, so as to obtain 69.6mg of a target product.
The target product yield of this example was 82%.
Performing nuclear magnetism characterization on a target product, wherein the results are as follows:1H NMR(500MHz,CDCl3):7.34(d,J＝7.5Hz,2H),7.29(t,J＝7.5Hz,2H),7.22(t,J＝7.2Hz,1H),6.57(d,J＝15.7Hz,1H),6.25(dt,J＝15.3,7.5Hz,1H),4.22-4.08(m,4H),3.63(dd,J＝15.1,7.5Hz,2H),1.31(t,J＝7.1Hz,6H)；13C NMR(125MHz,CDCl3):135.9,133.0,128.2,127.5,126.0,124.4(d,J＝4.6Hz),63.2(d,J＝5.8Hz),33.0(d,J＝3.9Hz),15.7(d,J＝7.3Hz)；
example 3
The preparation method of the S-allyl O, O-diisopropyl thiophosphate comprises the following steps:
0.3mmol of O, O-diisopropyl thiophosphonic acid and 0.3mmol of cinnamyl alcohol are weighed in a test tube, and 0.33mmol of p-TSA is added.H2And O, sealing the test tube, and stirring and reacting for 1h at the temperature of 30 ℃ to obtain a reaction solution.
The obtained reaction solution is firstly added with ethyl acetate for dissolving, and then washed by saturated saline solution, an organic phase is collected, dried and concentrated, and then column chromatography separation is carried out on a concentrate by taking ethyl acetate/petroleum ether (1/3 (v/v)) as a developing agent, so as to obtain 82.8mg of a target product.
The target product yield of this example was 88%.
Performing nuclear magnetism characterization on a target product, wherein the results are as follows:1H NMR(500MHz,CDCl3):7.36(d,J＝7.3Hz,2H),7.30(t,J＝7.5Hz,2H),7.23(t,J＝7.2Hz,1H),6.59(d,J＝15.6Hz,1H),6.27(dt,J＝15.4,7.5Hz,1H),4.81-4.71(m,2H),3.67(dd,J＝14.2,7.5Hz,2H),1.35(dd,J＝14.8,6.2Hz,12H).13C NMR(125MHz,CDCl3):136.2,133.2,128.5,127.7,126.3,124.8(d,J＝5.4Hz),72.6(d,J＝6.4Hz),33.6(d,J＝3.8Hz),23.65(dd,J＝31.4,4.8Hz)；31P NMR(500MHz,CDCl3):23.34.
example 4
The preparation method of the S-allyl O-isopropylphenyl thiophosphate comprises the following steps:
weighing 0.3mmol of O-isopropylphenyl thiophosphonic acid and 0.33mmol of cinnamyl alcohol in a test tube, and then adding 0.33mmol of p-TSA.H2And O, sealing the test tube, and stirring and reacting for 1h at the temperature of 30 ℃ to obtain a reaction solution.
The obtained reaction solution is firstly added with ethyl acetate for dissolution, and then washed by saturated saline solution, the organic phase is collected, dried and concentrated, and then column chromatography separation is carried out on the concentrate by taking ethyl acetate/petroleum ether (1/3 (v/v)) as a developing agent, so as to obtain 86.6mg of target product.
The target product yield of this example was 87%.
Performing nuclear magnetic characterization on target productThe results are as follows:1H NMR(500MHz,CDCl3):7.86(dd,J＝13.8,7.7Hz,2H),7.48(t,J＝7.3Hz,1H),7.43-7.39(m,2H),7.26-7.23(m,2H),7.21-7.18(m,3H),6.41(d,J＝15.6Hz,1H),6.03(dt,J＝15.2,7.4Hz,1H),4.94(dh,J＝17.7,5.8Hz,1H),3.57(dd,J＝13.6,6.4Hz,2H),1.40(d,J＝6.1Hz,3H),1.37(d,J＝6.1Hz,3H)；13C NMR(125MHz,CDCl3):136.1,133.0,133.0(d,J＝150.5Hz),132.2(d,J＝3.0Hz),131.1(d,J＝11.0Hz),128.3(d,J＝14.9Hz),128.3,127.6,126.2,124.5(d,J＝4.4Hz),71.8(d,J＝7.0Hz),33.0(d,J＝2.5Hz),24.0(dd,J＝25.2,4.3Hz)；31P NMR(500MHz,CDCl3):41.27.
example 5
A process for the preparation of (allyl) dibenzo [ c, e ] [1,2] oxaphosphazene 6-oxide comprising the steps of:
0.33mmol of 6-mercaptodibenzo [ c, e ] was weighed][1,2]Oxaphosphazene 6-oxides
0.3mmol of cinnamyl alcohol in a test tube, and then 0.33mmol of p-TSA.H2And O, sealing the test tube, and stirring and reacting for 1h at the temperature of 30 ℃ to obtain a reaction solution.
The obtained reaction solution is firstly added with ethyl acetate for dissolution, and then washed by saturated saline solution, the organic phase is collected, dried and concentrated, and then column chromatography separation is carried out on the concentrate by taking ethyl acetate/petroleum ether (1/3 (v/v)) as a developing agent, thus obtaining 97.1mg of target product.
The target product yield of this example was 89%.
Performing nuclear magnetism characterization on a target product, wherein the results are as follows:1H NMR(500 MHz,CDCl3):7.99(dd,J＝15.1,7.6Hz,1H),7.87(t,J＝7.8Hz,2H),7.63(t,J＝7.7Hz,1H),7.45(td,J＝7.4,3.4Hz,1H),7.33-7.25(m,3H),7.23-7.20(m,4H),7.13(d,J＝8.1Hz,1H),6.41(d,J＝15.7Hz,1H),6.12(dd,J＝15.4,7.7Hz,1H),3.69(dtd,J＝60.4,13.6,7.5Hz,2H)；13C NMR(125MHz,CDCl3):149.3(d,J＝9.7Hz),136.0,135.9(d,J＝7.4Hz),133.6,133.5,130.5,130.4(d,J＝11.0Hz),128.5(d,J＝15.0Hz),128.4,127.8,126.3,125.8(d,J＝135.0Hz),125.0,124.8,124.2(d,J＝4.1Hz),123.7(d,J＝11.1Hz),122.0(d,J＝12.0Hz),120.3(d,J＝6.8Hz),32.7(d,J＝3.3Hz)；31P NMR(500MHz,CDCl3):35.45.31P NMR(500MHz,CDCl3):35.45.
Claims (8)
1. a preparation method of allyl thio or seleno phosphate and phosphonate is characterized by comprising the following specific steps:
1) mixing cinnamyl alcohol and a sulfur reagent or a selenium reagent, and adding TsOH & H2O, reacting for 1-3 h at the temperature of 20-40 ℃ to obtain a crude product; wherein: the sulfur reagent or selenium reagent has a structure as shown in the formula
Wherein X is S or Se, R1、R2Independently selected from any one of aryl, aryloxy or alkoxy;
2) separating and purifying the crude product obtained in the step 1) to obtain allyl sulfo-or selenophosphonate, or allyl sulfo-or selenophosphonate.
2. The method according to claim 1, wherein in step 1), the aryl group is a phenyl group, a substituted phenyl group, a naphthyl group or a substituted naphthyl group; aryloxy is phenoxy, substituted phenoxy, naphthoxy or substituted naphthoxy; alkoxy is C1-C30An alkoxy group.
3. The method according to claim 2, wherein the substituted phenyl group is mono-or polysubstituted, and the substituent is selected from the group consisting of halogen and C1-C30Any one or more of alkyl and nitro; the substituted naphthyl is mono-substituted or multi-substituted, and the substituent is selected from halogen and C1-C30Any one or more of alkyl and nitro.
4. The method according to claim 1, wherein in step 1), cinnamyl alcohol, a sulfur reagent and TsOH-H2The molar ratio of O is(1～2)：1：(1～2)。
5. The method of claim 1, wherein in step 1), cinnamyl alcohol, a selenium reagent and TsOH-H2The molar ratio of O is (1-2) 1: (1-2).
6. The preparation method according to claim 1, wherein in the step 1), the reaction temperature is 25-35 ℃ and the reaction time is 1-2 h.
7. The method according to claim 1, wherein the crude product is separated and purified after washing with saturated brine in the step 2).
8. The preparation method of claim 1, wherein in the step 2), the separation and purification are carried out by using a column chromatography method, the developing solvent is a mixture of ethyl acetate and petroleum ether, and the volume ratio of the ethyl acetate to the petroleum ether is 1/1-1/10.
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