CN111943980B - Allyl phosphorus compound and preparation method thereof - Google Patents
Allyl phosphorus compound and preparation method thereof Download PDFInfo
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- CN111943980B CN111943980B CN202010965287.7A CN202010965287A CN111943980B CN 111943980 B CN111943980 B CN 111943980B CN 202010965287 A CN202010965287 A CN 202010965287A CN 111943980 B CN111943980 B CN 111943980B
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- -1 Allyl phosphorus compound Chemical class 0.000 title claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 16
- 239000011574 phosphorus Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 11
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 238000004809 thin layer chromatography Methods 0.000 claims description 14
- 239000003208 petroleum Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 claims description 7
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 claims description 4
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 3
- WOCANVLUXHJDRV-UHFFFAOYSA-N (5-methyl-2-propan-2-ylcyclohexyl)-phenylphosphane Chemical compound CC(C)C1CCC(C)CC1PC1=CC=CC=C1 WOCANVLUXHJDRV-UHFFFAOYSA-N 0.000 claims description 2
- BWCBFYRNWOIXIB-UHFFFAOYSA-N 1-methyl-2-(2-methylphenyl)phosphonoylbenzene Chemical compound CC1=CC=CC=C1P(=O)C1=CC=CC=C1C BWCBFYRNWOIXIB-UHFFFAOYSA-N 0.000 claims description 2
- GGIQQYHOHRKDNO-UHFFFAOYSA-N 1-methyl-3-(3-methylphenyl)phosphonoylbenzene Chemical compound CC1=CC=CC(P(=O)C=2C=C(C)C=CC=2)=C1 GGIQQYHOHRKDNO-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- BVXOPEOQUQWRHQ-UHFFFAOYSA-N dibutyl phosphite Chemical compound CCCCOP([O-])OCCCC BVXOPEOQUQWRHQ-UHFFFAOYSA-N 0.000 claims description 2
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims description 2
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 claims description 2
- AWAYSUMOANJULO-UHFFFAOYSA-N 1-(3,5-dimethylphenyl)phosphonoyl-3,5-dimethylbenzene Chemical compound CC1=CC(C)=CC(P(=O)C=2C=C(C)C=C(C)C=2)=C1 AWAYSUMOANJULO-UHFFFAOYSA-N 0.000 claims 1
- WMQXKXZCFOGSFU-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)phosphonoylbenzene Chemical compound C1=CC(F)=CC=C1P(=O)C1=CC=C(F)C=C1 WMQXKXZCFOGSFU-UHFFFAOYSA-N 0.000 claims 1
- WOVYHPRWFRQYII-UHFFFAOYSA-N 1-methoxy-2-(2-methoxyphenyl)phosphonoylbenzene Chemical compound COC1=CC=CC=C1P(=O)C1=CC=CC=C1OC WOVYHPRWFRQYII-UHFFFAOYSA-N 0.000 claims 1
- WILMTQKUPOOLFE-UHFFFAOYSA-N 1-methoxy-4-(4-methoxyphenyl)phosphonoylbenzene Chemical compound C1=CC(OC)=CC=C1P(=O)C1=CC=C(OC)C=C1 WILMTQKUPOOLFE-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 150000004808 allyl alcohols Chemical group 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001308 synthesis method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004009 herbicide Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 102000003958 Glutamate Carboxypeptidase II Human genes 0.000 description 2
- 108090000369 Glutamate Carboxypeptidase II Proteins 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 238000006880 cross-coupling reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- MWYXORYWUKRJEX-UHFFFAOYSA-N bis(2-methoxyphenyl)-oxophosphanium Chemical compound COC1=CC=CC=C1[P+](=O)C1=CC=CC=C1OC MWYXORYWUKRJEX-UHFFFAOYSA-N 0.000 description 1
- LMXRTXPFJNGAAX-UHFFFAOYSA-N bis(3,5-dimethylphenyl)-oxophosphanium Chemical compound CC1=CC(C)=CC([P+](=O)C=2C=C(C)C=C(C)C=2)=C1 LMXRTXPFJNGAAX-UHFFFAOYSA-N 0.000 description 1
- MIYITCTXDGORJJ-UHFFFAOYSA-N bis(4-fluorophenyl)-oxophosphanium Chemical compound C1=CC(F)=CC=C1[P+](=O)C1=CC=C(F)C=C1 MIYITCTXDGORJJ-UHFFFAOYSA-N 0.000 description 1
- RREGWFNURZJKNB-UHFFFAOYSA-N bis(4-methoxyphenyl)-oxophosphanium Chemical compound C1=CC(OC)=CC=C1[P+](=O)C1=CC=C(OC)C=C1 RREGWFNURZJKNB-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- ZXHUJRZYLRVVNP-UHFFFAOYSA-N dibenzofuran-4-ylboronic acid Chemical compound C12=CC=CC=C2OC2=C1C=CC=C2B(O)O ZXHUJRZYLRVVNP-UHFFFAOYSA-N 0.000 description 1
- 229940042399 direct acting antivirals protease inhibitors Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000137 peptide hydrolase inhibitor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
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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 Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5325—Aromatic phosphine oxides or thioxides (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
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4056—Esters of arylalkanephosphonic acids
-
- 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
- C07F9/655—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
- C07F9/65517—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 condensed with carbocyclic rings or carbocyclic ring systems
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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 Table
- 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
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- General Health & Medical Sciences (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an allyl phosphorus compound and a preparation method thereof. The invention comprises the following steps of mixing allyl alcohol, a phosphine compound and tris (pentafluorophenyl) borane in a molar ratio of (0.2-0.6): (0.3-0.9): (0.01-0.03) adding the mixture into a reaction container for mixing, reacting for 2-12 hours at the temperature of 80-100 ℃ in an inert gas environment to obtain a reaction product, and purifying the reaction product to obtain the allyl phosphorus compound. The allyl alcohol used in the method is a secondary allyl alcohol raw material with simple synthesis and high conversion rate, the substrate has wide application range, and the method is suitable for various secondary allyl alcohols, for example, the secondary allyl alcohol can be various aryl, heterocycle and alkyl, and the raw material does not need an organic catalyst, and also can select the characteristics of high economy and wide market sources without adding a solvent; the used raw materials are free of pollution, and the reaction byproduct is only water, so that the method has the characteristic of environmental protection; the method has the characteristics of very mild reaction conditions, few reaction steps and simple operation.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to an allyl phosphorus compound and a preparation method thereof.
Background
The organophosphorus compounds play an important role in organic synthesis, are widely used as C-H activation guide groups, multifunctional organic synthesis reagents, organic catalysts and metal ligands, are also widely present in bioactive molecules and some medicines (such as NAALADase inhibitors, partial bacteria removal agents, herbicides and the like), and are also gaining more and more attention in the aspect of photoelectric materials.
In addition, the increasing distribution of the allylic phosphorus backbone in biologically and pharmaceutically active molecules (e.g., NAALADase inhibitors, antimicrobials, herbicides) has also attracted considerable attention from researchers. The research on the synthesis method of allyl phosphorus correspondingly becomes one of the hot spots of the research on organic synthetic chemistry. The previously reported synthesis methods mainly included: (1) the method comprises the following steps of (1) carrying out (oxidation) -cross-coupling reaction catalyzed by transition metal and a ligand thereof, (2) carrying out addition reaction of a phosphorus-hydrogen compound to an unsaturated bond under the catalysis of strong base, and (3) carrying out direct cross-coupling reaction catalyzed by alkaline earth metal. However, the above synthesis method has the disadvantages of high cost of raw materials and catalysts, expensive ligands, need of quantitative oxidant, harsh conditions, poor atom economy and the like. From an environmental and economic point of view, it is considered to be an ideal solution to develop an energy-saving and efficient green synthesis method using non-toxic, inexpensive, readily available and relatively environmentally friendly raw materials. In particular, a process for dehydrating coupling by the direct use of allyl alcohol as a raw material and water as a by-product, which does not require the use of a metal catalyst and does not require the use of a large amount of an organic solvent, is very attractive.
Disclosure of Invention
The invention aims to provide a preparation method of an allyl phosphorus compound, and aims to overcome the defects of high cost of raw materials and catalysts, expensive ligands, need of quantitative oxidants, harsh conditions, poor atom economy and the like in the conventional synthesis method.
The invention further aims to provide the allyl phosphorus compound with potential pharmaceutical activity and biological activity obtained by the preparation method.
The invention is realized in such a way that the preparation method of the allyl phosphorus compound comprises the following steps:
(1) allyl alcohol, a phosphine compound and tris (pentafluorophenyl) borane are mixed according to a molar ratio of (0.2-0.6): (0.3-0.9): (0.01-0.03) is added into a reaction vessel for mixing, and the mixture reacts for 2-12 hours in an inert gas environment at the temperature of 80-100 ℃ to obtain a reaction product
(2) And purifying the reaction product to obtain the allyl phosphorus compound.
Preferably, in step (1), the allyl alcohol is selected from the group consisting of 1-phenyl-3-phenyl-2-en-1-ol, 1- (2 ' -methylphenyl) -3- (2 ' -methylphenyl) -2-en-1-ol, 1-tert-butyl-3-phenyl-2-en-1-ol, 1- (4 ' -bromophenyl) -3-phenyl-2-en-1-ol, 1- (3 ' -methylphenyl) -3(3 ' -methylphenyl) -2-en-1-ol, 1- (4 ' -methylphenyl) -3- (4 ' -methylphenyl) -2-en-1-ol, and, 1- (3 '-fluorophenyl) -3- (3' -fluorophenyl) -2-en-1-ol, 1- (2 '-fluorophenyl) -3- (2' -fluorophenyl) -2-en-1-ol, 1- (4 '-fluorophenyl) -3- (4' -fluorophenyl) -2-en-1-ol, 1- (4 '-bromophenyl) -3- (4' -bromophenyl) -2-en-1-ol, 1- (4 '-chlorophenyl) -3- (4' -chlorophenyl) -2-en-1-ol, 1- (4 '-tert-butylphenyl) -3- (4' -tert-butylphenyl) -2-en-1-ol Any one of alcohol, 1- (4 '-methoxyphenyl) -3- (4' -methoxyphenyl) -2-en-1-ol, 1- (2-thienyl) -3- (2-thienyl) -2-en-1-ol, and cinnamyl alcohol.
Preferably, the phosphine is selected from any one of dimethyl phosphite, diethyl phosphite, dibutyl phosphite, diphenyl phosphine oxide, bis (2-methylphenyl) phosphine oxide, bis (3-methylphenyl) phosphine oxide, bis (4-methoxyphenyl) phosphine oxide, bis (4-fluorophenyl) phosphine oxide, bis (2 '-naphthyl) phosphine oxide, bis (2-methoxyphenyl) phosphine oxide, bis (3, 5-dimethylphenyl) phosphine oxide, bis (1' -naphthyl) phosphine oxide and menthylphenyl phosphine oxide.
Preferably, in step (1), the mixed product further comprises a solvent, the solvent comprising xylene, acetonitrile; wherein, allyl alcohol, phosphine, tris (pentafluorophenyl) borane and solvent are mixed according to the mol volume ratio (0.2-0.6) mmol: (0.3-0.9) mmol: (0.01-0.03) mmol: adding 1-3 mL of the mixed solution into a reaction container for mixing to obtain a mixed product.
Preferably, in step (1), the inert gas comprises argon;
in the step (2), the reaction product is purified by thin layer chromatography, the developing solvent system is petroleum ether/ethyl acetate, and the ratio of the petroleum ether to the ethyl acetate is 1: 1.
the invention further discloses an allyl phosphorus compound obtained by the preparation method, and the chemical structural formula of the compound is shown as the following formula (I):
in the formula (I), R1Is selected from C6H5、2-MeC6H4、tBu、4-BrC6H4、3-MeC6H4、4-MeC6H4、3-FC6H4、2-FC6H4、4-FC6H4、4-ClC6H4、4-tBuC6H4、4-OMeC6H4And 2-thiophene;
R2is selected from C6H5、2-MeC6H4、tBu、4-BrC6H4、3-MeC6H4、4-MeC6H4、3-FC6H4、2-FC6H4、4-FC6H4、4-ClC6H4、4-tBuC6H4、4-OMeC6H4And 2-thiophene;
R3selected from OMe, OEt, OBu, C6H5、2-MeC6H4、3-MeC6H4、4-MeC6H4、4-FC6H4、2-nathphyl、4-OMeC6H4、2-OMeC6H4、3-OMeC6H4、3,5-Me2C6H41-nathpryl and (R)P) - (-) -menthyl;
R4selected from OMe, OEt, OnBu、C6H5、2-MeC6H4、3-MeC6H4、4-MeC6H4、4-FC6H4、2-nathphyl、4-OMeC6H4、2-OMeC6H4、3-OMeC6H4、3,5-Me2C6H41-nathpryl and (R)P) - (-) -menthyl.
Compared with the defects and shortcomings of the prior art, the invention has the following beneficial effects:
(1) the allyl alcohol used in the method is a secondary allyl alcohol raw material with simple synthesis and high conversion rate, the substrate has wide application range, and the method is suitable for various secondary allyl alcohols, for example, the secondary allyl alcohol can be various aryl, heterocycle and alkyl, and the raw material does not need an organic catalyst, and also can select the characteristics of high economy and wide market sources without adding a solvent; the used raw materials are free of pollution, and the reaction byproduct is only water, so that the method has the characteristic of environmental protection; in addition, the method of the invention has the characteristics of very mild reaction conditions, few reaction steps and simple operation;
(2) the allyl phosphorus compound has wide distribution in biologically and pharmaceutically active molecules (such as protease inhibitors, antibacterial agents and herbicides), and has wide application prospect.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of trans-1-phenyl-3-phenyl-2-en-1-diphenylphosphine oxide in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of trans-1-phenyl-3-phenyl-2-en-1-diphenylphosphine oxide in example 1 of the present invention;
FIG. 3 is a NMR phosphorus spectrum of trans-1-phenyl-3-phenyl-2-en-1-diphenylphosphine oxide in example 1 of the present invention;
FIG. 4 is a NMR spectrum of trans-1-phenyl-3-phenyl-2-en-1-diethoxyphosphineoxide in example 2 of the present invention;
FIG. 5 is a NMR spectrum of trans-1-phenyl-3-phenyl-2-en-1-diethoxyphosphineoxide in example 2 of the present invention;
FIG. 6 is a NMR phosphorus spectrum of trans-1-phenyl-3-phenyl-2-en-1-diethoxyphosphine oxide in example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
(1) In a 10mL Schlenk tube, trans-1, 3-phenyl-2-en-1-ol (0.20mmol, 0.0420g), diphenylphosphine oxide (0.30mmol, 0.607g), tris (pentafluorophenyl) borane (5 mol%, 0.0055g) were sequentially added under nitrogen, and the reaction was stirred at 100 ℃ for 2 hours, according to the equation:
(2) after TLC monitoring the reaction was complete, the mixture was dissolved in dichloromethane and the product was isolated by thin layer chromatography (1: 1 petroleum ether/ethyl acetate) as white solid compound 1 in 98% yield. The chemical structure and NMR chart of the white solid are shown in figures 1-3.
Example 2
(1) In a 10ml Schlenk's tube, trans-1, 3-phenyl-2-en-1-ol (0.20mmol, 0.0420g), diethyl phosphite (0.30mmol, 0.0414g), tris (pentafluorophenyl) borane (5 mol%, 0.0055g) were sequentially added under nitrogen atmosphere, and the reaction was stirred at 100 ℃ for 12 hours, the equation being:
(2) after TLC monitoring the reaction was complete, the mixture was taken out with dichloromethane and the product was isolated by thin layer chromatography (petroleum ether: ethyl acetate 1:1) as light yellow liquid compound 2 in 86% yield. The chemical structure and nuclear magnetic resonance image of the light yellow liquid are shown in fig. 4-6.
Example 3
(1) In a 10mL Schlenk tube, trans- (1, 3-bis (4-bromophenyl) allyl) diphenylphosphine oxide (0.10mmol, 0.554g), 4-dibenzofuranboronic acid (0.40mmol, 0.0848g), tetrakis (triphenylphosphine) palladium (10 mol%, 0.0116g), cesium fluoride (0.50mmol, 0.760g) and xylene as a solvent (2mL) were sequentially added under nitrogen, and the reaction was stirred at 60 ℃ for 12 hours, according to the equation:
(2) after completion of the TLC detection reaction, the solvent was distilled off under reduced pressure, and the product was isolated by thin layer chromatography (petroleum ether: ethyl acetate 1:1) as a white solid compound 3 in 96% yield.
Example 4
(1) In a 10mL tube, trans- (1, 3-diphenylallyl) diphenylphosphine oxide (0.2mmol, 0.0789g), dichloroethane (2mL) as solvent, m-chloroperoxybenzoic acid (80%, 0.4mmol, 0.0863g) were added in this order and stirred at room temperature for 24 hours, according to the reaction equation:
(2) after completion of the TLC detection reaction, the solvent was distilled off under reduced pressure and the product was isolated by thin layer chromatography (petroleum ether: ethyl acetate 4: 1) as a white solid compound 4 in 57% yield.
Example 5
(1) In a 10mL Schlenk tube, under nitrogen atmosphere, trans-1, 3-phenyl-2-en-1-ol (0.60mmol), diphenylphosphine oxide (0.90mmol), tris (pentafluorophenyl) borane (0.01mmol) and then 3mL of acetonitrile were added, and the reaction was stirred at 80 ℃ for 12 hours, the reaction equation being:
(2) after TLC monitoring the reaction was complete, the mixture was dissolved in dichloromethane and the product was isolated by thin layer chromatography (1: 1 petroleum ether/ethyl acetate) as white solid compound 5 in 96% yield.
Example 6
(1) In a 10mL Schlenk tube, under nitrogen atmosphere, trans-1, 3-phenyl-2-en-1-ol (0.40mmol), diphenylphosphine oxide (0.50mmol), tris (pentafluorophenyl) borane (0.03mmol) and 1mL of xylene were sequentially added, and the reaction was stirred at 80 ℃ for 8 hours, the reaction equation being:
(2) after TLC monitoring the reaction was complete, the mixture was dissolved in dichloromethane and the product was isolated by thin layer chromatography (1: 1 petroleum ether/ethyl acetate) as white solid compound 6 in 97% yield.
Examples 7 to 15
Examples 7-15 are substantially the same as example 1 above, with the following differences as shown in table 1 below:
TABLE 1 Difference comparison
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 and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (3)
1. A preparation method of an allyl phosphorus compound is characterized by comprising the following steps:
(1) allyl alcohol, a phosphine compound and tris (pentafluorophenyl) borane are mixed according to a molar ratio of (0.2-0.6): (0.3-0.9): (0.01-0.03) adding the mixture into a reaction container for mixing, and reacting for 2-12 hours at the temperature of 80-100 ℃ in an inert gas environment to obtain a reaction product;
in step (1), the allyl alcohol is selected from the group consisting of 1-phenyl-3-phenyl-2-en-1-ol, 1- (2 '-methylphenyl) -3- (2' -methylphenyl) -2-en-1-ol, 1-tert-butyl-3-phenyl-2-en-1-ol, 1- (4 '-bromophenyl) -3-phenyl-2-en-1-ol, 1- (3' -methylphenyl) -3(3 '-methylphenyl) -2-en-1-ol, 1- (4' -methylphenyl) -3- (4 '-methylphenyl) -2-en-1-ol, 1-tert-butyl-3-phenyl-2-en-1-ol, 1- (4' -methylphenyl) -2-en-1-ol, and, 1- (3 '-fluorophenyl) -3- (3' -fluorophenyl) -2-en-1-ol, 1- (2 '-fluorophenyl) -3- (2' -fluorophenyl) -2-en-1-ol, 1- (4 '-fluorophenyl) -3- (4' -fluorophenyl) -2-en-1-ol, 1- (4 '-bromophenyl) -3- (4' -bromophenyl) -2-en-1-ol, 1- (4 '-chlorophenyl) -3- (4' -chlorophenyl) -2-en-1-ol, 1- (4 '-tert-butylphenyl) -3- (4' -tert-butylphenyl) -2-en-1-ol Any one of alcohol, 1- (4 '-methoxyphenyl) -3- (4' -methoxyphenyl) -2-en-1-ol, 1- (2-thienyl) -3- (2-thienyl) -2-en-1-ol and cinnamyl alcohol;
the phosphine is selected from any one of dimethyl phosphite, diethyl phosphite, dibutyl phosphite, diphenyl phosphine oxide, di (2-methylphenyl) phosphine oxide, di (3-methylphenyl) phosphine oxide, di (4-methoxyphenyl) phosphine oxide, di (4-fluorophenyl) phosphine oxide, di (2 '-naphthyl) phosphine oxide, di (2-methoxyphenyl) phosphine oxide, di (3, 5-dimethylphenyl) phosphine oxide, di (1' -naphthyl) phosphine oxide and menthylphenyl phosphine oxide;
(2) and purifying the reaction product to obtain the allyl phosphorus compound.
2. The method of claim 1, wherein in step (1), further comprising a solvent comprising xylene, acetonitrile; wherein, allyl alcohol, phosphine, tris (pentafluorophenyl) borane and solvent are mixed according to the mol volume ratio (0.2-0.6) mmol: (0.3-0.9) mmol: (0.01-0.03) mmol: adding 1-3 mL of the mixed solution into a reaction container for mixing to obtain a mixed product.
3. The method according to claim 1, wherein in step (1), the inert gas comprises argon;
in the step (2), the reaction product is purified by thin layer chromatography, the developing solvent system is petroleum ether/ethyl acetate, and the ratio of the petroleum ether to the ethyl acetate is 1: 1.
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