CN106674277A - Preparation method of olefin phosphate compound - Google Patents
Preparation method of olefin phosphate compound Download PDFInfo
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- CN106674277A CN106674277A CN201611199880.5A CN201611199880A CN106674277A CN 106674277 A CN106674277 A CN 106674277A CN 201611199880 A CN201611199880 A CN 201611199880A CN 106674277 A CN106674277 A CN 106674277A
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- Prior art keywords
- preparation
- reaction
- phosphoric acid
- styrenes
- acid ester
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- -1 olefin phosphate compound Chemical class 0.000 title claims abstract description 43
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 12
- 239000010452 phosphate Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000004440 column chromatography Methods 0.000 claims abstract description 7
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 5
- 239000007800 oxidant agent Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 7
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 6
- NFORZJQPTUSMRL-UHFFFAOYSA-N dipropan-2-yl hydrogen phosphite Chemical group CC(C)OP(O)OC(C)C NFORZJQPTUSMRL-UHFFFAOYSA-N 0.000 claims description 5
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical class C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 4
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical class BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 claims description 3
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical class ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 claims description 3
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical class CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 claims description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 3
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- JAMNSIXSLVPNLC-UHFFFAOYSA-N (4-ethenylphenyl) acetate Chemical class CC(=O)OC1=CC=C(C=C)C=C1 JAMNSIXSLVPNLC-UHFFFAOYSA-N 0.000 claims description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical class COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 claims description 2
- PDELBHCVXBSVPJ-UHFFFAOYSA-N 2-ethenyl-1,3,5-trimethylbenzene Chemical class CC1=CC(C)=C(C=C)C(C)=C1 PDELBHCVXBSVPJ-UHFFFAOYSA-N 0.000 claims description 2
- ORNUPNRNNSVZTC-UHFFFAOYSA-N 2-vinylthiophene Chemical class C=CC1=CC=CS1 ORNUPNRNNSVZTC-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide 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
- 238000002156 mixing Methods 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 239000010953 base metal Substances 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 2
- 150000001879 copper Chemical class 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 238000002390 rotary evaporation Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 150000001345 alkine derivatives Chemical class 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001805 chlorine compounds Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- SULWMEGSVQCTSK-UHFFFAOYSA-N diethyl hydrogen phosphite Chemical class CCOP(O)OCC SULWMEGSVQCTSK-UHFFFAOYSA-N 0.000 description 3
- 238000006130 Horner-Wadsworth-Emmons olefination reaction Methods 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 2
- URCAYJXJXYLGTI-UHFFFAOYSA-N ethene fluorobenzene Chemical class C=C.FC1=CC=CC=C1 URCAYJXJXYLGTI-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- DDOQBQRIEWHWBT-VKHMYHEASA-N (2S)-2-amino-4-phosphonobutanoic acid Chemical compound OC(=O)[C@@H](N)CCP(O)(O)=O DDOQBQRIEWHWBT-VKHMYHEASA-N 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical class CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 208000018737 Parkinson disease Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
- 208000015114 central nervous system disease Diseases 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- OSPSWZSRKYCQPF-UHFFFAOYSA-N dibutoxy(oxo)phosphanium Chemical compound CCCCO[P+](=O)OCCCC OSPSWZSRKYCQPF-UHFFFAOYSA-N 0.000 description 1
- DLQDGVZAEYZNTG-UHFFFAOYSA-N dimethyl hydrogen phosphite Chemical compound COP(O)OC DLQDGVZAEYZNTG-UHFFFAOYSA-N 0.000 description 1
- 235000013766 direct food additive Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- C07F9/38—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
Landscapes
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of an olefin phosphate compound. The method comprises the following steps: arylethylene and phosphate according to a mol ratio 1:4-6 are used as raw materials; ferric chloride and copper salt are used as catalysts, and di-tert-butyl peroxide is used as an oxidizing agent; the raw materials and triethylamine are mixed, an organic solvent is added, and under the protection of inert gas, a reaction is carried out at 90-110 DEG C; after the reaction ends, washing is carried out, rotary evaporation is used for removing the solvent, and column chromatography is carried out in order to obtain the olefin phosphate compound. Base metal copper and iron are used as catalysts, reactant arylethylene and phosphate have low price, toxicity is low, the oxidizing agent is green and environmentally friendly, and the yield of the synthetic reaction of the olefin phosphate compound is high.
Description
Technical field
The invention belongs to organic synthesis field, and in particular to a kind of preparation method of alkenyl phosphoric acid ester type compound.
Background technology
Alkenyl phosphoric acid ester type compound is the extremely extensive organic synthesis intermediate of a class application, can be used to synthesising biological work
Property molecule, fire retardant, and polymeric additive etc..Alkenyl phosphoric acid ester type compound is also widely applied to Michael additions,
Horner-Wadsworth-Emmons (HWE) reacts, so as to realize the synthesis of compound.Meanwhile, alkenyl phosphoric acid ester type compound is also
Can be used as before the active drug L-AP4 for treating the central nervous diseases such as parkinson and alzheimer's disease
Body.Therefore, development efficiently synthesizes the methodology of organic synthesis of alkenyl phosphoric acid ester type compound and has important function.
At present, the topmost synthetic method of alkenyl phosphoric acid ester type compound is the addition phosphating reaction and sense of alkynes
The phosphating reaction of the alkene of dough.Although the coupling reaction of transition metal-catalyzed halo alkynes and phosphate ester can be effective
Synthesis alkenyl phosphoric acid ester type compound, but the by-product for having equivalent is generated.Therefore, alkynes and phosphate compounds is direct
Additive reaction due to its 100% Atom economy, so as to be widely used in the synthesis of alkenyl phosphoric acid ester type compound.Transition gold
Category Pd, Pt, Rh etc. can effectively realize the hydrogen phosphatization of terminal alkyne, so as to realize the synthesis of alkenyl phosphoric acid ester, but this side
Method often there is also some drawbacks, and the bad control of stereo selectivity of such as course of reaction can generate two kinds of anomeric products of Z/E
Mixture, or reaction need noble metal to be catalyzed ([1] Liu, L.；et al.Experimental and
Theoretical Studies on Nickel–Zinc-Catalyzed Cross-Coupling of Gem-
Dibromoalkenes with P(O)–H Compounds[J].RSC Advances.2014,4：2322-2326.[2]Han,
L.；et al.Palladium-Catalyzed Dehydrogenative Cis Double Phosphorylation of
Alkynes with H-Phosphonate Leading to(Z)-Bisphosphoryl-1-
alkenes.J.Am.Chem.Soc[J].2008:130,2752-2753.).The phosphating reaction of substituted olefine is also a kind of
The method for effectively synthesizing alkenyl phosphoric acid ester type compound, but the by-product that reaction has equivalent is generated, so Atom economy
It is not high.Therefore, how using cheap catalyst, efficiently prepare and there is single-minded stereoselective alkenyl phosphoric acid ester type compound tool
There is preferable application prospect.
The content of the invention
It is an object of the invention to provide a kind of preparation method of alkenyl phosphoric acid ester type compound.
Realize that the technical scheme of the object of the invention is as follows：
A kind of preparation method of alkenyl phosphoric acid ester type compound, concrete reaction equation is as follows:
Comprise the following steps that：
With mol ratio as 1:4~6 aryl ethylene and phosphate ester are raw material, and ferric chloride and mantoquita are catalyst, two uncles
Butylperoxide is oxidant, after mixing with triethylamine, organic solvent is added, under inert gas shielding, at 90~110 DEG C
Reaction, after reaction terminates, washing, revolving removes solvent, and Jing column chromatographies obtain alkenyl phosphoric acid ester type compound.
Described aryl ethylene is selected from styrene, 4- methyl styrenes, 2,4,6- trimethyl styrenes, 4- methoxybenzene second
Alkene, 4- t-butyl styrenes, 4- acetoxy-styrenes, 4- fluorobenzene ethenes, 4- chlorostyrenes, 4- bromstyrols, Alpha-Methyl benzene
Ethylene, the one kind in 2- vinylpyridines and 2- vinyl thiophenes.
Described phosphate ester is selected from diisopropyl phosphite, the one kind in dibutyl phosphite and dimethylphosphite.
Described mantoquita is selected from Cu-lyt., trifluoromethayl sulfonic acid copper or Red copper oxide.
Described organic solvent is dimethyl sulfoxide or N, N '-dimethyl Methanamide.
Compared with prior art, advantages of the present invention is as follows：
The relatively low aryl ethylene of cheap, toxicity and phosphate ester are adopted for raw material, using base metal copper and ferrum as urging
Agent, it is to avoid the use of noble metal, oxidant di-tert-butyl peroxide environmental protection, reaction yield is high, realizes alkene phosphorus
Acid esters compound is efficiently synthesized.
Specific embodiment
Embodiment 1
0.05mmol Cu-lyt .s are taken, 0.1mmol ferric chlorides in adding reaction tube, the air in reaction tube are replaced
Into argon, 0.5mmol styrene, 2.0mmol diethyl phosphites, 1.0mmol di-tert-butyl peroxides, 0.5mmol are added
Triethylamine, 2mL dimethylsulfoxide solvents, in 110 DEG C of oil bath, stopped reaction after reaction 16h is filtered, washing, and revolving removing has
Machine solvent, by column chromatography silica gel, obtains pure alkenyl phosphoric acid ester, and yield is 78%.
Embodiment 2
0.05mmol Cu-lyt .s are taken, 0.1mmol ferric chlorides in adding reaction tube, the air in reaction tube are replaced
Into argon, 0.5mmol p-methylstyrenes, 2.0mmol diethyl phosphites are added, 1.0mmol di-tert-butyl peroxides,
0.5mmol triethylamines, 2mL dimethylsulfoxide solvents, in 110 DEG C of oil bath, stopped reaction after reaction 16h is filtered, washing, rotation
Organic solvent is evaporated off, by column chromatography silica gel, pure target product is obtained, yield is respectively 82%.
Embodiment 3
The present embodiment is identical with the step of embodiment 2, unique except for the difference that styrene to be substituted for into 2,4,6- trimethylbenzenes
Ethylene, yield is 63%.
Embodiment 4
The present embodiment is identical with the step of embodiment 2, unique except for the difference that styrene to be substituted for into 4- methoxy styrenes,
Yield is 76%.
Embodiment 5
The present embodiment is identical with the step of embodiment 2, unique except for the difference that styrene to be substituted for into 4- t-butyl styrenes,
Yield is 81%.
Embodiment 6
The present embodiment is identical with the step of embodiment 2, unique except for the difference that styrene to be substituted for into 4- acetyloxy phenyl second
Alkene, yield is 75%.
Embodiment 7
The present embodiment is identical with the step of embodiment 2, unique except for the difference that styrene to be substituted for into 4- fluorobenzene ethenes, yield
For 72%.
Embodiment 8
The present embodiment is identical with the step of embodiment 2, unique except for the difference that styrene to be substituted for into 4- chlorostyrenes, yield
For 69%.
Embodiment 9
The present embodiment is identical with the step of embodiment 2, unique except for the difference that styrene to be substituted for into 4- bromstyrols, yield
For 71%.
Embodiment 10
The present embodiment is identical with the step of embodiment 2, unique except for the difference that styrene to be substituted for into α-methylstyrene, produces
Rate is 65%.
Embodiment 11
0.05mmol Cu-lyt .s are taken, 0.1mmol ferric chlorides in adding reaction tube, the air in reaction tube are replaced
Into argon, 0.5mmol 2- vinylpyridines are added, 2.0mmol diethyl phosphites, 1.0mmol tert-butyl peroxides,
0.5mmol triethylamines, 2mL dimethylsulfoxide solvents, in 110 DEG C of oil bath, stopped reaction after reaction 16h is filtered, washing, rotation
Organic solvent is evaporated off, by column chromatography silica gel, pure target product is obtained, yield is respectively 45%.
Embodiment 12
The present embodiment is identical with the step of embodiment 11, unique except for the difference that 2- vinylpyridines to be replaced with into 2- vinyls
Thiophene, yield is 78%.
Embodiment 13
0.05mmol Cu-lyt .s are taken, 0.1mmol ferric chlorides in adding reaction tube, the air in reaction tube are replaced
Into argon, 0.5mmol styrene, 2.0mmol diisopropyl phosphites, 1.0mmol tert-butyl peroxides, 0.5mmol are added
Triethylamine, 2mL dimethylsulfoxide solvents, in 110 DEG C of oil bath, stopped reaction after reaction 16h is filtered, washing, and revolving removing has
Machine solvent, by column chromatography silica gel, obtains pure target product, and yield is respectively 73%.
Embodiment 14
The present embodiment is identical with the step of embodiment 13, unique except for the difference that diisopropyl phosphite to be substituted for into phosphorous acid
Dibutyl ester, yield is 56%.
Embodiment 15
The present embodiment is identical with the step of embodiment 13, unique except for the difference that diisopropyl phosphite to be substituted for into phosphorous acid
Dimethyl ester, yield is 62%.
Embodiment 16
Reactions steps are identical with embodiment 1, and difference is：
Mantoquita is trifluoromethayl sulfonic acid copper, and alkenyl phosphoric acid ester yield is 45%.
Embodiment 17
Reactions steps are identical with embodiment 1, and difference is：
Mantoquita is Red copper oxide, and alkenyl phosphoric acid ester yield is 33%.
Embodiment 18
The present embodiment is identical with the step of embodiment 1, it is unique unlike reaction dissolvent be N, N '-dimethyl Methanamide,
Alkenyl phosphoric acid ester yield is 68%.
Embodiment 19
The present embodiment is identical with the step of embodiment 1, and unique except for the difference that reaction temperature is 100 DEG C, alkenyl phosphoric acid ester yield
For 30%.
Embodiment 20
The present embodiment is identical with the step of embodiment 1, and unique except for the difference that reaction temperature is 90 DEG C, and alkenyl phosphoric acid ester yield is
25%.
Embodiment 21
The present embodiment is identical with the step of embodiment 1, the material ratio of unique except for the difference that styrene and diethyl phosphite
For 1:5, alkenyl phosphoric acid ester yield is 75%.
Embodiment 22
The present embodiment is identical with the step of embodiment 1, the material ratio of unique except for the difference that styrene and diethyl phosphite
For 1:6, alkenyl phosphoric acid ester yield is 77%.
Claims (5)
1. a kind of preparation method of alkenyl phosphoric acid ester type compound, it is characterised in that comprise the following steps that：With mol ratio as 1:4~6
Aryl ethylene and phosphate ester be raw material, ferric chloride and mantoquita are catalyst, and di-tert-butyl peroxide is oxidant, with three
After ethamine mixing, organic solvent is added, under inert gas shielding, reacted at 90~110 DEG C, after reaction terminates, washing, revolving
Solvent is removed, Jing column chromatographies obtain alkenyl phosphoric acid ester type compound.
2. preparation method according to claim 1, it is characterised in that described aryl ethylene is selected from styrene, 4- methyl
Styrene, 2,4,6- trimethyl styrenes, 4- methoxy styrenes, 4- t-butyl styrenes, 4- acetoxy-styrenes, 4- fluorine
Styrene, 4- chlorostyrenes, 4- bromstyrols, α-methyl styrene, the one kind in 2- vinylpyridines and 2- vinyl thiophenes.
3. preparation method according to claim 1, it is characterised in that described phosphate ester is selected from diisopropyl phosphite,
One kind in dibutyl phosphite and dimethylphosphite.
4. preparation method according to claim 1, it is characterised in that described mantoquita is selected from Cu-lyt., fluoroform
Sulfonic acid copper or Red copper oxide.
5. preparation method according to claim 1, it is characterised in that described organic solvent is dimethyl sulfoxide or N, N '-
Dimethylformamide.
Priority Applications (1)
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Cited By (4)
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| CN110229187A (en) * | 2019-06-20 | 2019-09-13 | 苏州大学 | A method of alkylphosphines acylate is prepared by peroxide |
| CN111004283A (en) * | 2019-12-04 | 2020-04-14 | 南京理工大学 | Preparation method of 3-phosphoryl indole compound |
| CN111799511A (en) * | 2020-07-08 | 2020-10-20 | 重庆金美新材料科技有限公司 | Flame-retardant additive for lithium battery, preparation method, electrolyte and lithium battery |
| CN114181251A (en) * | 2020-09-15 | 2022-03-15 | 中国石油化工股份有限公司 | Alkenyl phosphonic acid compound and synthesis method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110229187A (en) * | 2019-06-20 | 2019-09-13 | 苏州大学 | A method of alkylphosphines acylate is prepared by peroxide |
| CN110229187B (en) * | 2019-06-20 | 2021-12-10 | 苏州大学 | Method for preparing alkyl phosphonyl compound from peroxide |
| CN111004283A (en) * | 2019-12-04 | 2020-04-14 | 南京理工大学 | Preparation method of 3-phosphoryl indole compound |
| CN111799511A (en) * | 2020-07-08 | 2020-10-20 | 重庆金美新材料科技有限公司 | Flame-retardant additive for lithium battery, preparation method, electrolyte and lithium battery |
| CN111799511B (en) * | 2020-07-08 | 2021-09-17 | 重庆金美新材料科技有限公司 | Flame-retardant additive for lithium battery, preparation method, electrolyte and lithium battery |
| CN114181251A (en) * | 2020-09-15 | 2022-03-15 | 中国石油化工股份有限公司 | Alkenyl phosphonic acid compound and synthesis method and application thereof |
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