CN114606520A - Synthetic method of aryl phosphate - Google Patents
Synthetic method of aryl phosphate Download PDFInfo
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- CN114606520A CN114606520A CN202210313780.XA CN202210313780A CN114606520A CN 114606520 A CN114606520 A CN 114606520A CN 202210313780 A CN202210313780 A CN 202210313780A CN 114606520 A CN114606520 A CN 114606520A
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- aryl
- sulfone
- aryl phosphate
- triphenyl phosphite
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- -1 aryl phosphate Chemical compound 0.000 title claims abstract description 64
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 23
- 239000010452 phosphate Substances 0.000 title claims abstract description 22
- 238000010189 synthetic method Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 230000035484 reaction time Effects 0.000 claims abstract description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 29
- 239000000047 product Substances 0.000 claims description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 238000003487 electrochemical reaction Methods 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- UYGNQHYYBKGZCG-UHFFFAOYSA-N N-(4-methoxyphenyl)iminomethanesulfonamide Chemical compound CS(=O)(=O)N=NC1=CC=C(C=C1)OC UYGNQHYYBKGZCG-UHFFFAOYSA-N 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 238000010898 silica gel chromatography Methods 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims 1
- 239000012895 dilution Substances 0.000 claims 1
- 239000011363 dried mixture Substances 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 238000012822 chemical development Methods 0.000 abstract description 2
- 238000010511 deprotection reaction Methods 0.000 abstract description 2
- 238000001212 derivatisation Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 235000021317 phosphate Nutrition 0.000 description 13
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- 238000004679 31P NMR spectroscopy Methods 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- 150000001499 aryl bromides Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000006366 phosphorylation reaction Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005654 Michaelis-Arbuzov synthesis reaction Methods 0.000 description 2
- NSGDYZCDUPSTQT-UHFFFAOYSA-N N-[5-bromo-1-[(4-fluorophenyl)methyl]-4-methyl-2-oxopyridin-3-yl]cycloheptanecarboxamide Chemical compound Cc1c(Br)cn(Cc2ccc(F)cc2)c(=O)c1NC(=O)C1CCCCCC1 NSGDYZCDUPSTQT-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005954 phosphonylation reaction Methods 0.000 description 2
- 230000026731 phosphorylation Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- DJHASRVNBMMHLB-UHFFFAOYSA-N ethoxy(phenyl)phosphinite Chemical compound CCOP([O-])C1=CC=CC=C1 DJHASRVNBMMHLB-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- NHEJMCHRGUAKFT-UHFFFAOYSA-N tetrafluorophosphonium Chemical compound F[P+](F)(F)F NHEJMCHRGUAKFT-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
Abstract
The invention provides a synthesis method of aryl phosphate, which takes aryl azo sulfone as a raw material to react with triphenyl phosphite under electrochemical conditions to obtain a corresponding aryl phosphate compound. The method has the advantages of cheap and easily obtained raw materials, simple operation, mild and green reaction conditions, high yield and greatly shortened reaction time. The invention uses electrons as reactants to realize selective oxidation or reduction conversion, avoids using stoichiometric oxidant, metal catalyst and alkali, and meets the requirement of green chemical development. The reaction of the present invention is highly selective, thereby avoiding derivatization reactions, such as protection/deprotection, and is suitable for industrial production.
Description
Technical Field
The invention relates to a novel synthesis method of aryl phosphate compounds, belonging to the technical field of electrochemical organic synthesis.
Background
The aryl phosphonate ester serving as an important organic phosphorus compound has wide application in the fields of pharmaceutical chemistry, material science and organic synthesis, so that the synthesis of the compound has important significance. The phosphorus-containing moiety acts as a ligand to coordinate with a transition metal or bind to a biological receptor, thereby modulating a physiological process or material function. Therefore, the development of efficient and mild phosphonylation reactions has been the subject of extensive synthetic research. The field has been dominated by transition metal catalysis for a long time, but in recent years, people pay more and more attention to reports on obtaining aryl phosphonate compounds by using visible light redox catalysis and electrocatalysis as a mild and effective strategy.
Li et al completed (ArO) by using a unique palladium-PhX (X ═ OTf, I) catalyst3P to ArP (O) (OAr)2To give the corresponding rearrangement product, reference 1(C.Li, L-B.Han. Palladium-catalyst-Free Preparation of Aryl phosphates ArP (O) (OAr) in excellent yields2from(ArO)3P via the Michaelis-Arbuzov Rearrangement[J]Organometallics,39,3613-3617, 2020). Compared with the traditional method, the new method has high atom efficiency and universality, and can be easily expanded to aryl phosphonites and phosphonites. However, this method still has some limitations such as the use of a transition metal catalyst and the requirement of higher temperatures. The reaction formula is as follows:
r.s.shaikh et al demonstrated phosphonylation of aryl halides to their corresponding phosphonates without metal visible light drive (r.s.shaikh, s.j.s.d. ussel, B.
Visible-Light Photo-Arbuzov Reaction of Aryl Bromides and Trialkyl Phosphites Yielding Aryl Phosphonates[J]ACS Catal, 6,8410-8414, 2016). The reaction conditions are mild, the substrate range is wide, and the reaction can be compatible with various functional groups. Furthermore, the method allows for the introduction of phosphonate groups into complex and sensitive pharmaceutically active molecules. However, expensive photocatalysts are used in the reaction. The reaction formula is as follows:
qiu et al reported the successful construction of a C-P bond using aryl azo Sulfones in a phosphorylation Reaction with triphenyl phosphite under visible Light drive (D.Qiu, C.Lian, J.Mao, Y.Ding, Z.Liu, L.Wei, M.Fagnoni, S.Protti.visible Light-drive, Photocatalyst-Free Arbuzov-Like Reaction of aryl azo sulfides [ J ]. adv.Synth.Catal.,361, 5239-. This method shows excellent compatibility with electron-rich aromatic and (hetero) aromatic compounds, compared to sandmeyer-type phosphorylation. The reaction system does not use a photocatalyst and the reaction conditions are mild, but there is a problem that the reaction time is too long. The reaction formula is as follows:
Y.Bai et al developed a nickel Catalyzed Electrochemical cross-coupling reaction of Aryl bromide with dialkyl phosphite, ethyl phenylphosphonite and diphenylphosphine oxide (Y.Bai, N.Liu, S.Wang, S.Wang, S.Ning, L.Shi, L.Cui, Z.Zhang, J.Xiang.Nickel-catalysis Electrochemical Phosphorylation of Aryl Bromides [ J ] org.Lett.,21,17, 6835-D6838, 2019). The reaction has a wide substrate range and the corresponding product is obtained in moderate to excellent yields under mild conditions. Also, the reaction uses a transition metal nickel catalyst and a base. The reaction formula is as follows:
disclosure of Invention
In order to solve the problems in the prior art, the invention provides a novel synthesis method of aryl phosphate, which takes aryl azo sulfone as a raw material to react with triphenyl phosphite under an electrochemical condition to obtain a corresponding aryl phosphate compound, wherein the raw material is cheap and easy to obtain, the method is simple to operate, the reaction condition is mild and green, the yield is high, and the reaction time is greatly shortened.
Except for special description, the parts are parts by weight, and the percentages are mass percentages.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for synthesizing an aryl phosphate ester (C), which is characterized in that: taking aryl azo sulfone (A) and triphenyl phosphite (B) as raw materials to electrochemically synthesize an aryl phosphate compound (C).
The aryl azo sulfone (A), triphenyl phosphite (B) and aryl phosphate (C) have the following structural formulas:
wherein G is H, one or more substituted C1-6Alkyl, -O-C1-6Alkyl, halogen or halogeno C1-6An alkyl group.
The term "halogen" as used herein refers to fluorine, chlorine, bromine or iodine. The term "C" as used herein1-6Alkyl "means a saturated, linear or branched hydrocarbon or cycloalkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, cyclopropyl, cyclopentyl or cyclohexyl. The term "-O-C" as used in the present invention1-6Alkyl "means a saturated straight or branched chain alkoxy group having 1 to 6 carbon atoms, such as methoxy, ethoxy, t-butoxy, and the like. As used herein, the term "halogen-substituted C1-6Alkyl "refers to one or more halogen-substituted saturated straight or branched chain hydrocarbon groups having 1 to 6 carbon atoms, such as difluoromethyl, trifluoromethyl, and the like.
In the compounds, G can be independently ortho, meta or para, and can be simultaneously substituted or independently substituted at the ortho, meta or/and para positions.
Further, formula (A) is selected from 1- (4-methoxyphenyl) -2- (methylsulfonyl) diazene or 1- (2-chloro-4-methylphenyl) -2- (methylsulfonyl) diazene.
In the above method, the electrolyte for electrochemical reaction is selected from LiClO4(lithium perchlorate) nBu4NPF6、nBu4NClO4Preferably tetrabutylammonium tetrafluoroborate.
The molar ratio of the dosage of the aryl azo sulfone (A) to the dosage of the triphenyl phosphite (B) is 1: 1-3, preferably 1: 1.5.
the molar ratio of the using amount of the electrolyte tetrabutylammonium tetrafluoroborate to the using amount of the aryl azo sulfone (A) is 1-3: 1, preferably 1.6: 1.
the solvent of the electrochemical reaction is MeCN, DMSO and CH3OH、H2One or a combination of more of O; a mixed solvent of acetonitrile and water is preferred. Further, the volume ratio of the acetonitrile to the water is 3-7: 1, preferably 7: 1.
the reaction constant current of the invention is 5-15mA, preferably 10 mA.
The anode electrode is a graphite rod. The cathode electrode is a nickel electrode or a platinum sheet electrode, and preferably a platinum sheet electrode.
The reaction temperature is room temperature, and the reaction time is 1.3-4h, preferably 2 h.
Specifically, the synthesis method of the aryl phosphate (C) is characterized by comprising the following steps: taking aryl azo sulfone (A) and triphenyl phosphite (B) as raw materials to electrochemically synthesize an aryl phosphate compound (C);
the reaction formula is as follows:
formula (A) is selected from 1- (4-methoxyphenyl) -2- (methylsulfonyl) diazene or 1- (2-chloro-4-methylphenyl) -2- (methylsulfonyl) diazene. The electrolyte is tetrabutylammonium tetrafluoroborate. The molar ratio of the dosage of the aryl azo sulfone (A) to the dosage of the triphenyl phosphite (B) is 1: 1.5; the molar ratio of the amount of the electrolyte tetrabutylammonium tetrafluoroborate to the amount of the aryl azo sulfone (A) is 1.6: 1.
graphite rod for electrochemical catalytic reaction
As an anode, a platinum sheet (15.0 mm. times.10.0 mm. times.0.3 mm) was used as a cathode. The solvents for the electrochemical reaction being acetonitrile and waterThe volume ratio is 7: 1. Electrochemical reaction was carried out at room temperature for 2 hours at a constant current of 10.0 mA. After the reaction is finished, the reaction solution is separated and purified to obtain the aryl phosphate compound (C).
The method for separating and purifying the reaction liquid comprises the following steps: after the reaction, the reaction mixture was diluted with ethyl acetate, and the resulting mixture was extracted three times with water (20.0 × 3mL), dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure, and the resulting crude product was separated and purified by silica gel column chromatography (petroleum ether/ethyl acetate ═ 10: 1) to give an aryl phosphate ester product C.
Has the advantages that:
the invention provides a novel synthesis method of aryl phosphate, which takes aryl azo sulfone as a raw material to react with triphenyl phosphite under electrochemical conditions to obtain a corresponding aryl phosphate compound. The method has the advantages of cheap and easily obtained raw materials, simple operation, mild and green reaction conditions, high yield and greatly shortened reaction time. The invention uses electrons as reactants to realize selective oxidation or reduction conversion, avoids using stoichiometric oxidant, metal catalyst and alkali, and meets the requirement of green chemical development. The reaction of the present invention is highly selective, thereby avoiding derivatization reactions, such as protection/deprotection, and is suitable for industrial production.
Drawings
FIG. 1 shows the product C11H NMR chart;
FIG. 2 shows the product C113C NMR chart;
FIG. 3 shows the product C131A P NMR chart;
FIG. 4 shows the product C21H NMR chart;
FIG. 5 is the product C213C NMR chart;
FIG. 6 is the product C231P NMR chart.
Detailed Description
The present invention is described in detail below with reference to specific examples, which are given for the purpose of further illustrating the invention and are not to be construed as limiting the scope of the invention, and the invention may be modified and adapted by those skilled in the art in light of the above disclosure. The raw materials and reagents are all commercial products.
Example 1 synthesis of compound C1:
the reaction formula is as follows:
the operation steps are as follows:
to a dry clean two-port pressure tube equipped with a magnetic rotor, 1- (4-methoxyphenyl) -2- (methylsulfonyl) diazene a1(107mg, 0.5mmol), triphenyl phosphite B (233mg, 1.5eq), tetrabutylammonium tetrafluoroborate (263mg, 1.6eq) were added in this order, to which was added a volume ratio of 7: 1 acetonitrile/water (8 mL). Subsequently using graphite stick
As an anode, a platinum piece (15.0 mm. times.10.0 mm. times.0.3 mm) was immersed as a cathode in the reaction solution to a depth of about 16.0 mm. The reaction mixture was stirred and reacted at room temperature for 2h at a constant current of 10.0 mA. After the reaction was completed, 10.0mL of ethyl acetate was added, and then the resulting mixture was extracted three times with water (20.0 × 3mL), dried over anhydrous sodium sulfate and filtered, the solvent was removed by rotary evaporation under reduced pressure, and the resulting crude product was isolated and purified by silica gel column chromatography (petroleum ether/ethyl acetate ═ 10: 1) to give product C1 in 83% yield.
Product C11H NMR chart shown in FIG. 1, product C113C NMR chart of FIG. 2, product C131The P NMR chart is shown in FIG. 3.
The characterization data for product C1 are as follows:1H NMR(500MHz,CDCl3)δ7.81(dd,J＝13.3,8.7Hz,2H),7.20(dd,J＝14.1,6.5Hz,4H),7.11(d,J＝8.5Hz,4H),7.05(t,J＝7.4Hz,2H),6.90(dd,J＝8.7,3.7Hz,2H),3.77(s,3H).13C NMR(126MHz,CDCl3)δ162.3(d,J＝3.6Hz),149.3(d,J＝7.4Hz),133.2(d,J＝11.9Hz),128.5(s),123.8(s),119.47(d,J＝4.6Hz),116.7(d,J＝200.3Hz),113.0(d,J＝16.9Hz),54.2(s).31P NMR(202MHz,CDCl3)δ12.76(t,J＝13.0Hz).
referring to example 1, the inventors searched for the reaction conditions (current intensity, reaction time, electrolyte, electrode type, solvent, etc.) under which compound a1 was reacted with triphenyl phosphite B under electrochemical conditions to produce compound C1, and the results are shown in table 1.
TABLE 1 Effect of Current intensity, reaction time, electrolyte, electrode type, solvent and other reaction conditions
The results show that when the current magnitude and reaction time of the reaction were varied and the other conditions were unchanged (table 1, entries 2, 3), the yield of the reaction was reduced compared to the standard conditions, 72% and 65%, respectively. When LiClO is used separately4(lithium perchlorate) nBu4NPF6、nBu4NClO4When the electrolyte was used under otherwise unchanged conditions, the yields of the products were slightly reduced to 80%, 77% and 73%, respectively (Table 1, entries 4 to 6). When the cathode electrode was replaced with a nickel electrode, the yield of compound C2 was 78% (table 1, entry 7). After changing the composition or the ratio of the solvents, it was found that when a volume ratio of 7: 1, the yield of the product is highest when the mixed solvent of acetonitrile and water is used. In the absence of electrical power, no product was detected (table 1, entry 11), indicating that the current plays a crucial role in the reaction. Finally, the reaction was carried out under nitrogen protection with almost unchanged yield of the desired product (table 1, entry 12).
Example 2
Synthesis of Compound C2
The reaction formula is as follows:
the operation steps are as follows:
1- (2-chloro-4-methylphenyl) -2- (methylsulfonyl) diazene A2(116mg, 0.5mmol), triphenyl phosphite B (233mg, 1.5eq), and tetrabutyl tetrafluoro phosphonium chloride were sequentially added to a dry, clean, two-port pressure-resistant tube equipped with a magnetic rotorAmmonium borate (263mg, 1.6eq), to which was added a volume ratio of 7: 1 acetonitrile/water (8 mL). Using the stick of ink subsequently
As an anode, a platinum sheet (15.0 mm. times.10.0 mm. times.0.3 mm) as a cathode was immersed in the reaction solution to a depth of about 16.0 mm. The reaction mixture was stirred and reacted at room temperature for 2h at a constant current of 10.0 mA. After the reaction was completed, 10.0mL of ethyl acetate was added, and then the resulting mixture was extracted three times with water (20.0 × 3mL), dried over anhydrous sodium sulfate and filtered, the solvent was removed by rotary evaporation under reduced pressure, and the resulting crude product was isolated and purified by silica gel column chromatography (petroleum ether/ethyl acetate ═ 10: 1) to give product C2 in 81% yield.
Product C21The H NMR is shown in FIG. 4, and the product C213The C NMR chart is shown in FIG. 5, and the product C231The P NMR chart is shown in FIG. 6.
The characterization data for product C2 are as follows:1H NMR(500MHz,CDCl3)δ7.93(dd,J＝14.7,8.2Hz,1H),7.29–7.19(m,6H),7.08(dd,J＝13.3,7.5Hz,6H),2.66(s,3H).13C NMR(126MHz,CDCl3)δ149.1(d,J＝7.8Hz),142.9(d,J＝11.6Hz),138.5(d,J＝4.1Hz),134.77(d,J＝12.1Hz),130.4(d,J＝16.5Hz),128.6(s),124.9(d,J＝16.6Hz),124.1(s),123.1(d,J＝192.8Hz),119.2(d,J＝4.6Hz),20.2(d,J＝3.3Hz).31P NMR(202MHz,CDCl3)δ11.44(d,J＝14.4Hz)。
Claims (10)
1. a method for synthesizing an aryl phosphate ester (C), which is characterized in that: taking aryl azo sulfone (A) and triphenyl phosphite (B) as raw materials to electrochemically synthesize an aryl phosphate compound (C); the electrolyte for electrochemical reaction is selected from LiClO4、nBu4NPF6、nBu4NClO4One or a combination of more of the above; the aryl azo sulfone (A), triphenyl phosphite (B) and aryl phosphate (C) have the following structural formulas:
wherein G is H, one or more substituted C1-6Alkyl, -O-C1-6Alkyl, halogen or halogeno C1-6An alkyl group.
2. The method of claim 1, wherein: the "halogen" refers to fluorine, chlorine, bromine or iodine; said "C1-6Alkyl "refers to methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, cyclopropyl, cyclopentyl, or cyclohexyl; said "-O-C1-6Alkyl "means methoxy, ethoxy or tert-butoxy; said "halogen-substituted C1-6Alkyl "refers to difluoromethyl or trifluoromethyl.
3. The method of claim 1, wherein: formula (A) is selected from 1- (4-methoxyphenyl) -2- (methylsulfonyl) diazene or 1- (2-chloro-4-methylphenyl) -2- (methylsulfonyl) diazene.
4. The method of claim 1, wherein: the electrolyte of the electrochemical reaction is tetrabutylammonium tetrafluoroborate.
5. The method of claim 4, wherein: the molar ratio of the dosage of the aryl azo sulfone (A) to the dosage of the triphenyl phosphite (B) is 1: 1-3; the molar ratio of the using amount of electrolyte tetrabutylammonium tetrafluoroborate to the using amount of the aryl azo sulfone (A) is 1-3: 1.
6. the method of any one of claims 1-5, wherein: the solvent for electrochemical reaction is MeCN, DMSO, CH3OH、H2O or a combination of several O.
7. The method of claim 6, wherein: the solvent of the electrochemical reaction is a mixed solvent of acetonitrile and water, and the volume ratio of the acetonitrile to the water is 3-7: 1.
8. the method of any one of claims 1-5, wherein: the reaction constant current is 5-15 mA; the reaction temperature is room temperature, and the reaction time is 1.3-4 h.
9. The method of any one of claims 1-5, wherein: the anode electrode of the reaction is a graphite rod, and the cathode electrode is a nickel electrode or a platinum sheet electrode.
10. A method for synthesizing an aryl phosphate ester (C), which is characterized by comprising the following steps: taking aryl azo sulfone (A) and triphenyl phosphite (B) as raw materials to electrochemically synthesize an aryl phosphate compound (C); the reaction formula is as follows:
formula (a) is selected from 1- (4-methoxyphenyl) -2- (methylsulfonyl) diazene or 1- (2-chloro-4-methylphenyl) -2- (methylsulfonyl) diazene; the electrolyte is tetrabutylammonium tetrafluoroborate; the molar ratio of the used aryl azo sulfone (A) to the used triphenyl phosphite (B) is 1: 1.5; the molar ratio of the amount of the electrolyte tetrabutylammonium tetrafluoroborate to the amount of the aryl azo sulfone (A) is 1.6: 1; the graphite rod is used as an anode and the platinum sheet is used as a cathode in the electrochemical reaction; the volume ratio of acetonitrile to water is 7: 1, a mixed solvent; the electrochemical reaction is carried out for 2 hours at room temperature under the constant current of 10.0 mA; after the reaction is finished, separating and purifying the reaction liquid to obtain an aryl phosphate compound (C); the separation and purification method of the reaction liquid comprises the steps of adding ethyl acetate into the reaction liquid for dilution after the reaction is finished, extracting the obtained mixture for three times by using water, drying the mixture by using anhydrous sodium sulfate, filtering the dried mixture, carrying out reduced pressure rotary evaporation to remove the solvent, and separating and purifying the obtained crude product by using silica gel column chromatography to obtain the aryl phosphate ester product C.
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