CN114606520B - Synthesis method of aryl phosphate - Google Patents
Synthesis method of aryl phosphate Download PDFInfo
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- CN114606520B CN114606520B CN202210313780.XA CN202210313780A CN114606520B CN 114606520 B CN114606520 B CN 114606520B CN 202210313780 A CN202210313780 A CN 202210313780A CN 114606520 B CN114606520 B CN 114606520B
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- sulfone
- aryl phosphate
- triphenyl phosphite
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- -1 aryl phosphate Chemical compound 0.000 title claims abstract description 63
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 18
- 239000010452 phosphate Substances 0.000 title claims abstract description 18
- 238000001308 synthesis method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 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 14
- 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 26
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 238000003487 electrochemical reaction Methods 0.000 claims description 8
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 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
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 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
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 238000010898 silica gel chromatography Methods 0.000 claims description 4
- PHXQIAWFIIMOKG-UHFFFAOYSA-N NClO Chemical compound NClO PHXQIAWFIIMOKG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 150000003457 sulfones Chemical class 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
- 229910013684 LiClO 4 Inorganic materials 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
- 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
- 239000012046 mixed solvent Substances 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
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 7
- 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
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 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
- 150000001875 compounds Chemical class 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 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
- 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
- 230000026731 phosphorylation Effects 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
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 239000011369 resultant mixture Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 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
- YJSXLGKPMXKZJR-UHFFFAOYSA-N ethoxy-oxo-phenylphosphanium Chemical compound CCO[P+](=O)C1=CC=CC=C1 YJSXLGKPMXKZJR-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005954 phosphonylation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000011913 photoredox catalysis Methods 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- 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 and reacts with triphenyl phosphite under electrochemical conditions to obtain a corresponding aryl phosphate compound. The method has the advantages of low cost and easy acquisition of raw materials, simple operation, mild 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, and belongs to the technical field of electrochemical organic synthesis.
Background
Aryl phosphonate is used as an important organophosphorus compound and 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 coordinates to a transition metal or binds to a biological receptor as a ligand, thereby modulating a physiological process or material function. Thus, the development of efficient and gentle phosphonylation reactions has been the subject of extensive synthetic research. The field has long been dominated by transition metal catalysis, but reports on the use of visible light photo-redox catalysis and electrocatalysis as a gentle and efficient strategy for obtaining aryl phosphonates have been receiving increasing attention in recent years.
Li et al completed (ArO) by using a unique palladium-PhX (X=OTf, I) catalyst 3 P to ArP (O) (OAr) 2 The corresponding rearrangement product is obtained in excellent yieldDocument 1 (C.Li, L-B.Han. Palladium-Catalyzed Solvent-Free Preparation of Aryl phosphonates ArP (O) (OAr) 2 from(ArO) 3 P via the Michaelis-Arbuzov Rearrangement[J]Organometallics,39,3613-3617,2020). Compared with the traditional method, the novel method has high atomic efficiency and is universal, and can be easily extended to aryl phosphonites and phosphonites. However, this method still has some limitations such as the use of transition metal catalysts and the requirement of higher temperatures. The reaction formula is as follows:
shakh et al demonstrate that aryl halides are phosphonated to their corresponding phosphonates without metallic visible light actuation (R.S.Shaikh, S.J.S.D usel, B).Visible-Light Photo-Arbuzov Reaction of Aryl Bromides and Trialkyl Phosphites Yielding Aryl Phosphonates[J]ACS catalyst, 6,8410-8414,2016). The reaction condition is mild, the substrate range is wide, and the catalyst is compatible with various functional groups. Furthermore, the method allows the incorporation of phosphonate groups into complex and sensitive pharmaceutically active molecules. However, expensive photocatalysts are used in the reaction. The reaction formula is as follows:
qia et al reported successful construction of C-P bonds by phosphorylation of aryl azo sulfones with triphenyl phosphite under visible Light driving (D.Qiu, C.Lian, J.Mao, Y.Ding, Z.Liu, L.Wei, M.Fagnoni, S.Protti.Visible Light-drive, photoatalyst-Free Arbuzov-Like Reaction via Arylazo Sulfones [ J ]. Adv. Synth. Catalyst., 361,5239-5244,2019). This method exhibits excellent compatibility with electron-rich aromatic hydrocarbons and (hetero) aromatic compounds, compared to sandmeyer-type phosphorylation. The photocatalyst is not used in the reaction system and the reaction conditions are mild, but there is a problem that the reaction time is too long. The reaction formula is as follows:
a nickel-catalyzed electrochemical cross-coupling reaction of aryl bromides with dialkyl phosphites, ethyl phenylphosphinate and diphenyl phosphine oxide was developed by Bai et al (Y.Bai, N.Liu, S.Wang, S.Wang, S.Ning, L.Shi, L.Cui, Z.Zhang, J.Xiang.Nickel-Catalyzed Electrochemical Phosphorylation of Aryl Bromides [ J ]. Org.Lett.,21,17,6835-6838,2019). The reaction has a broad substrate range and gives the corresponding product in moderate to excellent yields under mild conditions. Likewise, 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, and reacts with triphenyl phosphite under electrochemical conditions to obtain a corresponding aryl phosphate compound, the raw material is cheap and easy to obtain, the method is simple to operate, the reaction condition is mild, the yield is high, and the reaction time is greatly shortened.
Except for special descriptions, the parts are parts by weight, and the percentages are mass percentages.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a synthesis method of aryl phosphate (C) is characterized in that: aryl azo sulfone (A) and triphenyl phosphite (B) are used as raw materials to electrochemically synthesize 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 C 1-6 Alkyl, -O-C 1-6 Alkyl, halogen or halogenated C 1-6 An alkyl group.
The term "halogen" as used herein refers to fluorine, chlorine, bromine or iodine. The term "C" as used herein 1-6 Alkyl "means a saturated, straight-chain or branched hydrocarbon group having 1 to 6 carbon atoms or cycloalkyl group, 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 invention 1-6 Alkyl "refers to saturated, straight or branched chain alkoxy groups having 1 to 6 carbon atoms, such as methoxy, ethoxy, t-butoxy, and the like. The term "halogen-substituted C" as used herein 1-6 Alkyl "refers to one or more halogen substituted saturated straight or branched hydrocarbon groups having 1 to 6 carbon atoms, such as difluoromethyl, trifluoromethyl and the like.
In the compounds herein, G may independently be ortho, meta or para, may be simultaneously substituted with ortho, meta or/and para, or may be independently substituted.
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 of the electrochemical reaction is selected from LiClO 4 (lithium perchlorate), nBu 4 NPF 6 、nBu 4 NClO 4 Preferably tetrabutylammonium tetrafluoroborate.
The molar ratio of the aryl azo sulfone (A) to the triphenyl phosphite (B) is 1:1-3, preferably 1:1.5.
the molar ratio of the amount of the electrolyte tetrabutylammonium tetrafluoroborate to the amount of the aryl azo sulfone (A) is 1-3:1, preferably 1.6:1.
the electrochemical device of the inventionThe solvent of the reaction is MeCN, DMSO, CH 3 OH、H 2 One or a combination of several of O; a mixed solvent of acetonitrile and water is preferable. Further, the volume ratio of acetonitrile to water is 3-7:1, preferably 7:1.
the reaction constant current according to the invention is 5-15mA, preferably 10mA.
The anode electrode is a graphite rod. The cathode electrode is a nickel electrode or a platinum sheet electrode, preferably a platinum sheet electrode.
The reaction temperature is room temperature, and the reaction time is 1.3-4h, preferably 2h.
Specifically, the synthesis method of the aryl phosphate (C) is characterized by comprising the following steps: aryl azo sulfone (A) and triphenyl phosphite (B) are used as raw materials, and aryl phosphate compounds (C) are synthesized electrochemically;
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 aryl azo sulfone (A) to the triphenyl phosphite (B) is 1:1.5; the molar ratio of the amount of tetrabutylammonium tetrafluoroborate electrolyte to the amount of arylazo sulfone (a) was 1.6:1.
graphite rod for electrochemical catalytic reactionAs an anode, a platinum sheet (15.0 mm. Times.10.0 mm. Times.0.3 mm) was used as a cathode. The volume ratio of acetonitrile to water as solvent for electrochemical reaction is 7:1. The electrochemical reaction was carried out at room temperature for 2h at a constant current of 10.0 mA. After the reaction is finished, the reaction liquid is separated and purified to obtain the aryl phosphate compound (C).
The reaction liquid is separated and purified by the following steps: after the reaction was completed, ethyl acetate was added to the reaction mixture to dilute it, and then the resulting mixture was extracted three times with water (20.0x3 mL), dried over anhydrous sodium sulfate, filtered, the solvent was removed by rotary evaporation under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether/ethyl acetate=10:1) to give aryl phosphate product C.
The beneficial effects are that:
the invention provides a novel synthesis method of aryl phosphate, which takes aryl azo sulfone as a raw material and reacts with triphenyl phosphite under electrochemical conditions to obtain a corresponding aryl phosphate compound. The method has the advantages of low cost and easy acquisition of raw materials, simple operation, mild 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 is product C1 1 H NMR chart;
FIG. 2 is product C1 13 C NMR chart;
FIG. 3 is product C1 31 P NMR map;
FIG. 4 is product C2 1 H NMR chart;
FIG. 5 is product C2 13 C NMR chart;
FIG. 6 is product C2 31 P NMR chart.
Detailed Description
The present invention is described in detail below by way of specific examples, which are given herein for the purpose of further illustration only and are not to be construed as limiting the scope of the present invention, as many insubstantial modifications and variations of the present invention will become apparent to those skilled in the art in light of the foregoing disclosure. The raw materials and the reagents are all commercial products.
Example 1 synthesis of compound C1:
the reaction formula is:
the operation steps are as follows:
to a dry and clean two-port pressure-resistant tube equipped with a magnetic rotor were successively added 1- (4-methoxyphenyl) -2- (methylsulfonyl) diazene A1 (107 mg,0.5 mmol), triphenyl phosphite B (233 mg,1.5 eq) and tetrabutylammonium tetrafluoroborate (263 mg,1.6 eq), to which were added a volume ratio of 7: acetonitrile/water (8 mL) of 1. Subsequently using graphite rodsAs an anode, a platinum sheet (15.0 mm. Times.10.0 mm. Times.0.3 mm) was immersed in the reaction solution as a cathode to a depth of about 16.0mm. The reaction mixture was stirred and reacted at room temperature for 2 hours at a constant current of 10.0 mA. After the completion of the reaction, 10.0mL of ethyl acetate was added, and then the resultant mixture was extracted three times with water (20.0x3 mL), dried over anhydrous sodium sulfate, filtered, the solvent was removed by rotary evaporation under reduced pressure, and the obtained crude product was purified by separation using silica gel column chromatography (petroleum ether/ethyl acetate=10:1), to give product C1 in 83% yield.
Product C1 1 H NMR chart of FIG. 1, product C1 13 C NMR chart of FIG. 2, product C1 31 The P NMR chart is shown in FIG. 3.
Characterization data for product C1 are as follows: 1 H NMR(500MHz,CDCl 3 )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). 13 C NMR(126MHz,CDCl 3 )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). 31 P NMR(202MHz,CDCl 3 )δ12.76(t,J＝13.0Hz).
referring to example 1, the inventors have searched for reaction conditions (amperage, reaction time, electrolyte, electrode type, solvent, etc.) under which compound A1 and triphenyl phosphite B are reacted under electrochemical conditions to produce compound C1, and the results are shown in table 1.
TABLE 1 influence of reaction conditions such as amperage, reaction time, electrolyte, electrode type, solvent, etc
The results showed that when the current level and reaction time of the reaction were changed and the other conditions were unchanged (table 1, entries 2, 3), the yield of the reaction was reduced by 72% and 65%, respectively, as compared with the standard conditions. When LiClO is used separately 4 (lithium perchlorate), nBu 4 NPF 6 、nBu 4 NClO 4 The yields of the products were slightly reduced as electrolytes under other conditions, respectively 80%, 77% and 73% (Table 1, entries 4-6). In addition, when the cathode electrode was replaced with a nickel electrode, the yield of the compound C2 was 78% (table 1, entry 7). After changing the composition or proportion of the solvent, it was found that when a volume ratio of 7:1 and water, and the yield of the product is highest. In the absence of power, no product was detected (table 1, entry 11), indicating that current plays a critical 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:
the operation steps are as follows:
to a dry and clean two-port pressure-resistant tube equipped with a magnetic rotor were successively added 1- (2-chloro-4-methylphenyl) -2- (methylsulfonyl) diazene A2 (116 mg,0.5 mmol), triphenyl phosphite B (233 mg,1.5 eq), tetrabutylammonium tetrafluoroborate (263 mg,1.6 eq), to which was added a volume ratio of 7: acetonitrile/water (8 mL) of 1. Subsequently using graphite rodsAs yangThe electrode was immersed in the reaction solution with a platinum sheet (15.0 mm. Times.10.0 mm. Times.0.3 mm) as a cathode to a depth of about 16.0mm. The reaction mixture was stirred and reacted at room temperature for 2 hours at a constant current of 10.0 mA. After the completion of the reaction, 10.0mL of ethyl acetate was added, and then the resultant mixture was extracted three times with water (20.0x3 mL), dried over anhydrous sodium sulfate, filtered, the solvent was removed by rotary evaporation under reduced pressure, and the obtained crude product was purified by separation using silica gel column chromatography (petroleum ether/ethyl acetate=10:1), to give product C2 in a yield of 81%.
Product C2 1 H NMR chart of FIG. 4, product C2 13 C NMR chart of FIG. 5, product C2 31 The P NMR chart is shown in FIG. 6.
Characterization data for product C2 are as follows: 1 H NMR(500MHz,CDCl 3 )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). 13 C NMR(126MHz,CDCl 3 )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). 31 P NMR(202MHz,CDCl 3 )δ11.44(d,J＝14.4Hz)。
Claims (7)
1. a synthesis method of aryl phosphate (C) is characterized in that: aryl azo sulfone (A) and triphenyl phosphite (B) are used as raw materials, and aryl phosphate compounds (C) are synthesized electrochemically; the electrolyte of the electrochemical reaction is selected from LiClO 4 、nBu 4 NPF 6 、nBu 4 NClO 4 One or a combination of more than one of tetrabutylammonium tetrafluoroborate; 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 C 1-6 Alkyl, -O-C 1-6 Alkyl, halogen or halogenated C 1-6 An alkyl group;
electrochemical reactionSolvent of MeCN, DMSO, CH 3 OH、H 2 One or a combination of several of O;
the constant current of the reaction is 5-15mA; the reaction temperature is room temperature and the reaction time is 1.3-4h.
2. The method of claim 1, wherein: the "halogen" refers to fluorine, chlorine, bromine or iodine; the "C 1-6 Alkyl "means methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, cyclopropyl, cyclopentyl or cyclohexyl; the' -O-C 1-6 Alkyl "means methoxy, ethoxy or t-butoxy; the "halogen-substituted C 1-6 Alkyl "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 molar ratio of the aryl azo sulfone (A) to the triphenyl phosphite (B) used is 1:1-3; the molar ratio of the amount of the electrolyte tetrabutylammonium tetrafluoroborate to the amount of the aryl azo sulfone (A) is 1-3:1.
5. the method of any one of claims 1-4, wherein: the solvent for electrochemical reaction is a mixed solvent of acetonitrile and water, and the volume ratio of the acetonitrile to the water is 3-7:1.
6. the method of any one of claims 1-4, wherein: the anode electrode of the reaction is a graphite rod, and the cathode electrode is a nickel electrode or a platinum sheet electrode.
7. A synthesis method of aryl phosphate (C) is characterized in that: aryl azo sulfone (A) and triphenyl phosphite (B) are used as raw materials, and aryl phosphate compounds (C) are synthesized electrochemically; the reaction formula is:
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 aryl azo sulfone (A) to the triphenyl phosphite (B) used is 1:1.5; the molar ratio of the amount of tetrabutylammonium tetrafluoroborate electrolyte to the amount of arylazo sulfone (a) was 1.6:1, a step of; the electrochemical reaction uses a graphite rod as an anode and a platinum sheet as a cathode; the volume ratio of acetonitrile to water as solvent for electrochemical reaction is 7: 1; 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 aryl phosphate compounds (C); after the reaction is finished, the reaction liquid is diluted by adding ethyl acetate, the obtained mixture is extracted with water for three times, dried by anhydrous sodium sulfate, filtered, the solvent is removed by rotary evaporation under reduced pressure, and the obtained crude product is separated and purified by using a silica gel column chromatography, so that an aryl phosphate product C is obtained.
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| CN109943861A (en) * | 2019-03-29 | 2019-06-28 | 南京大学 | A kind of method that electrochemistry oxygen is combined to alpha-amido phosphate |
| CN111621804A (en) * | 2020-05-13 | 2020-09-04 | 南昌大学 | Method for electrochemically synthesizing acyl phosphate |
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| CN109943861A (en) * | 2019-03-29 | 2019-06-28 | 南京大学 | A kind of method that electrochemistry oxygen is combined to alpha-amido phosphate |
| CN111621804A (en) * | 2020-05-13 | 2020-09-04 | 南昌大学 | Method for electrochemically synthesizing acyl phosphate |
| CN112921345A (en) * | 2021-01-21 | 2021-06-08 | 浙江工业大学 | Direct electrochemical synthesis method of thiophosphate compound |
Non-Patent Citations (3)
| Title |
|---|
| Catalyst-free phosphorylation of aryl halides with trialkyl phosphites through electrochemical reduction;Shuai Wang et al.;《Chem. Commun.》;第55卷;第14035--14038页 * |
| Electrochemical Thiolation and Borylation of Arylazo Sulfones with Thiols and B 2 pin 2;Rongkang Wang et al.;《Adv. Synth. Catal.》;第363卷;第1904–1911页 * |
| Electrochemically driven synthesis of phosphorothioates from trialkyl phosphites and aryl thiols;Lingmin Zhao et al.;《Electrochimica Acta》;第389卷;第138748（1-10）页 * |
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