CN110981720A - Diaryl acetate compound and preparation method thereof - Google Patents
Diaryl acetate compound and preparation method thereof Download PDFInfo
- Publication number
- CN110981720A CN110981720A CN201911345042.8A CN201911345042A CN110981720A CN 110981720 A CN110981720 A CN 110981720A CN 201911345042 A CN201911345042 A CN 201911345042A CN 110981720 A CN110981720 A CN 110981720A
- Authority
- CN
- China
- Prior art keywords
- diaryl
- reaction
- preparation
- acetate
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 Diaryl acetate compound Chemical class 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 claims abstract description 17
- 239000011941 photocatalyst Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 8
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001298 alcohols Chemical class 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000004440 column chromatography Methods 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- JAMNHZBIQDNHMM-UHFFFAOYSA-N pivalonitrile Chemical compound CC(C)(C)C#N JAMNHZBIQDNHMM-UHFFFAOYSA-N 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 229910052723 transition metal Inorganic materials 0.000 abstract description 4
- 150000003624 transition metals Chemical class 0.000 abstract description 4
- 230000001678 irradiating effect Effects 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 238000010898 silica gel chromatography Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 6
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- PUNIIEHHUHGISF-UHFFFAOYSA-N (2-fluorophenyl) acetate Chemical compound CC(=O)OC1=CC=CC=C1F PUNIIEHHUHGISF-UHFFFAOYSA-N 0.000 description 2
- QQYNGKGFOZQMHD-UHFFFAOYSA-N (3-methoxyphenyl) acetate Chemical compound COC1=CC=CC(OC(C)=O)=C1 QQYNGKGFOZQMHD-UHFFFAOYSA-N 0.000 description 2
- IENDTEDHWNXFQX-UHFFFAOYSA-N (4-butylphenyl) acetate Chemical compound CCCCC1=CC=C(OC(C)=O)C=C1 IENDTEDHWNXFQX-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CBAIJJMMUDSHOD-UHFFFAOYSA-N [3-(trifluoromethyl)phenyl] acetate Chemical compound CC(=O)OC1=CC=CC(C(F)(F)F)=C1 CBAIJJMMUDSHOD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LDBRZDPBCLPCAI-UHFFFAOYSA-N ethyl 2,2-bis(4-chlorophenyl)acetate Chemical compound C=1C=C(Cl)C=CC=1C(C(=O)OCC)C1=CC=C(Cl)C=C1 LDBRZDPBCLPCAI-UHFFFAOYSA-N 0.000 description 2
- MBKQSFDLKVDUTP-UHFFFAOYSA-N ethyl 2,2-bis(4-fluorophenyl)acetate Chemical compound C=1C=C(F)C=CC=1C(C(=O)OCC)C1=CC=C(F)C=C1 MBKQSFDLKVDUTP-UHFFFAOYSA-N 0.000 description 2
- PYPHPZOQIVEWHN-UHFFFAOYSA-N ethyl 2,2-diphenylacetate Chemical compound C=1C=CC=CC=1C(C(=O)OCC)C1=CC=CC=C1 PYPHPZOQIVEWHN-UHFFFAOYSA-N 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- QZAYGJVTTNCVMB-UHFFFAOYSA-N serotonin Chemical compound C1=C(O)C=C2C(CCN)=CNC2=C1 QZAYGJVTTNCVMB-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 1
- CJPVPOYTTALCNX-UHFFFAOYSA-N (2-chlorophenyl) acetate Chemical compound CC(=O)OC1=CC=CC=C1Cl CJPVPOYTTALCNX-UHFFFAOYSA-N 0.000 description 1
- PHDIJLFSKNMCMI-ITGJKDDRSA-N (3R,4S,5R,6R)-6-(hydroxymethyl)-4-(8-quinolin-6-yloxyoctoxy)oxane-2,3,5-triol Chemical compound OC[C@@H]1[C@H]([C@@H]([C@H](C(O1)O)O)OCCCCCCCCOC=1C=C2C=CC=NC2=CC=1)O PHDIJLFSKNMCMI-ITGJKDDRSA-N 0.000 description 1
- QRDAPCMJAOQZSU-KQQUZDAGSA-N (e)-3-[4-[(e)-3-(3-fluorophenyl)-3-oxoprop-1-enyl]-1-methylpyrrol-2-yl]-n-hydroxyprop-2-enamide Chemical compound C1=C(\C=C\C(=O)NO)N(C)C=C1\C=C\C(=O)C1=CC=CC(F)=C1 QRDAPCMJAOQZSU-KQQUZDAGSA-N 0.000 description 1
- JNPGUXGVLNJQSQ-BGGMYYEUSA-M (e,3r,5s)-7-[4-(4-fluorophenyl)-1,2-di(propan-2-yl)pyrrol-3-yl]-3,5-dihydroxyhept-6-enoate Chemical compound CC(C)N1C(C(C)C)=C(\C=C\[C@@H](O)C[C@@H](O)CC([O-])=O)C(C=2C=CC(F)=CC=2)=C1 JNPGUXGVLNJQSQ-BGGMYYEUSA-M 0.000 description 1
- VAVHMEQFYYBAPR-ITWZMISCSA-N (e,3r,5s)-7-[4-(4-fluorophenyl)-1-phenyl-2-propan-2-ylpyrrol-3-yl]-3,5-dihydroxyhept-6-enoic acid Chemical compound CC(C)C1=C(\C=C\[C@@H](O)C[C@@H](O)CC(O)=O)C(C=2C=CC(F)=CC=2)=CN1C1=CC=CC=C1 VAVHMEQFYYBAPR-ITWZMISCSA-N 0.000 description 1
- HIHOEGPXVVKJPP-JTQLQIEISA-N 5-fluoro-2-[[(1s)-1-(5-fluoropyridin-2-yl)ethyl]amino]-6-[(5-methyl-1h-pyrazol-3-yl)amino]pyridine-3-carbonitrile Chemical compound N([C@@H](C)C=1N=CC(F)=CC=1)C(C(=CC=1F)C#N)=NC=1NC=1C=C(C)NN=1 HIHOEGPXVVKJPP-JTQLQIEISA-N 0.000 description 1
- REDUQXCPUSNJOL-UHFFFAOYSA-N C(C1=CC=CC=C1)NC(CN(C(C1=CC=C(C=C1)C(C)C)=O)CC1=CC=C(C=C1)C(NO)=O)=O Chemical compound C(C1=CC=CC=C1)NC(CN(C(C1=CC=C(C=C1)C(C)C)=O)CC1=CC=C(C=C1)C(NO)=O)=O REDUQXCPUSNJOL-UHFFFAOYSA-N 0.000 description 1
- CYSWUSAYJNCAKA-FYJFLYSWSA-N ClC1=C(C=CC=2N=C(SC=21)OCC)OC1=CC=C(C=N1)/C=C/[C@H](C)NC(C)=O Chemical compound ClC1=C(C=CC=2N=C(SC=21)OCC)OC1=CC=C(C=N1)/C=C/[C@H](C)NC(C)=O CYSWUSAYJNCAKA-FYJFLYSWSA-N 0.000 description 1
- QBXVXKRWOVBUDB-GRKNLSHJSA-N ClC=1C(=CC(=C(CN2[C@H](C[C@H](C2)O)C(=O)O)C1)OCC1=CC(=CC=C1)C#N)OCC1=C(C(=CC=C1)C1=CC2=C(OCCO2)C=C1)C Chemical compound ClC=1C(=CC(=C(CN2[C@H](C[C@H](C2)O)C(=O)O)C1)OCC1=CC(=CC=C1)C#N)OCC1=C(C(=CC=C1)C1=CC2=C(OCCO2)C=C1)C QBXVXKRWOVBUDB-GRKNLSHJSA-N 0.000 description 1
- YLEIFZAVNWDOBM-ZTNXSLBXSA-N ac1l9hc7 Chemical compound C([C@H]12)C[C@@H](C([C@@H](O)CC3)(C)C)[C@@]43C[C@@]14CC[C@@]1(C)[C@@]2(C)C[C@@H]2O[C@]3(O)[C@H](O)C(C)(C)O[C@@H]3[C@@H](C)[C@H]12 YLEIFZAVNWDOBM-ZTNXSLBXSA-N 0.000 description 1
- SRVFFFJZQVENJC-IHRRRGAJSA-N aloxistatin Chemical compound CCOC(=O)[C@H]1O[C@@H]1C(=O)N[C@@H](CC(C)C)C(=O)NCCC(C)C SRVFFFJZQVENJC-IHRRRGAJSA-N 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 150000001543 aryl boronic acids Chemical class 0.000 description 1
- 150000001499 aryl bromides Chemical class 0.000 description 1
- RNOAANRGEYCUQZ-UHFFFAOYSA-N azido acetate Chemical compound CC(=O)ON=[N+]=[N-] RNOAANRGEYCUQZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KDPAWGWELVVRCH-UHFFFAOYSA-M bromoacetate Chemical compound [O-]C(=O)CBr KDPAWGWELVVRCH-UHFFFAOYSA-M 0.000 description 1
- FOANIXZHAMJWOI-UHFFFAOYSA-N bromopropylate Chemical compound C=1C=C(Br)C=CC=1C(O)(C(=O)OC(C)C)C1=CC=C(Br)C=C1 FOANIXZHAMJWOI-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000002825 dopamine reuptake Effects 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- QHDRKFYEGYYIIK-UHFFFAOYSA-N isovaleronitrile Chemical compound CC(C)CC#N QHDRKFYEGYYIIK-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QAPTWHXHEYAIKG-RCOXNQKVSA-N n-[(1r,2s,5r)-5-(tert-butylamino)-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](NC(C)(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 QAPTWHXHEYAIKG-RCOXNQKVSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229940076279 serotonin Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a diaryl acetate compound and a preparation method thereof, and the preparation method comprises the following steps: (1) adding diaryl 1, 2-diketone compounds, alcohol compounds, trialkyl phosphite and a photocatalyst into a reaction vessel, and adding a solvent for dissolving to obtain a reaction solution; (2) irradiating the reaction solution by using a light source and stirring the reaction solution until the reaction is complete; (3) and after the reaction is finished, recovering the solvent under reduced pressure and purifying by column chromatography to obtain the diaryl acetate compound. The invention starts from easily obtained diaryl 1, 2-diketone, has mild and green reaction conditions, does not need precious transition metal catalysis, is economic and environment-friendly, and has higher practicability.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to diaryl acetate compounds and a preparation method thereof.
Background
Diaryl acetate structures are widespread among natural products and are available for many pharmaceutical molecules such as swertin and dinitrogen. Research shows that the structure has antiviral, rheumatism eliminating, antitumor, central nervous activity and serotonin dopamine reuptake inhibiting activity. The related documents are: (a) Xu, H.; Lv, M.; Tian, X. Curr. Med. chem.2009, 16, 327, (b) Keller, H.; Schafner, R.; Carruba, M. O.; Burkard, W.P.; Pieri, M.; Bonetti, E. P.; Scherschlich, R.; Prada, M. D.; Haefely, W.E. adv. biochem. Psychopharmacol. 1982, 31, 249. (c) Jacob, J. N.; Nichols, D. E.; Kohli, J. D.; Glock, D.J. chem. 1981, 24, 1013.
The preparation of diaryl acetic acid is mainly a transition metal catalyzed coupling method starting from monoaryl acetic acid ester. The recently developed metal coupling method of 2-azido acetate overcomes the harsh conditions of high temperature, strong alkali and the like of the traditional method.
Related preparation and activity patents are also: (1) in the Chinese patent application of Zjunliang, university of east China, "a method for selective C-H bond functionalization of phenol and aniline under the catalysis of gold" (CN 103936537A), a method for realizing coupling of phenol or aniline and azido acetate by utilizing a gold catalyst is disclosed, and synthesis of diaryl acetate is realized; (2) international patent publication WO2007033781A1 discloses a palladium catalyzed coupling reaction between an aryl acetate and an aryl bromide directly under strongly basic conditions; (3) leehen in International patent WO2002079339A2 discloses the coupling of 2-bromoacetate and arylboronic acid under Pd (0) catalysis to form diarylacetate; (4) zhejiang Hebei pesticide chemical Co Ltd discloses a synthesis method for synthesizing diaryl acetate-bromopropylate by using glyoxylic acid, bromobenzene and isopropanol in Chinese patent 'a synthesis method of bromopropylate' (CN 103936537A).
However, the above preparation methods all use severe conditions such as strong alkali, and the reaction is not economical because the catalyst is catalyzed by expensive transition metal.
Disclosure of Invention
The invention provides a diaryl acetate compound and a preparation method thereof, which solve the problems of harsh reaction conditions and low efficiency in the prior art.
The technical scheme for realizing the invention is as follows:
a preparation method of diaryl acetate compounds comprises the following steps:
(1) adding diaryl 1, 2-diketone compounds, alcohol compounds, trialkyl phosphite and a photocatalyst into a reaction vessel, and adding a solvent for dissolving to obtain a reaction solution;
(2) irradiating the reaction solution by using a light source and stirring the reaction solution until the reaction is complete;
(3) and after the reaction is finished, recovering the solvent under reduced pressure and purifying by column chromatography to obtain the diaryl acetate compound.
The structural formula of the diaryl 1, 2-diketone compound in the step (1) is as follows:wherein Ar is1And Ar2The same or different, and is selected from any one of phenyl, substituted phenyl, aromatic heterocycle, condensed ring aryl and condensed aromatic heterocycle substituent.
The structural formula of the alcohols in the step (1) is ROH, wherein R is a linear chain or branched chain alkyl of C1-C20.
The photocatalyst in the step (1) is DPZ, and the specific synthesis steps can be referred to as ZHao, Y., Zhang, C., Chin, K, F., Pyrela, O., Wei, G., Liu, H., Bure š, F., Jiang, Z.RSC A,dv.2014.4(57), 30062. The structural formula of the photocatalyst is as follows:。
the structural formula of the trialkyl phosphite in the step (1) is as follows: p (OR')3Wherein R' is a linear or branched alkyl of C1-C10.
The solvent in the step (1) is any one of acetonitrile, propionitrile, isopropyl nitrile, n-butyl nitrile, isobutyl nitrile, tert-butyl nitrile, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, benzene, toluene, ethylbenzene, p-xylene, diethyl ether, THF, dioxane and dimethoxyethane.
In the step (1), the molar ratio of diaryl 1, 2-diketone compound, alcohol compound, trialkyl phosphite and photocatalyst is 1 (1-10): (1-3): (0.001-0.1), and the concentration of diaryl 1, 2-dione compound in the reaction solution is 0.01-1.0M.
The light source in the step (2) is a CFL bulb, sunlight or an LED lamp, the power range of the CFL bulb is 9-100W, the wavelength range of the LED lamp is 445-455nm, and the power is 1-10W.
The reaction process in the step (2) is protected by argon or nitrogen, and the reaction time is 2-7 days
The structural formula of the prepared diaryl acetate compound is as follows:
wherein Ar is1And Ar2The same or different, is selected from phenyl, substituted phenyl, aromatic heterocycle, condensed ring aryl and condensed aromatic heterocycle substituent; r is a straight chain or branched chain alkyl of C1-C20.
The reaction formula is as follows:
wherein Ar is1And Ar2The same or different, is selected from phenyl, substituted phenyl, aromatic heterocycle, condensed ring aryl and condensed aromatic heterocycle substituent; r is a straight chain or branched chain alkyl of C1-C20; r' is a straight chain or branched chain alkyl of C1-C10.
The invention has the beneficial effects that: the invention starts from easily obtained diaryl 1, 2-diketone, has mild and green reaction conditions, does not need precious transition metal catalysis, is economic and environment-friendly, and has higher practicability.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
Preparation of ethyl 2, 2-diphenylacetate (2 a):
the specific synthesis steps and the characterization are as follows:
benzil 1a (21 mg, 0.1 mmol, 1.0 equiv.) and P (OEt) were combined in a 10 ml Schlenk tube3(33.2 mg, 0.2mmol, 2.0 equiv.) was dissolved in DCE (1.0 ml), EtOH (11.7. mu.L, 0.2mmol, 2.0 equiv.) and photocatalyst DPZ (0.0354 mg, 0.1. mu. mol) were added, the reaction was stirred for 48 hours under 3W LED (450 nm) irradiation at room temperature, and the reaction was completed by TLC. The reaction solution was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography (volume ratio, the same applies hereinafter, PE: EA = 20: 1) to give the diaryl acetate compound 2a, 21.5 mg, 90%.
1H NMR (300 MHz, Chloroform-d) δ 7.41 – 7.23 (m, 10H), 5.04 (s, 1H),4.24 (q,J= 7.1 Hz, 2H), 1.28 (t,J= 7.1 Hz, 3H)。
13C NMR (75 MHz, CDCl3) δ 172.44, 138.80, 128.59, 128.54, 127.18,61.15, 57.16, 14.12; HRMS (ESI) m/z 241.1226 (M+H+), calc. for C6H17O2241.1223。
Using the procedure of example 1, varying the reaction conditions, the results are shown in the following table:
example 2
Preparation of ethyl 2, 2-bis (4-butylphenyl) acetate (2 b):
the specific synthesis steps and the characterization are as follows:
benzil compound 1b (32.2 mg, 0.1 mmol, 1.0 equiv.) and P (OEt) were combined in a 10 ml Schlenk tube3(33.2 mg, 0.2mmol, 2.0 equiv.) was dissolved in DCE (1.0 ml), EtOH (11.7. mu.L, 0.2mmol, 2.0 equiv.) and photocatalyst DPZ (0.0354 mg, 0.1. mu. mol) were added, the reaction was stirred for 48 hours under 3W LED (450 nm) irradiation at room temperature, and the reaction was completed by TLC. The reaction solution was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography (volume ratio, the same applies hereinafter, PE: EA = 20: 1) to give a diaryl acetate compound 2b, 27 mg, 77%.
1H NMR (300 MHz, Chloroform-d) δ 7.14 (d,J= 7.9 Hz, 4H), 7.04 (d,J= 8.0 Hz, 4H), 4.86 (s, 1H), 4.11 (q,J= 7.1 Hz, 2H), 2.49 (t,J= 7.7 Hz,4H), 1.55 – 1.43 (m, 4H), 1.33 – 1.22 (m, 4H), 1.17 (t,J= 7.1 Hz, 3H), 0.83(t,J= 7.3 Hz, 6H)。
13C NMR (75 MHz, CDCl3) δ 172.9, 141.7, 136.2, 128.7, 128.6, 128.4,128.4, 61.1, 56.5, 35.3, 33.5, 22.4, 14.2, 14.0;HRMS (ESI) m/z 353.2480 (M+H+), calc. for C24H33O2353.2475。
Example 3
Preparation of ethyl 2, 2-bis (4-chlorophenyl) acetate (2 c):
the specific synthesis steps and the characterization are as follows:
benzil compound 1c (27.9 mg, 0.1 mmol, 1.0 equiv.) and P (OEt) were combined in a 10 ml Schlenk tube3(33.2 mg, 0.2mmol, 2.0 equiv.) was dissolved in DCE (1.0 ml), EtOH (11.7. mu.L, 0.2mmol, 2.0 equiv.) and photocatalyst DPZ (0.0354 mg, 0.1. mu. mol) were added, the reaction was stirred for 48 hours under 3W LED (450 nm) irradiation at room temperature, and the reaction was completed by TLC. The reaction mixture was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography (volume ratio, the same applies hereinafter, PE: EA = 20: 1) to give a diarylacetate compound 2c, 22 mg, 71%。
1H NMR (300 MHz, Chloroform-d) δ 7.30 (d,J= 8.6 Hz, 4H), 7.22 (d,J= 8.6 Hz, 4H), 4.94 (s, 1H), 4.21 (q,J= 7.1 Hz, 2H), 1.26 (t,J= 7.1 Hz,3H)。
13C NMR (75 MHz, CDCl3) δ 171.8, 136.8, 133.4, 129.9, 128.8, 61.5,55.8, 14.1;HRMS (ESI) m/z 309.0445 (M+H+), calc. for C16H15Cl2O2309.0444。
Example 4
Preparation of ethyl 2, 2-bis (4-fluorophenyl) acetate (2 d):
the specific synthesis steps and the characterization are as follows:
benzil compound 1d (24.6 mg, 0.1 mmol, 1.0 equiv.) and P (OEt) were combined in a 10 ml Schlenk tube3(33.2 mg, 0.2mmol, 2.0 equiv.) was dissolved in DCE (1.0 ml), EtOH (11.7. mu.L, 0.2mmol, 2.0 equiv.) and photocatalyst DPZ (0.0354 mg, 0.1. mu. mol) were added, the reaction was stirred for 48 hours under 3W LED (450 nm) irradiation at room temperature, and the reaction was completed by TLC. The reaction solution was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography (volume ratio, the same applies hereinafter, PE: EA = 20: 1) to give a diaryl acetate compound 2d, 13 mg, 47%.
1H NMR (300 MHz, Chloroform-d) δ 7.26 (dd,J= 8.4, 5.6 Hz, 4H), 7.01(t,J= 8.7 Hz, 4H), 4.95 (s, 1H), 4.20 (q,J= 7.1 Hz, 2H), 1.25 (t,J= 7.2Hz, 3H)。
13C NMR (75 MHz, CDCl3) δ 172.2, 163.7, 160.4, 134.4, 134.4, 130.1,130.0, 115.7, 115.4, 77.4, 77.0, 76.6, 61.4, 55.5, 14.1;HRMS (ESI) m/z277.1033 (M+H+), calc. for C16H15F2O2277.1035。
Example 5
Preparation of ethyl 2, 2-bis (3-methoxyphenyl) acetate (2 e):
the specific synthesis steps and the characterization are as follows:
benzil compound 1e (27 mg, 0.1 mmol, 1.0 equiv.) and P (OEt) were combined in a 10 ml Schlenk tube3(33.2 mg, 0.2mmol, 2.0 equiv.) was dissolved in DCE (1.0 ml), EtOH (11.7. mu.L, 0.2mmol, 2.0 equiv.) and photocatalyst DPZ (0.0354 mg, 0.1. mu. mol) were added, the reaction was stirred for 48 hours under 3W LED (450 nm) irradiation at room temperature, and the reaction was completed by TLC. The reaction solution was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography (volume ratio, the same shall apply hereinafter, PE: EA = 20: 1) to give the diaryl acetate compound 2e, 13 mg, 43%.
1H NMR (300 MHz, Chloroform-d) δ 7.23 (t,J= 7.8 Hz, 2H), 6.95 –6.83 (m, 4H), 6.80 (dd,J= 8.3, 2.5 Hz, 2H), 4.95 (s, 1H), 4.21 (q,J= 7.1Hz, 2H), 3.77 (s, 6H), 1.26 (t,J= 7.2 Hz, 3H)。
13C NMR (75 MHz, CDCl3) δ 172.2, 159.7, 140.0, 129.5, 121.0, 114.5,112.5, 61.2, 57.0, 55.2, 14.2;HRMS (ESI) m/z 301.1437 (M+H+), calc. forC18H21O4301.1434。
Example 6
Preparation of ethyl 2, 2-bis (2-fluorophenyl) acetate (2 f):
the specific synthesis steps and the characterization are as follows:
benzil compound 1f (24.6 mg, 0.1 mmol, 1.0 equiv.) and P (OEt) were combined in a 10 ml Schlenk tube3(33.2 mg, 0.2mmol, 2.0 equiv.) was dissolved in DCE (1.0 ml), EtOH (11.7. mu.L, 0.2mmol, 2.0 equiv.) and photocatalyst DPZ (0.0354 mg, 0.1. mu. mol) were added, and the mixture was irradiated with a 3W LED (450 nm) at room temperature, followed by stirring and reacting for 48 hoursIn hours, the reaction was complete by TLC. The reaction solution was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography (volume ratio, the same applies hereinafter, PE: EA = 20: 1) to give a diaryl acetate compound 2f, 16 mg, 58%.
1H NMR (300 MHz, Chloroform-d) δ 7.33 – 7.14 (m, 4H), 7.14 – 6.96 (m,4H), 5.53 (s, 1H), 4.23 (q,J= 7.1 Hz, 2H), 1.24 (t,J= 7.1 Hz, 3H)。
13C NMR (75 MHz, CDCl3) δ 171.2, 162.2, 159.0, 130.0, 130.0, 129.3,129.2, 124.9, 124.7, 124.2, 124.2, 115.7, 115.4, 61.6, 43.4, 14.1;HRMS (ESI)m/z 277.1035 (M+H+), calc. for C16H15F2O2277.1035。
Example 7
Preparation of ethyl 2, 2-bis (2-chlorophenyl) acetate (2 g):
the specific synthesis steps and the characterization are as follows:
in a 10 ml Schlenk tube, 1g (27.9 mg, 0.1 mmol, 1.0 equiv.) of a benzil compound and P (OEt)3(33.2 mg, 0.2mmol, 2.0 equiv.) was dissolved in DCE (1.0 ml), EtOH (11.7. mu.L, 0.2mmol, 2.0 equiv.) and photocatalyst DPZ (0.0354 mg, 0.1. mu. mol) were added, the reaction was stirred for 48 hours under 3W LED (450 nm) irradiation at room temperature, and the reaction was completed by TLC. The reaction solution was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography (volume ratio, the same applies hereinafter, PE: EA = 20: 1) to obtain 2g, 21.6 mg, 70% of the diarylacetate compound.
1H NMR (300 MHz, Chloroform-d) δ 7.48 – 7.35 (m, 2H), 7.23 (td,J=7.4, 6.5, 3.6 Hz, 4H), 7.13 – 7.02 (m, 2H), 5.81 (s, 1H), 4.25 (q,J= 7.1Hz, 2H), 1.26 (t,J= 7.1 Hz, 3H)。
13C NMR (75 MHz, CDCl3) δ 171.4, 135.3, 134.7, 129.8, 129.8, 128.8,126.9, 61.6, 51.7, 14.1.;HRMS (ESI) m/z 309.0446 (M+H+), calc. for C16H15Cl2O2309.0444。
Example 8
Preparation of ethyl 2, 2-bis (3-trifluoromethylphenyl) acetate (2 h):
the specific synthesis steps and the characterization are as follows:
benzil compound 1h (34.6 mg, 0.1 mmol, 1.0 equiv.) and P (OEt) in a 10 ml Schlenk tube3(33.2 mg, 0.2mmol, 2.0 equiv.) was dissolved in DCE (1.0 ml), EtOH (11.7. mu.L, 0.2mmol, 2.0 equiv.) and photocatalyst DPZ (0.0354 mg, 0.1. mu. mol) were added, the reaction was stirred for 48 hours under 3W LED (450 nm) irradiation at room temperature, and the reaction was completed by TLC. The reaction solution was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography (volume ratio, the same applies hereinafter, PE: EA = 20: 1) to give a diaryl acetate compound 2h, 19 mg, 50%.
1H NMR (300 MHz, Chloroform-d) δ 7.48 – 7.35 (m, 2H), 7.23 (td,J=7.4, 6.5, 3.6 Hz, 4H), 7.13 – 7.02 (m, 2H), 5.81 (s, 1H), 4.25 (q,J= 7.1Hz, 2H), 1.26 (t,J= 7.1 Hz, 3H)。
13C NMR (75 MHz, CDCl3) δ 171.4, 135.3, 134.7, 129.8, 129.8, 128.8,126.9, 61.6, 51.7, 14.1.;HRMS (ESI) m/z 377.0977 (M+H+), calc. for C18H15F6O2377.0971。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911345042.8A CN110981720B (en) | 2019-12-24 | 2019-12-24 | Diaryl acetate compound and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911345042.8A CN110981720B (en) | 2019-12-24 | 2019-12-24 | Diaryl acetate compound and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110981720A true CN110981720A (en) | 2020-04-10 |
CN110981720B CN110981720B (en) | 2020-11-03 |
Family
ID=70076209
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201911345042.8A Active CN110981720B (en) | 2019-12-24 | 2019-12-24 | Diaryl acetate compound and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110981720B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112939836A (en) * | 2021-03-17 | 2021-06-11 | 河南大学 | Beta-lactam compound and preparation method thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070010568A1 (en) * | 2003-02-07 | 2007-01-11 | Anita Mehta | Substituted azabicyclo hexane derivatives as muscarinic receptor antagonists |
JP2008222654A (en) * | 2007-03-14 | 2008-09-25 | Nissan Chem Ind Ltd | Vitamin b12-titania hybrid compound and dehalogenation catalyst |
US20090093483A1 (en) * | 2006-12-18 | 2009-04-09 | Amgen Inc. | Naphthalenone compounds exhibiting prolyl hydroxylase inhibitory activity, compositions, and uses thereof |
CN103936537A (en) * | 2014-04-24 | 2014-07-23 | 华东师范大学 | Method for performing gold-catalyzed selective C-H bond functionalization on phenol and aniline |
CN106659697A (en) * | 2014-05-30 | 2017-05-10 | 斯菲叶尔制药私有公司 | Novel compounds as anti-tubercular agents |
-
2019
- 2019-12-24 CN CN201911345042.8A patent/CN110981720B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070010568A1 (en) * | 2003-02-07 | 2007-01-11 | Anita Mehta | Substituted azabicyclo hexane derivatives as muscarinic receptor antagonists |
US20090093483A1 (en) * | 2006-12-18 | 2009-04-09 | Amgen Inc. | Naphthalenone compounds exhibiting prolyl hydroxylase inhibitory activity, compositions, and uses thereof |
JP2008222654A (en) * | 2007-03-14 | 2008-09-25 | Nissan Chem Ind Ltd | Vitamin b12-titania hybrid compound and dehalogenation catalyst |
CN103936537A (en) * | 2014-04-24 | 2014-07-23 | 华东师范大学 | Method for performing gold-catalyzed selective C-H bond functionalization on phenol and aniline |
CN106659697A (en) * | 2014-05-30 | 2017-05-10 | 斯菲叶尔制药私有公司 | Novel compounds as anti-tubercular agents |
Non-Patent Citations (1)
Title |
---|
RAVEENDRA BABU KOTHAPALLI 等: "Synthesis of Chiral α-Diarylacetic Esters by Stereospecific 1,2-Aryl Migration Promoted by in Situ Generated Acetals from Benzoins", 《ORG. LETT.》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112939836A (en) * | 2021-03-17 | 2021-06-11 | 河南大学 | Beta-lactam compound and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN110981720B (en) | 2020-11-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5738185B2 (en) | Process for preparing amines from alcohols and ammonia | |
CN108276287B (en) | Synthesis method of 4-oxo acrylate derivative catalyzed by visible light | |
JP7199401B2 (en) | Synthesis of N-heterocyclic carbenes and their intermediates | |
US20070270593A1 (en) | Ruthenium(II) catalysts for use in stereoselective cyclopropanations | |
CN108299296B (en) | A kind of preparation method of phenanthridine heterocyclic compound | |
EP2193134A1 (en) | Method for the organocatalytic activation of carboxylic acids for chemical reactions using orthosubstituted arylboronic acids | |
CN110981720A (en) | Diaryl acetate compound and preparation method thereof | |
Chen et al. | Synthetic studies on (+)-biotin, part 15: A chiral squaramide-mediated enantioselective alcoholysis approach toward the total synthesis of (+)-biotin | |
CN113480468B (en) | A kind of method of visible light catalytic synthesis isoindigo derivative | |
Sladek et al. | 3-Fluoropyridyl nickel complexes as useful tools for the selective synthesis of new 2, 4, 5, 6-tetrafluoropyridines: a route complementing the established methods to access fluorinated pyridines | |
CN113979918A (en) | A kind of C-3 five-membered spirocyclic indolone derivative containing all-carbon tetra-substituted alkene structure and its preparation and application | |
CN107641101A (en) | A kind of preparation method of phenanthridines ketone compounds | |
CN112778191A (en) | Visible light mediated method for synthesizing allyl alcohol compound containing indole skeleton | |
CN112010882A (en) | Method for stereoselectively preparing 1, 3-disubstituted cyclohexane compounds and application | |
CN111253334A (en) | Mild photocatalytic synthesis method of C2 ether substituted 2H-benzothiazole derivative | |
CN112390800B (en) | Preparation method of L-erythro biopterin compound | |
JP6721891B2 (en) | 1,3-diamine derivative | |
CN114957266B (en) | Total synthesis method of natural product auraticloav racemate | |
JP5099932B2 (en) | Carbon-carbon bond formation reaction using fluorenone imine | |
CN110938079B (en) | Spirooxoindole derivative and preparation method thereof | |
KR102285494B1 (en) | Halogen-substituted dimethylchalcone derivatives and preparation method thereof | |
CN112441921B (en) | A kind of method for iridium photocatalytic synthesis of 9-acetoxy-9,10-dihydrophenanthrene compounds | |
CN108929226B (en) | A kind of method for preparing benzoylformate derivatives | |
CN111196778A (en) | Synthetic method of 3-ethylamino pyrrole compound | |
JPWO2005070876A1 (en) | Enantioselective method of nucleophilic addition reaction of enamide to imine and synthesis method of α-amino-γ-keto acid ester |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |