CN115838330B - Method for synthesizing dicarboxylic acid compound based on non-activated olefin remote carboxyl - Google Patents
Method for synthesizing dicarboxylic acid compound based on non-activated olefin remote carboxyl Download PDFInfo
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- CN115838330B CN115838330B CN202111106015.2A CN202111106015A CN115838330B CN 115838330 B CN115838330 B CN 115838330B CN 202111106015 A CN202111106015 A CN 202111106015A CN 115838330 B CN115838330 B CN 115838330B
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- remote
- dicarboxylic acid
- olefin
- reaction
- carboxyl
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- -1 dicarboxylic acid compound Chemical class 0.000 title claims abstract description 94
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 34
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000011941 photocatalyst Substances 0.000 claims abstract description 19
- 150000001991 dicarboxylic acids Chemical class 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 238000006473 carboxylation reaction Methods 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 16
- 239000001569 carbon dioxide Substances 0.000 claims description 11
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 230000021523 carboxylation Effects 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 239000012973 diazabicyclooctane Substances 0.000 claims description 3
- 150000004673 fluoride salts Chemical class 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 3
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 2
- GSCCALZHGUWNJW-UHFFFAOYSA-N N-Cyclohexyl-N-methylcyclohexanamine Chemical compound C1CCCCC1N(C)C1CCCCC1 GSCCALZHGUWNJW-UHFFFAOYSA-N 0.000 claims description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 21
- 239000000047 product Substances 0.000 abstract description 17
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 82
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 43
- 125000000217 alkyl group Chemical group 0.000 description 42
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 26
- 229910052739 hydrogen Inorganic materials 0.000 description 23
- 239000001257 hydrogen Substances 0.000 description 23
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 22
- 150000001408 amides Chemical class 0.000 description 20
- 125000003118 aryl group Chemical group 0.000 description 20
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 20
- 125000001072 heteroaryl group Chemical group 0.000 description 20
- 150000002431 hydrogen Chemical class 0.000 description 20
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 20
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 20
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 20
- 150000002148 esters Chemical class 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 125000003342 alkenyl group Chemical group 0.000 description 18
- 125000000304 alkynyl group Chemical group 0.000 description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical group CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 15
- 125000004093 cyano group Chemical group *C#N 0.000 description 13
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 125000004423 acyloxy group Chemical group 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 125000004104 aryloxy group Chemical group 0.000 description 6
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 150000003568 thioethers Chemical class 0.000 description 6
- 238000004293 19F NMR spectroscopy Methods 0.000 description 5
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 5
- XRKQMIFKHDXFNQ-UHFFFAOYSA-N n-cyclohexyl-n-ethylcyclohexanamine Chemical compound C1CCCCC1N(CC)C1CCCCC1 XRKQMIFKHDXFNQ-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- TXNLQUKVUJITMX-UHFFFAOYSA-N 4-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine Chemical compound CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1 TXNLQUKVUJITMX-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VYKNVAHOUNIVTQ-UHFFFAOYSA-N 1,2,2,3,3-pentamethylpiperidine Chemical compound CN1CCCC(C)(C)C1(C)C VYKNVAHOUNIVTQ-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- GCGRXVMGBHYMDA-UHFFFAOYSA-N 5-fluoro-2,4,6-tris(N-phenylanilino)benzene-1,3-dicarbonitrile Chemical compound C1(=CC=CC=C1)N(C1=C(C#N)C(=C(C(=C1C#N)N(C1=CC=CC=C1)C1=CC=CC=C1)F)N(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 GCGRXVMGBHYMDA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001370 alpha-amino acid derivatives Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229930192474 thiophene Chemical group 0.000 description 2
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OYNJAUIAADXAOW-UHFFFAOYSA-N 2,3,5,6-tetra(carbazol-9-yl)benzene-1,4-dicarbonitrile Chemical compound C1=CC=CC=2C3=CC=CC=C3N(C1=2)C1=C(C(=C(C(=C1C#N)N1C2=CC=CC=C2C=2C=CC=CC1=2)N1C2=CC=CC=C2C=2C=CC=CC1=2)C#N)N1C2=CC=CC=C2C=2C=CC=CC1=2 OYNJAUIAADXAOW-UHFFFAOYSA-N 0.000 description 1
- PRWATGACIORDEL-UHFFFAOYSA-N 2,4,5,6-tetra(carbazol-9-yl)benzene-1,3-dicarbonitrile Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=C(C#N)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C(N2C3=CC=CC=C3C3=CC=CC=C32)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C1C#N PRWATGACIORDEL-UHFFFAOYSA-N 0.000 description 1
- ZOMQCVKHGOMNER-UHFFFAOYSA-N 2,4,5,6-tetrakis(N-phenylanilino)benzene-1,3-dicarbonitrile Chemical compound C(#N)C1=C(C(=C(C(=C1N(C1=CC=CC=C1)C1=CC=CC=C1)N(C1=CC=CC=C1)C1=CC=CC=C1)N(C1=CC=CC=C1)C1=CC=CC=C1)C#N)N(C1=CC=CC=C1)C1=CC=CC=C1 ZOMQCVKHGOMNER-UHFFFAOYSA-N 0.000 description 1
- QMXFUIUEGUOSEV-UHFFFAOYSA-N 3,4,5,6-tetra(carbazol-9-yl)benzene-1,2-dicarbonitrile Chemical compound N#Cc1c(C#N)c(c(c(c1-n1c2ccccc2c2ccccc12)-n1c2ccccc2c2ccccc12)-n1c2ccccc2c2ccccc12)-n1c2ccccc2c2ccccc12 QMXFUIUEGUOSEV-UHFFFAOYSA-N 0.000 description 1
- YODXOCMXXDFKEV-UHFFFAOYSA-N 3,4,5,6-tetrakis(3,6-diphenylcarbazol-9-yl)benzene-1,2-dicarbonitrile Chemical compound C1(=CC=CC=C1)C=1C=CC=2N(C3=CC=C(C=C3C=2C=1)C1=CC=CC=C1)C=1C(=C(C(=C(C=1N1C2=CC=C(C=C2C=2C=C(C=CC1=2)C1=CC=CC=C1)C1=CC=CC=C1)N1C2=CC=C(C=C2C=2C=C(C=CC1=2)C1=CC=CC=C1)C1=CC=CC=C1)N1C2=CC=C(C=C2C=2C=C(C=CC1=2)C1=CC=CC=C1)C1=CC=CC=C1)C#N)C#N YODXOCMXXDFKEV-UHFFFAOYSA-N 0.000 description 1
- INVGTCJGWUABRZ-UHFFFAOYSA-N 3,4,5,6-tetrakis(3,6-ditert-butylcarbazol-9-yl)benzene-1,2-dicarbonitrile Chemical compound C(C)(C)(C)C=1C=CC=2N(C3=CC=C(C=C3C=2C=1)C(C)(C)C)C1=C(C(C#N)=C(C(=C1N1C2=CC=C(C=C2C=2C=C(C=CC1=2)C(C)(C)C)C(C)(C)C)N1C2=CC=C(C=C2C=2C=C(C=CC1=2)C(C)(C)C)C(C)(C)C)N1C2=CC=C(C=C2C=2C=C(C=CC1=2)C(C)(C)C)C(C)(C)C)C#N INVGTCJGWUABRZ-UHFFFAOYSA-N 0.000 description 1
- VPCXVCNTHAMRBT-UHFFFAOYSA-N 3,5-difluoro-2,4,6-tris(n-phenylanilino)benzonitrile Chemical compound FC1=C(N(C=2C=CC=CC=2)C=2C=CC=CC=2)C(C#N)=C(N(C=2C=CC=CC=2)C=2C=CC=CC=2)C(F)=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 VPCXVCNTHAMRBT-UHFFFAOYSA-N 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- ORNBQBCIOKFOEO-YQUGOWONSA-N Pregnenolone Natural products O=C(C)[C@@H]1[C@@]2(C)[C@H]([C@H]3[C@@H]([C@]4(C)C(=CC3)C[C@@H](O)CC4)CC2)CC1 ORNBQBCIOKFOEO-YQUGOWONSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000008206 alpha-amino acids Nutrition 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 150000003939 benzylamines Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- JCKYGMPEJWAADB-UHFFFAOYSA-N chlorambucil Chemical compound OC(=O)CCCC1=CC=C(N(CCCl)CCCl)C=C1 JCKYGMPEJWAADB-UHFFFAOYSA-N 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940041616 menthol Drugs 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229960000249 pregnenolone Drugs 0.000 description 1
- OZZAYJQNMKMUSD-DMISRAGPSA-N pregnenolone succinate Chemical compound C1C=C2C[C@@H](OC(=O)CCC(O)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](C(=O)C)[C@@]1(C)CC2 OZZAYJQNMKMUSD-DMISRAGPSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- ZHPPJUUSHATRPV-UHFFFAOYSA-N tortuosine Chemical compound COC1=C(OC)C=C2C3=CC(OC)=CC(CC4)=C3[N+]4=CC2=C1 ZHPPJUUSHATRPV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing dicarboxylic acid compounds based on non-activated olefin remote carboxyl, which belongs to the technical field of organic synthesis and mainly comprises the following steps: adding an olefin compound, a photocatalyst and alkali into a reaction container, then adding a reducing agent and a solvent under the atmosphere of CO 2, stirring at room temperature under the condition of visible light irradiation for reacting for 0.1-100 h, and separating and purifying a reaction product to prepare a dicarboxylic acid compound; the preparation method provided by the invention has excellent reactivity for non-activated olefin substrates, realizes non-activated olefin remote carboxylation reaction at room temperature, and has the characteristics of convenience in operation, low-cost and easily available raw materials, mild reaction conditions, wide substrate universality and high product yield.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for synthesizing dicarboxylic acid compounds based on remote carboxyl synthesis of non-activated olefin.
Background
The wide existence of olefin compounds plays a very important role in organic synthetic chemistry, and various compounds can be synthesized through functionalization of olefin double bonds, so that the olefin compounds are widely applied to the fields of pharmaceutical chemistry, polymer chemistry, material chemistry and the like.
In recent years, with the efforts of chemists, the difunctional of activated olefins has progressed greatly and has become an effective means of efficiently constructing complex compound molecules, but the difunctional of non-activated olefins still faces a great challenge. The synthesis of dicarboxylic acids of different chain lengths is more challenging because the chemical inertness of the non-activated olefin and CO 2 makes the double carboxylation reaction of the non-activated olefin very well reported. On the other hand, carbon dioxide is widely used in various chemical syntheses as an excellent carbon-synthon which is widely available, inexpensive and renewable in source. In view of the above, it would be of great interest to provide a method for the remote carboxylation of non-activated olefins to dicarboxylic acids using carbon dioxide.
Disclosure of Invention
Aiming at the defects, the invention aims to provide a method for synthesizing dicarboxylic acid compounds based on remote carboxylation of non-activated olefin, which can effectively solve the problem of the prior art that the remote double carboxylation reaction of the non-activated olefin is realized by using carbon dioxide, and simultaneously has the characteristics of convenient operation, low-cost and easily obtained raw materials, mild reaction conditions, wide substrate universality and high product yield.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a method for synthesizing dicarboxylic acid compounds based on remote carboxyl of non-activated olefin, which comprises the following steps:
Adding an olefin compound, a photocatalyst and alkali into a reaction container, then adding a reducing agent and a solvent under the atmosphere of CO 2, stirring at room temperature under the condition of visible light irradiation for reacting for 0.1-100 h, and separating and purifying a reaction product to prepare a dicarboxylic acid compound; wherein the mol ratio of the olefin compound, the photocatalyst, the alkali and the reducing agent is 1 (0.001-0.5): 0.1-10): 1-10;
The structural general formula of the olefin compound is shown as follows:
wherein R 1 is hydrogen, ester, carboxyl, amide, cyano, aryl, heteroaryl, alkynyl, alkenyl, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 2 is hydrogen, ester, carboxyl, amide, cyano, aryl, heteroaryl, alkynyl, alkenyl, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 3 is hydrogen, aryl, heteroaryl, alkynyl, alkenyl, ester, carboxyl, amide, cyano, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 4 is hydrogen, aryl, heteroaryl, ester, carboxyl, amide, cyano, fluoro, chloro, bromo, iodo, boron, silicon, phosphine, thioether, alkoxy, acyloxy, aryloxy, amino, alkynyl, alkenyl, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 5 is hydrogen, methoxycarbonyl, ethoxycarbonyl, or t-butoxycarbonyl or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 6 is hydrogen, aryl, heteroaryl, alkynyl, alkenyl, ester, carboxyl, amide, cyano, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 7 is hydrogen, aryl, heteroaryl, ester, carboxyl, amide, cyano, fluoro, chloro, bromo, iodo, boron, silicon, phosphine, thioether, alkoxy, acyloxy, aryloxy, amino, alkynyl, alkenyl, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 8 is hydrogen, aryl, heteroaryl, alkynyl, alkenyl, ester, carboxyl, amide, cyano, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 9 is hydrogen, aryl, heteroaryl, alkynyl, alkenyl, ester, carboxyl, amide, cyano, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 10 is hydrogen, aryl, heteroaryl, ester, carboxyl, amide, cyano, fluoro, chloro, bromo, iodo, boron, silicon, phosphine, thioether, alkoxy, acyloxy, aryloxy, amino, alkynyl, alkenyl, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 11 is hydrogen or alkyl; n is 1 or 2 or 3; the virtual ring is an aromatic or heteroaromatic ring (e.g., pyridine, furan or thiophene ring), preferably a benzene ring.
Further, the molar ratio of the olefin compound, the photocatalyst, the alkali and the reducing agent is 1 (0.005-0.1): 4.5-6.5): 2.5.
Further, the structural formula of the olefin compound is as follows:
further, the photocatalyst is a D-A type photocatalyst or an Ir photocatalyst.
Further, the photocatalyst is at least one of 4CzIPN、4DPAIPN、3DPAFIPN、3DPA2FBN、5CzBN、4CzPN、DPZ、4CzPN-Ph、4CzPN-Bu、4CzTPN、4CzTPN-Bu、Ir(dFCF3ppy)2(dtbbpy)PF6、fac-Ir(dF(ppy)3)、fac-Ir(ppy)3 and Ir (ppy) 2(dtbbpy)PF6.
Further, the carbonate of the base is Cs 2CO3、K2CO3、Na2CO3 or Li 2CO3; bicarbonate is CsHCO 3、KHCO3 or NaHCO 3; the fluoride salt is CsF or KF; the tert-butoxide is KO tBu、NaOt Bu or LiO t Bu; phosphate is K 3PO4 or Na 3PO4; carboxylate is CsOAc, KOAc, naOAc, csOPiv or KOPiv; the organic base is DBU, TBD, DABCO, TMG or DBN.
Further, the reducing agent organic amine compound is Cy 2NEt、Cy2NMe、iPr2NEt、NEt3 or PMP (pentamethylpiperidine).
Further, the wavelength of the visible light is 400 to 560nm, and the power of the visible light is 3 to 60W, preferably 20 to 30W.
Further, the carbon dioxide pressure is 0.5 to 30 times the atmospheric pressure, preferably 1 to 5 times the atmospheric pressure.
Further, the concentration of the solvent is 0.01 to 10.0M, and the solvent is preferably DMSO, NMP, DMF, DMAc, THF, DCM, meOH or MeCN or the like.
Further, the reaction time is 2 to 60 hours.
The reaction formula of the invention is as follows:
wherein R 1 is hydrogen, ester, carboxyl, amide, cyano, aryl, heteroaryl, alkynyl, alkenyl, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 2 is hydrogen, ester, carboxyl, amide, cyano, aryl, heteroaryl, alkynyl, alkenyl, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 3 is hydrogen, aryl, heteroaryl, alkynyl, alkenyl, ester, carboxyl, amide, cyano, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 4 is hydrogen, aryl, heteroaryl, ester, carboxyl, amide, cyano, fluoro, chloro, bromo, iodo, boron, silicon, phosphine, thioether, alkoxy, acyloxy, aryloxy, amino, alkynyl, alkenyl, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 5 is hydrogen, methoxycarbonyl, ethoxycarbonyl, or t-butoxycarbonyl or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 6 is hydrogen, aryl, heteroaryl, alkynyl, alkenyl, ester, carboxyl, amide, cyano, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 7 is hydrogen, aryl, heteroaryl, ester, carboxyl, amide, cyano, fluoro, chloro, bromo, iodo, boron, silicon, phosphine, thioether, alkoxy, acyloxy, aryloxy, amino, alkynyl, alkenyl, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 8 is hydrogen, aryl, heteroaryl, alkynyl, alkenyl, ester, carboxyl, amide, cyano, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 9 is hydrogen, aryl, heteroaryl, alkynyl, alkenyl, ester, carboxyl, amide, cyano, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 10 is hydrogen, aryl, heteroaryl, ester, carboxyl, amide, cyano, fluoro, chloro, bromo, iodo, boron, silicon, phosphine, thioether, alkoxy, acyloxy, aryloxy, amino, alkynyl, alkenyl, or alkyl (alkyl includes methyl, ethyl, isopropyl, t-butyl, hydroxymethyl, acetoxymethyl, trifluoromethyl, etc.); r 11 is hydrogen or alkyl; n is 1 or 2 or 3; the virtual ring is an aromatic or heteroaromatic ring (e.g., pyridine, furan or thiophene ring), preferably a benzene ring.
The reaction mechanism of the invention is shown in figure 1, and the specific process is as follows: take Ir III catalyst as an example; firstly, light excites an Ir III catalyst to generate [ Ir III]* species, carbon dioxide is further reduced into carbon dioxide radical anions and Ir IV species under the action of light, and the Ir IV species is reduced into Ir III species by an electron reducing agent; the formed carbon dioxide radical anions carry out radical addition on olefin to generate an alkyl carbon radical intermediate (I); then the intramolecular 1, n-hydrogen migration occurs to generate more stable benzyl radical (II); the benzyl radical (II) is further reduced to generate a benzyl carbanion intermediate; finally, the target dicarboxylic acid derivative is obtained after carbon dioxide attack and acidification.
In summary, the invention has the following advantages:
1. The invention provides a method for synthesizing dicarboxylic acid compounds based on remote carboxyl of non-activated olefin, which comprises the steps of preparing dicarboxylic acid compounds by taking non-activated olefin compounds as reaction substrates and carbon dioxide as a carboxylic acid source under the catalysis of visible light, and simultaneously adding a photocatalyst, a reducing agent and alkali; the method has the characteristics of convenient operation and cheap and easily available raw materials;
2. The preparation method provided by the invention has excellent reactivity for non-activated olefin substrates, realizes non-activated olefin remote carboxylation reaction at room temperature, and has the characteristics of mild reaction conditions, wide substrate universality and high product yield.
Drawings
FIG. 1 is a diagram showing the reaction mechanism in the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the particular embodiments described herein are illustrative only and are not intended to limit the invention, i.e., the embodiments described are merely some, but not all, of the embodiments of the invention.
Thus, the following detailed description of the embodiments of the invention, as provided, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present invention.
Example 1
The example provides a method for synthesizing dicarboxylic acid compounds based on non-activated olefin remote carboxyl, which comprises the following specific processes:
After a 25mL Schlenk reaction tube equipped with a stirrer was dried by heating under vacuum, 0.2mmol of non-activated olefin (added at this time as a solid reaction substrate; added by a syringe in the former step of adding a solvent as a liquid reaction substrate) and photocatalyst fac-Ir (ppy) 3 (1 mol%) were added, followed by placing in a glove box, adding 4.5 equivalents of Cs 2CO3, sealing the tube, taking out the glove box, evacuating under a double-row tube of CO 2 atmosphere three times, and after the evacuation, adding 2.5 equivalents of DCyEA (dicyclohexylethylamine) and 2mL of DMSO under a CO 2 gas stream; after the addition of the solvent, the tube was capped 1cm from the 30W blue LEDs, stirred at room temperature for 48h, after the reaction was completed, 3mL of 2N HCl and 3mL of ethyl acetate were added, stirred for 5min, then 15mL of water was added, extraction was performed 6 times with ethyl acetate, the organic phases were combined and spin-dried on a rotary evaporator; the solid residue is separated by a silica gel column to obtain the target product 2 of the dicarboxylated derivative. The specific results are as follows:
Note that: the above results are all separation results, and the brackets are the raw materials for recovery; [a] representing a 4 millimole scale, the reaction time was 94 hours; [b] represented by the use of 6.5 equivalents of Cs 2CO3; [c] represented by the use of 5.5 equivalents of Cs 2CO3; [d] represented by esterification by TMSCH 2N2; [e] represented by complete conversion of the substrate.
The above experimental results show that long chain olefinic substrates modified with different substituents are compatible with both electron-rich groups, electron-poor groups and electron-neutral groups, and can yield the target dicarboxylated product in moderate upward yields. A variety of functional groups or substituents are compatible in the reaction system, including: fluorine, methyl methoxy, phenyl, carboxyl, amide. In addition, the system can also be compatible with long-chain olefins derived from dibenzopyran, mono-aryl substituted olefins and the like, and has good reaction effect.
Example 2
The example provides a method for synthesizing dicarboxylic acid compounds based on non-activated olefin remote carboxyl, which comprises the following specific processes:
After a 25mL Schlenk reaction tube equipped with a stirrer was dried by heating under vacuum, 0.2mmol of non-activated olefin (added at this time as a solid reaction substrate; added by a syringe in the former step of adding a solvent as a liquid reaction substrate) and photocatalyst fac-Ir (ppy) 3 (0.5 mol%) were added, followed by placing in a glove box, adding 5 equivalents of Cs 2CO3, sealing the tube, taking out the glove box, evacuating under a double-row tube of CO 2 atmosphere three times, and after the evacuation, adding 2.5 equivalents of DCyEA and 2mL of DMSO under a CO 2 gas stream; after the addition of the solvent, the reaction liquid-sealed tube was placed at a distance of 1cm from the 30W blue LEDs, stirred at room temperature for 48 hours, after the reaction was completed, 3mL of 2N HCl and 3mL of ethyl acetate were added, stirred for 5 minutes, then 15mL of water was added, extraction was performed 6 times with ethyl acetate, the organic phases were combined, and spin-dried on a rotary evaporator; the solid residue is separated by a silica gel column to obtain a carboxylic acid target product 5 or 6. The specific results are as follows:
Note that: the above results are all separation results, and the brackets are the raw materials for recovery; [a] represented by column separation after acidification; [b] represented by fac-Ir (ppy) 3 (1 mol%); [c] represented by fac-Ir (ppy) 3(1mol％),Cs2CO3 (4.5 equivalents).
The above experimental results show that the reaction of the present invention is compatible with many common functional groups, such as: carboxyl, ester, amide and cyano groups, all give the corresponding dicarboxylated products in moderate upward yields. In addition, natural product derived substrates such as pregnenolone, menthol, can also provide the desired product in moderate yields. The corresponding target products can also be obtained for flexible olefins when no bridging group is present in the substrate. Notably, when the radical after migration is in the amino group alpha position, a distal carboxyl group containing alpha-amino acid derivative can be constructed.
Example 3
The example provides a method for synthesizing dicarboxylic acid compounds based on non-activated olefin remote carboxyl, which comprises the following specific processes:
After a 25mL Schlenk reaction tube equipped with a stirrer was dried by heating under vacuum, 0.2mmol of non-activated olefin (added at this time as a solid reaction substrate; added by a syringe in the former step of adding a solvent as a liquid reaction substrate) and photocatalyst fac-Ir (ppy) 3 (1 mol%) were added, then placed in a glove box, 4.5 equivalents of Cs 2CO3 were added, the glove box was taken out after sealing, three times of air exchange were performed under a double-row tube of CO 2 atmosphere, and after the air exchange, 2.5 equivalents of DCyEA and 2mL of DMSO were added under a CO 2 air flow; after the addition of the solvent, the tube was capped 1cm from the 30W blue LEDs, stirred at room temperature for 48h, after the reaction was completed, 3mL of 2N HCl and 3mL of ethyl acetate were added, stirred for 5min, then 15mL of water was added, extraction was performed 6 times with ethyl acetate, the organic phases were combined and spin-dried on a rotary evaporator; the solid residue is separated by a silica gel column to obtain the target product 9 or 10 of the dicarboxylated derivative. The specific results are as follows:
Note that: the above results are all separation results, and the brackets are the raw materials for recovery; [a] represented by Cs 2CO3 (5.5 equivalents); [b] represented by 1 HNMR assay 9 l:9c=7.1:1, 7l:7c=1:1; [c] represented by fac-Ir (ppy) 3(1mol％)Cs2CO3 (5 equivalents).
The experimental results show that: when a benzylamine derivative containing a non-activated olefin is selected as a substrate, a series of functionalized alpha amino acid derivatives can be obtained. The reaction is compatible with electron donating groups, electrically neutral groups and electron withdrawing groups, and is compatible with common various functional groups such as halogen fluorine atoms, carboxyl groups, ester groups, amide groups, methoxy groups, phenoxy groups and the like. It is noted that the reaction is compatible with substrates containing chlorine atoms, but that small amounts of dechlorinated products may also be present, presumably due to the direct reduction of the C-Cl bond by the CO 2 - formed. In addition, the reaction is less affected by steric hindrance, and the ortho-substituent groups can all obtain the corresponding target product in a medium and upper yield. The reaction is also compatible with disubstituted substrates and can construct all-carbon alpha amino acids. For disubstituted olefins, although the conversion is not high, the desired product can be obtained in moderate yields with good selectivity. It is desirable that the biscarboxylated product be obtained in good yields also for substrates that do not contain amine substitutions.
Example 4
In this example, diethyl 2-allyl-2- (3, 3-diphenylpropyl) malonate was used as a reaction substrate, and the effect on the reaction yield was examined by changing the reaction conditions. The specific process is as follows:
Note that: the above intermediate yields and conversions are the nuclear magnetic yields with DMAP as internal standard and the isolated yields in brackets. PC1 = Ir (ppy) 2(dtbbpy)PF6, PC2 = 3DPAFIPN.
The experimental results show that the nuclear magnetic yield of the corresponding carboxylic acid is up to 82% under the reaction condition of the invention, and a series of control experiments show that the iridium photocatalyst, alkali, reducing agent, light and carbon dioxide are all necessary, and the target product cannot be obtained due to the lack of any item. DMSO, cs 2CO3 and DCyEA are obviously used for promoting the reaction. When other photocatalysts, solvents, bases or reducing agents are used, the yield is significantly reduced.
And carrying out nuclear magnetic resonance and mass spectrum characterization analysis on the product prepared by the method, wherein the nuclear magnetic resonance and mass spectrum characterization data result is consistent with the obtained product. The specific characterization data are as follows:
5, 5-bis (ethoxycarbonyl) -2, 2-diphenylazelaic acid
13C NMR(101MHz,CD3OD)δ175.68,175.31,171.35,142.97,128.66,127.46,126.43,60.90,59.53,56.97,33.30,32.12,30.72,26.93,18.84,12.95;HRMS(ESI-):calculated for C27H31O8 -[M-H]-483.2024,found 483.2126.
5, 5-Bis (methoxycarbonyl) -2, 2-diphenylazelaic acid
MHz,CD3OD)δ175.64,175.30,171.77,142.91,128.63,127.47,126.45,59.51,57.09,51.44,33.19,32.13,30.80,27.08,18.86;HRMS(ESI-):calculated for C24H27O6 -[M-H-CO2]-411.1813,found 411.1810.
5, 5-Bis (t-Butoxycarbonyl) -2, 2-diphenylazelaic acid
CD3OD)δ175.61,175.32,170.70,143.13,128.71,127.44,126.42,80.91,59.48,57.75,33.45,32.12,30.39,26.62,26.41,18.73;HRMS(ESI-):calculated for C30H39O6 -[M-H-CO2]-492.2752,found 492.2752.
5, 5-Bis (acetoxymethyl) -2, 2-diphenylazelaic acid
1.18–1.05(m,2H);13C NMR(101MHz,CD3OD)δ175.84,175.66,171.21,143.31,128.81,127.49,126.44,65.17,59.77,39.25,33.77,30.98,29.95,25.70,19.38,17.65;HRMS(ESI-):calculated for C26H31O6 -[M-H-CO2]-439.2126,found 439.2129.
5, 5-Bis (hydroxymethyl) -2, 2-diphenylazelaic acid
13C NMR(101MHz,CD3OD)δ176.65,176.18,143.34,128.86,127.38,126.29,64.72,60.03,41.39,34.11,30.99,29.44,25.58,17.75;HRMS(ESI-):calculated for C22H27O4 -[M-H-CO2]-355.1915,found 355.1914.
5- (Ethoxycarbonyl) -2, 5-triphenylazelaic acid
CD3OD)δ176.07,175.81,175.67,143.10,143.01,142.20,128.76,128.75,127.95,127.45,126.42,126.39,126.12,60.52,59.72,53.30,33.71,33.57,32.27,29.29,19.17,12.93;HRMS(ESI-):calculated for C29H31O4 -[M-H-CO2]-443.2228,found 443.2225.
2- ([ 1,1' -Biphenyl ] -4-yl) -5, 5-bis (ethoxycarbonyl) -2-phenyl azelaic acid
0.9Hz,6H);13C NMR(101MHz,CDCl3)δ180.76,180.29,171.20,171.19,141.95,141.04,140.50,139.85,129.44,128.98,128.76,128.07,127.35,127.19,127.05,126.64,61.22,59.73,56.99,34.30,31.89,30.54,26.53,18.91,14.00;HRMS(ESI-):calculated for C32H35O6 -[M-H-CO2]-515.2439,found 515.2444.
2- (4-Carboxyphenyl) -5, 5-bis (ethoxycarbonyl) -2-phenyl azelaic acid
CD3OD)δ175.37,175.01,171.37,168.20,148.47,142.48,128.97,128.92,128.87,128.56,127.75,126.79,61.03,59.77,57.04,33.27,32.10,30.83,27.07,18.91,12.99;HRMS(ESI-):calculated for C27H31O8 -[M-H-CO2]-483.2024,found 483.2021.
2- (4- (Diethylcarbamoyl) phenyl) -5, 5-bis (ethoxycarbonyl) -2-phenylazelaic acid
135.11,129.07,128.56,127.71,126.73,125.50,61.00,59.58,57.04,43.63,39.51,33.31,32.14,30.89,27.20,18.94,13.05,13.03,11.71;HRMS(ESI-):calculated for C31H40NO7 -[M-H-CO2]-538.2810,found 538.2804.
5, 5-Bis (ethoxycarbonyl) -2- (4-fluorophenyl) -2-phenylazelaic acid
175.44,175.32,171.38,161.59(d,J＝245.0Hz),142.90,139.06(d,J＝3.3Hz),130.63(d,J＝8.0Hz),128.53,127.64,126.62,114.07(d,J＝21.4Hz),60.99,59.07,57.04,33.31,32.31,30.85,27.10,18.92,13.00;19F NMR(376MHz,CD3OD)δ-118.02;HRMS(ESI-):calculated for C26H30FO6 -[M-H-CO2]-457.2032,found 457.2031.
5, 5-Bis (ethoxycarbonyl) -2- (2-fluorophenyl) -2-phenylazelaic acid
4.4Hz,1H),1.35–1.27(m,2H),1.22(dt,J＝8.9,7.1Hz,6H);13C NMR(101MHz,CD3OD)δ175.36,175.29,171.32,160.99(d,J＝246.9Hz),140.06,130.57(d,J＝11.9Hz),130.36(d,J＝3.9Hz),128.81(d,J＝8.9Hz),128.38,127.72,126.96,123.22(d,J＝3.2Hz),115.53(d,J＝23.4Hz),61.03(d,J＝1.8Hz),57.09,56.64,33.41,31.21,29.34,27.29,19.13,13.02,12.98;19F NMR(376MHz,CD3OD)δ-109.59;HRMS(ESI-):calculated for C26H30FO6 -[M-H-CO2]-457.2032,found 457.2028.
4, 4-Diethyl-1, 7-dimethyl-1-phenyl-1- (o-tolyl) heptane-1,4,4,7-tetracarboxylic acid ester
2.18(m,3H),1.94–1.81(m,5H),1.74–1.66(m,2H),1.35–1.24(m,2H),1.21(t,J＝7.1Hz,3H),1.17(t,J＝7.1Hz,3H);13C NMR(101MHz,CDCl3)δ174.48,173.26,171.28,171.24,141.92,140.67,137.19,132.29,128.78,128.68,127.90,127.13,126.72,125.46,61.20,58.85,57.07,52.32,51.51,34.04,31.98,31.62,27.52,20.95,19.29,14.05,14.00;HRMS(ESI+):calculated for C30H38NaO8 +[M+Na]+549.2459,found 549.2455.
1, 4-Diethyl-1, 7-dimethyl-1, 1-di-p-tolylheptane-1,4,4,7-tetracarboxylic acid ester
MHz,CDCl3)δ174.52,173.31,171.34,139.65,136.42,128.67,128.63,61.15,59.24,57.09,52.31,51.50,34.04,32.43,31.33,27.20,20.96,19.25,14.02;HRMS(ESI+):calculated for C31H40NaO8 +[M+Na]+563.2615,found 563.2612.
5, 5-Bis (ethoxycarbonyl) -2- (2-fluorophenyl) -2- (4-fluorophenyl) azelaic acid
＝13.8,3.8Hz,1H),1.49(dtd,J＝26.3,13.0,12.1,5.7Hz,2H),1.14(t,J＝7.1Hz,3H),1.11(t,J＝7.1Hz,3H);13C NMR(101MHz,CDCl3)δ180.13,180.09,171.13,171.08,162.12(d,J＝247.3Hz),160.71(d,J＝248.4Hz),135.03(d,J＝3.3Hz),130.64(d,J＝3.3Hz),130.54(d,J＝8.0Hz),129.48(d,J＝11.7Hz),129.30(d,J＝8.8Hz),123.65(d,J＝3.4Hz),116.10(d,J＝22.9Hz),115.16(d,J＝21.5Hz),61.30,56.98,56.52,33.96,30.57,29.10,26.35,18.86,13.97,13.91;19FNMR(376MHz,CDCl3)δ-107.62,-114.81;HRMS(ESI-):calculated for C27H29F2O8 -[M-H]-519.1836,found 519.1828.
5, 5-Bis (ethoxycarbonyl) -2, 2-bis (4-fluorophenyl) azelaic acid
1.18(t,J＝7.1Hz,6H);13C NMR(101MHz,CD3OD)δ1175.32,175.20,171.34,161.64(d,J＝245.2Hz),138.98(d,J＝3.3Hz),130.48(d,J＝8.0Hz),114.20(d,J＝21.6Hz),61.02,58.56,57.01,33.27,32.42,30.83,27.12,18.91,12.98;19F NMR(376MHz,CD3OD)δ-117.84;HRMS(ESI-):calculated for C26H29F2O6 -[M-H-CO2]-475.1938,found 475.1935.
5, 5-Bis (ethoxycarbonyl) -2- (4-fluorophenyl) -2- (4-methoxyphenyl) azelaic acid
175.30,171.34,161.49(d,J＝244.9Hz),158.51,139.31(d,J＝3.4Hz),134.63,130.53(d,J＝8.0Hz),129.58,113.98(d,J＝21.4Hz),112.87,60.95,58.33,56.96,54.25,33.26,32.34,30.73,26.98,18.86,12.96;19F NMR(376MHz,CD3OD)δ-118.18;HRMS(ESI-):calculated for C27H32FO7 -[M-H-CO2]-487.2138,found 487.2134.
9- (6-Carboxy-3, 3-bis (ethoxycarbonyl) hexyl) -9H-ton-9-carboxylic acid
175.59,175.24,171.14,150.73,128.63,126.80,123.13,121.10,116.30,60.96,56.70,49.27,34.35,33.26,30.74,26.16,18.81,12.95;HRMS(ESI-):calculated for C27H29O9 -[M-H]-497.1817,found497.1814.
3, 3-Diethyl-1, 7-dimethyl-1- ([ [1,1' -biphenyl ] -4-yl) heptane-1,3,3,7-tetracarboxylic acid ester
4.12–4.05(m,1H),3.96(dq,J＝10.8,7.1Hz,1H),3.74(dd,J＝7.6,5.0Hz,1H),3.67(s,3H),3.66(s,3H),2.84(dd,J＝14.7,7.6Hz,1H),2.40(dd,J＝14.7,5.1Hz,1H),2.29(t,J＝7.5Hz,2H),1.92(tt,J＝14.3,7.2Hz,2H),1.71–1.54(m,2H),1.32–1.10(m,8H);13C NMR(101MHz,CDCl3)δ173.93,173.78,171.19,170.95,140.67,140.40,138.41,128.78,128.42,127.40,127.34,127.05,61.38,61.25,56.83,52.23,51.49,46.99,35.91,33.68,32.78,25.04,23.59,14.02,13.90;HRMS(ESI+):calculated for C29H36NaO8 +[M+Na]+535.2302,found 535.2273.
3, 3-Diethyl-1, 6-dimethyl-1- ([ [1,1' -biphenyl ] -4-yl) hexane-1,3,3,6-tetracarboxylic acid ester
J＝10.8,7.1Hz,1H),3.95(dq,J＝10.8,7.1Hz,1H),3.80(dd,J＝7.7,5.1Hz,1H),3.69(s,3H),3.67(s,3H),2.86(dd,J＝14.8,7.7Hz,1H),2.44(dd,J＝14.8,5.1Hz,1H),2.38–2.23(m,2H),2.04–1.86(m,2H),1.61–1.43(m,2H),1.27(t,J＝7.1Hz,3H),1.21(t,J＝7.2Hz,3H);13C NMR(101MHz,CDCl3)δ173.88,173.31,171.03,170.76,140.62,140.34,138.24,128.74,128.39,127.35,127.30,127.01,61.46,61.29,56.59,52.23,51.59,46.78,35.72,33.86,32.47,19.50,13.99,13.85;HRMS(ESI+):calculated for C28H34NaO8 +[M+Na]+521.2146,found 521.2131.
1- ([ 1,1' -Biphenyl ] -4-yl) tetramethyl-1,3,3,6-tetracarboxylic acid ester
Hz,1H),3.71(s,3H),3.69(s,3H),3.67(s,3H),3.58(s,3H),2.86(dd,J＝14.8,7.9Hz,1H),2.44(dd,J＝14.8,5.1Hz,1H),2.31(td,J＝7.3,3.0Hz,2H),2.07–1.88(m,2H),1.59–1.43(m,2H);13C NMR(101MHz,CDCl3)δ173.82,173.30,171.46,171.18,140.56,140.36,138.07,128.76,128.37,127.40,127.33,127.01,56.57,52.62,52.38,52.27,51.64,46.75,35.93,33.75,32.71,19.52;HRMS(ESI+):calculated for C26H31O8 +[M+H]+470.2013,found 470.2015.
1, 3-Di-tert-butyl 1, 6-dimethyl-1- ([ [1,1' -biphenyl ] -4-yl) hexane-1,3,3,6-tetracarboxylic acid ester
14.9,7.7Hz,1H),2.30(dd,J＝14.9,4.7Hz,1H),2.24–2.06(m,2H),1.83–1.66(m,2H),1.54–1.43(m,10H),1.40–1.26(m,10H);13C NMR(101MHz,CDCl3)δ174.07,173.34,170.33,170.21,140.75,140.35,138.92,128.75,128.40,127.45,127.29,127.06,81.72,81.61,58.08,52.21,51.46,46.90,35.24,34.07,31.92,27.87,27.81,26.92,19.48;HRMS(ESI+):calculated for C32H42NaO8 +[M+Na]+577.2772,found 577.2771.
3, 3-Diethyl-1, 6-dimethyl-1- (4- (methoxycarbonyl) phenyl) hexane-1,3,3,6-tetracarboxylic acid ester
7.39(d,J＝7.9Hz,2H),4.22–4.02(m,3H),3.97–3.87(m,4H),3.83(dd,J＝7.6,5.1Hz,1H),3.68(s,3H),3.63(s,3H),2.83(dd,J＝14.8,7.9Hz,1H),2.42–2.24(m,3H),2.01–1.84(m,2H),1.58–1.39(m,2H),1.24(t,J＝7.3Hz,3H),1.19(t,J＝7.3Hz,3H);13C NMR(101MHz,CDCl3)δ173.32,173.27,170.92,170.65,166.72,144.42,129.96,129.31,128.07,61.51,61.34,56.58,52.31,52.10,51.58,47.20,35.66,33.80,32.59,19.48,13.97,13.84;HRMS(ESI+):calculated for C24H32NaO10 +[M+Na]+503.1388,found 503.1377.
4, 4-Bis (ethoxycarbonyl) -2- (4- (ethoxycarbonyl) phenyl) suberic acid
Hz,2H),4.06(dq,J＝10.8,7.2Hz,1H),3.91(dq,J＝10.8,7.1Hz,1H),3.82(dd,J＝7.7,5.0Hz,1H),2.80(dd,J＝14.8,7.7Hz,1H),2.38–2.21(m,3H),1.95(qdd,J＝14.1,11.5,5.1Hz,2H),1.59–1.46(m,1H),1.40(t,J＝7.1Hz,3H),1.25(t,J＝7.1Hz,3H),1.19(t,J＝7.1Hz,3H);13CNMR(101MHz,CD3OD)δ175.27,174.57,170.95,170.74,166.26,145.26,129.35,129.23,127.94,61.18,61.00,60.75,56.44,47.13,35.34,33.14,32.17,19.16,13.18,12.91,12.75;HRMS(ESI-):calculated for C22H29O8 -[M-H-CO2]-421.1868,found 421.1870.
3, 3-Diethyl-1, 6-dimethyl-1- (4- (diethylcarbamoyl) phenyl) hexane-1,3,3,6-tetracarboxylic acid ester
Hz,1H),3.78(dd,J＝8.5,4.3Hz,1H),3.68(s,3H),3.62(s,3H),3.58–3.46(m,2H),3.33–3.20(m,2H),2.80(dd,J＝14.7,8.5Hz,1H),2.39–2.26(m,3H),2.02–1.83(m,2H),1.58–1.38(m,2H),1.29–1.18(m,9H),1.18–1.07(m,3H);13C NMR(101MHz,CDCl3)δ173.53,173.29,170.94,170.82,170.70,140.38,136.33,127.96,126.66,61.47,61.30,56.52,52.20,51.59,46.92,43.19,39.14,35.70,33.78,32.53,19.42,14.22,13.96,13.85,12.84;HRMS(ESI+)：calculated for C27H39NO9 +[M+H]+522.2698,found 522.2697.
2- (4-Cyanophenyl) -4, 4-bis (ethoxycarbonyl) suberic acid
Hz,1H),2.80(dd,J＝14.8,7.7Hz,1H),2.36–2.23(m,3H),2.04–1.88(m,2H),1.58–1.47(m,1H),1.45–1.36(m,1H),1.25(t,J＝7.1Hz,3H),1.20(t,J＝7.1Hz,3H);13C NMR(101MHz,CD3OD)δ175.27,174.11,170.88,170.65,145.51,132.12,128.88,118.08,110.81,61.22,61.03,56.35,35.21,33.06,32.17,19.09,12.89,12.74;HRMS(ESI-):calculated for C21H24NO8 -[M-H]-418.1507,found 418.1505.
4, 4-Bis (ethoxycarbonyl) -2- (4- (((3 s,8s,9s,10r,13s,14 s) -17-acetyl-10, 13-dimethyl-2, 3,4,7,8,9, 10,11,12,13,14,15,16, 17-decatetrahydro-1H-cyclopenta [ a ] phenanthryl-3-yl) carbonyl) phenyl) suberic acid
Hz,1H),2.85(dd,J＝14.9,7.5Hz,1H),2.56(t,J＝8.9Hz,1H),2.46(d,J＝8.1Hz,2H),2.43–2.29(m,3H),2.26–1.87(m,11H),1.83–1.37(m,12H),1.31–1.18(m,7H),1.15(t,J＝7.1Hz,3H),1.11–0.94(m,5H),0.66(s,3H);13CNMR(101MHz,CDCl3)δ209.87,178.83,178.38,170.82,170.61,165.62,143.83,139.63,130.13,130.01,128.12,122.50,74.54,63.70,61.59,61.41,56.85,56.60,49.90,47.19,44.04,38.80,38.13,37.04,36.66,35.10,33.60,32.28,31.84,31.80,31.56,27.83,24.50,22.85,21.07,19.38,19.09,13.98,13.82,13.24;HRMS(ESI-):calculated for C41H55O9 -[M-H-CO2]-691.3852,found 691.3849.
4, 4-Bis (ethoxycarbonyl) -2- (4- ((((2-isopropyl-5-methylcyclohexyl) oxy) carbonyl) phenyl) suberic acid
7.37(d,J＝8.1Hz,2H),4.91(td,J＝10.8,4.4Hz,1H),4.21–4.08(m,2H),4.07–3.97(m,1H),3.88–3.79(m,1H),3.75(dt,J＝7.9,4.1Hz,1H),2.87(ddd,J＝15.0,7.5,2.0Hz,1H),2.46–2.27(m,3H),2.16–2.06(m,1H),1.95(tp,J＝21.1,6.8,6.1Hz,3H),1.72(dt,J＝12.6,3.0Hz,2H),1.65–1.50(m,3H),1.40(dq,J＝13.0,6.5,6.1Hz,1H),1.21(t,J＝7.1Hz,3H),1.17–1.03(m,5H),0.91(dd,J＝9.0,6.8Hz,7H),0.77(d,J＝6.9Hz,3H);13C NMR(101MHz,CDCl3)δ179.02,178.58,170.77,170.75,170.59,170.57,165.66,143.75,143.68,130.14,129.98,128.11,128.07,74.90,61.55,61.38,61.37,56.59,56.57,47.20,47.10,40.87,34.93,34.79,34.26,33.55,32.00,31.94,31.40,26.50,26.46,23.61,22.01,20.72,20.70,18.97,16.51,16.47,13.95,13.76;HRMS(ESI-):calculated for C30H43O8 -[M-H-CO2]-531.2963,found 531.2957.
2, 2-Diphenyl suberic acid
2H),1.39–1.27(m,2H),1.18–1.08(m,2H);13C NMR(101MHz,CD3OD)δ176.33,176.16,143.42,128.66,127.32,126.21,59.98,37.75,33.33,29.15,24.84,24.40;HRMS(ESI-):calculated for C20H21O4 -[M-H]-325.1445,found 325.1442.
2- ([ [1,1' -Biphenyl ] -4-yl) -2-phenylsuberic acid
1H),2.44–2.31(m,2H),2.18(t,J＝7.4Hz,2H),1.50(p,J＝7.4Hz,2H),1.37–1.25(m,2H),1.12(tq,J＝12.4,7.8,6.2Hz,2H);13C NMR(101MHz,CD3OD)δ176.27,176.20,143.40,142.54,140.50,139.26,129.21,128.66,128.41,127.40,126.88,126.49,126.48,126.27,125.83,59.78,37.75,33.36,29.19,24.90,24.42;HRMS(ESI-):calculated for C25H25O2 -[M-H-CO2]-357.1860,found 357.1861.
2- ([ [1,1' -Biphenyl ] -4-yl) -2-methyl suberic acid
J＝13.3,9.3,6.6Hz,1H),1.98–1.89(m,1H),1.66–1.50(m,5H),1.42–1.32(m,2H),1.30–1.20(m,2H);13C NMR(101MHz,CD3OD)δ178.53,176.23,143.34,140.62,139.31,128.43,126.87,126.50,126.42,126.31,49.67,38.80,33.44,29.33,24.50,24.26,22.02;HRMS(ESI-):calculated for C21H23O4 -[M-H]-339.1602,found 339.1600.
2-Benzoylamino-2-phenylsuberic acid
2.92–2.82(m,1H),2.69–2.59(m,1H),2.28(t,J＝7.3Hz,2H),1.63(p,J＝7.2Hz,2H),1.51–1.38(m,3H),1.33–1.25(m,1H);13C NMR(101MHz,CD3OD)δ176.11,174.16,167.09,140.03,134.39,131.54,128.39,127.95,127.18,126.70,125.85,65.54,33.29,32.51,28.68,24.44,23.77;HRMS(ESI-):calculated for C21H22NO5 -[M-H]-368.1503,found 368.1506.
4- (2- (Benzoylamino (carboxy) methyl) phenyl) butanoic acid
Hz,2H),2.36(t,J＝7.4Hz,2H),2.02–1.91(m,2H);13C NMR(101MHz,CD3OD)δ175.82,172.93,168.64,140.63,134.73,133.80,131.44,129.79,128.19,128.10,127.43,127.26,126.36,53.40,33.14,31.80,26.27;HRMS(ESI-):calculated for C18H18NO3 -[M-H,-CO2]-296.1292,found 296.1287.
4- (4- (Benzoylamino (carboxy) methyl) - [1,1' -biphenyl ] -3-yl) butanoic acid
6.04(s,1H),2.97(t,J＝8.0Hz,2H),2.44(t,J＝7.2Hz,2H),2.06(tt,J＝15.5,7.5Hz,2H);13CNMR(101MHz,CD3OD)δ175.87,172.89,168.65,141.27,141.09,140.48,133.83,133.80,131.47,128.47,128.38,128.12,127.99,127.27,127.13,126.62,124.94,53.25,33.10,31.96,26.25;HRMS(ESI-):calculated for C25H22NO5 -[M-H]-416.1503,found 416.1501.
4- (2- (Benzoylamino (carboxy) methyl) -5-fluorophenyl) butanoic acid
Hz,1H),5.97(s,1H),2.90(td,J＝7.5,3.1Hz,2H),2.42(t,J＝7.3Hz,2H),2.10–1.89(m,2H);13C NMR(101MHz,CD3OD)δ175.67,172.69,168.55,162.48(d,J＝245.7Hz),143.52(d,J＝7.4Hz),133.63,131.46,130.92(d,J＝3.2Hz),129.44(d,J＝8.8Hz),128.08,127.21,115.95(d,J＝21.5Hz),112.94(d,J＝21.6Hz),52.83,32.96,31.71,25.90;19F NMR(376MHz,CD3OD)δ-115.92;HRMS(ESI-):calculated for C19H17FNO5 -[M-H]-358.1096,found 358.1096.
4- (2- (Benzoylamino (carboxy) methyl) -5-methylphenyl) butanoic acid
1.8Hz,1H),7.03(dd,J＝8.0,1.8Hz,1H),5.90(s,1H),2.80(dd,J＝8.8,7.1Hz,2H),2.35(t,J＝7.4Hz,2H),2.30(s,3H),2.01–1.87(m,2H);13C NMR(101MHz,CD3OD)δ175.82,173.09,168.58,140.38,138.03,133.74,131.56,131.37,130.38,128.04,127.34,127.21,126.97,53.15,33.10,31.75,26.29,19.74;HRMS(ESI-):calculated for C20H20NO5 -[M-H]-354.1347,found 354.1347.
4- (Benzoylamino (carboxymethyl) -3- (3-carboxypropyl) benzoic acid
(td,J＝7.2,2.0Hz,2H),2.44(t,J＝7.3Hz,2H),2.17–1.95(m,2H);13C NMR(101MHz,CD3OD)δ175.65,172.17,168.54,168.02,141.01,140.02,133.59,131.49,130.85,130.40,128.09,127.57,127.47,127.22,53.20,33.03,31.72,26.01;HRMS(ESI-):calculated for C19H18NO5 -[M-H-CO2]-340.1190,found 340.1188.
4- (2- (Benzoylamino (carboxy) methyl) -5- (ethoxycarbonyl) phenyl) butanoic acid
1H),7.47–7.40(m,2H),6.05(s,1H),4.35(q,J＝7.1Hz,2H),2.96(td,J＝7.3,2.1Hz,2H),2.42(t,J＝7.3Hz,2H),2.02(dq,J＝9.0,7.3Hz,2H),1.38(t,J＝7.1Hz,3H);13C NMR(101MHz,CD3OD)δ175.69,172.25,168.51,166.38,141.17,140.39,133.67,131.54,130.59,130.13,128.15,127.67,127.25,127.22,60.85,53.34,33.09,31.76,26.04,13.21;HRMS(ESI-):calculated for C21H22NO5 -[M-H-CO2]-368.1503,found 368.1500.
4- (2- (Benzoylamino (carboxy) methyl) -5- (diethylcarbamoyl) phenyl) butanoic acid
7.12(m,2H),5.87(d,J＝7.4Hz,1H),3.41(s,2H),3.19(s,2H),2.78(t,J＝7.9Hz,2H),2.28(t,J＝7.5Hz,2H),1.98–1.73(m,2H),1.25–0.91(m,6H);13C NMR(101MHz,d6-DMSO)δ175.62,172.38,171.84,168.56,141.34,136.74,136.52,133.70,131.52,128.14,127.88,127.44,127.26,124.12,53.18,43.56,39.45,32.99,31.68,26.07,13.03,11.67;HRMS(ESI-):calculated for C23H27N2O4 -[M-H-CO2]-395.1976,found 395.1975.
4- (2- (Benzoylamino (carboxy) methyl) -5-methoxyphenyl) butanoic acid
5.86(s,1H),3.77(s,3H),2.81(t,J＝8.0Hz,2H),2.36(t,J＝7.3Hz,2H),2.09–1.80(m,2H);13CNMR(101MHz,CD3OD)δ175.82,173.24,168.64,159.75,142.18,133.84,131.40,128.74,128.09,127.25,126.66,115.02,111.77,54.29,53.02,33.08,31.99,26.17;HRMS(ESI-):calculated for C20H20NO6 -[M-H]-370.1296,found 370.1291.
4- (2- (Benzoylamino (carboxy) methyl) -4-methoxyphenyl) butanoic acid
Hz,1H),6.88(dd,J＝8.5,2.8Hz,1H),5.96(s,1H),3.79(s,3H),2.83(t,J＝7.8Hz,2H),2.38(t,J＝7.3Hz,2H),2.09–1.91(m,2H);13C NMR(101MHz,CD3OD)δ175.88,172.84,168.65,158.32,135.58,133.73,132.41,131.39,130.75,128.04,127.24,113.58,112.87,54.27,53.41,33.03,31.04,26.39;HRMS(ESI-):calculated for C20H20NO6 -[M-H]-370.1296,found 370.1292.
4- (2- (Benzoylamino (carboxy) methyl) -4-phenoxyphenyl) butanoic acid
7.05(t,J＝7.3Hz,1H),6.99–6.91(m,2H),6.88(dd,J＝8.4,2.6Hz,1H),5.95(s,1H),2.84(dd,J＝9.4,6.5Hz,2H),2.38(t,J＝7.3Hz,2H),1.97(p,J＝7.4Hz,2H);13C NMR(101MHz,CD3OD)δ175.84,172.57,168.64,157.27,155.77,136.57,135.53,133.76,131.46,131.10,129.46,128.11,127.26,122.94,118.39,118.32,117.84,53.42,33.13,31.18,26.30;HRMS(ESI-):calculated for C24H22NO4 -[M-H,-CO2]-388.1554,found 388.1554.
4- (3- (Benzoylamino (carboxy) methyl) - [1,1' -biphenyl ] -4-yl) butanoic acid
(d,J＝8.0Hz,1H),7.35–7.30(m,1H),6.07(s,1H),2.94(dd,J＝9.3,6.5Hz,2H),2.43(t,J＝7.3Hz,2H),2.11–1.98(m,2H);13C NMR(101MHz,CD3OD)δ175.80,172.99,168.71,140.39,139.61,139.44,135.21,133.73,131.40,130.29,128.42,128.05,127.27,126.93,126.57,126.42,126.08,53.44,33.10,31.49,26.22;HRMS(ESI-):calculated for C25H22NO5 -[M-H]-416.1503,found 416.1501.
4- (2- (Benzoylamino (carboxy) methyl) -4-chlorophenyl) butanoic acid
7.47–7.40(m,3H),7.29–7.21(m,2H),5.97(s,1H),2.86(td,J＝7.5,2.9Hz,2H),2.38(t,J＝7.3Hz,2H),2.08–1.87(m,2H);13C NMR(101MHz,CD3OD)δ175.71,172.28,168.57,139.37,137.15,133.63,131.85,131.53,131.28,128.13,128.06,127.43,127.28,53.14,33.04,31.27,26.05;HRMS(ESI-):calculated for C18H17ClNO3 -[M-H,-CO2]-330.0902,found 330.0904.
4- (2- (Benzoylamino (carboxy) methyl) -6-methylphenyl) butanoic acid
1.97–1.83(m,2H);13C NMR(101MHz,CD3OD)δ175.77,173.17,168.61,139.16,136.93,134.88,133.80,131.44,130.30,128.11,127.26,126.06,125.24,53.70,33.61,28.37,25.00,18.79;HRMS(ESI-):calculated for C20H20NO5 -[M-H]-354.1347,found 354.1343.
4- (2- (Benzoylamino (carboxy) methyl) -4, 5-dimethoxyphenyl) butanoic acid
(s,3H),3.80(s,3H),2.82(t,J＝7.9Hz,2H),2.37(t,J＝7.3Hz,2H),2.03–1.90(m,2H);13CNMR(101MHz,CD3OD)δ175.94,173.32,168.60,148.86,147.46,133.81,133.40,131.36,128.04,127.23,126.60,113.07,111.06,55.03,54.93,53.26,33.00,31.49,26.43;HRMS(ESI-):calculated for C21H22NO7 -[M-H]-400.1402,found 400.1399.
4- (2- (Benzoylamino (carboxy) methyl) -5-fluoro-3-methylphenyl) butanoic acid
1H NMR(400MHz,CD3OD)δ7.87–7.76(m,2H),7.54–7.47(m,1H),7.45–7.38(m,2H),7.27(dd,J＝7.5,1.7Hz,1H),7.18–7.08(m,2H),6.00(s,1H),2.86(t,J＝8.5Hz,2H),2.44(t,J＝7.3Hz,2H),2.37(s,3H),1.97–1.83(m,2H);13C NMR(101MHz,CD3OD)δ175.77,173.17,168.61,139.16,136.93,134.88,133.80,131.44,130.30,128.11,127.26,126.06,125.24,53.70,33.61,28.37,25.00,18.79;HRMS(ESI-):calculated for C20H19FNO5 -[M-H]-372.1253,found 372.1257.4-(2-( Benzamido (carboxy) (phenyl) methyl) phenyl butyric acid
(t,J＝7.2Hz,2H),1.69–1.55(m,1H),1.47–1.34(m,1H);13C NMR(101MHz,CD3OD)δ175.62,173.50,167.69,140.82,138.53,138.07,134.14,131.59,130.38,130.16,128.32,128.30,127.59,127.40,127.33,127.05,124.34,70.16,33.36,32.09,25.87;HRMS(ESI-):calculated for C24H22NO3 -[M-H,-CO2]-372.1605,found 372.1602.
4- (2- (Benzoylamino (carboxy) methyl) phenyl) -3-methylbutanoic acid
J＝12.7,6.2Hz,2H),2.68(ddd,J＝13.8,7.6,4.1Hz,2H),2.36(ddt,J＝15.0,9.5,4.2Hz,4H),2.16(ddd,J＝15.0,9.0,4.5Hz,2H),1.01(d,J＝6.4Hz,3H),0.96(d,J＝6.3Hz,3H);13C NMR(101MHz,CD3OD)δ175.36,175.32,173.00,172.97,168.69,168.66,139.45,139.39,135.02,135.00,133.76,133.75,131.37,130.65,130.59,128.04,128.03,127.90,127.51,127.34,127.25,127.23,126.48,126.42,53.39,53.33,40.63,40.59,39.42,39.19,31.75,31.67,18.59,18.54;HRMS(ESI-):calculated for C19H20NO3 -[M-H,-CO2]-310.1449,found 310.1446.
4- (4- (Carboxy (pivaloylamino) methyl) - [1,1' -biphenyl ] -3-yl) butanoic acid
2.43(t,J＝7.2Hz,2H),2.04(p,J＝7.5Hz,2H);13C NMR(101MHz,CD3OD)δ179.25,175.81,172.99,141.03,140.99,140.44,134.10,128.43,128.26,127.51,127.06,126.56,124.82,52.81,38.14,33.10,31.89,26.24,26.11;HRMS(ESI-):calculated for C23H26NO5 -[M-H]-395.1816,found 398.1811.
4- (2- (1- ([ (1, 1' -Biphenyl ] -4-yl) -1-carboxyethyl) phenyl) butanoic acid
2H);13C NMR(101MHz,CD3OD)δ177.55,175.88,143.24,142.47,140.85,140.51,139.38,130.07,128.39,128.37,127.32,126.87,126.73,126.52,126.06,125.34,55.14,33.63,32.24,26.94,25.89;HRMS(ESI-):calculated for C25H23O4 -[M-H]-387.1602,found 387.1607.
4- (4- (2-Carboxypropan-2-yl) - [1,1' -biphenyl ] -3-yl) butanoic acid
(t,J＝7.4Hz,2H),2.08–1.91(m,2H),1.61(s,6H);13C NMR(101MHz,CD3OD)δ180.85,175.94,141.63,140.62,140.39,139.34,128.37,128.29,126.78,126.42,125.51,124.05,45.61,33.69,31.44,26.73,26.37;HRMS(ESI-):calculated for C20H21O4 -[M-H]-325.1445,found 325.1442.
4- (2- (1-Carboxy-1-phenylethyl) phenyl) butanoic acid
2H),2.13(t,J＝7.5Hz,2H),1.95(s,3H),1.80–1.63(m,2H);13C NMR(101MHz,CD3OD)δ177.58,175.85,144.12,142.55,140.82,130.01,127.83,127.55,127.33,126.68,126.30,125.27,55.33,33.59,32.21,26.90,25.80;HRMS(ESI-):calculated for C19H19O4 -[M-H]-311.1289,found 311.1291.
The foregoing is merely illustrative and explanatory of the invention as it is claimed, as modifications and additions may be made to, or similar to, the particular embodiments described, without the benefit of the inventors' inventive effort, and as alternatives to those of skill in the art, which remain within the scope of this patent.
Claims (5)
1. A method for synthesizing dicarboxylic acid compounds based on non-activated olefin remote carboxyl, which is characterized by comprising the following steps: adding an olefin compound, a photocatalyst and alkali into a reaction container, then adding a reducing agent and a solvent under the atmosphere of CO 2, stirring at room temperature under the condition of visible light irradiation for reaction of 0.1-100 h, and separating and purifying a reaction product to prepare a dicarboxylic acid compound; wherein the molar ratio of the olefin compound, the photocatalyst, the alkali and the reducing agent is 1:0.001-0.5:0.1-10:1-10;
the structural formula of the olefin compound is shown as follows:
the photocatalyst is a D-A type photocatalyst or an Ir photocatalyst;
The alkali is carbonate, bicarbonate, fluoride salt, tert-butoxide, phosphate, hydrogen phosphate, carboxylate or organic alkali;
the reducing agent is an organic amine compound.
2. The method for the remote carboxylation of non activated olefins to dicarboxylic acids according to claim 1, wherein the carbonate is Cs 2CO3、K2CO3、Na2CO3 or Li 2CO3; the bicarbonate is CsHCO 3、KHCO3 or NaHCO 3; the fluoride salt is CsF or KF; the tert-butoxide is KO tBu、NaOt Bu or LiO t Bu; the phosphate is K 3PO4 or Na 3PO4; the carboxylate is CsOAc, KOAc, naOAc, csOPiv or KOPiv; the organic base is DBU, TBD, DABCO, TMG or DBN.
3. The method for synthesizing dicarboxylic acid compounds based on remote carboxylation of non-activated olefins according to claim 1, wherein the organic amine compound is Cy 2NEt、Cy2NMe、iPr2NEt、NEt3, DABCO or PMP.
4. The method for synthesizing dicarboxylic acid compounds based on remote carboxylation of non-activated olefins according to claim 1, wherein the wavelength of visible light is 400-560 nm, the power of visible light is 3-60W, and the pressure of carbon dioxide is 0.5-30 times of atmospheric pressure.
5. The method for synthesizing a dicarboxylic acid compound based on a remote carboxylic acid of an inactive olefin according to claim 1, wherein the concentration of the solvent is 0.01 to 10.0M.
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