CN110105212A - method for preparing β -hydroxycarbonyl compound - Google Patents
method for preparing β -hydroxycarbonyl compound Download PDFInfo
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- CN110105212A CN110105212A CN201910518611.8A CN201910518611A CN110105212A CN 110105212 A CN110105212 A CN 110105212A CN 201910518611 A CN201910518611 A CN 201910518611A CN 110105212 A CN110105212 A CN 110105212A
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- Prior art keywords
- alkyl
- aryl
- base
- heteroaryl
- compound
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 51
- -1 itrile group Chemical group 0.000 claims description 33
- 125000001072 heteroaryl group Chemical group 0.000 claims description 30
- 125000000623 heterocyclic group Chemical group 0.000 claims description 29
- 125000003118 aryl group Chemical group 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 26
- 229910052736 halogen Inorganic materials 0.000 claims description 24
- 150000002367 halogens Chemical class 0.000 claims description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 17
- 125000003545 alkoxy group Chemical group 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 12
- 229910052740 iodine Inorganic materials 0.000 claims description 12
- 239000011630 iodine Substances 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 11
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- 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
- 125000002837 carbocyclic group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910021579 Iron(II) iodide Inorganic materials 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000004076 pyridyl group Chemical group 0.000 claims description 5
- 125000000335 thiazolyl group Chemical group 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000003814 drug Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 125000005493 quinolyl group Chemical group 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000003205 fragrance Substances 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000005956 isoquinolyl group Chemical group 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 239000000575 pesticide Substances 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 229940079593 drug Drugs 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims 2
- 150000001350 alkyl halides Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 150000001299 aldehydes Chemical class 0.000 abstract description 2
- 150000002576 ketones Chemical class 0.000 abstract description 2
- 230000001404 mediated effect Effects 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 6
- FANCTJAFZSYTIS-IQUVVAJASA-N (1r,3s,5z)-5-[(2e)-2-[(1r,3as,7ar)-7a-methyl-1-[(2r)-4-(phenylsulfonimidoyl)butan-2-yl]-2,3,3a,5,6,7-hexahydro-1h-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol Chemical compound C([C@@H](C)[C@@H]1[C@]2(CCCC(/[C@@H]2CC1)=C\C=C\1C([C@@H](O)C[C@H](O)C/1)=C)C)CS(=N)(=O)C1=CC=CC=C1 FANCTJAFZSYTIS-IQUVVAJASA-N 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000003810 ethyl acetate extraction Methods 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 125000004414 alkyl thio group Chemical group 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 238000006680 Reformatsky reaction Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000000000 cycloalkoxy group Chemical group 0.000 description 2
- 125000005366 cycloalkylthio group Chemical group 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000004415 heterocyclylalkyl group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 125000003226 pyrazolyl group Chemical group 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 125000004823 1,2-dimethylpropylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])(C([H])([H])[H])C([H])([H])[*:2] 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- 125000006042 4-hexenyl group Chemical group 0.000 description 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 102000005915 GABA Receptors Human genes 0.000 description 1
- 108010005551 GABA Receptors Proteins 0.000 description 1
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001352 cyclobutyloxy group Chemical group C1(CCC1)O* 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000003678 cyclohexadienyl group Chemical group C1(=CC=CCC1)* 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000004852 dihydrofuranyl group Chemical group O1C(CC=C1)* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 229960003692 gamma aminobutyric acid Drugs 0.000 description 1
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N methylethylethylene Natural products CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- 125000002911 monocyclic heterocycle group Chemical group 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005958 tetrahydrothienyl group Chemical group 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000004568 thiomorpholinyl group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
the present invention relates to a process for the preparation of β -hydroxycarbonyl compounds, essentially providing a process for the preparation of the corresponding β -hydroxycarbonyl compounds by the reaction of α -halocarbonyl compounds with aldehydes/ketones mediated by inexpensive commercial iron powders.
Description
Technical field
The invention belongs to chemical and medicine industry fields, are related to a kind of method for preparing beta-hydroxy carbonyls, the process yield
Well, there is wide functional group tolerance and good compatibility.
Background technique
Important intermediate of the beta-hydroxy carbonyls as organic synthesis is knot generally existing in many natural products
Structure unit, has a wide range of applications in synthetic organic chemistry.Especially tool has been displayed in the beta-hydroxy carbonyls containing fluorine
There are many bioactivity, such as the fluoro- 3- hydroxyl propyl- of 3- (4- acetyl phenyl) -1- ((3R, 5R, 7R)-adamantane -1- base) -2,2- bis-
1- ketone, structure is as follows, after clinically relevant GABA receptor assessment, it has been determined that it is as a kind of effective GABA excitement
Agent, and preliminary intra-body data is also presented in mouse being addicted to drink, the compound tend to reduce Auditory Startle reaction, this with
Feature antianxity is consistent.
Organometallic reagent has had completely changed modern organic synthesis, has witnessed organometallic reagent in the past few decades
The fast-developing and its extensive use in organic synthesis and material science.In the known various preparations of beta-hydroxy carbonyls
In method, the Reformatsky reaction that metal mediates is a kind of effective and direct method, as metallic zinc, magnesium or suddenly mediate.
Compared to other metals, metallic iron activity is lower, is not caused in organic synthesis using ferrous metal too many
Concern, especially Reformatsky reaction in, but iron be in nature it is generally the least expensive, almost the smallest metal of toxicity.
The α-halogenatedcarbonylcompounds and aldehyde/ketone that the present invention provides a kind of to be mediated using cheap business iron powder are anti-
It answers, to provide corresponding beta-hydroxy carbonyls.This method reveals excellent functional group's compatibility, and the reaction is preparing medicine
There is extraordinary application prospect in object, fragrance or pesticide.
Summary of the invention
The present invention provides a kind of preparation method of compound shown in Formulas I, comprising: in metallic iron and iodine or FeI2Catalytic condition
Under, formula A compound reacts the step of forming compound of formula I with formula B compound,
Wherein, R1Selected from alkenyl, aryl or heteroaryl, preferably C2-4Alkenyl, C6-12Aryl or 5 yuan are to 12 unit's heteroaryls, institute
Alkenyl, aryl or heteroaryl are stated optionally by selected from halogen, hydroxyl, alkyl, alkoxy, nitro, itrile group, alkyl, naphthenic base, halogenated
Replaced one or more substituent groups in alkyl, halogenated cycloalkyl, heterocycle, aryl and heteroaryl；
R2Selected from hydrogen or alkyl, preferably hydrogen or C1-6Alkyl, the alkyl are optionally selected from halogen, hydroxyl, alkyl, alcoxyl
One or more in base, nitro, itrile group, alkyl, naphthenic base, halogenated alkyl, halogenated cycloalkyl, heterocycle, aryl and heteroaryl
Replaced a substituent group；
R3Selected from alkyl, OR' or NR'(R "), preferably C1-6Alkyl, OR' or NR'(R "), the alkyl is optionally selected from halogen
One or more substituent groups in element, hydroxyl, alkoxy, nitro, itrile group, naphthenic base, heterocycle, aryl and heteroaryl are taken
In generation, wherein R' or R " is independently selected from alkyl, aryl or heteroaryl, and the alkyl, aryl or heteroaryl are optionally by one or more
It is a to be selected from replaced halogen, alkyl, naphthenic base, hydroxyl, nitro, itrile group, aryl or heteroaryl；
RaOr RbIt is each independently selected from hydrogen, halogen, alkyl, naphthenic base, heterocycle, preferably hydrogen, halogen, C1-6Alkyl, C3-8
Naphthenic base or 3 yuan to 8 circle heterocyclic ring bases, the alkyl, naphthenic base or heterocycle are optionally selected from alkyl, cycloalkanes by one or more
Base, heterocycle, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, nitro, itrile group, hydroxyl, replaced halogen, alternatively, RaOr RbWith
Its adjacent carbon atom is formed together 3 yuan to 12 yuan carbocyclic rings, heterocycles, preferably 3 yuan to 8 yuan carbocyclic rings, heterocycles, and the carbocyclic ring or heterocycle are appointed
Choosing is by selected from alkyl, halogen, hydroxyl, amino, oxygroup, carboxyl, nitro, cyano, alkoxy, naphthenic base, heterocycle, aryl, miscellaneous
Replaced one or more substituent groups in aryl；
X is selected from chlorine, bromine, iodine.
In some embodiments, the dosage of metallic iron of the present invention and the molar ratio of formula A compound are 1:1~5:1,
Non-limiting embodiment includes arbitrary value between 1:1,1:2,1:3,1:4,1:5 or two numerical value, preferably 3:1.
In other embodiments, the present invention reacts solvent for use selected from non-protonic solvent, including but not limited to second
At least one of nitrile, tetrahydrofuran, toluene, isopropyl ether, methyltetrahydrofuran or methylene chloride, preferably acetonitrile.
Further, in preferred embodiments, reaction temperature be selected from 30~100 DEG C, can for 30 DEG C, 40 DEG C, 45 DEG C,
Arbitrary value between 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C or both, preferably
40~80 DEG C.
On the other hand, iodine or FeI2Presence can effectively facilitate the process and yield of reaction.Further, in reaction iodine or
FeI2Dosage and formula A compound molar ratio be 0.1:1~1:1, non-limiting embodiment includes 0.1:1,0.2:1,0.3:
1, arbitrary value, preferably 0.2:1~0.5:1 between 0.4:1,0.5:1,0.6:1,0.7:1,0.8:1,0.9:1,1:1 or two numerical value.
In some embodiments, heretofore described R1Selected from vinyl, phenyl, naphthalene, thiazolyl, ferrocenyl,
Quinolyl, isoquinolyl, pyridyl group or pyrrole radicals, it is the vinyl, phenyl, naphthalene, thiazolyl, ferrocenyl, quinolyl, different
Quinolyl, pyridyl group or pyrrole radicals are optionally selected from halogen, hydroxyl, alkyl, alkoxy, nitro, itrile group, alkane by one or more
Replaced base, naphthenic base, halogenated alkyl, halogenated cycloalkyl, heterocycle, aryl and heteroaryl.
In some embodiments, heretofore described R2Selected from hydrogen, methyl, ethyl or isopropyl.
Further, in some embodiments, heretofore described RaOr RbBe each independently selected from hydrogen, fluorine, methyl or
Ethyl.
Typical compound shown in Formulas I, including but not limited to:
Further, in preparation method of the present invention further include any in being filtered, washed, be concentrated, dry or purifying
Step obtains the target product compound of formula I of purifying.
Another aspect of the present invention provides a kind of method for preparing drug, fragrance and pesticide, including Formulas I of the present invention
The preparation method of shown compound.
For example,
Or
On the other hand, the present invention also provides the method for preparation formula II compound,
It include: the step of Formula II-A compound is reacted with Formula II-B compound under the conditions of metallic iron and catalysis of iodine,
Unless stated to the contrary, the term used in the specification and in the claims has following meanings.
" alkyl " refers to the aliphatic hydrocarbon group of saturation, straight chain and branched group including 1 to 20 carbon atom.Preferably comprise 1
To the alkyl of 12 carbon atoms, the alkyl of further preferably 1 to 6 carbon atom.Non-limiting embodiment include methyl, ethyl,
N-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, sec-butyl, n-pentyl, 1,1- dimethyl propyl, 1,2- dimethyl propylene
Base, 2,2- dimethyl propyl, 1- ethyl propyl, 2- methyl butyl, 3- methyl butyl and its various branched isomers etc..Alkyl
It can be substituted or unsubstituted, when substituted, substituent group can be substituted on any workable tie point, preferably
For one or more following groups, independently selected from replaced aryl, heteroaryl, halogen." alkenyl " includes having 2 to 12 carbon
The branch and linear alkene of atom or alkene containing aliphatic hydrocarbon group.Such as " C2-6Alkenyl " indicates there is 2,3,4,5 or 6
The alkenyl of carbon atom.The example of alkenyl includes but is not limited to, vinyl, allyl, 1- acrylic, 1- cyclobutenyl, 2- cyclobutenyl,
3- cyclobutenyl, 2- methyl but-2-ene base, 3- methyl but-1-ene base, 1- pentenyl, 3- pentenyl and 4- hexenyl.
Term " naphthenic base " refers to the unsaturated monocycle of saturation or part or polycyclic cyclic hydrocarbon substituent, cycloalkyl ring include 3 to
20 carbon atoms, preferably comprise 3 to 12 carbon atoms, more preferably include 3 to 6 carbon atoms.Monocyclic cycloalkyl it is non-limiting
Example includes cyclopropyl, cyclobutyl, cyclopenta, cyclopentenyl, cyclohexyl, cyclohexenyl group, cyclohexadienyl, suberyl, cycloheptyl
Trialkenyl, cyclooctyl etc.；Polycyclic naphthene base includes the naphthenic base of loop coil, condensed ring and bridged ring.
Term " heterocycle " refers to the unsaturated monocycle of saturation or part or polycyclic cyclic hydrocarbon substituent, and it includes 3 to 20 rings
Atom, wherein one or more annular atoms are the hetero atom selected from nitrogen, oxygen or S (O) m (wherein m is integer 0 to 2), but are not wrapped
The loop section of-O-O- ,-O-S- or-S-S- are included, remaining annular atom is carbon.3 to 12 annular atoms are preferably comprised, wherein 1~4
It is hetero atom；It more preferably include 3 to 6 annular atoms.The non-limiting example of monocyclic heterocycles base includes pyrrolidinyl, imidazolidine
Base, tetrahydrofuran base, tetrahydro-thienyl, glyoxalidine base, dihydrofuryl, pyrazoline base, pyrrolin base, piperidyl,
Piperazinyl, morpholinyl, thio-morpholinyl, high piperazine base etc..
Term " aryl " refers to that 6 to 14 yuan of full carbon monocycles of the pi-electron system with conjugation or fused polycycle are (namely shared
The ring of adjacent carbon atoms pair) group, preferably 6 to 10 yuan, such as phenyl and naphthalene.
Aryl can be substituted or non-substituted, and when substituted, substituent group is preferably one or more following groups,
It is independently selected from alkyl, alkenyl, alkynyl, alkoxy, alkylthio group, alkyl amino, halogen, sulfydryl, hydroxyl, nitro, cyano, ring
Alkyl, Heterocyclylalkyl, aryl, heteroaryl, cycloalkyloxy, heterocyclylalkoxy groups, cycloalkylthio, heterocycle alkylthio group, carboxyl or carboxylic acid
Ester group, preferably phenyl.
Term " heteroaryl " refers to the heteroaromatic system comprising 1 to 4 hetero atom, 5 to 14 annular atoms, and wherein hetero atom selects
From oxygen, sulphur and nitrogen.Heteroaryl is preferably 5 to 12 yuan, such as imidazole radicals, furyl, thienyl, thiazolyl, pyrazolyl, oxazole
Base, pyrrole radicals, tetrazole radical, pyridyl group, pyrimidine radicals, thiadiazoles, pyrazinyl etc., preferably imidazole radicals, pyrazolyl, pyrimidine radicals or thiophene
Oxazolyl.Heteroaryl can be optionally replacing or non-substituted.
Term " alkoxy " refers to-O- (alkyl) and-O- (non-substituted naphthenic base), and wherein alkyl is as defined above.
The non-limiting example of alkoxy includes: methoxyl group, ethyoxyl, propoxyl group, butoxy, cyclopropyl oxygroup, cyclobutoxy group, penta oxygen of ring
Base, cyclohexyloxy.Alkoxy can be optionally replacing or non-substituted, and when substituted, substituent group is preferably one or more
A following group, independently selected from alkyl, alkenyl, alkynyl, alkoxy, alkylthio group, alkyl amino, halogen, sulfydryl, hydroxyl,
Nitro, cyano, naphthenic base, Heterocyclylalkyl, aryl, heteroaryl, cycloalkyloxy, heterocyclylalkoxy groups, cycloalkylthio, heterocycle alkane sulphur
Base, carboxyl or carboxylate.
Term " halogenated alkyl " refers to the alkyl being optionally substituted by halogen, and wherein alkyl is as defined above.
Term " halogenated cycloalkyl " refers to the ring group being optionally substituted by halogen, and wherein naphthenic base is as defined above.
Term " hydroxyl " refers to-OH group.
Term " halogen " refers to fluorine, chlorine, bromine or iodine.
Term " cyano " refers to-CN.
Term " nitro " refers to-NO2。
" optional " or " optionally " mean event or environment described later can with but need not occur, which includes
The occasion that the event or environment occur or do not occur.For example, meaning that alkyl can be with " optionally by alkyl-substituted heterocyclic group "
But necessarily exist, the explanation include heterocyclic group by alkyl-substituted situation and heterocyclic group not by alkyl-substituted situation.
" substituted " refers to one or more hydrogen atoms in group, preferably at most 5, more preferably 1~3 hydrogen atom
Replaced independently of one another by the substituent group of respective number.Self-evident, substituent group is only in their possible chemical position, this
Field technical staff, which can determine in the case where not paying excessive make great efforts and (pass through experiment or theoretical), may or impossible take
Generation.It may be unstable when for example, amino or hydroxyl with free hydrogen are in conjunction with the carbon atom with unsaturated (such as olefinic) key
Fixed.
Specific embodiment
The present invention is explained in detail below with reference to specific example, so that this hair is more fully understood in those skilled in the art
Bright specific example is only used to illustrate the technical scheme of the present invention, and does not limit the present invention in any way.
Embodiment 1:
By 4- chlorobenzaldehyde (1mmol), alpha-bromo ethyl acetate (3mmol), iron powder (168mg, 3mmol), acetonitrile (2ml)
And catalyst 2 is added in 10ml reaction flask, 60 DEG C of heating is stirred to react 24 hours, and 20ml ammonium chloride solution, acetic acid second is added
Ester extraction, salt water washing dries, filters, and is concentrated to give compound 3a, by Isosorbide-5-Nitrae-dimethoxy benzene as internal standard compound,1HNMR inspection
Survey compound 3a must be measured and calculated yield, data are as follows:
Note: silica gel column chromatography yield
Compound 3a: colorless oil；
1HNMR(400MHz,CDCl3): δ 7.63 (d, J=8.3Hz, 2H), 7.48 (d, J=8.2Hz, 2H), 5.16 (t, J
=6.0Hz, 1H), 4.16 (q, J=7.1Hz, 2H), 3.72 (s, 1H), 2.69-2.67 (m, 2H), 1.24 (t, J=7.1Hz,
3H)ppm.
13C NMR(100MHz,CDCl3):δ172.2,141.5,131.5,127.4,121.5,69.6,61.0,43.1,
14.1ppm.
Embodiment 2
By 4- chlorobenzaldehyde (1mmol), alpha-bromo ethyl acetate (3mmol), iron powder (168mg, 3mmol), iodine
(0.2mmol) and solvent are added in 10ml reaction flask, and 60 DEG C of heating is stirred to react 24 hours, and 20ml ammonium chloride solution is added,
Ethyl acetate extraction, salt water washing dries, filters, and is concentrated to give compound 3a, by Isosorbide-5-Nitrae-dimethoxy benzene as internal standard compound,1HNMR detection compound 3a must be measured and calculated yield, and data are as follows:
Note: silica gel column chromatography yield
Embodiment 3
Respectively by aldehyde compound 1b-n (1mmol) and alpha-bromo ethyl acetate (3mmol), iron powder (168mg, 3mmol),
Iodine (0.2mmol) and solvent (2ml) are added in 10ml reaction flask, and 60 DEG C of heating is stirred to react to fully reacting, and 20ml is added
Ammonium chloride solution, ethyl acetate extraction, salt water washing dry, filter, are concentrated, obtain target product 3b- through silica gel chromatograph column purification
N, calculates separately yield, and specific data are as follows:
Note: solvent is tetrahydrofuran
Embodiment 4
Respectively by compound 2b-g (3mmol) and 4- chlorobenzaldehyde (1mmol), iron powder (168mg, 3mmol), iodine
(0.2mmol) and acetonitrile (2ml) are added in 10ml reaction flask, and 60 DEG C of heating is stirred to react to fully reacting, and 20ml chlorine is added
Change ammonium salt solution, ethyl acetate extraction, salt water washing dries, filters, is concentrated, obtains target product 4b-g through silica gel chromatograph column purification,
Yield is calculated separately, specific data are as follows:
Embodiment 5
Respectively by compound 5b-h (1mmol) and alpha-bromo ethyl acetate (3mmol), iron powder (168mg, 3mmol), iodine
(0.2mmol) and acetonitrile (2ml) are added in 10ml reaction flask, and 60 DEG C of heating is stirred to react to fully reacting, and 20ml chlorine is added
Change ammonium salt solution, ethyl acetate extraction, salt water washing dries, filters, is concentrated, obtains target product 5b-h through silica gel chromatograph column purification,
Yield is calculated separately, specific data are as follows:
Claims (10)
1. a kind of preparation method of compound shown in Formulas I,
It include: in metallic iron and iodine or FeI2Under catalytic condition, formula A compound reacts to form compound of formula I with formula B compound
Step,
Wherein, R1Selected from alkenyl, aryl or heteroaryl, preferably C2-4Alkenyl, C6-12Aryl or 5 yuan are to 12 unit's heteroaryls, the alkene
Base, aryl or heteroaryl are optionally selected from halogen, hydroxyl, alkyl, alkoxy, nitro, itrile group, alkyl, naphthenic base, alkyl halide
Replaced one or more substituent groups in base, halogenated cycloalkyl, heterocycle, aryl and heteroaryl；
R2Selected from hydrogen or alkyl, preferably hydrogen or C1-6Alkyl, the alkyl are optionally selected from halogen, hydroxyl, alkyl, alkoxy, nitre
One or more substitutions in base, itrile group, alkyl, naphthenic base, halogenated alkyl, halogenated cycloalkyl, heterocycle, aryl and heteroaryl
Replaced base；
R3Selected from alkyl, OR' or NR'(R "), preferably C1-6Alkyl, OR' or NR'(R "), the alkyl is optionally selected from halogen, hydroxyl
Replaced one or more substituent groups in base, alkoxy, nitro, itrile group, naphthenic base, heterocycle, aryl and heteroaryl, wherein
R' or R " is optionally selected from halogen by one or more independently selected from alkyl, aryl or heteroaryl, the alkyl, aryl or heteroaryl
Replaced element, alkyl, naphthenic base, hydroxyl, nitro, itrile group, aryl or heteroaryl；
RaOr RbIt is each independently selected from hydrogen, halogen, alkyl, naphthenic base, heterocycle, preferably hydrogen, halogen, C1-6Alkyl, C3-8Cycloalkanes
Base or 3 yuan are to 8 circle heterocyclic ring bases, and the alkyl, naphthenic base or heterocycle are optionally by one or more selected from alkyl, naphthenic base, miscellaneous
Ring group, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, nitro, itrile group, hydroxyl, replaced halogen, alternatively, RaOr RbWith its phase
Adjacent carbon atom is formed together 3 yuan to 12 yuan carbocyclic rings, heterocycles, preferably 3 yuan to 8 yuan carbocyclic rings, heterocycles, the carbocyclic ring or heterocycle optionally quilt
Selected from alkyl, halogen, hydroxyl, amino, oxygroup, carboxyl, nitro, cyano, alkoxy, naphthenic base, heterocycle, aryl, heteroaryl
In one or more substituent groups replaced；
X is selected from chlorine, bromine, iodine.
2. the method as described in claim 1, wherein the dosage of the metallic iron and the molar ratio of formula A compound are 1:1~5:
1。
3. it is method according to claim 1 or 2, wherein the iodine or FeI2Dosage and formula A compound molar ratio be 0.1:
1~1:1, preferably 0.2:1~0.5:1.
4. the method according to claim 1, wherein reaction solvent for use is selected from non-protonic solvent, preferably second
At least one of nitrile, tetrahydrofuran, toluene, isopropyl ether, methyltetrahydrofuran or methylene chloride.
5. method according to any of claims 1-4, wherein R1Selected from vinyl, phenyl, naphthalene, thiazolyl, ferrocene
Base, quinolyl, isoquinolyl, pyridyl group or pyrrole radicals, the vinyl, phenyl, naphthalene, thiazolyl, ferrocenyl, quinoline
Base, isoquinolyl, pyridyl group or pyrrole radicals are optionally selected from halogen, hydroxyl, alkyl, alkoxy, nitro, nitrile by one or more
Replaced base, alkyl, naphthenic base, halogenated alkyl, halogenated cycloalkyl, heterocycle, aryl and heteroaryl.
6. the method according to claim 1 to 5, wherein R2Selected from hydrogen, methyl, ethyl or isopropyl.
7. as the method according to claim 1 to 6, wherein R3Selected from OCH3、OC2H5、NMe2Or OBn.
8. the method according to claim 1 to 7, wherein RaOr RbIt is each independently selected from hydrogen, fluorine, methyl or ethyl.
9. a kind of method for preparing drug, fragrance or pesticide, including chemical combination shown in Formulas I described in claim 1-8 any one
The preparation method of object.
10. the method for preparation formula II compound,
It include: the step of Formula II-A compound is reacted with Formula II-B compound under the conditions of metallic iron and catalysis of iodine,
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