CN105884730A - 芳基醇和杂芳基醇的制备方法 - Google Patents
芳基醇和杂芳基醇的制备方法 Download PDFInfo
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- CN105884730A CN105884730A CN201610081488.4A CN201610081488A CN105884730A CN 105884730 A CN105884730 A CN 105884730A CN 201610081488 A CN201610081488 A CN 201610081488A CN 105884730 A CN105884730 A CN 105884730A
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- -1 Aryl alcohol Chemical compound 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims description 7
- 238000000034 method Methods 0.000 claims abstract description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims description 35
- 125000000217 alkyl group Chemical group 0.000 claims description 31
- 125000003118 aryl group Chemical group 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 19
- 229910052801 chlorine Inorganic materials 0.000 claims description 18
- 239000002585 base Substances 0.000 claims description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- 229910052731 fluorine Inorganic materials 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 125000003545 alkoxy group Chemical group 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229910052794 bromium Inorganic materials 0.000 claims description 12
- 229910052740 iodine Inorganic materials 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000006197 hydroboration reaction Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 5
- 125000000304 alkynyl group Chemical group 0.000 claims description 5
- 150000001639 boron compounds Chemical class 0.000 claims description 5
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 4
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 229930192474 thiophene Natural products 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- QZHPTGXQGDFGEN-UHFFFAOYSA-N chromene Chemical compound C1=CC=C2C=C[CH]OC2=C1 QZHPTGXQGDFGEN-UHFFFAOYSA-N 0.000 claims description 3
- 150000002085 enols Chemical class 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 2
- 238000003682 fluorination reaction Methods 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 9
- 125000002577 pseudohalo group Chemical group 0.000 abstract description 3
- 239000004327 boric acid Substances 0.000 abstract 1
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 description 15
- AIGRXSNSLVJMEA-FQEVSTJZSA-N ethoxy-(4-nitrophenoxy)-phenyl-sulfanylidene-$l^{5}-phosphane Chemical compound O([P@@](=S)(OCC)C=1C=CC=CC=1)C1=CC=C([N+]([O-])=O)C=C1 AIGRXSNSLVJMEA-FQEVSTJZSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 125000001072 heteroaryl group Chemical group 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 150000002367 halogens Chemical group 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 208000035126 Facies Diseases 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 125000004093 cyano group Chemical group *C#N 0.000 description 5
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 4
- 0 CCC(*)(*)CC(*)(*)**1C=CCC1 Chemical compound CCC(*)(*)CC(*)(*)**1C=CCC1 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 150000002118 epoxides Chemical class 0.000 description 4
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- 238000012805 post-processing Methods 0.000 description 4
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 3
- 241001597008 Nomeidae Species 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 125000005605 benzo group Chemical group 0.000 description 3
- XSCHRSMBECNVNS-UHFFFAOYSA-N benzopyrazine Natural products N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 3
- 229910000085 borane Inorganic materials 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 2
- DXBHBZVCASKNBY-UHFFFAOYSA-N 1,2-Benz(a)anthracene Chemical compound C1=CC=C2C3=CC4=CC=CC=C4C=C3C=CC2=C1 DXBHBZVCASKNBY-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- SCXIUXBKBXLUCZ-UHFFFAOYSA-N 3-(4-hydroxyphenyl)-6,8-bis(3-hydroxypropyl)chromen-2-one Chemical compound C=1C2=CC(CCCO)=CC(CCCO)=C2OC(=O)C=1C1=CC=C(O)C=C1 SCXIUXBKBXLUCZ-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
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical class C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000005194 alkoxycarbonyloxy group Chemical group 0.000 description 2
- 125000005278 alkyl sulfonyloxy group Chemical group 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 150000004826 dibenzofurans Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003233 pyrroles Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- SLGBZMMZGDRARJ-UHFFFAOYSA-N triphenylene Chemical compound C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- ZFXBERJDEUDDMX-UHFFFAOYSA-N 1,2,3,5-tetrazine Chemical compound C1=NC=NN=N1 ZFXBERJDEUDDMX-UHFFFAOYSA-N 0.000 description 1
- UGUHFDPGDQDVGX-UHFFFAOYSA-N 1,2,3-thiadiazole Chemical class C1=CSN=N1 UGUHFDPGDQDVGX-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- HTJMXYRLEDBSLT-UHFFFAOYSA-N 1,2,4,5-tetrazine Chemical compound C1=NN=CN=N1 HTJMXYRLEDBSLT-UHFFFAOYSA-N 0.000 description 1
- YGTAZGSLCXNBQL-UHFFFAOYSA-N 1,2,4-thiadiazole Chemical class C=1N=CSN=1 YGTAZGSLCXNBQL-UHFFFAOYSA-N 0.000 description 1
- FYADHXFMURLYQI-UHFFFAOYSA-N 1,2,4-triazine Chemical compound C1=CN=NC=N1 FYADHXFMURLYQI-UHFFFAOYSA-N 0.000 description 1
- 150000004868 1,2,5-thiadiazoles Chemical class 0.000 description 1
- UUSUFQUCLACDTA-UHFFFAOYSA-N 1,2-dihydropyrene Chemical compound C1=CC=C2C=CC3=CCCC4=CC=C1C2=C43 UUSUFQUCLACDTA-UHFFFAOYSA-N 0.000 description 1
- 150000004869 1,3,4-thiadiazoles Chemical class 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 1
- JUUZQMUWOVDZSD-UHFFFAOYSA-N 1h-imidazole;pyrazine Chemical class C1=CNC=N1.C1=CN=CC=N1 JUUZQMUWOVDZSD-UHFFFAOYSA-N 0.000 description 1
- PFRPMHBYYJIARU-UHFFFAOYSA-N 2,3-diazatetracyclo[6.6.2.04,16.011,15]hexadeca-1(14),2,4,6,8(16),9,11(15),12-octaene Chemical compound C1=CC=C2N=NC3=CC=CC4=CC=C1C2=C43 PFRPMHBYYJIARU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- UXGVMFHEKMGWMA-UHFFFAOYSA-N 2-benzofuran Chemical compound C1=CC=CC2=COC=C21 UXGVMFHEKMGWMA-UHFFFAOYSA-N 0.000 description 1
- HCCNHYWZYYIOFM-UHFFFAOYSA-N 3h-benzo[e]benzimidazole Chemical class C1=CC=C2C(N=CN3)=C3C=CC2=C1 HCCNHYWZYYIOFM-UHFFFAOYSA-N 0.000 description 1
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- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical class [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- 125000001148 pentyloxycarbonyl group Chemical group 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
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- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical compound N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
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- 235000009566 rice Nutrition 0.000 description 1
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- FMKFBRKHHLWKDB-UHFFFAOYSA-N rubicene Chemical compound C12=CC=CC=C2C2=CC=CC3=C2C1=C1C=CC=C2C4=CC=CC=C4C3=C21 FMKFBRKHHLWKDB-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical compound COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 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
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
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- YGPLLMPPZRUGTJ-UHFFFAOYSA-N truxene Chemical compound C1C2=CC=CC=C2C(C2=C3C4=CC=CC=C4C2)=C1C1=C3CC2=CC=CC=C21 YGPLLMPPZRUGTJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/14—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 6 and unsubstituted in position 7
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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Abstract
本发明涉及通过将芳族卤素或拟卤素化合物偶合至环状硼酸酯制备芳基醇和杂芳基醇的方法。
Description
技术领域
本发明涉及通过将芳族卤素或拟卤素化合物偶合至环状硼酸酯制备芳基醇和杂芳基醇的方法。
背景技术
类型1的芳基醇和杂芳基醇
是已知的,尤其是作为药物活性化合物或其前体,或还作为性能化学品,例如液晶或其前体。化合物2和3可以通过实例的方式引用。
有效和可行地获得结构类型1对于经济制备是必要的。至今,类型1衍生物的合成已经主要通过前体结构的反应进行,其通常以还原的方式进行,如在方案1中通过C3醇的实例所概述的。
方案1.Ar=芳基,HetAr=杂芳基,M=金属,PG=保护基团,R=烷基。
然而,这些合成通常是复杂的和/或在多个反应步骤中进行,这导致了收率的损失。
发明内容
因此,本发明具有以下目的:提供制备芳基醇或杂芳基醇的方法,其以高收率和高纯度得到了所需的产物,并且优选避免了已知方法的所述缺点。
令人意外地,已经发现该目的以及未明确提及但可以容易由在引言中本文所讨论的相互关系衍生或发展出的其他目的通过制备具有专利权利要求1的所有特征的芳族化合物的方法实现。根据本发明的方法的有利的修改在从属于权利要求1的权利要求中得以保护。
特别地,已经发现芳基醇和杂芳基醇可以有效地且以高收率在一步法中由芳基和杂芳基的卤化物或拟卤化物通过Suzuki偶合至环状硼酸衍生物制备。
因此,本发明涉及制备式(I)的化合物的方法,
其中Ar代表任选取代的单环或多环的芳环或杂芳环体系,
p表示1、2、3、4、5或6,和
n表示1、2、3或4,
包括在碱和过渡金属催化剂的存在下使式(II)的起始材料
Ar-[X]p (II),
其中Ar和p具有以上给出的含义和X表示卤素优选Cl、Br或I,或氟化的烷基磺酸酯(盐)或芳基磺酸酯(盐),
与式(III)的硼化合物反应,
其中n具有以上给出的含义和R表示OH、OR'或NR'R",其中R'和R"各自彼此独立地表示具有1-15个C原子的(环)烷基,具有2-15个C原子的烯基,或芳基。
所获得的芳基醇和杂芳基醇可以有利地转化成更高度精制的衍生物,例如通过官能化羟基官能为(甲基)丙烯酸酯。因此,根据本发明的其它方法包括制备式(V)的可聚合化合物,
其特征在于式(I)的化合物通过根据本发明的方法制备,并且随后转化成式(V)的(甲基)丙烯酸酯。为此,例如,式(I)的醇化合物与甲基丙烯酸或丙烯酸以及缩合剂反应。备选地,该反应可以使用(甲基)丙烯酰氯进行。
根据本发明的方法基于将式(II)的芳基-或杂芳基-X基体Suzuki偶合至式(III)的硼酸衍生物,使得能够缩短、非常有效并且通常地得到式(I)的芳基醇和杂芳基醇。因为采用的Suzuki偶合在相对温和催化条件下进行并且既不需要使用氢或贵金属催化剂的金属化或氢化条件,也不需要使用金属氢化物还原,所以一般合成方法变得可能。这种选择首次使得能够在一个步骤中将具有例如同时存在的(parallel)硝基、烯烃基、炔基和/或羰基官能的式(II)的基体转化成式(I)的相应结构。
通过根据本发明的方法可获得的羟基烷基化合物以纯产物的高纯度和高收率获得。此外,可以总体廉价并且无需危及环境地获得产物。
本发明的方法使其能够获得特别是式(I)的芳族和杂芳族化合物,其中基团Ar代表任选取代的,单环或多环的芳环或杂芳环体系。所述反应也可以在分子的两个或更多个位置处进行,使得引入两个或更多个羟基烷基官能团。在多个反应中心的反应的情况下,高选择性转化成所需的醇特别是有利的。
所述反应适用于与Suzuki反应的条件相容的所有基团Ar。
本领域技术人员已知这种类型的可聚合化合物作为有用的辅助剂。它们主要具有一个或两个可聚合基团。在引发聚合之后,它们形成聚合物,其取决于浓度和交联程度,充当成膜剂(表面涂层)、粘合剂、树脂、增稠剂、稳定剂或其它添加剂,在液晶领域中特别作为用于特定匹配和稳定配向的添加剂。具有多个可聚合基团的化合物经常充当交联剂。在基团Ar和OH或(甲基)丙烯酸酯之间的间隔基团允许在功能添加剂领域中两个基团的独立功能。
在本发明的意义中的芳环体系在环体系中包含6-60个,优选6-40个和特别优选6-20个C原子。在本发明的意义中的杂芳环体系在环体系中包含2-60个,优选2-40个和特别优选2-20个C原子和至少一个杂原子,条件是C原子和杂原子的总和为至少5。杂原子优选选自Si、N、P、O、S和/或Se。
此外,在本发明的意义中芳环和杂芳环体系旨在是指不必须仅包含芳基或杂芳基的体系,而是其中此外多个芳基或杂芳基可以被非芳族单元中断,例如sp3-杂化C原子、N或O原子。因此,例如9,9'-螺二芴、9,9-二芳基芴、三芳基胺、二芳基醚、茋等的体系在本发明的意义中也应当是指芳环体系,其中两个或更多个芳基例如被直链或环烷基或被硅烷基中断的体系也应当是指芳环体系。
具有5-60个环原子的芳环或杂芳环体系,其在每种情况下也可以被任何所需的基团L(参见以下)取代和其可以经由芳环或杂芳环体系上任何所需的位置连接,特别是指得自以下的基团:苯、萘、蒽、菲、芘、苝、荧蒽、并四苯、并五苯、苯并芘、芴、螺双芴、二氢菲、二氢芘、四氢芘、顺式或反式茚并芴、三聚茚(truxene)、异三聚茚、螺三聚茚、螺异三聚茚、呋喃、苯并呋喃、异苯并呋喃、二苯并呋喃、噻吩、苯并噻吩、异苯并噻吩、二苯并噻吩、吡咯、吲哚、异吲哚、咔唑、吡啶、喹啉、异喹啉、吖啶、菲啶、苯并-5,6-喹啉、苯并-6,7-喹啉、苯并-7,8-喹啉、吩噻嗪、吩嗪、吡唑、吲唑、咪唑、苯并咪唑、萘并咪唑、菲并咪唑、吡啶并咪唑、吡嗪并咪唑、喹喔啉并咪唑、唑、苯并唑、萘并唑、蒽并唑、菲并唑、异唑、1,2-噻唑、1,3-噻唑、苯并噻唑、哒嗪、苯并哒嗪、嘧啶、苯并嘧啶、喹喔啉、1,5-二氮杂蒽、2,7-二氮杂芘、2,3-二氮杂芘、1,6-二氮杂芘、1,8-二氮杂芘、4,5-二氮杂芘、4,5,9,10-四氮杂苝、、吡嗪、吩嗪、荧红环、萘啶、氮杂咔唑、苯并咔啉、菲咯啉、1,2,3-三唑、1,2,4-三唑、苯并三唑、1,2,3-二唑、1,2,4-二唑、1,2,5-二唑、1,3,4-二唑、1,2,3-噻二唑、1,2,4-噻二唑、1,2,5-噻二唑、1,3,4-噻二唑、1,3,5-三嗪、1,2,4-三嗪、1,2,3-三嗪、四唑、1,2,4,5-四嗪、1,2,3,4-四嗪、1,2,3,5-四嗪、嘌呤、蝶啶、中氮茚、苯并噻二唑、苯并蒽烯(benzanthrene)、苯并蒽、玉红省和苯并菲(triphenylene)。
根据本发明的式(I)的环体系Ar任选被一个或多个基团,优选基团L取代,如果它们出现多于一次那么它们将被独立定义。
作为环体系Ar的替代提及的基团L在每种情况下彼此独立地优选表示F、Cl、Br、I、-CN、-NO2、-OH、-OSi(R0)3、-C(=O)N(R0)2、-C(=O)R0,具有3-20个C原子的任选取代的芳基或环烷基,其它基团Ar,或具有1-25个C原子的直链或支链的烷基、烯基、炔基、烷氧基、烷基羰基、烷氧基羰基、烷基羰基氧基或烷氧基羰基氧基,其中此外一个或多个H原子可以被F、Cl、-OH或-OSi(R0)3代替,其中R0在每种情况下彼此独立地表示具有1-12个C原子,优选1-6个C原子的烷基。
在其中基团L表示其它的基团Ar的情况下,这反之任选被一个或多个独立的基团L等取代。此处,基团Ar可以采用不同的含义。其在每种情况下优选为苯环。总共包括在式(I)和(II)中的基团Ar的数目优选为1、2、3或4,特别优选1、2或3。
关于本发明,表述“烷基”表示具有1-15(即1、2、3、4、5、6、7、8、9、10、11、12、13、14或15)个碳原子的直链或支链,饱和的脂族烃基。
烷氧基是指其中氧原子直接连接至被烷氧基基团取代的基团或直接连接至取代的环的O-烷基,并且烷基如上所定义。优选的烷氧基基团为甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基和辛氧基,其中这些基团中的每一个还可以优选被一个或多个氟原子取代。烷氧基特别优选-OCH3、-OC2H5、-O-n-C3H7、-O-n-C4H9、-O-t-C4H9、-OCF3、-OCHF2、-OCHF或-OCHFCHF2。
关于本发明,表述“氧杂烷基”表示其中至少一个非末端CH2基团已经被-O-以不存在相邻的杂原子(O,S)的方式代替的烷基基团。氧杂烷基优选包括式CaH2a+1-O-(CH2)b-的直链基团,其中a和b各自彼此独立地表示1、2、3、4、5、6、7、8、9或10;特别优选a为1-6的整数和b为1或2。
关于本发明,表述“烯基”表示其中存在一个或多个-CH=CH-基团的如上所定义的烷基。如果在基团中存在两个-CH=CH-基团,这也可以被称为“二烯基”。烯基基团可以包含2-15(即,2、3、4、5、6、7、8、9、10、11、12、13、14或15)个碳原子并且为支链或优选为直链。所述基团是未取代的或相同或不同地特别被F、Cl、Br、I和/或CN单取代或多取代。此外,一个或多个CH2基团在每种情况下彼此独立地以杂原子(O,S)不彼此直接连接的方式被-O-、-S-、-C≡C-、-CO-O-、-OC-O-替代。如果在两个碳原子上的CH=CH基团带有不是氢的基团,例如若其是非末端基团,则CH=CH基团可以两种构型存在,即E异构体和Z异构体。通常,E异构体(反式)是优选的。所述烯基基团优选包含2、3、4、5、6或7个碳原子并且表示乙烯基、1E-丙烯基、1E-丁烯基、1E-戊烯基、1E-己烯基、1E-庚烯基、2-丙烯基、2E-丁烯基、2E-戊烯基、2E-己烯基、2E-庚烯基、3-丁烯基、3E-戊烯基、3E-己烯基、3E-庚烯基、4-戊烯基、4Z-己烯基、4E-己烯基、4Z-庚烯基、5-己烯基或6-庚烯基。特别优选的烯基基团为乙烯基、1E-丙烯基和3E-丁烯基。
如果烷基基团中的一个或多个CH2基团已经被-C≡C-代替,那么存在炔基基团。一个或多个CH2基团也可以被-CO-O-或-O-CO-代替。此处优选以下这些基团:乙酰氧基、丙酰氧基、丁酰氧基、戊酰氧基、己酰氧基、乙酰氧基甲基、丙酰氧基甲基、丁酰氧基甲基、戊酰氧基甲基、2-乙酰氧基乙基、2-丙酰氧基乙基、2-丁酰氧基乙基、2-乙酰氧基丙基、3-丙酰氧基丙基、4-乙酰氧基丁基、甲氧基羰基、乙氧基羰基、丙氧基羰基、丁氧基羰基、戊氧基羰基、甲氧基羰基甲基、乙氧基羰基甲基、丙氧基羰基甲基、丁氧基羰基甲基、2-(甲氧基羰基)乙基、2-(乙氧基羰基)乙基、2-(丙氧基羰基)乙基、3-(甲氧基羰基)丙基、3-(乙氧基羰基)丙基或4-(甲氧基羰基)丁基。
关于本发明,表述“环烷基”表示具有3-16个碳原子的环状脂族(脂环族)基团,其是饱和的或部分不饱和的并且是未取代的或被卤素、羧基、硝基、烷基、烷氧基、-NH2和/或被-N(烷基)2单取代或多取代,其中多取代可以通过相同或不同的取代基进行。所述环烷基基团优选是未取代的并且具有5、6或7个碳原子。特别地,环烷基代表环己基基团。
关于本发明,“亚烷基”代表在链中具有1、2、3、4、5、6、7或8个碳原子的二价脂族烃基团,其也可以任选被卤素、CN、羧基、硝基、烷基、烷氧基、-NH2和/或被-N(烷基)2单取代或多取代,其中多取代可以通过相同或不同的取代基进行。“亚烷基”优选代表具有1、2、3、4、5或6个碳原子的直链饱和脂族基团,其是未取代的或被甲基单或二取代的,特别是-CH2CH2CH2-和-CH2C(CH3)2CH2-。
关于本发明“卤素”代表氟、氯、溴或碘。
关于本发明,表述“芳基”–如果其不在说明书或在权利要求中它处在个别情况下不同定义-则表示具有6-14个碳原子的芳族烃,其任选被卤素、硝基、烷基、烷氧基、-NH2和/或被-N(烷基)2单取代或多取代,其中多取代通过相同或不同的取代基进行。特别地,“芳基”代表未取代的或取代的苯基或萘基。
关于本发明,表述“芳氧基”代表芳基-O-基团,特别是苯基-O-基团。
关于本发明,表述“芳烷基”代表芳基-烷基基团,即代表其中芳基取代基经由烷基桥连接到原子、链、其它环、另一基团或官能团的基团。烷基桥优选是饱和二价烃基团(“亚烷基”),特别是亚甲基(-CH2-)或亚乙基(-CH2-CH2-)。芳烷基基团优选的实例是苄基和苯乙基。对于本发明的目的,“芳烷基-O-基团”是芳烷基基团,其经由键连到烷基桥的氧原子连接到其它原子、链、另一基团或官能团。芳烷基-O-基团优选的实例是O-苄基和O-CH2CH2-苯基。
式(I)和(II)中的基团Ar优选独立地表示选自以下的环基团:苯、萘、色烯、2-氧代-1H-色烯、色烯2-酮、吡啶、噻吩、芴或二苯并呋喃,其任选地被一个或多个基团L取代,
在式(I)和(III)中下标n优选为1或2,特别优选为1。
可由本发明方法获得的式(I)的特别优选的化合物选自以下优选的结构:
其中:
R1独立地表示H、卤素、具有1-25个C原子的直链、支链或环状烷基,其中此外一个或多个不相邻的CH2基团可以O和/或S不直接彼此连接的方式被-O-、-S-、-CO-、-CO-O-、-O-CO-、-O-CO-O-代替,和其中此外一个或多个H原子可以被F或Cl代替。
L1在每种情况下独立地表示如上下文对于L所定义的基团,优选在每种情况下彼此独立地为F、Cl、Br、I、-CN、-OH、-OSi(R0)3、-NO2或具有1-25个C原子的直链或支链的烷基、烷氧基、烷基羰基、烷氧基羰基、烷基羰基氧基或烷氧基羰基氧基,其中此外一个或多个H原子可以被F或Cl代替,
其中R0在每种情况下彼此独立地表示具有1-12个C原子,优选具有1-6个C原子的烷基,和
p在每种情况下彼此独立地表示0、1、2、3或4,优选0、1或2。
因此,在优选的实施方案中,在式(I)中,基团
Ar代表选自芳族部分的结构
其中
p在每种情况下独立地为0、1、2、3或4,和L1在每种情况下独立地如上下文所定义。
特别优选式(II)的起始材料选自以下结构:
其中
p在每种情况下独立地为0、1、2、3或4,
L1在每种情况下彼此独立地表示F、Cl、Br、I、-CN、-OH、-OSi(R0)3、-NO2或具有1-25个C原子的直链或支链的烷基、烷氧基、烷基羰基、烷氧基羰基、烷基羰基氧基或烷氧基羰基氧基,其中此外一个或多个H原子可以被F或Cl替代,
其中R0在每种情况下彼此独立地表示具有1-12个C原子,优选1-6个C原子的烷基,和
L在每种情况下彼此独立地表示F、Cl、Br、I、-CN、-NO2、-OH、-OSi(R0)3、-C(=O)N(R0)2、-C(=O)R0,具有3-20个C原子的任选取代的芳基或环烷基,或具有1-25个C原子的直链或支链的烷基、烯基、炔基、烷氧基、烷基羰基、烷氧基羰基、烷基羰基氧基或烷氧基羰基氧基,其中此外一个或多个H原子可以被F、Cl、-OH或-OSi(R0)3代替,
其中R0在每种情况下彼此独立地表示具有1-12个C原子,优选1-6个C原子的烷基,
对应于以上式(II)的起始材料,由其形成的式(I)的产物是本发明的优选实施方案。
式(II)的芳族或杂芳族起始材料优选选自以下子式:
式(III)的芳族或杂芳族起始材料的基团X优选选自系列氯、溴、碘和拟卤素,选自系列芳基磺酰氧基,其中特别是对-甲苯基磺酰氧基;烷基磺酰氧基,其任选被氟化,其中特别是甲基磺酰氧基(甲磺酸酯基)和全氟烷基磺酰氧基,例如全氟丁基磺酰氧基(全氟丁基磺酸酯基)、三氟甲基磺酰氧基(三氟甲磺酸酯基);烷基羰基氧基、芳基羰基氧基、烷基氧基羰基氧基和芳基氧基羰基氧基。烷基磺酰氧基和芳基磺酰氧基类的优选基团从而可以以式-OSO2RF总结,其中RF=三氟甲基、对-甲苯基或全氟丁基。特别地,此处使用式(III)的起始材料,其包含氯、溴、碘或三氟甲基磺酰氧基作为基团X。
式(III)的硼试剂可通过原则上已知的相应烯醇的硼氢化反应获得,如例如描述于Bioorg.and Med.Chem.Lett.2010,(20),3550-3556,Synthesis 1990,685或WO 2009/46098 A1中的。基团R的选择可视情况而优选。
式(III)的硼化合物中的R优选表示选自烷氧基和OH,特别是具有1-6个C原子的烷氧基的基团。R特别优选是乙氧基、正丙氧基或异丙氧基或正丁氧基。
式(I)和(III)中的下标n优选表示1-4的整数,即1、2、3或4,和特别优选1或2。
优选的方法特征在于式(III)的硼化合物由通式(IV)的烯醇通过硼氢化反应制备,
(参见Bioorg and Med Chem Lett 2010,(20),12,3550-3556;WO 2009/46098(2009);Synthesis(1990)685;Miyaura,N.,Science of Synthesis,(2005)6,275和Science of Synthesis_Online,Chap.6.1.7.4.2Variation 2:CatalyzedHydroboration,DOI:10.1055/sos-SD-006-00232)。
在优选的情况下,这是烯丙醇(n=1)或高烯丙基醇(n=2)。具有取代基R=烷基或烯基的式(III)的硼化合物可以使用盐酸水解得到硼单酯(R=H)或通过在过量的醇中酯交换被另一个基团R代替。
用于进行根据本发明的Suzuki偶合的催化剂是通常已知的并且优选包含钯。优选采用的催化剂可以由普通的钯(II)盐原位产生,例如,氯化钯、溴化钯、碘化钯、乙酸钯或乙酰丙酮钯,其可以任选地被其它的配体稳定,例如烷基腈,或由Pd(0)类物质原位产生,例如在活性碳上的钯,或三(二苯亚甲基丙酮)-二钯和膦配体PR1R2R3,其中Ri代表来自系列氢、直链和支链的C1-C8-烷基、乙烯基、芳基或来自系列吡啶、嘧啶、吡咯、噻吩和呋喃的杂芳基的取代基,其可以本身被其它的取代基取代,所述其它取代基来自系列直链和支链的C1-C8-烷基,优选C1-C8-烷基和C1-C8-芳基,直链和支链的C1-C8-烷基氧基和C1-C8-芳基氧基,卤化的直链和支链的C1-C8-烷基,优选C1-C8-烷基,和卤化的C1-C8-芳基,直链和支链的C1-C8-烷基,优选C1-C8-烷基和C1-C8-芳基氧基羰基,直链和支链的C1-C8-烷基氨基,直链和支链的C1-C8-二烷基氨基、C1-C8-芳基氨基、C1-C8-二芳基氨基、甲酰基、羟基、羧基、氰基和卤素例如F、Cl、Br和I。备选地,也可以采用定义的钯络合物,其已经在一个或多个方法步骤中由上述配体预先生成。特别地,可以特别优选采用双(三苯基膦)氯化钯(II)。
优选采用0.01mol%至20mol%的量的催化剂,基于式(II)的芳族或杂芳族起始材料。
待采用的碱优选选自例如氢氧化钠、甲醇钠、醋酸钠、氟化钾、磷酸钾或碳酸钾的碱(参见Zysman-Colman,E.,Science of Synthesis(2010)45,175,Chapter45.4.2.1.4Method 4:Alkylation of Arenes via Suzuki Reaction of Alkylboranesand Related Alkylboron Reagents with Aryl Halides;DOI:10.1055/sos-SD-045-00123)。
所述方法优选使用溶剂进行。这意味着起始材料优选在均相中溶解并且反应。待采用的溶剂包括极性和疏水溶剂。
优选的极性溶剂尤其包括醇,优选甲醇、乙醇、丁醇和戊醇,优选甲醇;极性非质子溶剂,例如二甲基甲酰胺(DMF)、环丁砜、碳酸乙烯酯和碳酸丙烯酯。
优选的疏水溶剂包括芳族烃,例如苯和甲苯,和脂族烃,特别是烷烃和环烷烃。特定的优点可以特别地通过使用具有5-15个碳原子的烷烃和环烷烃实现,其中正己烷、环己烷、正庚烷、甲基环己烷、辛烷、二甲基环己烷和壬烷是特别优选的。
所述方法和反应混合物的后续的后处理(work-up)原则上可以作为分批反应或在连续反应工序中进行。连续反应工序例如包括在连续搅拌槽式反应器、搅拌槽式级联(cascade)、环管反应器或错流反应器、流管中或在微反应器中的反应。根据需要,反应混合物的后处理任选通过经由固体相过滤、色谱法、不可互溶相之间的分离(例如萃取)、吸附在固体载体上、蒸出溶剂和/或共沸混合物、选择性蒸馏、升华、结晶、共结晶或通过膜上的纳米过滤进行。
本发明的实施方案和变体的进一步的组合产生自权利要求。
进一步优选的方法的变体由实施例揭示,其细节-也根据一般专业知识概括-是根据本发明的方法和其产品的优选实施方案的代表。
以下参考工作实施例更详细地解释本发明,但不因此加以限制。
具体实施方式
实施例
实施例1.1,2-氧杂环戊硼烷和1,2-氧杂环己硼烷的制备
实施例1.1.2-丁氧基-1,2-氧杂环戊硼烷
标题化合物根据WO 2009/046098 A1通过使用丁醇的硼氢化和酯交换制备。
实施例1.2.2-乙氧基-1,2-氧杂环戊硼烷
将起始材料2-丁氧基-1,2-氧杂环戊硼烷(1g)在10ml EtOH中在60℃下搅拌120分钟,和在4-8小时之后,在100毫巴下经受真空蒸馏。首先,分离出EtOH和BuOH,并且随后蒸馏出产物2-乙氧基-1,2-氧杂环戊硼烷。
实施例1.3.2-羟基-1,2-氧杂环戊硼烷
将水(50ml)和1N HCl(10ml)加入到5g的2-丁氧基-1,2-氧杂环戊硼烷,并且将混合物在20-30℃下搅拌6小时。将溶剂水、形成的丁醇和所采用的盐酸在30℃下真空移除,和形成了作为无定型固体的产物1,2-氧杂环戊硼烷-2-醇。
实施例1.4.2-丁氧基-1,2-氧杂环己硼烷
类似于实施例1.1通过使用丁醇的硼氢化和酯交换制备了标题化合物。
实施例2
实施例2.1.3-(4-羟基苯基)-6,8-双(3-羟丙基)色烯-2-酮
准备措施:A)在氮气下,制备Pd催化剂(0.267g/氯化钯(II))和0.176g的NaCl的在6.5ml的去离子水中的溶液。
B)制备配体(1.4g/2-二环己基膦基-2,6-二-异丙氧基-1,1-二联苯基)的溶液和在氮气下加入在5ml的THF中0.21ml的三乙胺。
C)制备85g NaCl在380ml去离子水中的溶液。
工序:起初将1.15kg的THF引入到具有搅拌器的经惰性化的(inertised)2L装置中,随后加入色烯酮起始材料(6,8-二溴-3-(4-羟苯基)-色烯-2-酮,59g)和碳酸钠(35g),之后加入硼酸酯(2-丁氧基-1,2-氧杂环戊硼烷,参见实施例1.1,49g)和催化剂以及配体溶液(A,B),和在搅拌下加入水性NaCl溶液(C)。使用氮气将混合物再惰性化两次并且随后在90℃下搅拌24小时。随后将混合物冷却至40℃,和分离出水性相。
后处理(work-up):将145g的NaCl溶液(18wt%)和12g的HCl(25%)加入到有机相中,并用其洗涤有机相。随后将水相分离。将160g的NaCl溶液(18wt%)加入到有机相中并且用其洗涤有机相。随后将水相分离。使用相同量的NaCl溶液(18wt%)重复一次该步骤。为了进一步纯化产物溶液,使用悬浮在25ml的THF中的活性炭(15g)填充Seitz过滤器,将有机相通过其过滤,和随后用250g的THF冲洗过滤器。
将产物溶液计量加入至2L装置中,所述装置已经在中间时期清理,和将溶剂THF在90℃下蒸出。此处随着增加真空(约1000毫巴至约300毫巴)移除溶剂。初次结晶在约200ml的残余体积时形成。随后分批(in portions)计量加入约580ml的乙腈,并且将约100g的THF/乙腈混合物蒸馏出。
将混合物冷却至50℃,随后在约6-10小时的期间冷却至0℃。将形成的结晶物质滤出并且每次用60ml的冷的乙腈冲洗两次。在40℃下,在真空下将无色结晶固体干燥至恒重。
收率:88%(>97%纯度,根据HPLC)。
形成的材料任选由乙腈/水(10:1)重结晶。
1H NMR(400MHz,DMSO-d6)δ9.70(br,1H),8.06(s,1H),7.58(d,J=8.7Hz,2H),7.39(d,J=2.1Hz,1H),7.29(d,J=2.1Hz,1H),6.84(d,J=8.7Hz,2H),4.51(t,J=5.1Hz,1H),4.47(t,J=5.1Hz,1H),3.47(q,J=5.2Hz,2H),3.43(q,J=5.2Hz,2H),2.84–2.76(m,2H),2.71–2.62(m,2H),1.85–1.70(m,4H)。
实施例2.2.2-甲基丙烯酸3-{3-[4-(2-甲基丙烯酰氧基)苯基]-6-[3-(2-甲基丙烯酰氧基)丙基]-2-氧代-2H-色烯-8-基}丙基酯(酯化成甲基丙烯酸酯)
在冰冷下,将甲基丙烯酸(8.5g,99.0mmol)和DMAP(0.5g),随后是1-(3-二甲基氨基丙基)-3-乙基碳化二亚胺(15.0g,96.6mmol)在20ml的二氯甲烷中的溶液加入至悬浮在230ml的二氯甲烷中的3-(4-羟基苯基)-6,8-双-(3-羟丙基)色烯-2-酮(10.1g,25.1mmol)中。在1小时之后,移除冰冷,并且在室温下搅拌反应12小时。真空移除溶剂,并且通过色谱法(二氯甲烷/乙酸乙酯)纯化残余物,得到无色晶体的2-甲基丙烯酸3-{3-[4-(2-甲基丙烯酰氧基)苯基]-6-[3-(2-甲基丙烯酰氧基)丙基]-2-氧代-2H-色烯-8-基}丙基酯。
熔点:49℃。
实施例3.4-[2-乙基-4-(4-戊基苯基)苯基]-2,6-双(3-羟丙基)苯酚
起初将2.90g(27.4mmol)的无水碳酸钠、100.0mg(0.56mmol)的氯化钯(II)、180.0mg(0.39mmol)的2-二环己基膦基-2',6'-二异丙基-1,1'-二联苯引入到30ml的水中,并且加入7.8g(13mmol)的二溴化(叔丁基(2,6-二溴-4-[2-乙基-4-(4-戊基苯基)苯基]苯氧基)二甲基硅烷)和4.10g(28.9mmol)的2-丁氧基-1,2-氧杂环戊硼烷在200ml的四氢呋喃中的溶液。加入120μl(0.87mmol)的三乙胺,并且使用氮气将混合物脱气20分钟并且随后在回流下搅拌18小时。将反应混合物冷却至室温,并且加入水和MTB醚。在反应溶液已经被搅拌之后,分离相,水相用MTB醚萃取,并且合并的有机相用饱和氯化钠溶液洗涤,使用硫酸钠干燥,过滤并且在真空中蒸发。将粗产物用甲苯/乙酸乙酯(1:1)通过350ml的硅胶过滤,并且将产物级分合并并且在真空中蒸发。
1H NMR(500MHz,DMSO-d6)
δ=0.89ppm(t,7.08Hz,3H,CH3),1.05(t,7.92Hz,3H,CH3),1.33(mc,4H,CH2),1.62(五重峰,7.29Hz,2H,CH2),1.73(五重峰,6.73Hz,2H,CH2),2.69–2.58(m,8H,苄基-CH2),3.45(q,6.42Hz,4H,CH2),4.52(t,5.04Hz,2H,OH),6.89(s,2H,芳族-H),7.2(d,7.9Hz,1H,芳族-H),7.29(d,8.98Hz,2H,芳族-H),7.46(dd,7.92,1.90Hz,1H,芳族-H),7.54(d,1.78Hz,1H,芳族-H),7.59(d,8.12Hz,2H,芳族-H),8.25(s,1H,芳族-OH)。
类似于实施例2制备了以下(杂)芳基醇:
实施例4.
与1当量的2-丁氧基-1,2-氧杂环戊硼烷的反应。
收率:61%,含量:97%。
实施例5.
与3当量的2-丁氧基-1,2-氧杂环戊硼烷的反应。
收率:38%,含量:84%。
实施例6.
与1当量的2-丁氧基-1,2-氧杂环戊硼烷的反应。
收率:97%,含量:>98%。
实施例7.
与1当量的反应。
收率:95%,含量:>98%。
实施例8.
与1当量的2-丁氧基-1,2-氧杂环戊硼烷的反应。
收率:97%,含量:>97%。
实施例9.
与1当量的2-丁氧基-1,2-氧杂环戊硼烷的反应。
收率:96%,含量:>98%。
后处理在每种情况下使用标准实验室方法进行。分析对应于文献值。
Claims (11)
1.制备式(I)的化合物的方法,
其中Ar代表任选取代的单环或多环的芳环或杂芳环体系,
p表示1、2、3、4、5或6,
和
n表示1、2、3或4,
包括在碱和过渡金属催化剂的存在下使式(II)的起始材料,
Ar-[X]p (II),
其中Ar具有以上给出的含义和X表示Br、Cl、I、任选氟化的烷基磺酸酯或芳基磺酸酯,
与式(III)的硼化合物反应
其中n具有以上给出的含义和
R表示OH、OR'或NR'R",其中
R'和R"各自彼此独立地表示具有1-15个C原子的(环)烷基,具有2-15个C原子的烯基,或芳基。
2.根据权利要求1的方法,其特征在于
n表示1或2。
3.根据权利要求1或2的方法,其特征在于
Ar表示选自苯、萘、色烯、2-氧代-1H-色烯、色烯-2-酮、吡啶、噻吩、芴或二苯并呋喃的环基团,其任选被一个或多个基团L取代,和
L在每种情况下彼此独立地表示F、Cl、Br、I、-CN、-NO2、-OH、-OSi(R0)3、-C(=O)N(R0)2、-C(=O)R0,具有3-20个C原子的任选取代的芳基或环烷基,基团Ar或具有1-25个C原子的直链或支链的烷基、烯基、炔基、烷氧基、烷基羰基、烷氧基羰基、烷基羰基氧基或烷氧基羰基氧基,其中此外一个或多个H原子可以被F、Cl、-OH或-OSi(R0)3代替,其中R0在每种情况下彼此独立地表示具有1-12个C原子的烷基。
4.根据权利要求1-3的一项或多项的方法,其特征在于
p为1或2。
5.根据权利要求1-4的一项或多项的方法,其特征在于
p为2。
6.根据权利要求1-5的一项或多项的方法,其特征在于,在式(I)中,基团
Ar代表选自以下的结构
其中
p在每种情况下独立地为0、1、2、3或4和
L1在每种情况下独立地如在权利要求3中的基团L所定义。
7.根据权利要求1-6的一项或多项的方法,其特征在于所述反应在溶剂中进行。
8.根据权利要求1-7的一项或多项的方法,其特征在于所述反应在含钯催化剂的存在下进行。
9.根据权利要求1-8的一项或多项的方法,其特征在于所述反应在碱的存在下进行,所述碱选自氢氧化钠、甲醇钠、醋酸钠、氟化钾、磷酸钾和碳酸钾。
10.根据权利要求1-9的一项或多项的方法,其特征在于式(III)的化合物由式(IV)的烯醇通过硼氢化制备
11.根据权利要求1-10的一项或多项的方法,其特征在于式(I)的化合物进一步被转化成式(V)的(甲基)丙烯酸酯,
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