TW200806683A - Borane ether complexes - Google Patents
Borane ether complexes Download PDFInfo
- Publication number
- TW200806683A TW200806683A TW096123065A TW96123065A TW200806683A TW 200806683 A TW200806683 A TW 200806683A TW 096123065 A TW096123065 A TW 096123065A TW 96123065 A TW96123065 A TW 96123065A TW 200806683 A TW200806683 A TW 200806683A
- Authority
- TW
- Taiwan
- Prior art keywords
- borane
- complex
- ether
- reaction
- tetrahydrofuran
- Prior art date
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- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 title claims description 128
- 229910000085 borane Inorganic materials 0.000 title claims description 70
- -1 Borane ether complexes Chemical class 0.000 title abstract description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000006053 organic reaction Methods 0.000 claims abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 74
- 230000009467 reduction Effects 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000006197 hydroboration reaction Methods 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910021538 borax Inorganic materials 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 239000004328 sodium tetraborate Substances 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims 2
- MCRSOWKAYFPRJY-UHFFFAOYSA-N B.[Bi] Chemical compound B.[Bi] MCRSOWKAYFPRJY-UHFFFAOYSA-N 0.000 claims 1
- YMRMGNMHZNFVAE-UHFFFAOYSA-N C(CCC)[Ru] Chemical compound C(CCC)[Ru] YMRMGNMHZNFVAE-UHFFFAOYSA-N 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 239000002689 soil Substances 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 25
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical class [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 41
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 38
- 238000006722 reduction reaction Methods 0.000 description 37
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 27
- 239000000203 mixture Substances 0.000 description 23
- 150000002576 ketones Chemical class 0.000 description 17
- UWTDFICHZKXYAC-UHFFFAOYSA-N boron;oxolane Chemical compound [B].C1CCOC1 UWTDFICHZKXYAC-UHFFFAOYSA-N 0.000 description 14
- 229910000033 sodium borohydride Inorganic materials 0.000 description 14
- 239000012279 sodium borohydride Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 229920006395 saturated elastomer Polymers 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- 239000012044 organic layer Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 239000012448 Lithium borohydride Substances 0.000 description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000005711 Benzoic acid Substances 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229940067107 phenylethyl alcohol Drugs 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- VUFKMYLDDDNUJS-UHFFFAOYSA-N 2-(ethoxymethyl)oxolane Chemical compound CCOCC1CCCO1 VUFKMYLDDDNUJS-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- FTHGKDLUXAQKFS-UHFFFAOYSA-N oxolane-2-thiol Chemical compound SC1CCCO1 FTHGKDLUXAQKFS-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- WAPNOHKVXSQRPX-ZETCQYMHSA-N (S)-1-phenylethanol Chemical compound C[C@H](O)C1=CC=CC=C1 WAPNOHKVXSQRPX-ZETCQYMHSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- OXMIDRBAFOEOQT-UHFFFAOYSA-N 2,5-dimethyloxolane Chemical compound CC1CCC(C)O1 OXMIDRBAFOEOQT-UHFFFAOYSA-N 0.000 description 2
- SHMWDOJMJAWMOZ-UHFFFAOYSA-N 2-decyloxolane Chemical compound CCCCCCCCCCC1CCCO1 SHMWDOJMJAWMOZ-UHFFFAOYSA-N 0.000 description 2
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 2
- 239000004472 Lysine Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- CHDFNIZLAAFFPX-UHFFFAOYSA-N ethoxyethane;oxolane Chemical class CCOCC.C1CCOC1 CHDFNIZLAAFFPX-UHFFFAOYSA-N 0.000 description 2
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 1
- MRDYKJRXPPGZKJ-UHFFFAOYSA-N 1,2,3,4-tetrachloropyrene Chemical compound C1=CC=C2C=C(Cl)C3=C(Cl)C(Cl)=C(Cl)C4=CC=C1C2=C43 MRDYKJRXPPGZKJ-UHFFFAOYSA-N 0.000 description 1
- YEYQUBZGSWAPGE-UHFFFAOYSA-N 1,2-di(nonyl)benzene Chemical compound CCCCCCCCCC1=CC=CC=C1CCCCCCCCC YEYQUBZGSWAPGE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 description 1
- VXZFLJLVIZALJW-UHFFFAOYSA-N 1h-indole;oxolane Chemical compound C1CCOC1.C1=CC=C2NC=CC2=C1 VXZFLJLVIZALJW-UHFFFAOYSA-N 0.000 description 1
- VRESBNUEIKZECD-UHFFFAOYSA-N 2-methyltetrazole Chemical compound CN1N=CN=N1 VRESBNUEIKZECD-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- ABGZOUGXSXBQQI-UHFFFAOYSA-N B.O Chemical compound B.O ABGZOUGXSXBQQI-UHFFFAOYSA-N 0.000 description 1
- BBYRUJKPCDTECG-UHFFFAOYSA-N B.O1CNCC1 Chemical compound B.O1CNCC1 BBYRUJKPCDTECG-UHFFFAOYSA-N 0.000 description 1
- IBHOPHUUVQOHCC-UHFFFAOYSA-N B.c1cocn1 Chemical compound B.c1cocn1 IBHOPHUUVQOHCC-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DFXIVBPJAOWKEQ-UHFFFAOYSA-N C(CCCCCCCCC)B Chemical compound C(CCCCCCCCC)B DFXIVBPJAOWKEQ-UHFFFAOYSA-N 0.000 description 1
- 101100101413 Caenorhabditis elegans ubh-4 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical class COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- 240000000731 Fagus sylvatica Species 0.000 description 1
- 235000010099 Fagus sylvatica Nutrition 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241000361919 Metaphire sieboldi Species 0.000 description 1
- USGWTBYEPDASSL-UHFFFAOYSA-N NC(=O)C1(C)CC=CC=C1 Chemical compound NC(=O)C1(C)CC=CC=C1 USGWTBYEPDASSL-UHFFFAOYSA-N 0.000 description 1
- UGBUZBZPLZAQKY-UHFFFAOYSA-N O1CCCC1.CCCCCCCCCC Chemical compound O1CCCC1.CCCCCCCCCC UGBUZBZPLZAQKY-UHFFFAOYSA-N 0.000 description 1
- GZKVGAKTIJPYAL-UHFFFAOYSA-N O1CCCC1.[S] Chemical compound O1CCCC1.[S] GZKVGAKTIJPYAL-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 206010036790 Productive cough Diseases 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229930182558 Sterol Natural products 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- KPSZQYZCNSCYGG-UHFFFAOYSA-N [B].[B] Chemical compound [B].[B] KPSZQYZCNSCYGG-UHFFFAOYSA-N 0.000 description 1
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009418 agronomic effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- HAXSCOGBPLMKKV-UHFFFAOYSA-N benzene;1h-indole Chemical compound C1=CC=CC=C1.C1=CC=C2NC=CC2=C1 HAXSCOGBPLMKKV-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- BEJRNLMOMBGWFU-UHFFFAOYSA-N bismuth boron Chemical compound [B].[Bi] BEJRNLMOMBGWFU-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910010277 boron hydride Inorganic materials 0.000 description 1
- RAXSQXIANLNZAF-UHFFFAOYSA-N boron;hydrazine Chemical compound [B].NN RAXSQXIANLNZAF-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
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- AILKHAQXUAOOFU-UHFFFAOYSA-N hexanenitrile Chemical compound CCCCCC#N AILKHAQXUAOOFU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 238000010952 in-situ formation Methods 0.000 description 1
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- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 208000014674 injury Diseases 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 125000000686 lactone group Chemical group 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
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- 125000002950 monocyclic group Chemical group 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002917 oxazolidines Chemical class 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
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- 229940049953 phenylacetate Drugs 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 210000003802 sputum Anatomy 0.000 description 1
- 208000024794 sputum Diseases 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003432 sterols Chemical class 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- ZVTQDOIPKNCMAR-UHFFFAOYSA-N sulfanylidene(sulfanylideneboranylsulfanyl)borane Chemical compound S=BSB=S ZVTQDOIPKNCMAR-UHFFFAOYSA-N 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- VZGDMQKNWNREIO-OUBTZVSYSA-N tetrachloromethane Chemical class Cl[13C](Cl)(Cl)Cl VZGDMQKNWNREIO-OUBTZVSYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- VSRBKQFNFZQRBM-UHFFFAOYSA-N tuaminoheptane Chemical compound CCCCCC(C)N VSRBKQFNFZQRBM-UHFFFAOYSA-N 0.000 description 1
- 229960003986 tuaminoheptane Drugs 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
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- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
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- C07C209/50—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of carboxylic acid amides
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- C07—ORGANIC CHEMISTRY
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- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
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- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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Description
200806683 九、發明說明: 【發明所屬之技術領域】 本發明係關於具有經取代之四氫呋喃醚之新穎甲说錯 合物’及將具有經取代之四氫呋喃醚之新穎甲硼烷錯合物 用於有機反應之方法。 【先前技術】 一删燒(Β#6)為有毒自燃性氣體,極易水解及氧化。處 理時必須極度小心,且必須在低於_2(rc之溫度下運輸及 存放。為了減小二硼烷之危險性,總是將甲硼烷(BH3)與 施體分子(如四氫呋喃、硫化物、胺及膦)之錯合物用於有 機反應,尤其用於官能基之還原及與烯烴及炔烴之硼氫化 反應。由此等甲硼烷錯合物還原之官能基包括醛基、酮 基内知基、環氧基、酯基、醯胺基、蔣基、亞胺基及腈 基。 最吊用之甲删娱;源為甲硼烧_四氫0夫喃(THF)錯合物之 THF溶液,該溶液可為市售的,通常濃度為丨m〇i/i。然 而,甲硼烷-THF錯合物容易藉由四氫呋喃環之醚裂解而發 生熱分解,從而產生丁氧基曱硼烷且最終產生硼酸三丁酯 作為分解產物。根據us 6,〇48,985,_溶液中之T棚 烧-THF錯合物之存放穩定性在低溫下顯著增加,甚至具有 較高濃度之溶液亦係如此。 吾人熟知四氫呋喃與曱硼烷比與直鏈醚(如乙醚)或衍生 自乙一酵之乙二醇二甲醚系列形成更強的錯合物。其他具 有五員環結構之鱗至今尚未查驗。具有其他錯合劑之T硼 122094.doc 200806683 :忒j可購侍’但有其固有缺點。舉例而言,硫化硼係高 濃度的’但由於有較強氣味而使其商業用途受限。胺基甲 Z之反應性常常不足以還原特定官能基。此外,此等錯 合劑有時難以自反應混合物移除,且所要產物之分離可能 變得較為艱難。 、=土貝而疋,使用甲硼烷試劑之硼氫化反應及還原反應 k吊可在% i兄溫度或低溫下完成,從而增加選擇性。缺 而,甲蝴燒試劑有時藉由如下方式加以使用:在反應容器 中將甲蝴烧試劑與基質(亦即,待與甲棚烧試劑發生反應 〇〇 物)起加熱,且防止釋出的氣態二硼烷自反應容 器散逸。由於某些甲㈣試劑之低熱穩定性及氣態二爛烧 之可能損1’通常在此等轉化中利用過量甲硼烧試劑。當 反應完成時’-般(例如)用醇中止反應混合物,以便在處 理(請k_up)之前破壞任何剩餘之甲職試劑。顯而易見 的’錯合劑種類強烈影響甲㈣試劑之穩定性及反應性, 以及可發生反應的壓力與溫度,及處理程序。 所以’需要研發具有改良敎性及反應性特性之新穎甲 職試劑及其利料1便在使料職試㈣行有機 化時達成較好效率。 【發明内容】 本發明提供包含經取代之四氫呋喃作為錯合劑及溶劑之 新賴甲㈣㈣合物。本發明之另—目標在於研發將 新顆甲㈣㈣合物用於有機反應之方法。 因此,已發現式1之新穎甲硼烷醚錯合物·· 122094.doc 200806683
其中 R1至R4彼此獨立地表示氫、c广CiQ烷基、C3_C6環烷基、苯 基、苄基、經取代之苯基或式CH2OR5之取代基,其中R5 為C】-C10烧基、CVC6環烷基或+CHR6CH20-]n-R7,其中R6 為氫或甲基,烷基,而11為1與20之間的整數, 或兩個相鄰取代基R^R4一起為選自由-ch2ch2-、 -CH(CH3)CH2-、-CH2CH2CH2-、-ch(ch3)ch(ch3)-、 -CH(CH2CH3)CH2^ > -C(CH3)2C(CH3)2. ^ -CH2C(CH3)2CH2. 及(C H2)6 -組成之群之二價基團,以與四氫吱喃環之 -CH-CH-部分形成環狀結構, 其限制條件為取代基R1至R4之至少一者不為氫。 本發明之新穎曱硼烷醚錯合物可藉由與用於合成甲硼 烧-四氫咬喃錯合物之方法類似的方法製備。一種方法包 含用各別、經取代之四氫咬喃中之删氫化鋼及三氟化侧原位 產生甲哪烧(參看 A· Pelter、Κ· Smith、H c Br〇wn, ”B〇rane Reagents”,第 421 至 422 頁,hess 1988)。較佳地,藉由將氣態二硼烷直接添加至各別經取 代之四氫夫喃而產生較鬲純度之該等新穎甲硼烷醚錯合 物。 本發明之新穎甲硼烷醚錯合物可用於許多有機轉化。實 122094.doc 200806683 J為g 3b基之還原及與稀烴及炔烴之棚氫化反應。由此等 曱硼烷錯合物還原之官能基可(例如)包括醛基、酮基、内 酉曰基、%氧基、酯基、醯胺基、肟基、亞胺基、羧酸基及 猜基。
與已知的未經取代之四氫呋喃之甲硼烷錯合物相比,本 發明之新賴甲硼烷醚錯合物提供許多優點。因為與未經取 代之四虱呋喃相比經取代之四氫呋喃具有大體較高之沸點 (例如,2-甲基四氫吱喃為78。〇,而THF為66。〇 )及閃點(例 如2-甲基四氫呋喃為-丨丨艺’而71^為_17。〇,所以該等化 合物存在較低易燃性危險。視連接至新穎化合物丨之五員 環的取代基種類、婁允目及位置而<,與未經取代之四氯咬 喃相比,該等新穎甲硼烷醚錯合物具有較小極性且醚錯合 劑展示與水之減小可混性’此有利於反應混合物之處理程 序。此外,該等新穎化合物熱分解時所釋放的能量在大多 數情況下遠遠低於甲爛烷-四氫呋喃,此導致該等新顆化 合物之重要安全性優點。 當在用甲基取代之掌性。惡_ „定催化劑(稱為m e e b s催 化劑,參看C⑽y,E丄等人,Angew Chem Int趾,37, 1986-2012 (1998))進行@同之對映選擇性還原的情況下使用 時,吾人驚㈣發現用該等新穎甲硼㈣錯合物獲得之對 映異構物過量高於甲硼烷-四氫吱喃。 【實施方式】 式1之化學結 本發明之新穎甲硼焼醚錯合物具有根據通 構: 122094.doc 200806683 R1 R3
bh3 其中 R1至R4彼此獨立地表示氫、Cl_ClG烷基、CrC6環烷基、笨 基、苄基、經取代之苯基或式CH2OR5之取代基,其中R5 為 CVC"烷基、c3-C6環烷基或+CHR6CH20-]n-R7,其中 R6 為氫或曱基,烷基,且η為1與20之間的整數, 或兩個相鄰取代基r1至r4 一起為選自由- CH2CH2-、 -ch(ch3)ch2-、-CH2CH2CH2-、-CH(CH3)CH(CH3)-、 -ch(ch2ch3)ch2-、-c(ch3)2c(ch3)2-、-ch2c(ch3)2ch2- 及-(C H2)6 -組成之群之二價基團,以與四氫呋喃環之 -c H - c Η -部分形成環狀結構, 其限制條件為取代基Rl至R4之至少一者不為氳。 本文所用之術語”CrCio烷基,,表示包含1與4個之間的碳 原子之支鏈或非支鏈飽和烴基。實例為甲基、乙基、丙 基、異丙基、正丁基、異丁基、第二丁基、第三丁基、己 基及辛基。 術語’’CrC6環烷基,,表示包含3與6個之間的碳原子之飽和 煙基(包括單環或多環結構部分)。實例為環丙基、環丁 基、環戊基及環己基。 術語”經取代之苯基,,表示至少一個氫原子經函原子(如 氧、氯、溴或碘)4Cl-C8烷氧基置換之苯基。 122094.doc -10- 200806683 術語"CrCs烷氧基”表 之支鏈或非支鏈脂族單 基、丙氧基、異丙氧基 基。 示衍生自包含丨與8個之間的碳原子 醇的基團。實例為甲氧基、乙氧 、正丁氧基、異丁氧基及正戊氧
術語”料”表示由三個鍵分開之兩個基團的相對位置。 應強調,所有立體異構體均包括於如下情況中:存在於 根據式為氫。 1之化合物之五員環上的_ 個以上取代基R1至R4不
本發明之新穎曱硼烷醚錯合物可藉由二硼烷與各別經取 代之四氫吱奴反應製備。為進行此反應,可藉由任何方 法(包括其原位生成,例如,自驗金屬删氫化物)使二侧烧 與各別經取代之四氮咬。南接觸。較佳藉由將氣態二硼烷直 接添加至各別經取代之四氫呋喃中製備較高純度之本發明 新顆曱棚烧鍵錯合物。在此合成中,經取代之四氫咬嚼與 二硼烷相比通常大大過量地存在,且因此既用作甲硼烷: 錯合劑又用作新生成的甲硼烷醚錯合物之溶劑。當然,亦 可存在對甲棚烧具有不良錯合能力、可與各別經取代之四 氫吱°南至少。ρ为此溶之其他溶劑,例如直鏈醚,如乙醚或 烴,如戊烷、己烷、庚烷、環己烷、甲苯或二曱苯。 新穎甲硼烷醚錯合物在含有各別經取代之四氫呋喃之溶 劑或溶劑混合物中之濃度一般處於〇 〇1 111〇1/1與3 m〇1/12 間’較佳處於〇·1 mol/1與1·5 m〇m之間,最佳處於〇5 mol/1與1.25 mol/1之間的範圍内。 本發明之新穎甲硼烷醚錯合物之形成反應通常係放熱 122094.doc 200806683 的。由於該等甲職㈣合物之熱不散性,因此一般最 好在反應過程中控制反應混合物之溫度。為了避免副反應 及形成雜質,反應混合物之溫度應低於環境溫度,較佳低 於〇°C且最佳低於-30°C。 因此,使氣態二硼烷與醚溶液接觸之方法對控制形成甲 職錯合物之放熱反應具有顯著重要性。若使用浸沒於驗 溶液表面下的液浸管或喷嘴將氣態二硼烷添加至溶液中, 則建議同時使用強冷卻與劇烈授掉及低添加速率以防止局 部加熱。當將二硼烧添加至含有所要醚溶液之反應容器頂 部空間時同樣如此,儘管在此情況下,反應將作為氣相且 在液相之整個表面上發生。若必要,則可在使二職與驗 錯合劑接觸之前用惰性氣體(如氮氣或氬氣)稀釋二删烧。 自低温存放之:職製備㈣職試_較於藉由原位途 徑製成的情況產生更高純度之甲硼烧試劑。此外,自蝴氯 V . 化納製備喊甲侧院試劑產生蝴氫化納及四氟棚酸納雜質, 该等雜質可能不利於不對稱還原。 口人^醚甲硼烷錯合物易於經歷熱分解。對於已知甲 ,、元氫夫南錯合物而言’熱分解藉由四氫呋喃環之醚 裂解而發生。甲删燒-四氫吱喃錯合物可在反應過程中或 在未適當存放時發生熱分解。高於5t之存放溫度導致幾 =便發生明顯分解。在存放期間,分解之初級模 了广袁崎)。在一…錯曰 基而。明_= 測到第一中間物單丁氧 - /、易於發生歧化而產生T硼烷_四氫 I22094.doc 200806683 吱喃及二 丁氧基甲棚烧(DiMare,M·,J. Org· Chem· 1996, 61(24),8378-8385)。二丁氧基甲硼烷僅緩慢歧化或進一步 反應,且在δ=27 ppm下於"B NMR光譜中觀測到為雙重峰 (4 (^44)=159 Hz)。在所有三個曱硼烷(B-H)鍵均發生反 應後’鄉酸三丁醋最終為終產物。 已知曱硼烷-四氫呋喃錯合物之溶液在不同濃度下的存 放fe疋性可藉由將該等溶液保持於低溫下(參看us 6,048,985)及/或藉由添加少量(通常小於i m〇1/1,較佳介於 0.001 mol/1與〇·〇2 mol/1之間)氫化物源(如硼氫化鈉、硼氫 化鉀或鹼金屬氫化物,諸如氫化鋰、氫化鈉或氫化鉀)(參 看US 3,634,277)而增加。自吾人之hb NMR光譜研究可 見,向曱硼烷-四氫呋喃錯合物溶液中添加氳化物會生成 ΒβΓ陰離子,該陰離子可用作實際穩定劑。 因此,以本發明新穎甲硼烷醚錯合物之溶液在多種條件 下進行保存期研究。舉例而言,圖1至圖4展示在不同溫度 (壤境溫度或0至5。〇下添加有或未添加硼氫化納 …基四氯咬喃於2·甲基四氣咬喃中之〇88μ溶 存期或分解研究之結果。相 ” 木相1乂於添加硼氫化鈉而言,俏、、西 時存放穩定性之挣如审% ^ ^ .i θ ^者。圖5將在環境溫度下添加有 ttr鈉的甲…甲基四氫條”基四: =中之1 M溶液與甲—V夫喃於四氯吱喃中二 或分解研究作比較。自此資料可看出,” 基四虱呋喃中之甲硼烷_ 2-甲 氫呋喃中之曱硼P .节基四虱呋喃錯合物比市售之四 甲删院一四氫吱喃錯合物略微穩定。 122094.doc 200806683 參看圖6,2,5-二甲基四氫呋喃之曱硼烷錯合物在環境溫 度下較不穩定且較快分解,速率為每天約1 %。 由於曱硼烷之高能含量,因此藉由差示掃描熱量測定 (DSC)研究本發明之某些新穎曱硼烷醚錯合物之熱降解時 的能量釋放,且將其與市售之四氫吱喊中之曱烧-四氫 呋喃錯合物之資料作比較。結果概述於表1中: 表1 :不同曱硼烷衍生物之能量釋放 化合物* 起始溫度(°C) AH(J/g) BH3-THF(1 Μ) 134 -250 具有0.005 MNaBH4之BHrTHF(l Μ) 130 -255 BH3-2 MeTHF(0.94 Μ) 139 -75 具有0.005 Μ NaBH4之BHr2 MeTHF(0.88 Μ) 140 -71 具有0.005 M LiBH4之BHr2 MeTHF(0.94 Μ) 152 -41 BH3-2 MeTHF(1.3 M) 125 -100 BHs-2 MeTHF(1.6M) 128 -229 BH3-2EMTHF(0.37 M) 158 -11 * MeTHF = 2-曱基四氫呋喃,EMTHF=2-(乙氧基甲基)-四 氫吱喃 在密封杯中以4度/分鐘之斜坡速率進行DSC量測。所發 生之分解為錯合劑醚環之醚裂解。對新穎甲硼烷-2-甲基四 氫呋喃錯合物之約1 Μ溶液而言,能量釋放小於甲硼烷-四 氫呋喃的三分之一,從而使該新穎化合物相比於標準市售 四氫吱喃錯合物而言具有顯著安全性優點,此係由於所釋 122094.doc -14- 200806683 放的較低分解能量。此外,對人 田I ^ 3有低〉農度氫化經之2- 曱基四氣呋喃中的甲硼烷-2 較高起始温度下釋放甚至更少白:能=喃之樣本而言,在 二π下對甲職_2-甲基四氣。夫喃錯合物於”基四氮 以_熱事件之發生。在此時期未發現熱事件。
本么月進#提供一種將該等新穎甲硼烷醚錯合物用於 有機反應之方法。該方法包含如下步驟:在反應容器中使 甲™錯合物與基質接觸且防止逸出之氣態二編反 應谷為散逸。較佳地,令右田Μ ^ 3有甲硼烷醚錯合物及基質之反應 容器配備有背壓調節器’且保持於大於約大氣廢之壓力 下。更佳地,壓力在高於大氣壓約3〇〇毫巴至約7〇〇〇毫巴 之範圍内。甚至更佳地,麼力在高於大氣塵約3〇〇毫巴至 約2500¾巴之範圍内。藉由防止二硼烷自反應容器散逸而 提供的優點包括更有效使用甲硼烷,從而消除使用過量甲 彌烧之需要且在反應過程中形成較少副產物。 在合適基質存在下,本發明之新穎甲硼烷醚錯合物易於 且優先與所要化合物反應。在此等條件下,熱分解及開環 反應因僅產生微量副產物而可忽略。 可根據本發明使用該等新穎甲硼烷醚錯合物之有機反應 尤其包括官能基之還原及與烯烴及快烴之硼氫化反應。此 外’待用於與該等新穎甲硼烷醚錯合物之還原反應的合適 基夤包括具有駿基、嗣基、内酯基、環氧基、酯基、醯胺 基、两基、亞胺基、缓酸基及腈基之有機化合物。有利 122094.doc -15 - 200806683 地,該等新穎甲硼烷醚錯合物可在掌性噁唑硼啶催化劑 (如MeCBS,其為以Corey、Bakshi及Shibata命名的經曱基 取代之掌性。惡嗤硼啶,參看Corey,E J·等人,Angew.
Chem· Int· Ed·,3 7,1986_20 12 (1998))存在下用於前掌性酮 - 及前掌性亞胺之對映選擇性還原。 - 使用掌性噁唑硼啶催化劑之不對稱還原為用於以高對映 異構物過量合成二級醇之良好手段(Catalysis 〇f
Chemical Synthesis,Roberts, S.M. ; P〇ignant,G·,(編), Wiley,& Sons,Ltd·: New York 2002·)。由掌性噁唑硼啶化 合物催化之前掌性酮之對映選擇性甲硼烷還原有效地與酶 促硼氫化反應及過渡金屬催化之硼氫化反應抗衡,此係由 於溫和反應條件、高對映選擇性、可預測性及高產量。該 還原同度有效且操作上較為簡單,所以良好適於工業背 景。若干噁唑硼啶化合物已用於擴大醫藥化合物規模。若 干專利涵蓋噁唑硼啶催化劑之合成及使用,例如,仍 " 4,943,635、US 5,189,177、US 5,264,574、US 5,264,585、 US 5,552,548、US 6,G05,133及 US 6,037,505。 逛原之精確立體控制起於如下環狀過渡狀態:噁唑硼啶 •經由配位而將酮固持至Lewis酸性硼,而藉由催化劑之胺 , #甲硼烷固持於附近。一般而言,將2_1〇莫耳%噁唑硼啶 (oxazaboroiide)催化劑與諸如甲硼烷-四氫呋喃、甲硼烷· 一甲基硫或甲烷-二乙基苯胺錯合物之曱爛烷源一起使 用。通常將酮緩慢添加至催化劑與甲魏之混合物中。同 時將甲㈣及酮添加至催化劑亦有效地最佳化對映選擇 122094.doc 200806683 性。US 6,21 8,585中略述了影響使用甲删烧-四氮咬喃錯合 物之經MeCBS催化的酮還原之對映選擇性的若干因素。已 顯示,硼氫化鈉作為穩定劑存在於市售曱硼烷_四氫呋喃 中不利於噁唑硼啶催化之還原的對映選擇性。通常,當經 硼氳化納穩定化之甲•四氫吱喃錯合物用於MeCB_ 化之苯乙酮還原時,在還原中獲得85_9〇% ^之對映選擇 性。硼氫化物為用於酮還原之有競爭力的非選擇性催化劑 (Jockel,H· ; Schmidt,R·,j· Chem s〇c per]dn 一 2 (1997),2719·2723。),因此當使用甲硼烷_四氫呋喃時, 用酸性化合物使硼氫化鈉失活對於高對映選擇性而言係必 需的。與US 6,21 8,585所揭示的]^“〇3及合作者之著作相 反σ人已散現硼氫化鐘作為穩定劑存在於甲蝴烧_2_甲基 四氫呋喃溶液中並未對噁唑硼啶催化之酮還原產生不利影 謇。(例如,麥看表2中之結果)。當然,使用催化劑之兩個 對映異構物(即(R)-MeCBS及(S)-MeCBS)已獲得取類似結 果。 。 與無硼氫化物之甲硼烷甲基四氫呋喃相比,使用含 有硼氫化鋰之甲硼烷基四氫呋喃的還原亦較快。實例 9及貫例10含有16-17%苯乙酮,而實例丨丨展示完整還原。 當使用無硼氫化鋰之〒硼烷甲基四氫呋喃的反應在添加 酮後再攪拌20分鐘時,還原達到完全程度且對映選擇性良 好(實例13)。將酮添加時間自2小時減少至3〇分鐘亦在苯乙 酮逛原中產生良好對映選擇性(實例14)。 與使用經硼氫化鈉穩定化之甲硼烷-四氫呋喃作為還原 122094.doc -17- 200806683
劑之標準文獻程序相比,在使用本發明之新穎曱硼烷醚錯 合物之還原中觀測到較高對映異構物過量。即使存在硼氫 化鈉亦未實質上減小使用甲硼烷-2-曱基四氫呋喃錯合物及 MeCBS之酮還原的對映選擇性(實例15P 表2 : 實例 編號 甲删烧-2-曱基四氫咬喃 剩餘 苯乙酮% 苯乙醇 % ee 9 無LiBH4,根據實例5製備 17 96.0 10 無LiBH4,根據實例7製備 16 94.4 11 具有LiBH4,根據實例5製備 0 94.8 12 (對比) 不存在氫化物穩定作用之曱硼烷-THF 0.7 95.2 13 無LiBH4,根據實例6製備 01 96.8 14 無LiBH4,根據實例7製備 93.7 15 具有NaBH4,根據實例1製備 6.21 93.2 在添加酮3 0分鐘後進行取樣 122094.doc -18 - 1 1 中止前3 0分鐘酮添加時間且固持2小時 在本發明之前,用於噁唑硼啶催化之酮不對稱還原之曱 硼烷-四氫呋喃錯合物不可作為未穩定化形式購得。本發 明允許製備穩定化及未穩定化之甲硼烷溶液作為2-甲基四 氫呋喃錯合物,該錯合物用於噁唑硼啶催化之酮及亞胺不 對稱還原可具有良好結果。 實例 以下實例在不限制本發明的情況下對其進行說明。曱硼 200806683 烧》辰度根據 Brown,H.C·、Kramer,G.W.、Levy,Α·Β.、 Midland,M.M.在 Organic Synthesis via Boranes,John Wiley and Sons,Inc·,New York 1973,第 241 至 244頁中所述之方 法用酸滴定曱蝴烧而量測。 實例1 : 2-甲基四氫呋喃之甲硼烷錯合物之合成 用氮氣淨化玻璃反應器,且裝入422.6 g 2-甲基四氫呋 喃(自鉀蒸餾)。將容器内含物冷卻至〇。將反應器之背壓 調節器設置為4400毫巴。經40分鐘的時間將二硼烷(8 g)鼓 泡入反應器中。反應器溫度達到4 · 5。〇之最大值,且達到 1400宅巴之頭壓。在完成二硼烷添加後,將反應器溶液攪 拌隔仗。B NMR光譜展示指定為產物的δ = -1·2 ppm(95%, J( B,H)=106 Hz)處之四重峰及指定為硼酸鹽雜質的δ=18 PPm(5%,單峰)處之第二信號。溶液密度在22。〇下為〇·848 g/ml,且甲硼烷濃度為0.88 Μ。 隨後將溶液分成兩個半份。用NaBH4(〇〇5 g)穩定化溶液 之一個半份。在添加NaBH4後,攪拌溶液24小時以溶解
NaBHU。隨後將穩定化及未穩定化半份均分為兩個相等部 分,以用於在室溫及〇至下進行穩定性研究(參看圖工至 圖4)。 實例2 : 2-曱基四氫呋喃之甲硼烷錯合物之合成 用氮氣淨化玻璃反應器,且裝入430 g 2_甲基四氫呋喃 (Aldrich,按接收時使用)。將容器内含物冷卻至ye。將 反應器之背壓調節器設置為44〇〇毫巴。經37分鐘的時間將 二職(1G g)鼓泡至反應器中。反應器溫度達狀代之最 122094.doc -19- 200806683 大值,且達到1700毫巴之頭壓。將硼氫化鈉(〇 〇9 g)添加 至溶液中。UB NMR光譜展示δ = ]·〇 ppm(95 %, 4^11)=106 Hz)處之四重峰、δ=18 ppm(4.5°/〇,單夸)處 之·酸鹽及δ=-26 ppm處之NaB^8跡線。溶液密度在22。〇 下為0.848 g/ml。甲棚烧濃度為0.94 Μ。 實例3 : 2,5-二甲基四氫呋喃之甲硼烷錯合物之合成 將二硼烷(〇·2 g、14 mm〇i Βη3)添加至冰浴槽中之燒瓶 中的2,5-二甲基四氫呋喃(4.9 g,5.9 ml)樣本中。混合物之 NMR 光譜清楚地展示 δ = -1·5 ppm(q5 Hz) 處之2,5-二甲基四氫呋喃之曱硼烷錯合物(62〇/〇),且亦展示 作為δ=1 7.9 ppmCW1 20, 60 Hz)處之多重峰的經溶 解二烷(24%)。最初形成之二烷氧基硼烷之量為約 14〇/〇(δ=28 ppm,d,Hz)。不清除過量二硼 烧,且將樣本保持於Ot:下。經6天於下對樣本之監測 展示相對小的變化,其中錯合甲硼烷由NMR監測保持 在約60%。隨後將樣本置於環境溫度下以監測醚開環(參看 圖6) 〇 貫例4 : 2-(乙氧基甲基)_四氫呋喃之甲硼烷錯合物之合成 在 〇°C 下將二硼烷(1·3 g,94 mm〇l BH3)添加至 1〇〇 ml 2· (乙氧基甲基)-四氫呋喃中。混合物之iiB NMR光譜清楚地 展示 δ=-0·96 ppm(寬峰 q,ij(i〗b,〗h)==96 Hz,71%)下的 2-(乙 氧基甲基)-四氫呋喃之甲硼烷錯合物及作為δ;=ΐ7.9 卩?(】(6311)-12〇5 60 112,26%)處之多重峰的經溶解二爛 烧才日疋為一燒氧基爛烧的δ = 29 ppm(d,々"β/Η) = 177 122094.doc -20- 200806683 3%)下之第三信號。基於光譜整合及所添加之二硼烷 置,2·(乙氧基甲基)-四氫呋喃之甲硼烷錯合物的濃度為 0/6 M。、經溶解二删㉟之濃度為約〇12 M。添加額二二: 氧基甲基)-四氫呋喃(100 ml)以錯合經溶解二硼烷。混合 • 物之11β NMR光譜此刻展示79.6%甲硼烷-2-(乙氧基甲基> . 四氫呋喃錯合物、6.1%二烷氧基硼烷及僅14%經溶解二硼 烷。因此,甲硼烷-2-(乙氧基甲基)_四氫呋喃錯合物之濃 f、 度為約0.37 Μ。 \ / 貫例5 : 2-甲基四氫呋喃之甲硼烷錯合物之合成 用氮氣淨化反應器,且裝入423 g 2_曱基四氫呋喃(penn Specialty Lot #2-5613)。將容器内含物冷卻至]2。〇。將反 應器之背壓調節器設置為4400毫巴。經95分鐘的時間將二 硼烷(16 g)添加至反應器中。反應器溫度達到8 9艺之最大 值,且達到2000毫巴之頭壓。在完成二硼烷添加後,判定 已添加過量二硼烷;甲硼烷滴定展示為148 M。用額外2_ w 曱基四氫呋喃(250 ml)稀釋反應器溶液以使濃度降低至j Μ,且將其攪拌隔夜。nB NMR光譜指示21%之硼酸鹽濃 度。後將溶液分成兩個半份。用LiBH4(0.037g)穩定化一 個半份。UBH4緩慢溶解,且在"b NMR光譜中在δ = -29 • Ppm處發現針對B3H8_Li+之小峰。隨後將穩定化及未穩定 化半伤均分為兩個相等部分,以在量筒中於室溫及〇下 用量規及液浸管進行穩定性研究。"B NMR光譜展示§二 15 ppm!:1"UB/11)= 106 Hz)處之四重峰。該澄清無色溶液 之社度在22C下為0.842 g/ml。濃度為0.96M。 122094.doc •21 - 200806683 實例6 : 2-甲基四氫呋喃之甲硼烷錯合物之合成 用氮氣淨化玻璃反應器,且裝入430 g 2-甲基四氫吱喃 (Penn Specialty Lot #2-5613)。將容器内含物冷卻至。 將反應器之背壓調節器設置為4400毫巴。經60分鐘的時間 將二硼烷(10 g)鼓泡至反應器中。反應器溫度達到8 t之 最大值,且達到1 800毫巴之頭壓。在完成二硼烷添加後, 藉由nBNMR判定存在5.5%硼酸鹽雜質。 實例7: 2 -甲基四氫吱喃之曱爛烧錯合物之合成 用氮氣淨化玻璃反應器,且裝入423 g 2-甲基四氮咬喃 (Penn Specialty Lot #2-5 613)。將容器内含物冷卻至 _3〇c。 將反應器之背壓調節器設置為4 4 0 0毫巴。經6 〇分鐘的時間 將二侧烷(10 g)饋入反應器之頂部空間。反應器溫度達到_ 〇.5°C之最大值,且達到2000毫巴之頭壓。在完成二硼烷添 加後,藉由nB NMR判定存在5%硼酸鹽雜質。密度經量測 為0.844 g/ml。曱硼烷濃度為UM。 實例8 : 1-辛烯與2-甲基四氫呋喃之甲硼烷錯合物的硼氫化 反應 在%境溫度下2-曱基四氫呋喃之甲硼烷錯合物(4 mm〇卜未穩定化)與丨辛烯(1·3 g,u 6匪〇1,BHs與烯烴 之莫耳比為1:3)於曱苯中之反應展示在3〇分鐘後甲硼烷 甲基四氫呋喃1〇0%轉化為產物。該反應係放熱的。發現 "B NMR光譜中三烷基硼烷(99%)處於§==89 ppm位置。 實例9至12 :笨乙酮之不對稱還原 將以下方法用於苯乙酮之不對稱還原,結果展示於表2 122094.doc -22- 200806683 中。在至溫下將苯乙酮藉由注射泵G 7 mi THF中之2 ml, 亦即17mmol)經2小時添加至丨〇 mm〇i各別甲硼烷錯合物(例 如1〇 ml 1 M溶液)及5 mol%(相對於苯乙酮)(R)-MeCBS 於甲苯中之溶液中。酮添加後攪拌10分鐘,接著添加 HC1(1 M’ 1〇 mi)以中止反應。用2〇 —無水乙醚萃取苯乙 醇及任何未反應之苯乙酮。用飽*KC1及飽和NaHc〇3溶液 洗滌有機層,隨後.NadO4乾燥。掌性GC分析展示苯乙 酮面積百分比(若有剩餘)及(R)-苯乙醇與(S)-苯乙醇之比 率,在表2中報導為% ee。 實例13及15 :經較長固持時間的苯乙酮之不對稱還原 在室溫下將苯乙酮藉由注射泵(17 ml THF中之2 ml,亦 即17mmol)經2小時添加至1〇 mm〇1各別甲硼烷錯合物(例 如,11.4 ml 〇·88 Μ溶液)及5 mol%(相對於苯乙酮)(R)_
MeCBS於甲苯中之溶液。酮添加後攪掉3〇分鐘,接著添加 HC1(1 M,10 mi)以中止反應。用2〇 mi無水乙醚萃取苯乙 酵及任何未反應之苯乙酮。用飽和尺以及飽和NaHc〇3溶液 洗滌有機層,接著經仏28〇4乾燥。掌性GC分析展示苯乙 酮面積百分比(若有剩餘)及(11)_苯乙醇〖與(s)_苯乙醇之比率 (參看表2)。 實例14 :經較長固持時間之苯乙酮(快速添加)之不對稱 還原
在室溫下將苯乙酮藉由注射泵(17 ml THF中之2 ml,亦 即17mmol)經30分鐘添加至1〇 mm〇1甲硼烷錯合物(例如, 7·7 ml 1.3 Μ溶液)及5 mol%(相對於笨乙酮)(R)_MeCBSK 122094.doc -23 > 200806683 甲苯中之溶液中。銅添加後攪拌2小時,接著添加HCi(i M,10 ml)以中止反應。用20 ml無水乙醚萃取笨乙醇及任 何未反應之苯乙酮。用飽和KC1及飽和NaHC〇3溶液洗滌有 機層,隨後使其經NkSO4乾燥。掌性析展示苯乙酮 面積百分比(若有剩餘)及(R)-苯乙醇與(s)_苯乙醇之比率 (參看表2)。 貫例1 6 ·•用2-甲基四氫呋喃之曱硼烷錯合物還原苯甲酸 在〇°C下將4〇 ml 2-甲基四氫呋喃中之12 21 g(0」则〗)苯 甲酸經1小時經由注射器添加至BH3_2_MeTHF((M25 之125 ml 1 Μ溶液令。在添加完成且氫析出停止後,將混 合物溫至室溫。在攪拌2小時後添加2 ml水,且用ι〇〇⑹
NhCO3飽和水溶液萃取混合物。對有機層之分析得到节醇 產率為97.1%且含水率為5.3%。 實例17(對比用四氫吱喃之甲删烧錯合物還原苯甲酸 在〇°C下將20 ml四氫呋喃中之12·21 g(〇l m〇i)苯甲酸經 1小時經由注射器添加至BHrTHF(〇 125 m〇i)2i25⑹工% /合液中纟添加凡成且氣析出停止後,冑混合物溫至室 溫。在授拌2小時後,添加2 -水,且用ι〇〇 -叫叫飽 和水令液萃取混合&。有機層之分析得到苄醇產率為 62·0%且含水率為11.0%。 土 乳ϋ天嗝< Τ,玩錯合物還原丙毆 在 〇C 下將 15 ml 2 - Ψ a rm ^ .,. ζ甲基四虱呋喃中之7·41 gW.i mol)丙 酸經1小時經由、、t鉍怒、工, 、 〆射口口 添加至 BH3-2-MeTHF(0.125 mol)之 125 ml 1 Μ溶液申。太$ L ' T 在添加元成且氫析出停止後,將混合 122094.doc -24- 200806683 物至至溫。在攪拌1小時後,添加2 ml水,且用100 ml Na2C〇3飽和水溶液萃取混合物。用1〇〇 — 2-甲基四氫呋喃 萃取水層。對組合有機層之分析得到正丙醇產率為96·50/〇 且含水率為5.0%。 貫例19(對比):用四氫呋喃之甲硼烷錯合物還原丙酸 在〇C下將15 ml四氫呋喃中之7·4ΐ §(〇·ι mol)丙酸經1小 時、、、工由注射杰添加至BH3-THF(0.125 mol)之125 ml 1 Μ溶 液中。在添加完成且氫析出停止後,將混合物溫至室溫。 在攪拌1小時後,添加2 ml水,且用1〇〇 Na2C〇3飽和水 溶液萃取混合物。用1 〇〇 ml 甲基四氫呋喃萃取水層。對 組合有機層之分析得到正丙醇產率為73·6。/。且含水率為 20.4% 〇 實例20 :用2-曱基四氫呋喃之曱硼烷錯合物還原庚腈 在〇 C下將10 ml 2-甲基四氫呋喃中之〇 〇2 mol庚腈經1小 時經由注射器添加至BH3-2-MeTHF(0.025 mol)之25 ml 1 Μ 溶液中。在添加完成後,將混合物加熱至回流3小時。在 再次冷卻至(TC後,緩慢添加〇·8 ml甲醇,且在氫析出停止 後,添加20 ml 1 Μ氯化氫且使混合物再次回流。3〇分鐘 後,將混合物冷卻至室溫,且用4〇 mi NhCOs飽和水溶液 萃取。用40 ml乙醚萃取水層。對組合有機層之分析得到 庚胺產率為84.5%且含水率為5.9%。 貫例2 1 (對比):用四氫呋喃之曱硼烷錯合物還原庚腈 在〇°C下將10 ml四氫呋喃中之0·02 m〇1庚腈經H、時經由 注射器添加至BH3-THF(0.025 mol)之25 ml i M溶液中。在 122094.doc -25 - 200806683 完成添加後,將混合物加熱至回流3小時。在再次冷卻至〇 °C後,缓慢添加〇·8 ml曱醇,且在氫析出停止後,添加2〇 ml 1 Μ氣化氫且再次使混合物回流。3 〇分鐘後,將混合物 冷卻至室溫,且用40 ml Na/O3飽和水溶液萃取。用4〇 ml 乙醚萃取水層。對組合有機層之分析得到庚胺產率為 . 80·7%且含水率為30.0%。 貫例22 :用2 -甲基四氫°夫σ南之甲烧錯合物還原n,N-二甲 /、 基苯甲醯胺 在環境溫度下將BH3-2-MeTHF(0.098 mol)之98 ml 1 Μ溶 液經1分鐘添加至1 〇〇 ml 2 -甲基四氳。夫喃中之u .48 g(0.085 mol)N,N-二甲基苯曱醯胺中,且攪拌12小時。在冷卻至〇 C後,緩慢添加8 ml甲醇,且隨後用1〇〇 mi Na2C03飽和水 溶液萃取混合物。經硫酸鈉乾燥有機層。對有機層之分析 得到二甲基苄胺產率為96.3〇/〇。 貫例23(對比):用四氫呋喃之曱硼烷錯合物還原N,N-二甲 \ / 基苯甲醯胺 在玉衣纟兄溫度下將6113-丁1^(0.09 8 111〇1)之98 11111]\4溶液經 1分鐘添加至1〇〇 ml四氫呋喃中之1148 g(〇〇85則1)1^,1^ —甲基苯甲醯胺中,且攪拌12小時。在冷卻至〇 °c後,緩 又〇、加8 m 1甲醇’且隨後用1 〇〇 m 1 na2CΟ3飽和水溶液萃取 、混合物。經硫酸鈉乾燥有機層。對有機層之分析得到二甲 基节胺產率為95.1%。 【圖式簡單說明】 圖1 "兒明在環境溫度下添加有及未添加硼氫化鈉之曱硼 122094.doc -26- 200806683 據實例!製備)二…基四氫“ )的保存期或分解研究。 圓2說明在产 喃於厶甲美四:兄溫度下及〇至5下甲硼烷-2-甲基四氫呋 存期或分咬喃中之〇·88 m溶液(根據實例1製備)的保 圖3說明在環境⑺ H2 ψ M ,里又下及〇至5它下添加有硼氫化鈉之甲 兀:甲基四氫呋喃於2 (根據實例1制#、 、 Τ基四氫呋喃中之〇·88 Μ溶液 =備)的保存期或分解研究。 ΰ次明在〇至下添加 卜 烷-2-甲基四百及未添加硼虱化鈉之甲硼 土 氧ϋ夫喃於2-甲其 尸 據實例1製備)的保存期或;^^°南中之G.88 Μ溶液㈠艮 圖5將在環境溫度下添研:。 炫-2-甲基四氫咦喃於及未添加删氫化納之甲硼 烧-四氫。夫喃於四氫吱喃中:四氫吱喃中之1 Μ溶液與甲领 作比較。 丨Μ溶液的保存期或分解研究 圖6說明在環境温度下甲蝴 二甲基四氫咳喃中的分解情况:,-甲基四氫咬喃於2,5- 122094.doc
Claims (1)
- 200806683 十、申請專利範圍: 1· 一種式1之曱硼烧醚錯合物:• bh3 其中: 示氫、CVC4烧基、c3-c6環烧基或 其中r5為Κ4烷基或c3-c6環烷R1至R4彼此獨立地表 式CH2〇R5之取代基 基, 或兩個相鄰取代基R^R4 一起為選自由_CH2CH2_、 CH(CH3)CH2- ^ -CH2CH2CH2- > -CH(CH3)CH(CH3)- ' (CH2CH3)CH2_、_C(CH3)2C(CH3)2_、_ch2c(ch3)2ch2- 及-(CH2)6_組成之群之二價基圓,以與四氫呋喃環之 -CH-CH-部分形成環狀結構, 其限制條件為該等取代基至R4之至少一者不為氫。 2. 如請求項}之甲硼烷醚錯合物,其中尺丨為甲基且R2至R4 每一者均為氫。 3. —種溶液,其包含至少一種如請求項丨之甲硼烷醚錯合 物及至少一種溶劑。 Y員3之,容液,其中該溶劑包含,該醚係用於使 甲硼烷醚錯合物中之甲硼烷與化學結構1錯合。 月长員3或4之溶液,其中該甲硼烷_錯合物之濃度在 〇·01 m〇1/1 至 3 mol/ι之範圍内。 122094.doc 200806683 6·:種將如請求項i之甲硼㈣錯合物用於有機反應之方 7·=項,使用曱W錯合物之方法,其中該有機 應為一遇原反應或硼氫化反應。 8. 一種使用如請求項丨之罕硼烷醚錯合 丨、/ 丁止 乃法,其包合 9. 乂驟:在-反應容器中使甲硼㈣錯合物與基 且防止逸出之氣態二㈣自該反應容器散逸。土' ::將如請求項丨之甲爾錯合物用於; 月女或肪之不對稱還原的方法,其 劑。 乃外使用掌性催化 10·-種將如請求W之甲硼_合物用於前掌性鲷、亞 胺或將之不對稱還原的方法’其包含另 硼啶催化劑。 手丨王心王 11·如請求項9或1〇之使用甲硼烷醚錯合 J <万法,甘包含 添加至少一種鹼金屬硼氫化物作為穩定劑。 〃 12·如請求項丨丨之使用甲硼烷醚 删氮化鐘作為穩定劑。。物之方法,其包含添加 13.如請求項U之使用曱硼烷醚錯人 蝴氮化納作為穩定劑。。物之方法’其包含添加 122094.doc
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