CN1675151A - 乙炔醇类的制备 - Google Patents
乙炔醇类的制备 Download PDFInfo
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- CN1675151A CN1675151A CNA038188317A CN03818831A CN1675151A CN 1675151 A CN1675151 A CN 1675151A CN A038188317 A CNA038188317 A CN A038188317A CN 03818831 A CN03818831 A CN 03818831A CN 1675151 A CN1675151 A CN 1675151A
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- ketone
- acetylene
- lithium
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- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 41
- -1 acetylene alcohols Chemical class 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 22
- 150000002576 ketones Chemical class 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims abstract description 4
- PSQYTAPXSHCGMF-BQYQJAHWSA-N β-ionone Chemical compound CC(=O)\C=C\C1=C(C)CCCC1(C)C PSQYTAPXSHCGMF-BQYQJAHWSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 18
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 claims description 12
- SFEOKXHPFMOVRM-UHFFFAOYSA-N (+)-(S)-gamma-ionone Natural products CC(=O)C=CC1C(=C)CCCC1(C)C SFEOKXHPFMOVRM-UHFFFAOYSA-N 0.000 claims description 11
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- DPLGXGDPPMLJHN-UHFFFAOYSA-N 6-Methylheptan-2-one Chemical compound CC(C)CCCC(C)=O DPLGXGDPPMLJHN-UHFFFAOYSA-N 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- HNZUNIKWNYHEJJ-UHFFFAOYSA-N geranyl acetone Natural products CC(C)=CCCC(C)=CCCC(C)=O HNZUNIKWNYHEJJ-UHFFFAOYSA-N 0.000 claims description 2
- ZPGYUDWZVQOWNY-UHFFFAOYSA-N hept-4-en-3-one Chemical compound CCC=CC(=O)CC ZPGYUDWZVQOWNY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 2
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 claims description 2
- JXJIQCXXJGRKRJ-KOOBJXAQSA-N pseudoionone Chemical compound CC(C)=CCC\C(C)=C\C=C\C(C)=O JXJIQCXXJGRKRJ-KOOBJXAQSA-N 0.000 claims description 2
- LTUMRKDLVGQMJU-UHFFFAOYSA-N famesylacetone Natural products CC(C)=CCCC(C)=CCCC(C)=CCCC(C)=O LTUMRKDLVGQMJU-UHFFFAOYSA-N 0.000 claims 1
- LTUMRKDLVGQMJU-IUBLYSDUSA-N farnesyl acetone Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\CCC(C)=O LTUMRKDLVGQMJU-IUBLYSDUSA-N 0.000 claims 1
- 150000005840 aryl radicals Chemical class 0.000 abstract 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- VGTCWWMCIQYNFC-UHFFFAOYSA-N acetylene;lithium Chemical compound [Li].C#C VGTCWWMCIQYNFC-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229930002839 ionone Natural products 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 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 3
- QDJUXILKYCINHD-UHFFFAOYSA-N N.C#C.[Li] Chemical compound N.C#C.[Li] QDJUXILKYCINHD-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- CDKCEZNPAYWORX-UHFFFAOYSA-N 1-tert-butyl-4-(4-tert-butylphenyl)benzene Chemical group C1=CC(C(C)(C)C)=CC=C1C1=CC=C(C(C)(C)C)C=C1 CDKCEZNPAYWORX-UHFFFAOYSA-N 0.000 description 1
- 125000006022 2-methyl-2-propenyl group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- JQZGUQIEPRIDMR-UHFFFAOYSA-N 3-methylbut-1-yn-1-ol Chemical compound CC(C)C#CO JQZGUQIEPRIDMR-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- JEBFVOLFMLUKLF-IFPLVEIFSA-N Astaxanthin Natural products CC(=C/C=C/C(=C/C=C/C1=C(C)C(=O)C(O)CC1(C)C)/C)C=CC=C(/C)C=CC=C(/C)C=CC2=C(C)C(=O)C(O)CC2(C)C JEBFVOLFMLUKLF-IFPLVEIFSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UIGKLMXJAQWUMT-UHFFFAOYSA-N C(C)C#C.C[SiH](C)C Chemical group C(C)C#C.C[SiH](C)C UIGKLMXJAQWUMT-UHFFFAOYSA-N 0.000 description 1
- OUGOCEHAIOQHPO-UHFFFAOYSA-N CC(C=C)C#CO Chemical compound CC(C=C)C#CO OUGOCEHAIOQHPO-UHFFFAOYSA-N 0.000 description 1
- 239000005997 Calcium carbide Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- QQAGXJMLHRUMJF-UHFFFAOYSA-N acetylene trimethylsilane Chemical group C#C.C[SiH](C)C QQAGXJMLHRUMJF-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- MQZIGYBFDRPAKN-ZWAPEEGVSA-N astaxanthin Chemical compound C([C@H](O)C(=O)C=1C)C(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)C(=O)[C@@H](O)CC1(C)C MQZIGYBFDRPAKN-ZWAPEEGVSA-N 0.000 description 1
- 235000013793 astaxanthin Nutrition 0.000 description 1
- 229940022405 astaxanthin Drugs 0.000 description 1
- 239000001168 astaxanthin Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- NRDQFWXVTPZZAZ-UHFFFAOYSA-N butyl carbonochloridate Chemical compound CCCCOC(Cl)=O NRDQFWXVTPZZAZ-UHFFFAOYSA-N 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Chemical group 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 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 1
- 230000000694 effects Effects 0.000 description 1
- 239000011737 fluorine Chemical group 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006038 hexenyl group Chemical group 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
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 1
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001400 nonyl 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])C([H])([H])[H] 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 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
- 238000005580 one pot reaction Methods 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 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
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
Classifications
-
- 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
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
- C07C403/08—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及制备通式(I)的乙炔醇类的方法:其中R1和R2可以相同或不同,并且各自独立地是氢、饱和或单-或多-不饱和C1-C30烷基、芳基、环烷基烷基或环烷基基团,其中每一者都可以被取代,或者是通式(II)的基团:其中R3和R4可以相同或不同,并且各自独立地是氢、或饱和的或单-或多-不饱和C1-C30烷基、芳基、环烷基烷基或环烷基基团,其中每一者都可以被取代,虚线可表示另外的双键;所述方法包括通过以下步骤使通式为R1-CO-R2的酮单乙炔基化:(a)使锂与C1-C10卤代烷烃反应,(b)通入乙炔气体,(c)加入酮。
Description
本发明涉及借助卤代烷烃和锂的反应使酮单乙炔基化制备乙炔醇类的方法。
本领域的现有技术是:在液体氨中与催化剂量的碱的存在下连续操作的酮与乙炔的乙炔基化(碱通常为KOH或在极性质子溶剂中的甲醇钾;10-40℃,20巴),例如在DE1232573中所描述的那样。
在另一个α,β-不饱和酮的1,2-乙炔基化的方法中,乙炔一锂络合物在惰性的有机溶剂中与适当的羰基化合物反应(CH642936)。通过在-30到-20℃下蒸发出乙炔锂-氨溶液中的氨并用一种有机溶剂代替它制备活性乙炔锂-氨络合物。另一种详细说明的方法是氨基化锂与乙炔在惰性有机溶剂中的反应。
US2,472,310描述了在碱性条件下对快速醛醇化酮(例如β-紫罗酮)进行乙炔基化的方法。为此所需的乙炔锂-氨络合物是在-40℃下通过将乙炔通入液态氨中并同时加入锂制备的(O.A.Shavrygina,D.V.Nazarova,S.M.Makin,Zh.Org.Khim.1966,2,1566-1568)。
上述方法的缺点是乙炔锂生成的选择性低,因为乙炔锂可以作为乙炔一锂与乙炔二锂存在,或者以两种成分的混合物存在。另一个缺点在于乙炔锂生成之后的溶剂交换和维持氨处于液态所要求的低温。
US2,425,201公开了使用乙炔钙制备α,B-不饱和酮的方法。乙炔基化是在-70到-40℃的温度下进行的。
DE1081883描述了通过乙炔钠与β-紫罗酮在有机溶剂中的反应制备乙炔基紫罗酮的方法。为了增加乙炔在反应混合物中的浓度,在带有压力的情况下使用乙炔。与常压下的方法相比较,乙炔基紫罗酮的产率得到了改进。
DE1768877描述了另一种通过乙醇钠与乙炔及适量的酮在压力下在有机溶剂中反应制备乙炔醇类的方法,其中压力大约是14巴。然而,从安全的观点来看,在压力下工作被认为是当使用乙炔时该方法的明显的缺点,并且相关的成本增加了。
在液体氨中使用钠代替锂也是可以的,尽管在乙炔钠生成之后,为了慢慢地蒸发出氨,必须类似地将酮加入到另外的溶剂中(P.Karrer,J.Benz,Helv.Chem.Acta 1948,31,390-295)。
在另一方法中,乙炔锂的合成是基于锂与萘和乙炔的反应的,首先通过电子转移生成萘阴离子(其随后起到碱的作用),并与乙炔生成乙炔锂。与β-紫罗酮的反应随后得到所要求的乙炔基紫罗酮,其产率为90%(K.Suga,S.Watanabe,T.Suzuki,Can.J.Chem.1968,46,3041-3045)。基于β-紫罗酮的半化学计量的萘的使用是不利的。
合成烷基锂化合物的催化方法也是已知的。在用作催化剂的4,4’-二叔丁基苯的存在下,锂通过简单电子转移生成自由基阴离子,然后通过与卤代烷烃的反应生成相应的烷基锂(P.K.Freeman,L.L.Hutchinson,Tetrahedron Letters,1976,22,1849-1852;P.k Freeman,L.L.Hutchinson,J.Org.Chem.,1983,48,4705-4713)。在某种情况下,萘也可以被用作催化剂。优选使用不同亲电试剂的烷基化的反应中得到的烷基锂(M.Yus,D.Ramon,J.Chem.Soc.,Chem.Comm.1991,398-400;T.R.van den Ancker,M.J.Hdgson,J.Chem.Soc.,Perkin Trans.1,1999,2869-2870)。
本发明的目的是:开发一种没有所描述的现有技术中的缺点的制备乙炔醇类的经济方法。
我们已经令人惊讶地发现,可以根据本发明通过制备通式(I)的乙炔醇类的单容器方法(one-pot process)达到上述目的:
其中R1和R2可以相同或不同,并且各自独立地是氢、饱和或单-或多-不饱和C1-C30烷基、芳基、环烷基烷基或环烷基基团,其中每一者都可以被取代,或者是通式(II)的基团:
其中R3和R4可以相同或不同,并且各自独立地是氢、或饱和的或单-或多-不饱和C1-C30烷基、芳基、环烷基烷基或环烷基基团,其中每一者都可以被取代,虚线可表示另外的双键;
所述方法包括通过以下步骤使通式为R1-CO-R2的酮单乙炔基化:
(a)使锂与C1-C10卤代烷烃反应,
(b)通入乙炔气体,
(c)加入酮。
优选在催化剂量的萘或4,4’-二叔丁基联苯的存在下,使用卤代烷烃与锂反应。为此使用的溶剂可以是四氢呋喃。
C1-C4-烷基基团是甲基、乙基、丙基、异丙基、丁基或叔丁基。
单-或多-不饱和直链或支化C1-C30-烷基基团,除特别说明外,例如是甲基、乙基、丙基、异丙基、正丁基、异丁基、叔丁基、戊基、己基、庚基、辛基、壬基、癸基、1-丙烯基、2-丙烯基、2-甲基-2-丙烯基、1-戊烯基、1-甲基-2-戊烯基、异丙烯基、1-丁烯基、己烯基、庚烯基、辛烯基、壬烯基、癸烯基基团,或者是下文列出的化合物的相应的基团。
环烷基可以是3-7员饱和的或是单-或多-不饱和的3-7员环,其CH2基团可以被O或NH替换,例如特别是环丙基、环丁基、环戊基、环己基或环庚基环,优选环戊烯或环己烯环。
芳基基团优选苯甲基、苯基、或萘基基团。
除了C1-C4-烷基外,其他取代基可以是甲基、乙基、丙基、异丙基、丁基、叔丁基、氟、氯、溴、碘、硝基或氨基基团。
例如,下列的酮可以用于乙炔基化:
丙酮、甲基乙烯基酮、β-紫罗酮、四氢香叶基丙酮、6-甲基庚酮、六氢金合欢基丙酮、二乙基酮、甲基乙基酮、环己酮、甲基叔丁基酮、假紫罗酮、甲基己烯酮、H-香叶基丙酮,优选丙酮、甲基乙烯基酮或β-紫罗酮。
在按照本发明的方法的第一步中,通过在催化剂量(12.5mol%)的4,4’-二叔丁基联苯存在下,在-20到-10℃、优选-15℃的温度下,通过锂与卤代烷烃(例如1-氯丁烷)反应,原位产生了烷基锂。随后将多余的锂从反应混合物中通过过滤除去,通入乙炔气体以制备乙炔锂。
单容器反应的最后一步是在0到10℃、优选0℃下加入酮。令人惊讶的是,没有发生生成乙炔二锂和乙炔的乙炔锂的歧化。
在本法中使用的溶剂可以是四氢呋喃。
在按照本发明的反应中,仅观察到了乙炔一锂的生成。而在商业烷基锂例如丁基锂与乙炔在-25℃以上的反应中,观察到生成乙炔和不溶解的乙炔二锂的歧化。在0℃下在四氢呋喃中的乙炔二锂与乙炔一锂达到平衡,亲电试剂的加入使平衡移动,生成相应的乙炔基化物。
按照本发明的方法允许从例如酮类丙酮、β-紫罗酮或甲基乙烯基酮出发,以好至很好的产率毫无问题地制备乙炔醇。β-紫罗酮和甲基乙烯基酮的乙炔基化作用产物是合成维生素A和虾青素的前体。
除了根据本发明的酮的反应之外,也可以使三甲基硅烷氯化物反应生成三甲基硅烷基乙炔。三甲基硅烷乙炔用于合成烯二炔(enediyne,一种抗肿瘤药物活性成分)。
以下实施例旨在举例说明本发明而不是对其进行限制。
实施例
在氩气氛下在两个250ml HWS容器中进行反应。首先,将2.4克(0.34mol)锂丝剪成小段,并与5.4克(20mmol)催化剂一起悬浮在在-15℃的200ml四氢呋喃中。一旦反应混合物变成深蓝色,在2小时之内通过滴液漏斗滴加20ml四氢呋喃中的14.8克(0.16mol)1-氯丁烷,然后继续搅拌两小时。通过将上层溶液转移到第二个250ml HWS容器中分离出锂,在-15℃下以4升/小时的流速向第二个250ml HWS容器中通入乙炔1.5小时。乙炔锂生成之后,通过滴液漏斗在0℃下在2小时滴加20ml四氢呋喃中的0.18摩尔对应的酮。加热到室温后,通过加入水使其水解,观察到相分离。
实施例 | 催化剂 | 酮 | 产物 | 转化率[%] | 选择性[%] | 产率[%] | 注释 |
1 | Biph | 丙酮 | MBY | 100 | 81.0 | 81.0 | - |
2 | Biph | MVK | VBY | 98.1 | 59.1 | 57.9 | 由于聚合,在-10℃下滴加MVK |
3 | Biph | β-紫罗酮 | 乙炔基紫罗酮 | 99.4 | 78.9 | 78.4 | β-紫罗酮加入后搅拌16小时 |
4 | Biph | TMS-Cl | TMS-乙炔 | 99.2 | 92.1 | 91.4 | - |
5 | Naph | 丙酮 | MBY | 98.9 | 57.1 | 56.5 | NP:naph烷基化 |
6 | Biph | 1,2-环氧丁烷 | - | - | - | - | 无产物 |
7 | Biph | 氯甲酸丁酯 | - | - | - | - | 无产物 |
8 | Biph | 氯甲酸甲酯 | - | - | - | - | 无产物 |
MBY:甲基丁炔醇
MVK:甲基乙烯基酮
VBK:乙烯基丁炔醇
Biph:4,4’-二叔丁基联苯
Naph:萘
Claims (3)
2、按照权利要求1的方法,其中,锂与C1-C10-卤代烷烃的反应是在起催化剂量的萘或4,4-二叔丁基联苯存在下进行的。
3、按照权利要求1或2的方法,其中所使用的酮选自丙酮、甲基乙烯基酮、β-紫罗酮、四氢香叶基丙酮、6-甲基庚酮、氢金合欢基丙酮、二乙基酮、甲乙酮、环己酮、甲基叔丁基酮、假紫罗酮、甲基己烯酮、H-香叶基丙酮。
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CN101212680B (zh) * | 2006-12-30 | 2011-03-23 | 扬智科技股份有限公司 | 图像数据的存储器存取方法及系统 |
CN105985219A (zh) * | 2015-12-31 | 2016-10-05 | 厦门金达威维生素有限公司 | 一种维生素a中间体未转位六碳醇的合成方法 |
CN113880691A (zh) * | 2021-09-27 | 2022-01-04 | 四川众邦制药有限公司 | 一种合成三甲基十二炔醇的方法 |
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CN1295201C (zh) * | 2004-12-24 | 2007-01-17 | 中国林业科学研究院林产化学工业研究所 | 由含羰基的酮或醛类化合物制备α,β-不饱和醇的方法 |
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FR2772023B1 (fr) * | 1997-12-08 | 2000-02-11 | Univ Rennes | Procede de preparation de composes acetyleniques vrais par reaction du monoacetylure de lithium avec un reactif electrophile |
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CN101212680B (zh) * | 2006-12-30 | 2011-03-23 | 扬智科技股份有限公司 | 图像数据的存储器存取方法及系统 |
CN105985219A (zh) * | 2015-12-31 | 2016-10-05 | 厦门金达威维生素有限公司 | 一种维生素a中间体未转位六碳醇的合成方法 |
CN105985219B (zh) * | 2015-12-31 | 2018-12-21 | 厦门金达威维生素有限公司 | 一种维生素a中间体未转位六碳醇的合成方法 |
CN113880691A (zh) * | 2021-09-27 | 2022-01-04 | 四川众邦制药有限公司 | 一种合成三甲基十二炔醇的方法 |
CN113880691B (zh) * | 2021-09-27 | 2023-09-01 | 四川众邦新材料股份有限公司 | 一种合成三甲基十二炔醇的方法 |
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