WO2000075095A1 - Verfahren zur herstellung von 2,2,4,4-tetrasubstituierten 1,3,5-cyclohexantrionen - Google Patents
Verfahren zur herstellung von 2,2,4,4-tetrasubstituierten 1,3,5-cyclohexantrionen Download PDFInfo
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- WO2000075095A1 WO2000075095A1 PCT/EP2000/004567 EP0004567W WO0075095A1 WO 2000075095 A1 WO2000075095 A1 WO 2000075095A1 EP 0004567 W EP0004567 W EP 0004567W WO 0075095 A1 WO0075095 A1 WO 0075095A1
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- Prior art keywords
- formula
- alkyl
- alkoxy
- radicals
- methyl
- Prior art date
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- -1 2,2,4,4-tetra-substituted 1,3,5-cyclohexanetriones Chemical class 0.000 title claims abstract description 474
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 11
- PZQGSZRQKQZCOJ-UHFFFAOYSA-N cyclobutane-1,3-dione Chemical class O=C1CC(=O)C1 PZQGSZRQKQZCOJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012038 nucleophile Substances 0.000 claims abstract description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 82
- 238000000034 method Methods 0.000 claims description 35
- 239000002585 base Substances 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 26
- 125000005842 heteroatom Chemical group 0.000 claims description 25
- 150000001412 amines Chemical class 0.000 claims description 24
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 21
- 150000002170 ethers Chemical class 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 229910052736 halogen Inorganic materials 0.000 claims description 18
- 150000002367 halogens Chemical class 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 17
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 14
- 125000004104 aryloxy group Chemical group 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000000623 heterocyclic group Chemical group 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 150000004820 halides Chemical class 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 7
- 239000011877 solvent mixture Substances 0.000 claims description 7
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 150000007529 inorganic bases Chemical class 0.000 claims description 6
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 5
- 239000002841 Lewis acid Substances 0.000 claims description 5
- 230000021736 acetylation Effects 0.000 claims description 5
- 238000006640 acetylation reaction Methods 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 150000007517 lewis acids Chemical class 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 claims description 3
- 125000003282 alkyl amino group Chemical group 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 150000007530 organic bases Chemical class 0.000 claims description 3
- 241000251730 Chondrichthyes Species 0.000 claims description 2
- SUEVWEWAIVZWCQ-UHFFFAOYSA-N cyclohexane-1,2,3-trione Chemical class O=C1CCCC(=O)C1=O SUEVWEWAIVZWCQ-UHFFFAOYSA-N 0.000 claims description 2
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 claims 1
- 238000006884 silylation reaction Methods 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 150000003254 radicals Chemical class 0.000 description 56
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 40
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 20
- 239000000203 mixture Substances 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 17
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 13
- 229960003975 potassium Drugs 0.000 description 13
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 12
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000003085 diluting agent Substances 0.000 description 12
- 229910052700 potassium Inorganic materials 0.000 description 12
- 239000011591 potassium Substances 0.000 description 12
- 229960005235 piperonyl butoxide Drugs 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 9
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 9
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 description 7
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- DOZWCONHUMHEPS-UHFFFAOYSA-N 2,2,4,4-tetramethylcyclohexane-1,3,5-trione Chemical compound CC1(C)C(=O)CC(=O)C(C)(C)C1=O DOZWCONHUMHEPS-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 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 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 6
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 5
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 4
- 239000012346 acetyl chloride Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 125000001188 haloalkyl group Chemical group 0.000 description 4
- 239000003701 inert diluent Substances 0.000 description 4
- 239000012442 inert solvent Substances 0.000 description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 4
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 4
- 239000002370 magnesium bicarbonate Substances 0.000 description 4
- 235000014824 magnesium bicarbonate Nutrition 0.000 description 4
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 4
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 description 4
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 4
- 238000003672 processing method Methods 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 125000005270 trialkylamine group Chemical group 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 3
- LTVRSJBNXLZFGT-UHFFFAOYSA-N 2-silylethenone Chemical compound [SiH3]C=C=O LTVRSJBNXLZFGT-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 3
- 239000000010 aprotic solvent Substances 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 235000010216 calcium carbonate Nutrition 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- JHLCADGWXYCDQA-UHFFFAOYSA-N calcium;ethanolate Chemical compound [Ca+2].CC[O-].CC[O-] JHLCADGWXYCDQA-UHFFFAOYSA-N 0.000 description 3
- OEPJXTZQPRTGCX-UHFFFAOYSA-N calcium;propan-1-olate Chemical compound [Ca+2].CCC[O-].CCC[O-] OEPJXTZQPRTGCX-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- WNJYXPXGUGOGBO-UHFFFAOYSA-N magnesium;propan-1-olate Chemical compound CCCO[Mg]OCCC WNJYXPXGUGOGBO-UHFFFAOYSA-N 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- OFUQHACUUVLBCT-UHFFFAOYSA-N methyl 2,2,4,4-tetramethyl-3,5-dioxohexanoate Chemical compound COC(=O)C(C)(C)C(=O)C(C)(C)C(C)=O OFUQHACUUVLBCT-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 description 3
- 239000011736 potassium bicarbonate Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 3
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 3
- SPTUSESLANQNTN-UHFFFAOYSA-N potassium;2-ethylhexan-1-olate Chemical compound [K+].CCCCC(CC)C[O-] SPTUSESLANQNTN-UHFFFAOYSA-N 0.000 description 3
- AWDMDDKZURRKFG-UHFFFAOYSA-N potassium;propan-1-olate Chemical compound [K+].CCC[O-] AWDMDDKZURRKFG-UHFFFAOYSA-N 0.000 description 3
- WQKGAJDYBZOFSR-UHFFFAOYSA-N potassium;propan-2-olate Chemical compound [K+].CC(C)[O-] WQKGAJDYBZOFSR-UHFFFAOYSA-N 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 3
- RCOSUMRTSQULBK-UHFFFAOYSA-N sodium;propan-1-olate Chemical compound [Na+].CCC[O-] RCOSUMRTSQULBK-UHFFFAOYSA-N 0.000 description 3
- WBQTXTBONIWRGK-UHFFFAOYSA-N sodium;propan-2-olate Chemical compound [Na+].CC(C)[O-] WBQTXTBONIWRGK-UHFFFAOYSA-N 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 125000004767 (C1-C4) haloalkoxy group Chemical group 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 2
- XLEYFDVVXLMULC-UHFFFAOYSA-N 2',4',6'-trihydroxyacetophenone Chemical compound CC(=O)C1=C(O)C=C(O)C=C1O XLEYFDVVXLMULC-UHFFFAOYSA-N 0.000 description 2
- RGCDVHNITQEYPO-UHFFFAOYSA-N 2,2,4,4-tetramethylcyclobutane-1,3-dione Chemical compound CC1(C)C(=O)C(C)(C)C1=O RGCDVHNITQEYPO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 2
- MXLMTQWGSQIYOW-UHFFFAOYSA-N 3-methyl-2-butanol Chemical compound CC(C)C(C)O MXLMTQWGSQIYOW-UHFFFAOYSA-N 0.000 description 2
- RNJOKCPFLQMDEC-UHFFFAOYSA-N 4(R),8-dimethyl-trans-2-nonenoyl-CoA Chemical compound COC(=O)CC(=O)CC(=O)OC RNJOKCPFLQMDEC-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 241001024304 Mino Species 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
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- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
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- 239000000292 calcium oxide Substances 0.000 description 2
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- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229940087373 calcium oxide Drugs 0.000 description 2
- MUJRNJDKBBSXSE-UHFFFAOYSA-N calcium;butan-1-olate Chemical compound [Ca+2].CCCC[O-].CCCC[O-] MUJRNJDKBBSXSE-UHFFFAOYSA-N 0.000 description 2
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- KQIADDMXRMTWHZ-UHFFFAOYSA-N chloro-tri(propan-2-yl)silane Chemical compound CC(C)[Si](Cl)(C(C)C)C(C)C KQIADDMXRMTWHZ-UHFFFAOYSA-N 0.000 description 2
- 125000004773 chlorofluoromethyl group Chemical group [H]C(F)(Cl)* 0.000 description 2
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- MIUOPKMSOKIHRL-UHFFFAOYSA-N ethyl 3,5,5-trimethyl-4-oxohexanoate Chemical compound CCOC(=O)CC(C)C(=O)C(C)(C)C MIUOPKMSOKIHRL-UHFFFAOYSA-N 0.000 description 2
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- 150000004678 hydrides Chemical class 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- QIYRVRBMVSPRJN-UHFFFAOYSA-N methyl 3,5,5-trimethyl-4-trimethylsilyloxyhex-3-enoate Chemical compound COC(=O)CC(C)=C(C(C)(C)C)O[Si](C)(C)C QIYRVRBMVSPRJN-UHFFFAOYSA-N 0.000 description 2
- JUKCTOHWTHYRPF-UHFFFAOYSA-N methyl 3,5-dioxohexanoate Chemical compound COC(=O)CC(=O)CC(C)=O JUKCTOHWTHYRPF-UHFFFAOYSA-N 0.000 description 2
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 2
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- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 2
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- MNKYQPOFRKPUAE-UHFFFAOYSA-N chloro(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 MNKYQPOFRKPUAE-UHFFFAOYSA-N 0.000 description 1
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- OJZNZOXALZKPEA-UHFFFAOYSA-N chloro-methyl-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](Cl)(C)C1=CC=CC=C1 OJZNZOXALZKPEA-UHFFFAOYSA-N 0.000 description 1
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- RVOJTCZRIKWHDX-UHFFFAOYSA-N cyclohexanecarbonyl chloride Chemical compound ClC(=O)C1CCCCC1 RVOJTCZRIKWHDX-UHFFFAOYSA-N 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
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 1
- 125000004785 fluoromethoxy group Chemical group [H]C([H])(F)O* 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 125000006343 heptafluoro propyl group Chemical group 0.000 description 1
- WGBBUURBHXLGFM-UHFFFAOYSA-N hexan-2-amine Chemical compound CCCCC(C)N WGBBUURBHXLGFM-UHFFFAOYSA-N 0.000 description 1
- HQLZFBUAULNEGP-UHFFFAOYSA-N hexan-3-amine Chemical compound CCCC(N)CC HQLZFBUAULNEGP-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
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000003037 imidazol-2-yl group Chemical group [H]N1C([*])=NC([H])=C1[H] 0.000 description 1
- 125000002140 imidazol-4-yl group Chemical group [H]N1C([H])=NC([*])=C1[H] 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- BMFVGAAISNGQNM-UHFFFAOYSA-N isopentylamine Chemical compound CC(C)CCN BMFVGAAISNGQNM-UHFFFAOYSA-N 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 125000001793 isothiazol-3-yl group Chemical group [H]C1=C([H])C(*)=NS1 0.000 description 1
- 125000004500 isothiazol-4-yl group Chemical group S1N=CC(=C1)* 0.000 description 1
- 125000004501 isothiazol-5-yl group Chemical group S1N=CC=C1* 0.000 description 1
- 125000004284 isoxazol-3-yl group Chemical group [H]C1=C([H])C(*)=NO1 0.000 description 1
- 125000004498 isoxazol-4-yl group Chemical group O1N=CC(=C1)* 0.000 description 1
- 125000004499 isoxazol-5-yl group Chemical group O1N=CC=C1* 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 229960000816 magnesium hydroxide Drugs 0.000 description 1
- HFTSQAKJLBPKBD-UHFFFAOYSA-N magnesium;butan-1-olate Chemical compound [Mg+2].CCCC[O-].CCCC[O-] HFTSQAKJLBPKBD-UHFFFAOYSA-N 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- WBOXSSGBVJMSSC-UHFFFAOYSA-N methyl 3,3,5,5-tetramethyl-4,6-dioxoheptanoate Chemical compound COC(=O)CC(C)(C)C(=O)C(C)(C)C(C)=O WBOXSSGBVJMSSC-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- QKYWADPCTHTJHQ-UHFFFAOYSA-N n,2-dimethylpropan-1-amine Chemical compound CNCC(C)C QKYWADPCTHTJHQ-UHFFFAOYSA-N 0.000 description 1
- ZQGJEUVBUVKZKS-UHFFFAOYSA-N n,2-dimethylpropan-2-amine Chemical compound CNC(C)(C)C ZQGJEUVBUVKZKS-UHFFFAOYSA-N 0.000 description 1
- QSOCODZVGPDGDA-UHFFFAOYSA-N n,3-dimethylbutan-1-amine Chemical compound CNCCC(C)C QSOCODZVGPDGDA-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- WCDOAVZNGVXEIL-UHFFFAOYSA-N n-ethyl-2-methylbutan-1-amine Chemical compound CCNCC(C)CC WCDOAVZNGVXEIL-UHFFFAOYSA-N 0.000 description 1
- FNLUJDLKYOWMMF-UHFFFAOYSA-N n-ethyl-2-methylpropan-1-amine Chemical compound CCNCC(C)C FNLUJDLKYOWMMF-UHFFFAOYSA-N 0.000 description 1
- XQOIBQBPAXOVGP-UHFFFAOYSA-N n-ethyl-2-methylpropan-2-amine Chemical compound CCNC(C)(C)C XQOIBQBPAXOVGP-UHFFFAOYSA-N 0.000 description 1
- TZTQUOTYYSUZNA-UHFFFAOYSA-N n-ethyl-3-methylbutan-1-amine Chemical compound CCNCCC(C)C TZTQUOTYYSUZNA-UHFFFAOYSA-N 0.000 description 1
- QHCCDDQKNUYGNC-UHFFFAOYSA-N n-ethylbutan-1-amine Chemical compound CCCCNCC QHCCDDQKNUYGNC-UHFFFAOYSA-N 0.000 description 1
- KFYKZKISJBGVMR-UHFFFAOYSA-N n-ethylbutan-2-amine Chemical compound CCNC(C)CC KFYKZKISJBGVMR-UHFFFAOYSA-N 0.000 description 1
- WSTNFGAKGUERTC-UHFFFAOYSA-N n-ethylhexan-1-amine Chemical compound CCCCCCNCC WSTNFGAKGUERTC-UHFFFAOYSA-N 0.000 description 1
- IMBQZPYQVQWPTP-UHFFFAOYSA-N n-ethylhexan-2-amine Chemical compound CCCCC(C)NCC IMBQZPYQVQWPTP-UHFFFAOYSA-N 0.000 description 1
- PKRKZKPXBIAUPP-UHFFFAOYSA-N n-ethylhexan-3-amine Chemical compound CCCC(CC)NCC PKRKZKPXBIAUPP-UHFFFAOYSA-N 0.000 description 1
- ICVFPLUSMYSIFO-UHFFFAOYSA-N n-ethylpentan-1-amine Chemical compound CCCCCNCC ICVFPLUSMYSIFO-UHFFFAOYSA-N 0.000 description 1
- MVAOLFCQWQECDS-UHFFFAOYSA-N n-ethylpentan-2-amine Chemical compound CCCC(C)NCC MVAOLFCQWQECDS-UHFFFAOYSA-N 0.000 description 1
- BWDGPBXONNMLIO-UHFFFAOYSA-N n-ethylpentan-3-amine Chemical compound CCNC(CC)CC BWDGPBXONNMLIO-UHFFFAOYSA-N 0.000 description 1
- XCVNDBIXFPGMIW-UHFFFAOYSA-N n-ethylpropan-1-amine Chemical compound CCCNCC XCVNDBIXFPGMIW-UHFFFAOYSA-N 0.000 description 1
- RIVIDPPYRINTTH-UHFFFAOYSA-N n-ethylpropan-2-amine Chemical compound CCNC(C)C RIVIDPPYRINTTH-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- XJINZNWPEQMMBV-UHFFFAOYSA-N n-methylhexan-1-amine Chemical compound CCCCCCNC XJINZNWPEQMMBV-UHFFFAOYSA-N 0.000 description 1
- SUOSRAKKOYHQBX-UHFFFAOYSA-N n-methylhexan-2-amine Chemical compound CCCCC(C)NC SUOSRAKKOYHQBX-UHFFFAOYSA-N 0.000 description 1
- NXSVCIHVZNCFHM-UHFFFAOYSA-N n-methylhexan-3-amine Chemical compound CCCC(CC)NC NXSVCIHVZNCFHM-UHFFFAOYSA-N 0.000 description 1
- IPBXLJFBVNLKFE-UHFFFAOYSA-N n-methylpentan-2-amine Chemical compound CCCC(C)NC IPBXLJFBVNLKFE-UHFFFAOYSA-N 0.000 description 1
- IFFVNFLXNMUQEL-UHFFFAOYSA-N n-methylpentan-3-amine Chemical compound CCC(CC)NC IFFVNFLXNMUQEL-UHFFFAOYSA-N 0.000 description 1
- XHFGWHUWQXTGAT-UHFFFAOYSA-N n-methylpropan-2-amine Chemical compound CNC(C)C XHFGWHUWQXTGAT-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000005246 nonafluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 125000004287 oxazol-2-yl group Chemical group [H]C1=C([H])N=C(*)O1 0.000 description 1
- 125000004304 oxazol-5-yl group Chemical group O1C=NC=C1* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- IGEIPFLJVCPEKU-UHFFFAOYSA-N pentan-2-amine Chemical compound CCCC(C)N IGEIPFLJVCPEKU-UHFFFAOYSA-N 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000004574 piperidin-2-yl group Chemical group N1C(CCCC1)* 0.000 description 1
- 125000004483 piperidin-3-yl group Chemical group N1CC(CCC1)* 0.000 description 1
- 125000004482 piperidin-4-yl group Chemical group N1CCC(CC1)* 0.000 description 1
- CBMSDILKECEMOT-UHFFFAOYSA-N potassium;2-methylpropan-1-olate Chemical compound [K+].CC(C)C[O-] CBMSDILKECEMOT-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004307 pyrazin-2-yl group Chemical group [H]C1=C([H])N=C(*)C([H])=N1 0.000 description 1
- 125000004289 pyrazol-3-yl group Chemical group [H]N1N=C(*)C([H])=C1[H] 0.000 description 1
- 125000002206 pyridazin-3-yl group Chemical group [H]C1=C([H])C([H])=C(*)N=N1 0.000 description 1
- 125000004940 pyridazin-4-yl group Chemical group N1=NC=C(C=C1)* 0.000 description 1
- 125000000246 pyrimidin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=C1[H] 0.000 description 1
- 125000004527 pyrimidin-4-yl group Chemical group N1=CN=C(C=C1)* 0.000 description 1
- 125000004528 pyrimidin-5-yl group Chemical group N1=CN=CC(=C1)* 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229940083542 sodium Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000004192 tetrahydrofuran-2-yl group Chemical group [H]C1([H])OC([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004187 tetrahydropyran-2-yl group Chemical group [H]C1([H])OC([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000004297 tetrahydropyrrol-2-yl group Chemical group [H]N1C([H])([H])C([H])([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004299 tetrazol-5-yl group Chemical group [H]N1N=NC(*)=N1 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 125000000437 thiazol-2-yl group Chemical group [H]C1=C([H])N=C(*)S1 0.000 description 1
- 125000004495 thiazol-4-yl group Chemical group S1C=NC(=C1)* 0.000 description 1
- 125000004496 thiazol-5-yl group Chemical group S1C=NC=C1* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- JSQJUDVTRRCSRU-UHFFFAOYSA-N tributyl(chloro)silane Chemical compound CCCC[Si](Cl)(CCCC)CCCC JSQJUDVTRRCSRU-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/385—Saturated compounds containing a keto group being part of a ring
- C07C49/417—Saturated compounds containing a keto group being part of a ring polycyclic
- C07C49/423—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system
- C07C49/453—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system having three rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/716—Esters of keto-carboxylic acids or aldehydo-carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
Definitions
- the present invention relates to a process for the preparation of 2, 2, 4, 4-tetrasubstituted 1, 3, 5-cyclohexanetrions of the formula I.
- Both the first and the second synthetic route mentioned above provide 2, 2, 4, 4-tetramethyl-1, 3, 5-cyclohexanetrione in unsatisfactory yields.
- the toxic dirnethyl cadmium is used in the multi-stage 2nd reaction sequence.
- the third synthesis variant requires two equivalents of base to prepare the silyl ether. Furthermore, work must be carried out at low temperatures (-78 ° C.), so that this process is also problematic from a technical point of view.
- R ⁇ R 2 -C 6 alkyl or C 3 -C 6 cycloalkyl where these two radicals can be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: -C 4 alkoxy, -C 4 -Alkylthio or Di- (-C-C 4 alkyl) amino; -CC 6 alkoxy, C 2 -C 6 alkenyl or C 2 -C 6 alkynyl; Aryl, aryloxy or heterocyclyl, which has up to three hetero atoms from the group 0, S and N, the aryl, aryloxy and heterocyclyl radicals being unsubstituted or partially or completely halogenated and / or substituted by the following radicals can: C ⁇ -C -alkyl, C 4 haloalkyl, C ⁇ -C 4 alkoxy, C 1 -C 4 halo-alkoxy or C ⁇ -C alkoxycarbonyl;
- radicals R 1 and R 2 which are bonded to the same carbon together form a - (CH 2 ) 2 . 6 chain, which can be substituted by the following radicals:
- R 1 and R 2 have the meaning given above, with a 0- or N-nucleophile, optionally in the presence of a base, and a silylating reagent to give the silylenol ether of the formula III, in which
- R 3 Ci-Cg alkoxy, amino, C ⁇ -C 6 alkylamino or di- (Ci-C ⁇ -alkyl) amino;
- R 1 and R 2 have the meaning given above;
- R 1 to R 3 have the meaning given above;
- Ci-C ⁇ alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-propan-1-ol, 2-methyl-propane are used as O-nucleophiles -2-ol, 1-pentanol,
- Suitable N-nucleophiles are ammonia, C 1 -C 6 -alkylamines, such as methylamine, ethylamino, 1-propylamine, 2-propylamine, 1-butylamine, 2-butylamine, 2-methylprop-1-ylamine, 2-methylprop-2-ylamine , 1-pentylamine, 2-pentylamine, 3 -pentylamine, 2-methyl-but-1-ylamine, 3-methylbut-1-ylamine, 1, 1-dimethylprop-1-ylamine, 1, 2-dimethylprop-1 -ylamine, 2,2-dimethylprop-1-ylamine, 1-hexylamine, 2-hexylamine or 3-hexylamine or di (Ci-C ⁇ -alkyl) amines such as dimethylamine, Diethylamine, di- (1-propyl) amine, di- (2-propyl) amine, di (l-butyl) amine, di- (2-butylamine
- alkali metal or alkaline earth metal salts of Ci-Cs alcohols, Ci-C ö alkylamines or di- (Ci-C ß- alkyl) amines and ammonia for example the lithium, sodium, potassium, Magnesium or calcium salts.
- Ci- Ca alcohols, ammonia, C ⁇ -C 6 -alkylamine or di (Ci-C ⁇ -alkyl) amine are used as O- or N-nucleophiles, it may be advantageous to use a base.
- hydrides such as sodium hydride or potassium hydride, carbonates such as sodium carbonate, potassium carbonate, hydrogen carbonates such as sodium hydrogen carbonate or potassium hydrogen carbonate or amine bases such as triethylamine, pyridine, etc. come into consideration.
- Preferred 0- and N-nucleophilic alkali alcoholates such as sodium methoxide, sodium ethanolate, sodium 1-propanolate,
- alkali alcoholates as listed above are suitable.
- Sodium methoxide or sodium ethanolate, in particular sodium methoxide, is particularly preferably used.
- Suitable silylating reagents are alkyl- and / or phenyl-substituted silyl halides, in particular trialkylsilyl halides such as trimethylsilyl chloride, triethylsilyl chloride, trimethylsilyl bromide, trimethylsilyl iodide, tert.
- Trialkylsilyl halides as indicated above are preferably used. Trimethylsilyl chloride is particularly suitable.
- R 1 -C 6 alkyl or C 3 -C 6 cycloalkyl where these two radicals can be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: C 1 -C 4 alkoxy, C 1 -C 4 Alkylthio or di (C 1 -C 4 alkyl) amino; C -C 6 alkenyl or C 2 -C 6 alkynyl;
- Aryl or heterocyclyl which has up to three heteroatoms from the group 0, S and N, where the aryl and heterocyclyl radicals may be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: -C-C 4 -alkyl, C 4 haloalkyl, C ⁇ -C 4 -alkoxy, C 4 -haloalkoxy or C ⁇ -C 4 alkoxycarbonyl;
- R 2 is a radical mentioned under R 1 , and also Ci-C ß -alkoxy or aryloxy, which may be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: C 1 -C 4 -alkyl, -C-C -haloalkyl, C 1 -C 4 alkoxy, Ci -C haloalkoxy or Ci -C 4 alkoxycarbonyl;
- radicals R 1 and R 2 which are bonded to the same carbon, together form a - (CH) 2-6 chain, which can be substituted by the following radicals:
- R 1, R 2 -C 6 -alkyl which may be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: -C 4 -C alkoxy, -C -C alkylthio or di - (Ci -C - alkyl) mino;
- radicals R 1 and R 2 which are bonded to the same carbon, together form a - (CH) -6 chain, which can be substituted by the following radicals:
- the reaction is usually carried out in a solvent or diluent.
- Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol or 2-butanol, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole or tetrahydrofuran, aromatic hydrocarbons such as toluene or xylene or are particularly suitable for this Dipolar aprotic solvents such as dimethylformamide or diethylformamide. However, mixtures of these can also be considered.
- alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol or 2-butanol or ethers
- ethers such as diethyl ether, diisopropyl ether, tert. -Butyl methyl ether, dioxane, anisole or tetrahydrofuran.
- ethers such as diethyl ether, diisopropyl ether, tert. -Butyl methyl ether, dioxane, anisole or tetrahydrofuran.
- the reaction is preferably carried out in an ether as indicated above or if an alcoholate is used as the O-nucleophile in the corresponding alcohol.
- ethers such as diethyl ether, methyl tert. -butyl ether or tetrahydrofuran.
- the 2, 2, 4, 4-tetrasubstituted cyclobutane-1, 3-dione, the 0- or N-nucleophile and the silylation reagent are approximately like the stoichiometric ratio (0.8: 1 - 1 , 2: 1) used.
- the reaction is generally carried out in a temperature range from 0 to 120 ° C., in particular from 0 to 60 ° C.
- this reaction is carried out at a pressure of 1 to 50 bar, preferably at 1 to 10 bar.
- the cyclobutane-1,3-dione of the formula II and the O / N nucleophile are placed in a solvent / diluent and the silylation reagent is added in the desired temperature range, preferably at room temperature while ensuring the mixing.
- the latter can be carried out in bulk or in a solvent / diluent.
- the processing takes place in analogy to known processing methods.
- acetyl halides such as acetyl chloride or acetyl bromide, acetyl cyanide, mixed anhydrides of acetic acid with inorganic acids, such as methylsulfonic acid or trifluoromethylsulfonic acid, acetylimidazolide or acetic anhydride, are used as acetylation reagents, for example.
- Acetyl halides in particular acetyl chloride, are preferred.
- the acetylation takes place in the presence of a Lewis acid.
- a Lewis acid In particular, zinc, aluminum, antimony, titanium, tin, boron, iron, nickel and cobalt halides are used, preferably the corresponding chlorides or bromides.
- ZnCl, A1C1 3 or SbCl 3 are used, particularly preferably ZnCl.
- the reaction is usually carried out in a solvent or diluent.
- Halogenated hydrocarbons such as methylene chloride, chloroform, 1, 2-dichloroethane or chlorobenzene, or ethers such as diethyl ether, diisopropyl ether, methyl tert. -butyl ether, dioxane, tetrahydrofuran or anisole or mixtures thereof.
- Aliphatic, halogenated hydrocarbons such as methylene chloride, chloroform or 1,2-dichloroethane or aliphatic / cycloaliphatic ethers such as diethyl ether, diisopropyl ether, methyl tert. -butyl ether, dioxane or tetrahydrofuran used.
- methylene chloride or diethyl ether or mixtures thereof can be considered.
- the silylenol ether of the formula III and the acetylating reagent are usually used in a stoichiometric ratio. However, it can also be advantageous to use an excess of acetylene reagent. It is preferable to work approximately in a stoichiometric ratio.
- the acetylation reagent and the Lewis acid are generally used in a ratio of 1: 0.1 to 1: 2 (mol ratio), preferably a ratio of 1: 0.5 to 1: 1.5, in particular approximately a ratio of 1: 1.
- Silylenol ethers of the formula III are preferably used, where R 3 is Ci-C ⁇ -alkoxy, in particular methoxy.
- Silylenol ethers of the formula III are particularly preferably used, where
- R i C ⁇ -C 6 alkyl or C 3 -C 6 cycloalkyl, where these two radicals may be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: -C -alkoxy, C 1 -C 4 -alkylthio or di (C 1 -C 4 alkyl) amino; C 2 -C 6 alkenyl or C 2 -C 6 alkynyl;
- Aryl or heterocyclyl which has up to three heteroatoms from the groups 0, S and N, where the aryl and heterocyclyl radicals can be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: -C 4 -Alkyl, -CC 4 -haloalkyl, -C-C 4 -alkoxy, -C-C 4 -haloalkoxy or -C-C 4 -alkoxycarbonyl;
- R 2 is a radical mentioned under R 1 , and also Ci-Cg -alkoxy or aryloxy, which may be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: -CC 4 -alkyl, -C-C 4 -haloalkyl, -C. -C 4 alkoxy, Ci -C -haloalkoxy or -C-C 4 alkoxycarbonyl;
- radicals i and R 2 which are bonded to the same carbon, together form a - (CH 2 ) 2-6 chain, which can be substituted by the following radicals:
- Silylenol ethers of the formula III are particularly preferably used, where:
- R 1, R 2 C 1 -C 6 -alkyl which may be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: C 1 -C 4 -alkoxy, C ⁇ -C 4 -alkylthio or di- (C 1 -C 4- alkyl) amino;
- radicals R 1 and R 2 which are bonded to the same carbon, together form a - (CH) 2-6 chain, which can be substituted by the following radicals:
- Halogen C 1 -C 4 -alkyl, C 4 haloalkyl, C 1 -C 4 alkoxy, C ⁇ -C4-haloalkoxy or C ⁇ -C 4 alkoxycarbonyl; mean.
- the reaction is generally carried out in a temperature range from -30 ° C. to the boiling point of the solvent / solvent mixture. Usually one works in a range of -15 to 40 ° C, preferably under ice cooling.
- this reaction is carried out at a pressure of 1 to 50 bar, preferably at normal pressure.
- the acetylating reagent and the Lewis acid are usually initially introduced into the solvent / diluent or a corresponding mixture and the silyl enol ether of the formula III in bulk or in a solvent / diluent or a corresponding mixture is added dropwise, the reaction temperature being kept in the desired range by cooling, if appropriate.
- the processing is carried out in analogy to known processing methods.
- inorganic bases such as alkali metal hydroxides, e.g. Sodium hydroxide or potassium hydroxide, alkaline earth metal hydroxides, e.g. Calcium hydroxide or magnesium hydroxide
- alkali alcoholates such as sodium methoxide, sodium ethanolate, sodium 1-propanolate, sodium 2-propanolate, sodium 1-butanolate, sodium 2-butoxide, sodium 2-methyl propane-1 -olate, sodium 2 -methyl-propane-2-olate, sodium 2-ethyl-hexan-1-olate, potassium methoxide, potassium ethanolate, potassium 1-propanolate, potassium 2-propanolate, potassium 1-butoxide, potassium 2-butoxide, potassium -2-methyl-propane-1 -olate, potassium-2-methyl-propane-2 -olate or potassium-2-ethyl-hexane-1 -olate or alkaline earth metal alcoholates such as calcium methylate, calcium ethanolate, calcium 1-propanolate,
- alkali oxides e.g. Sodium oxide or potassium oxide
- alkaline earth oxides e.g. Calcium oxide or magnesium oxide
- alkali hydrogen carbonates such as sodium hydrogen carbonate or potassium hydrogen carbonate
- earth alkali hydrogen carbonates such as magnesium hydrogen carbonate or calcium hydrogen carbonate
- alkali carbonates such as sodium carbonate or potassium carbonate or alkaline earth carbonates such as calcium carbonate or magnesium carbonate.
- Organic bases for example amine bases such as trialkylamines, e.g. Triethylamine, or aromatic nitrogen bases such as pyridine.
- hydrides such as sodium hydride, potassium hydride or lithium aluminum hydride or organometallic bases such as butyllithium, lithium diisopropylamide etc.
- inorganic bases as listed above, in particular alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal oxides, alkaline earth metal oxides, alkali metal hydrogen carbonates, alkaline earth metal hydrogen carbonates, alkali metal carbonates or alkaline earth metal carbonates, as described above, preferably alkali metal or alkaline earth metal hydroxides, are used.
- Amine bases as listed above, preferably trialkylamines, are likewise used in particular.
- Tricarbonyl compounds of the formula IV are preferably used, where R 3 is Ci-Cs-alkoxy, in particular methoxy.
- Tricarbonyl compounds of the formula IV are particularly preferably used, where
- R i Ci-C ⁇ -alkyl or C 3 -C 6 cycloalkyl, where these two radicals can be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: -C-C 4 alkoxy, C 1 -C 4 alkylthio or di- (-C 4 alkyl) amino; C 2 -C 6 alkenyl or C 2 -C 6 alkynyl;
- Aryl or heterocyclyl which has up to three heteroatoms from the groups 0, S and N, where the aryl and heterocyclyl radicals can be unsubstituted or partially or fully halogenated and / or substituted by the following radicals: C 1 -C 4 -alkyl, C 4 haloalkyl, C 1 -C 4 -alkoxy, C 4 -haloalkoxy or C 1 -C 4 alkoxycarbonyl;
- R 2 is a said under R 1, and C ⁇ -C6 alkoxy or aryloxy which is unsubstituted or may be partially or fully halogenated and / or substituted by the following radicals: C 4 -alkyl, C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy or C ⁇ -C 4 alkoxycarbonyl;
- radicals R 1 and R 2 which are bonded to the same carbon, together form a - (CH 2 ) 2-6 chain, which can be substituted by the following radicals:
- Tricarbonyl compounds of the formula IV are particularly preferably used, where
- R, R 2 Ci-C ⁇ -alkyl, which may be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: -CC 4 -alkoxy, -C-C 4 -alkylthio or di- (C 1 -C 4 - alkyl) amino;
- radicals i and R 2 which are bonded to the same carbon, together form a - (CH) -6 chain, which can be substituted by the following radicals:
- the reaction is usually carried out in an inert solvent or diluent.
- ethers such as diethyl ether, diisopropyl ether, methyl tert are suitable for this.
- Aliphatic / cycloaliphatic ethers such as diethyl ether, diisopropyl ether and methyl tert are preferred.
- Diethyl ether, tetrahydrofuran, dimethylformamide and dimethyl sulfoxide are particularly suitable.
- the tricarbonyl compound of the formula IV and the base are usually used in a ratio of 1: 1 to 1: 4 (molar ratio), preferably in a ratio of 1: 1 to 1: 2.5.
- the reaction is generally carried out in a temperature range from -75 ° C. to the boiling point of the solvent / solvent mixture. Is preferably carried out in a temperature range from -30 ° C to the boiling point of the solvent / solvent mixture.
- the procedure is preferably in a range from 0 to 120 ° C., preferably in a range from 20-100 ° C.
- this reaction is carried out at a pressure of 1 to 100 bar, preferably at a pressure of 1 to 20 bar, in particular at normal pressure.
- the base is placed in the solvent / diluent and the tricarbonyl compound of the formula IV, if appropriate in a solvent / diluent, is added in the desired temperature range while ensuring thorough mixing.
- the processing takes place in analogy to known processing methods.
- amine bases such as trialkylamines, e.g. Triethylamine or aromatic nitrogen base, e.g. Pyridine.
- Trialkylamines, in particular triethylamine, are preferably used.
- the chloride or bromide especially the acid chloride, is used as the acid halide.
- Acid halides of the formula V are particularly preferably used, where:
- R i Ci-C ⁇ -alkyl or C 3 -C 6 cycloalkyl where these two radicals can be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: C 1 -C 4 alkoxy, C 1 -C 4 - Alkylthio or di (C 1 -C 4 alkyl) amino; C 2 -C 6 alkenyl or C -C 6 alkynyl; Aryl or heterocyclyl, which has up to three heteroatoms from the group 0, S and N, where the aryl and heterocyclyl radicals may be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: -C 4 -alkyl , -C-C 4 -haloalkyl, -C-C 4 -alkoxy, C ⁇ -C 4 -haloalkoxy or Ci -C 4 -alkoxycarbonyl;
- R 2 is a radical mentioned under R 1 , and C 1 -C 6 -alkoxy or aryloxy, which may be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: -C 4 -alkyl, C 1 -C -haloalkyl, C 1 -C 4 alkoxy, Ci-C 4 haloalkoxy or C 1 -C 4 alkoxycarbonyl;
- radicals R 1 and R 2 which are bonded to the same carbon, together form a - (CH 2 ) 2 - 6 * chain, which can be substituted by the following radicals: halogen, C 1 -C 4 alkyl, C ⁇ -C 4 haloalkyl, C ⁇ -C 4 -alkoxy, C 4 -haloalkoxy or C 1 -C 4 alkoxycarbonyl; mean.
- Acid halides of the formula V are particularly preferably used, where: Ri, R 2 Ci-C ⁇ -alkyl, which can be unsubstituted or partially or fully halogenated and / or substituted by the following radicals: C ⁇ -C 4 alkoxy, C 1 -C 4 alkylthio or di - (Ci -C 4 - alkyl) amino;
- radicals R 1 and R 2 which are bonded to the same carbon, together form a - (CH 2 ) 2-6 chain, which can be substituted by the following radicals:
- the reaction is usually carried out in an inert solvent or diluent.
- ethers such as diethyl ether, diisopropyl ether and methyl tert are suitable for this.
- Aliphatic ethers such as diethyl ether, diisopropyl ether or methyl tert are preferred.
- glycols such as diethylene glycol dimethyl ether or aromatic hydrocarbons, such as benzene, toluene or xylene, in particular methyl tert. -butyl ether, diethylene glycol dimethyl ether or toluene.
- the acid halide of the formula V and the base are used in a ratio of 1: 1 to 1: 3, preferably in the range from 1: 1.5 to 1: 2.5.
- reaction is carried out at elevated temperature, in particular in the range of the boiling point of the solvent / diluent.
- reaction is carried out at a pressure of 1 to 100 bar.
- the acid chloride is usually initially introduced into the solvent / diluent and the base, if appropriate dissolved in a solvent / diluent, is added. The mixture is then heated to the reflux temperature of the solvent / diluent.
- the processing takes place in analogy to known processing methods. It is also possible to use the compounds II, III or IV in the next step without purification.
- stages a) and b) or b) and c) or al) and a) or a), b) and c) or al, a) and b) or al), a), b) and c) to be designed as a "one-pot process".
- solvents in particular ethers such as diethyl ether, methyl tert. butyl ether, tetrahydrofuran or dioxane or dipolar solvents such as dimethyl sulfoxide or mixtures thereof.
- Stage a) of the process according to the invention is a new and advantageous process for the preparation of silylenol ethers of the formula III.
- the present invention therefore also relates to the process described in step a).
- the preferred embodiments described there apply accordingly.
- stage c) of the process according to the invention if an oxide, hydroxide, hydrogen carbonate or carbonate of an alkali or alkaline earth metal is used as the base, is a new and advantageous process for preparing 2, 2, 4, 4-tetrasubstituted cyclohexane -1, 3, 5- trions of formula I. This is also the subject of the present invention.
- the bases include alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, alkaline earth metal hydroxides, such as calcium hydroxide or magnesium hydroxide, alkali metal oxides such as sodium oxide or potassium oxide, alkaline earth metal oxides, such as calcium oxide or magnesium oxide, alkali metal hydrogen carbonates, such as sodium hydrogen carbonate or potassium hydrogen carbonate, alkaline earth metal hydrogen carbonate or sodium carbonate, such as magnesium bicarbonate or sodium carbonate, such as magnesium bicarbonate, such as magnesium bicarbonate, Potassium carbonate or alkaline earth carbonates such as calcium carbonate or magnesium carbonate.
- alkali metal hydroxides such as sodium hydroxide or potassium hydroxide
- alkaline earth metal hydroxides such as calcium hydroxide or magnesium hydroxide
- alkali metal oxides such as sodium oxide or potassium oxide
- alkaline earth metal oxides such as calcium oxide or magnesium oxide
- alkali metal hydrogen carbonates such as sodium hydrogen carbonate or potassium hydrogen carbonate
- Alkali or alkaline earth metal hydroxides such as sodium, potassium, calcium or magnesium hydroxide, are preferably used.
- Sodium hydroxide is particularly preferably used.
- the reaction is usually carried out in an inert solvent or diluent.
- ethers such as diethyl ether, diisopropyl ether and methyl tert are suitable for this.
- -butyl ether, dioxane, tetrahydrofuran or anisole or aprotic solvents solvents such as dimethylformamide or dimethyl sulfoxide, or mixtures thereof.
- Aliphatic / cycloaliphatic ethers such as diethyl ether, diisopropyl ether, methyl tert-tert-ether, dioxane or tetrahydrofuran, or aprotic, dipolar solvents as mentioned above are preferably used.
- Diethyl ether, tetrahydrofuran and dirnethyl sulfoxide are particularly suitable.
- the tricarbonyl compounds of the formula IV and the base are usually used in a ratio of 1: 1 to 1: 4 (molar ratio), preferably in a ratio of 1: 1 to 1: 2.5. It can be advantageous to work in a stoichiometric ratio.
- the reaction is generally carried out in a temperature range from -75 ° C. to the boiling point of the solvent / solvent mixture.
- the process is preferably carried out in a range from -30 ° C. to the boiling point of the solvent / solvent mixture, particularly in the range from 0 to 120 ° C., in particular 20-100 ° C. Otherwise, the embodiments listed under stage c) apply.
- stage c) of the process according to the invention when an alkali or alkaline earth alcoholate in a ratio of 1: 1 to 1: 3 (compound IV: base; mol ratio) is used as the base, is a new and advantageous process for the preparation of 2, 2, 4, 4-tetrasubstituted cyclohexane-1, 3, 5-trions of the formula I.
- alkali alcoholates such as sodium methoxide, sodium ethanolate, sodium 1-propanolate, sodium 2-propanolate, sodium 2-butoxide, sodium 2-methyl-propane-1-olate, sodium 2-methyl - propane-2-olate, sodium 2-ethyl-hexane-1-olate, potassium methoxide, potassium ethanolate, potassium 1-propanolate, potassium 2-propanolate, potassium 1-butoxide, potassium 2-butoxide, potassium 2-methyl propane-1-olate, potassium 2-methyl propane-2-olate or potassium 2-ethyl-hexane-1-olate or alkaline earth alcoholates such as calcium methanolate, calcium ethanolate, calcium 1-propanolate, calcium 1-but- tanolate, magnesium methylate, magnesium methoxide, magnesium 1-propanolate or magnesium 1-butoxide.
- alkali alcoholates as listed above are used.
- Sodium methoxide, sodium ethoxide or potassium 2-methylpropan-2-olate are particularly used.
- the reaction is usually carried out in an inert solvent or diluent.
- ethers such as diethyl ether, diisopropyl ether, methyl tert are suitable for this.
- Aliphatic or cycloaliphatic ethers such as diethyl ether, diisopropyl ether, methyl tert are preferred. -butyl ether, dioxane or tetrahydrofuran used. Diethyl ether and tetrahydrofuran are particularly suitable.
- the tricarbonyl compound of the formula IV and the alkali metal or alkaline earth metal alcoholate are usually used in a ratio of 1: 1 to 1: 3 (molar ratio), preferably in a ratio of 1: 1 to 1: 2.5.
- the reaction is generally carried out in a temperature range from -75 ° C. to the boiling point of the solvent / solvent mixture. Is preferably carried out in a range from -30 ° C to boiling temperature, in particular at 20-100 ° C.
- the present invention further provides the new 2, 2, 4, 4-tetrasubstituted 1, 3, 5-cyclohexanetriones of the formula I ',
- Halogen C ⁇ -C 4 -alkyl, C 4 haloalkyl, C ⁇ -C 4 -alkoxy, C 4 genalkoxy -Halo- or C 1 -C 4 -alkoxycarbonyl.
- R i , R 2 -C 6 alkyl or C 3 -C 6 cycloalkyl where these two radicals can be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: C 1 -C 4 alkoxy, C ⁇ -C 4 alkylthio or di - (Ci-C 4 alkyl) amino;
- aryl, aryloxy and heterocyclyl which has up to three hetero atoms from the groups 0, S and N, where the aryl, aryloxy and heterocyclyl radicals can be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: C ⁇ -C 4 -alkyl, C 4 haloalkyl, C ⁇ -C 4 -alkoxy, C 4 -haloalkoxy or C 1 -C 4 alkoxycarbonyl;
- radicals R i and R 2 which are bonded to the same carbon, together form a - (CH) -6 chain, which can be substituted by the following radicals:
- R 3 amino, C ⁇ -C 6 alkylamino or di- (-CC 6 alkyl) amino
- R 3 represents di- (C I -C east alkyl) amino.
- the present invention furthermore relates to the new tricarbonyl compounds of the formula IV,
- Ci-C ⁇ -alkoxy C 2 -C 6 alkenyl or C 2 -C 6 alkynyl
- Aryl, aryloxy or heterocyclyl which has up to three hetero atoms from the groups 0, S and N, the aryl, aryloxy and heterocyclyl radicals being unsubstituted or partially or completely halogenated and / or substituted by the following radicals can be: -C 4 -alkyl, -C-C 4 -haloalkyl, -C-C -alkoxy, -C-C 4 -haloalkoxy or C 1 -C 4 -alkoxycarbonyl;
- radicals R 1 and R 2 which are bonded to the same carbon, together form a - (CH 2 ) 2-6 chain, which can be substituted by the following radicals:
- Halogen C 1 -C 4 -alkyl, C 4 haloalkyl, C ⁇ -C alkoxy, C ⁇ ⁇ C 4 haloalkoxy or C1-C4 alkoxycarbonyl;
- R 3 amino, Ci-C ⁇ alkylamino or di- (-CC 6 alkyl) amino.
- R 3 is di- (Ci-C ⁇ -alkyl) amino.
- the present invention also relates to the new tricarbonyl compounds of the formula IV ',
- R 1 and R 2 which are bonded to the same carbon, form a - (CH) -6 "chain which can be substituted by the following radicals:
- Halogen C 3 -C 4 -alkyl, C 4 haloalkyl, C ⁇ -C 4 -alkoxy, C 4 -Halo- genalkoxy or Ci-C4 alkoxycarbonyl;
- the compounds of the formula IV ' are particularly preferred, where R i and R 2 , which are bonded to the same carbon, form a - (CH 2 ) 2-6 chain.
- the organic molecule parts mentioned for the substituents R i to R 4 or as radicals on phenyl or heterocyclyl radicals represent collective terms of individual lists of the individual group members. All hydrocarbon chains, ie all alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio -, Alkylamino, dialkylamino or alkoxycarbonyl parts can be straight-chain or branched. Unless stated otherwise, halogenated substituents preferably carry one to five identical or different halogen atoms. Halogen is fluorine, chlorine, bromine or iodine.
- -C -C alkyl e.g. Methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1, 1-dimethylethyl;
- C 1 -C 4 -haloalkyl a C ⁇ -C 4 -alkyl radical as mentioned above which, chlorine, bromine / iodine or partially or completely substituted by fluorine and is substituted, eg chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl,
- C 1 -C 4 alkoxy for example methoxy, ⁇ thoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1, 1-dimethylethoxy;
- Ci-C ⁇ -alkoxy -C-C 4 alkoxy, as mentioned above, and for example pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy,
- Ci-C ⁇ -alkoxy C ⁇ -C 6 -alkoxy, as mentioned above and 1-heptoxy, 1-octoxy or 2-ethylhexoxy;
- - C ⁇ -C 4 -haloalkoxy a C ⁇ -C4-alkoxy as mentioned above which is partially or completely, chlorine, bromine substituted by fluorine and / or iodine, ie for example fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, Bromdi - fluoromethoxy , 2-fluoroethoxy, 2-chloroethoxy, 2-bromomethoxy, 2-iodoethoxy, 2, 2-difluoroethoxy, 2, 2, 2-trifluoroethoxy,
- 2-chloro-2-fluoroethoxy 2-chloro-2, 2-difluoroethoxy, 2,2-di-chloro-2-fluoroethoxy, 2, 2, 2-trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2- Chloropropoxy, 3-chloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 2, 2-difluoropropoxy, 2, 3-difluoropropoxy, 2, 3-dichloropropoxy, 3, 3, 3-trifluoropropoxy, 3,3,3-trichloropropoxy, 2, 2, 3, 3, 3-pentafluoropropoxy, heptafluoropropoxy, 1- (fluoromethyl) -2-fluoroethoxy, 1- (chloromethyl) -2-chloroethoxy, 1- (bromomethyl) -2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or
- C 1 -C 4 alkylthio for example methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio or 1, 1-dimethylethylthio;
- Ci-Cg-alkylamino e.g. methylamino, ethylamino, propylamino, 1-methylethylamino, butylamino, 1-methylpropylamino, 2-methylpropylamino, 1, 1-dimethylethylamino, pentylamino, 1-methylbutylamino, 2-methylbutylamino, 3-methylbutylamino 2-Dirnethylpropylamino, 1-Ethylpropylamino, Hexylamino, 1, 1-Dirnethylpropylamino, 1, 2-Dirnethylpropylamino, 1-Methyl-pentylamino, 2-Methylpentylamino, 3-Methylpentylamino, 4-Methylpentylamino, 1, 1-Dimethylbutylamino Dimethylbutylamino, 1, 3-dimethylbutylamino, 2, 2-dimethylbut
- Di- (-C-alkyl) amino e.g. N, N-dimethylamino, N, N-diethylamino, N, N-dipropylamino, N, N-di- (1-methylethyl) amino, N, N-dibutylamino, N, N-di- (1-methylpropyl ) amino, N, N-di- (2-methylpropyl) amino, N, N-di- (1, 1-dimethylethyl) - amino, N-ethyl-N-methylamino, N-methyl-N-propylamino, N- Methyl-N- (1-methylethyl) amino, N-butyl-N-methylamino, N-methyl-N- (1-methylpropyl) amino, N-methyl-N- (2-methylpropyl) amino, N- ( 1, 1-dimethylethyl) -N-methylamino, N-ethyl-N-prop
- Di- (-C 6 -alkyl) amino di- (C ⁇ -C 4 -alkyl) amino as mentioned above, and N, N-dipentylamino, N, N-dihexylamino, N-methyl-N-pentylamino, N- Ethyl-N-pentylamino, N-methyl-N-hexylamino or N-ethyl -N-hexylamino;
- C 2 -C 6 ⁇ alkenyl for example ethenyl, prop-2-en-1-yl, but-1-en-4-yl, 1-methyl-prop-2-en-1-yl, 2-methyl-prop -2-en-l-yl, 2-butene-l-yl, l-penten-3-yl, l-penten-4-yl, 2-penten-4-yl, 1-methyl-but -2-en-l-yl, 2-methyl-but-2-en-l-yl, 3-methyl-but-2-en-l-yl, l-methyl-but-3-en-l-yl , 2-methyl-but-3-en-1-yl, 3-methyl-but-3-en-1-yl, 1, 1-dimethyl-prop-2-en-1-yl, 1, 2-dimethyl -prop-2-en-l-yl, 1-ethyl-prop-2-en-l-yl, hex-3-en-l-yl, hex-4-en-l-yl
- 2-ethyl-3-en-1-yl 1, 1, 2-trimethyl-prop-2-en-1-yl, 1-ethyl-1-methyl-prop-2-en-1-yl or 1-ethyl-2-methyl-prop-2-en-1-yl;
- C 2 -C 6 alkynyl for example ethynyl, propargyl, but-1-yn-3-yl,
- Pent-1-in-5-yl Pent-2-in-1-yl, Pent-2-in-4-yl, Pent-2-in-5-yl, 3-methyl-but-1-yl 3-yl, 3-methyl-but-l-in-4-yl, hex-l-in-3-yl, hex-l-in-4-yl, hex-l-in-5-yl, hex l-in-6-yl,
- C 3 -C 6 cycloalkyl for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
- Aryl e.g. Phenyl or naphthy1;
- Heterocyclyl a saturated, partially saturated or unsaturated 5- or 6-membered, C-bonded, heterocyclic ring which contains one to four identical or different heteroatoms selected from the following group: oxygen, sulfur or nitrogen, i.e. e.g. 5-section
- 6-membered rings with a heteroatom such as:
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Abstract
Description
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Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
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EP00936762A EP1181264A1 (de) | 1999-06-02 | 2000-05-19 | Verfahren zur herstellung von 2,2,4,4-tetrasubstituierten 1,3,5-cyclohexantrionen |
US09/979,990 US6559343B1 (en) | 1999-06-02 | 2000-05-19 | Process for producing 2,2,4,4-tetra-substituted 1,3,5-cyclohexanetriones |
JP2001501577A JP2003501408A (ja) | 1999-06-02 | 2000-05-19 | 2,2,4,4−四置換された1,3,5−シクロヘキサントリオンの製造方法 |
CA002375651A CA2375651A1 (en) | 1999-06-02 | 2000-05-19 | Method for producing 2,2,4,4-tetra-substituted 1,3,5-cyclohexanetriones |
AU52143/00A AU5214300A (en) | 1999-06-02 | 2000-05-19 | Method for producing 2,2,4,4-tetra-substituted 1,3,5-cyclohexanetriones |
MXPA01012344A MXPA01012344A (es) | 1999-06-02 | 2000-05-19 | Metodo para producir 1,3,5-ciclohexanotrionas 2,2,4,4-tetra-substituidas. |
IL14657300A IL146573A0 (en) | 1999-06-02 | 2000-05-19 | Method for producing 2,2,4,4-tetra-substituted 1,3,5-cyclohexanetriones |
KR1020017015484A KR20020006051A (ko) | 1999-06-02 | 2000-05-19 | 2,2,4,4-테트라-치환된 1,3,5-시클로헥산트리온의 제조 방법 |
BR0011111-2A BR0011111A (pt) | 1999-06-02 | 2000-05-19 | Processos para a preparação de 1,3,5-ciclo-hexanotrionas 2,2,4,4- tetrassubstituìdas, para a preparaçãp de ésteres enol silìlicos, composto,uso de ciclobutano-1,3-dionas |
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DE19925145 | 1999-06-02 | ||
DE19925145.2 | 1999-06-02 |
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WO2000075095A1 true WO2000075095A1 (de) | 2000-12-14 |
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US (1) | US6559343B1 (de) |
EP (1) | EP1181264A1 (de) |
JP (1) | JP2003501408A (de) |
KR (1) | KR20020006051A (de) |
CN (1) | CN1353685A (de) |
AU (1) | AU5214300A (de) |
BR (1) | BR0011111A (de) |
CA (1) | CA2375651A1 (de) |
HU (1) | HUP0201400A3 (de) |
IL (1) | IL146573A0 (de) |
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Cited By (3)
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---|---|---|---|---|
WO2001060776A1 (de) * | 2000-02-18 | 2001-08-23 | Basf Aktiengesellschaft | Verfahren zur synthese von 2,2,4,4-tetrasubstituierten 1,3,5-cyclohexantrionen |
WO2010089211A1 (en) | 2009-02-04 | 2010-08-12 | Syngenta Limited | Novel herbicides |
EP2527333A1 (de) | 2007-06-28 | 2012-11-28 | Syngenta Limited | Pyrandion-, Thiopyrandion- und Cyclohexanetrionverbindungen mit herbiziden Eigenschaften |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103694083A (zh) * | 2013-12-05 | 2014-04-02 | 南京东纳生物科技有限公司 | 2,2,4,4-四甲基-1,3-环丁二醇的合成方法 |
CN112457170B (zh) * | 2021-01-26 | 2021-05-04 | 苏州亚科科技股份有限公司 | 一种2,2,4,4-四甲基-1,3-环丁二醇的制备方法 |
Citations (1)
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EP0283152A2 (de) * | 1987-03-19 | 1988-09-21 | Imperial Chemical Industries Plc | Verfahren zur Herstellung von substituierten Cyclohexan-1,3,5-trionen |
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2000
- 2000-05-19 AU AU52143/00A patent/AU5214300A/en not_active Abandoned
- 2000-05-19 WO PCT/EP2000/004567 patent/WO2000075095A1/de not_active Application Discontinuation
- 2000-05-19 BR BR0011111-2A patent/BR0011111A/pt not_active IP Right Cessation
- 2000-05-19 CN CN00808280A patent/CN1353685A/zh active Pending
- 2000-05-19 EP EP00936762A patent/EP1181264A1/de not_active Withdrawn
- 2000-05-19 HU HU0201400A patent/HUP0201400A3/hu unknown
- 2000-05-19 JP JP2001501577A patent/JP2003501408A/ja active Pending
- 2000-05-19 CA CA002375651A patent/CA2375651A1/en not_active Abandoned
- 2000-05-19 MX MXPA01012344A patent/MXPA01012344A/es not_active Application Discontinuation
- 2000-05-19 IL IL14657300A patent/IL146573A0/xx unknown
- 2000-05-19 KR KR1020017015484A patent/KR20020006051A/ko not_active Application Discontinuation
- 2000-05-19 US US09/979,990 patent/US6559343B1/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0283152A2 (de) * | 1987-03-19 | 1988-09-21 | Imperial Chemical Industries Plc | Verfahren zur Herstellung von substituierten Cyclohexan-1,3,5-trionen |
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BENBAKKAR, M. ET AL: "Synthesis of syncarpic acid and a related.beta.-oxo.delta.-enol lactone via selective O- or C-acylation of preformed enolates", SYNTH. COMMUN. (1989), 19(18), 3241-7, XP000957605 * |
HASEK ROBERT H ET AL: "Chemistry of dimethylketene dimer. I. Catalytic hydrogenation and ring cleavage by alcohols", JOURNAL OF ORGANIC CHEMISTRY., vol. 26, 1961, AMERICAN CHEMICAL SOCIETY. EASTON., US, pages 700 - 704, XP002151400, ISSN: 0022-3263 * |
HASEK ROBERT H ET AL: "The chemistry of dimethylketene dimer. III. Reactions with ammonia and amines", JOURNAL OF ORGANIC CHEMISTRY., vol. 26, 1961, AMERICAN CHEMICAL SOCIETY. EASTON., US, pages 4340 - 4344, XP002151401, ISSN: 0022-3263 * |
HASEK ROBERT H: "Chemistry of dimethylketene dimer. V. Reactions involving ester anions", JOURNAL OF ORGANIC CHEMISTRY., vol. 27, 1962, AMERICAN CHEMICAL SOCIETY. EASTON., US, pages 3106 - 3111, XP002151403, ISSN: 0022-3263 * |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001060776A1 (de) * | 2000-02-18 | 2001-08-23 | Basf Aktiengesellschaft | Verfahren zur synthese von 2,2,4,4-tetrasubstituierten 1,3,5-cyclohexantrionen |
EP2527333A1 (de) | 2007-06-28 | 2012-11-28 | Syngenta Limited | Pyrandion-, Thiopyrandion- und Cyclohexanetrionverbindungen mit herbiziden Eigenschaften |
WO2010089211A1 (en) | 2009-02-04 | 2010-08-12 | Syngenta Limited | Novel herbicides |
Also Published As
Publication number | Publication date |
---|---|
IL146573A0 (en) | 2002-07-25 |
AU5214300A (en) | 2000-12-28 |
HUP0201400A2 (en) | 2002-08-28 |
US6559343B1 (en) | 2003-05-06 |
KR20020006051A (ko) | 2002-01-18 |
HUP0201400A3 (en) | 2002-12-28 |
JP2003501408A (ja) | 2003-01-14 |
BR0011111A (pt) | 2002-02-19 |
MXPA01012344A (es) | 2002-07-09 |
EP1181264A1 (de) | 2002-02-27 |
CN1353685A (zh) | 2002-06-12 |
CA2375651A1 (en) | 2000-12-14 |
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