CN1051556C - 杂取代的乙缩醛类化合物的制备方法 - Google Patents
杂取代的乙缩醛类化合物的制备方法 Download PDFInfo
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- CN1051556C CN1051556C CN95103771A CN95103771A CN1051556C CN 1051556 C CN1051556 C CN 1051556C CN 95103771 A CN95103771 A CN 95103771A CN 95103771 A CN95103771 A CN 95103771A CN 1051556 C CN1051556 C CN 1051556C
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- Prior art keywords
- palladium
- alkyl
- aryl
- aryloxy
- vinyl compound
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- 238000000034 method Methods 0.000 title claims description 24
- 150000001241 acetals Chemical class 0.000 title abstract description 4
- 238000002360 preparation method Methods 0.000 title description 3
- -1 alkyl nitrites Chemical class 0.000 claims abstract description 63
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 150000002170 ethers Chemical class 0.000 claims abstract description 6
- 150000001298 alcohols Chemical class 0.000 claims abstract description 4
- 239000012429 reaction media Substances 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 229920002554 vinyl polymer Polymers 0.000 claims description 17
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 125000005842 heteroatom Chemical group 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000005864 Sulphur Substances 0.000 claims description 7
- 125000004104 aryloxy group Chemical group 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 230000026030 halogenation Effects 0.000 claims description 3
- 238000005658 halogenation reaction Methods 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-M benzoate Chemical compound [O-]C(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-M 0.000 claims description 2
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical group CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 description 13
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 150000002940 palladium Chemical class 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- QZECCVQKPJLQAW-UHFFFAOYSA-N 2,2-dimethoxyethylsulfonylbenzene Chemical compound COC(OC)CS(=O)(=O)C1=CC=CC=C1 QZECCVQKPJLQAW-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- JQJPBYFTQAANLE-UHFFFAOYSA-N Butyl nitrite Chemical compound CCCCON=O JQJPBYFTQAANLE-UHFFFAOYSA-N 0.000 description 1
- SXAVLPHRDIJVIZ-UHFFFAOYSA-N COC(COS(=O)(=O)c1ccccc1)OC Chemical compound COC(COS(=O)(=O)c1ccccc1)OC SXAVLPHRDIJVIZ-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- QQZWEECEMNQSTG-UHFFFAOYSA-N Ethyl nitrite Chemical compound CCON=O QQZWEECEMNQSTG-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- LRFVTYWOQMYALW-UHFFFAOYSA-N Xanthine Natural products O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- RNFJXKZHLUDESJ-UHFFFAOYSA-N [O].C(CCCCC)OCCCCCCC Chemical compound [O].C(CCCCC)OCCCCCCC RNFJXKZHLUDESJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- UJTPZISIAWDGFF-UHFFFAOYSA-N ethenylsulfonylbenzene Chemical group C=CS(=O)(=O)C1=CC=CC=C1 UJTPZISIAWDGFF-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010574 gas phase reaction Methods 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
- 125000000623 heterocyclic 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
- 238000009854 hydrometallurgy Methods 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- APNSGVMLAYLYCT-UHFFFAOYSA-N isobutyl nitrite Chemical compound CC(C)CON=O APNSGVMLAYLYCT-UHFFFAOYSA-N 0.000 description 1
- SKRDXYBATCVEMS-UHFFFAOYSA-N isopropyl nitrite Chemical compound CC(C)ON=O SKRDXYBATCVEMS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 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
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 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
- 125000005447 octyloxy 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])O* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- PBDBXAQKXCXZCJ-UHFFFAOYSA-L palladium(2+);2,2,2-trifluoroacetate Chemical compound [Pd+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F PBDBXAQKXCXZCJ-UHFFFAOYSA-L 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- CILDJVVXNMDAGY-UHFFFAOYSA-N phenyl ethenesulfonate Chemical compound C=CS(=O)(=O)OC1=CC=CC=C1 CILDJVVXNMDAGY-UHFFFAOYSA-N 0.000 description 1
- 239000004476 plant protection product Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KAOQVXHBVNKNHA-UHFFFAOYSA-N propyl nitrite Chemical compound CCCON=O KAOQVXHBVNKNHA-UHFFFAOYSA-N 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003420 transacetalization reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/24—Sulfones; Sulfoxides having sulfone or sulfoxide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- 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 System
- 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
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/30—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reactions not involving the formation of esterified sulfo groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/02—Monohydroxylic acyclic alcohols
- C07C31/04—Methanol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
-
- 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 System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/083—Syntheses without formation of a Si-C bond
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
通过使式(Ⅱ)的乙烯基化合物与式(Ⅲ)的亚硝酸烷基酯反应可得到式(Ⅰ)的杂取代的乙缩醛类化合物，该反应在以金属或键合形式的钯存在下和在作反应介质的醇类或醚类中，在0-120℃下进行。
Description
本发明涉及在以金属或键合形式存在的钯的存在下，通过将杂取代的乙烯基化合物与亚硝酸烷基酯反应制备杂取代的乙缩醛类化合物的方法。
以下后文中详述的式(I)杂取代的乙缩醛类化合物适宜作为合成其它有机化合物如药物、植物保护剂或染料的起始原料。因此，例如，2，2-二甲氧基乙基膦酸二乙酯可用于酮类和醛类的链增长(Org.Synth.53(1973)，44-48)，此外，该化合物的缩醛链转移作用(transacetalization)可制备含磷的聚合物(J.Polym.Sci，22(1984)，3335-3342；J.Polym.Sci.A 26(1988)，2997-3014)；这种类型的聚合物被用于耐焰剂、湿法冶金学和膜技术领域中。
按照DE-A 3419750将苯磺酰基乙醛缩二乙醇进行反应得到制备拟除虫菊酯类用的前体。
苯氧基磺酰基乙醛缩二烷基醇可转化为1，2-苯并黄质(xathiine)-2，2-二氧化物，其可按EP 128116和EP 337947进行反应得到除草剂。
现有个别文献描述了在钯盐存在下通过将母体烯烃与亚硝酸烷基酯反应制备乙缩醛类化合物。因此，例如，EP 55108描述了如乙烯、丙烯、丁烯、环己烯、丙烯酸酯和丙烯腈化合物的氧化反应。然而在这些氧化反应中所得的产率是低的，因此任何工业上使用不得不考虑在产品分离和催化剂及溶剂的再循环方面的相当大的费用。特别是在EP 55108中建议的气相反应不能用于制备以下后文中详述的式(I)乙缩醛类化合物，因为在该反应所需的高温下，将预料到会发生分解反应和其它副反应。
J.Heterocyclic Chem.29(1992)，1625中描述了2-硝基苯乙烯类与亚硝酸烷基酯在液相中，同时在氧气氛下进行反应得到相应的乙缩醛类化合物。然而该反应可能产生可燃性的混合物，尤其在工业实施的情况下，这一事实使得用于必需的安全措施的设备方面需要花费相当大的费用。
因而现有文献中只描述了用未取代的烯烃、或在至少一个碳原子上用另一个碳原子单取代或二取代的烯烃进行反应所用的方法；特别是文献中并没有描述可将杂取代的乙烯基化合物转化为乙缩醛类所用的方法。然而由于杂取代的乙缩醛类可能有许多应用，因此需要提供它们的制备方法。
现已发现通过将以下后文中详述的式(II)乙烯基化合物与亚硝酸烷基酯在本发明方法的条件下进行反应，可令人吃惊地以高产率得到式(I)乙缩醛类化合物。
本发明涉及制备下式杂取代的乙缩醛类化合物的方法：其中：
R1代表直链或支链C1-C8烷基，优选C1-C2烷基，特别优选甲基，和
A1代表杂原子，其选自硅、氧、硫、硒、碲、氮和磷，所述杂原子在其键合能力的范围内带有一个或多个相同或不同的取代基，这些取代基选自双键氧、C1-C8烷氧基、C1-C8烷基、芳氧基、取代的芳氧基、芳基和取代的芳基，这些杂原子可另外带有正电荷，其特征在于，在金属或键合形式的钯存在下和在作反应介质的醇类或醚类或其两者或多者的混合物中，在0至120℃，优选40-80℃下，使式(II)乙烯基化合物：
CH2＝CH-A1 (II)其中：A1具有上述定义，与式(III)的亚硝酸烷基酯反应：
R1-ONO (III)其中：R1具有上述定义。
直链或支链C1-C8烷基为，例如甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、异构的戊基、己基、庚基和辛基。烷基优选为甲基或乙基，特别优选为甲基。
直链或支链C1-C8烷氧基为，例如甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基、异丁氧基、叔丁氧基、异构的戊氧基、己氧基、庚氧基和辛氧基。C1-C4烷氧基是优选的，甲氧基和乙氧基是特别优选的。
芳基具有6至12个碳原子，并且为例如苯基、联苯基或萘基。芳基可被1至3个相同或不同的选自于甲基、乙基、甲氧基、乙氧基、氯和溴的取代基所取代。芳氧基同样具有6至12个碳原子，是从所述的芳基衍生的，为未取代的或取代的形式。
A1为杂原子，其选自于硅、氧、硫、硒、碲、氮和磷，优选选自于硅、氧、硫、氮和磷，最优选为硫和磷。
据此，优选的乙烯基化合物为式(IV)的化合物：
CH2＝CH-A2 (IV)其中A2为选自硅、氧、硫、氮和磷的被取代的杂原子。
特别重要的乙烯基化合物为下列的化合物：
CH2＝CH-O-R2 
CH2＝CH-S-R2 在这些特别重要的乙烯基化合物中，R2、R3和R4彼此独立地为直链或支链C1-C8烷氧基、C1-C8烷基、C6-C12芳氧基或C6-C12芳基，其中芳基和/或芳氧基可按上述方式被取代。由以上的化学式明显可见，当其中杂原子带有正电荷时，这样的化合物含有一个阴离子X-，其为氯、溴、1/2硫酸根、硝酸根、乙酸根、三氟乙酸根、甲酸根、丙酸根或苯甲酸根。以上系列化合物中，特别重要的乙烯基化合物以它们的化学式列出，以下是优选的：在这些化学式中：
R5和R6彼此独立地为甲基、乙基或苯基。
钯可以金属或键合的形式使用。当钯以金属形式使用时，在本发明反应过程中，其可至少部分被转变为键合的形式。然而，优选以键合的形式使用钯。这种键合形式包括简单盐类、配盐，以及配位化合物，其中钯的化合价为零。这种钯盐应当全部或部分溶于反应混合物中。可提及的钯盐的例子为：氯化钯、溴化钯、乙酸钯、三氟乙酸钯，有机羧酸如丙酸、苯甲酸或其它脂肪族或其他芳香族羧酸的钯盐，杂多酸钯盐，尤其是衍生于钒、钼、铌和钨的杂多酸钯盐。优选的适宜钯化合物为所述的卤化钯，特别是氯化钯。以键合形式的钯，尤其是以所述盐形式的钯可补充其它金属如碱金属或碱土金属盐，或具有不同取代度的铵或胺盐。对这些盐适宜的阴离子包括上述对钯所详述的那些阴离子。许多这些盐与键合形式的钯形成配合物，因此它们也为上述钯配盐的实例。这种补充盐优选为氯化锂或氯化钠，优选氯化锂。
适用于实施本发明方法的醇类和醚类为C1-C4链烷醇类，如甲醇、乙醇、丙醇、异丙醇、丁醇、异丁醇或叔丁醇，以及乙二醇、1，2-或1，3-丙二醇或1，2-、1，3-、1，4-或2，3-丁二醇，它们彼此间的醚类或半醚类，如乙二醇二甲醚或二甘醇，还有二噁烷或四氢呋喃。这些物质彼此间的醚还包括如二异丙醚、二丁醚、和二甘醇单和二乙醚。为了简化反应方法和处理步骤，优选在所述的C1-C4链烷醇类之一中进行反应。特别优选在本发明反应中所用的亚硝酸烷基酯所基于的链烷醇中进行反应。
可提出的亚硝酸烷基酯的例子为亚硝酸甲酯、亚硝酸乙酯、亚硝酸丙酯、亚硝酸异丙酯、亚硝酸丁酯或亚硝酸异丁酯。
本发明的方法是在0-120℃，优选40-80℃温度范围内进行的。实施本发明反应所用的压力不是关键性的，可以在0.5-10巴范围内，优选1.0-6巴，且特别优选1-5巴。然而反应也可在较高的或较低的压力下进行。
为实施本发明的反应，例如可以首先将以金属或键合形式的钯悬浮于或全部或部分溶解于一种所述溶剂中。在所述温度下，将若需要可与部分相关溶剂混合的乙烯基化合物加入该悬浮液或全部溶解或部分溶解的溶液中。然后连续或分批地加入液态或气态形式的亚硝酸烷基酯。然而也可以同时加入乙烯基化合物和亚硝酸烷基酯。当使用优选的亚硝酸甲酯时，其与惰性气体作为混合物通入反应溶液是有利的。适宜的惰性气体的实例为氮气、氩气或二氧化碳，优选氮气。在使用其它亚硝酸烷基酯的情况下，例如基于安全的考虑，反应显然也要在惰性气体存在下进行。溶剂的用量相对于每摩尔所用的乙烯基化合物为1至100摩尔，优选5至40摩尔。
乙烯基化合物(II)与亚硝酸烷基酯(III)的摩尔比为1∶1至1∶10，优选1∶1.5至1∶5。
金属或键合形式的钯的用量，以金属计量，相对于每摩尔乙烯基化合物为0.001至0.2克原子，优选0.001至0.1克原子。
反应产物按本领域技术人员熟知的方法进行分离和处理，例如通过蒸馏溶剂，然后在减压下精馏反应产物，通过结晶法或者用这些方法的组合，以及若需要的话用色谱法来完成。
实施例1：
将200ml甲醇、0.4g(2.3mmol)氯化钯和0.2g(4.7mmol)氯化锂的混合物加热至60℃。
然后连续加入包括10l/h氮气和0.2mol/h亚硝酸甲酯的气体物流。
15分钟后，在10分钟内滴加32.8g(0.2mol)乙烯基膦酸二乙酯。
然后的2小时中，将在氮气流中的亚硝酸甲酯通入反应液，以致总共消耗约0.5mol亚硝酸甲酯。
当加完亚硝酸甲酯时，将混合物在氮气氛下搅拌1小时。
从溶液中蒸馏出甲醇，并将剩余物在真空下蒸馏，得到38.2g(理论值的85％)2，2-二甲氧基乙基膦酸二乙酯。
沸点：90-92℃/1mbar。
实施例2
将200ml甲醇、0.25g(1.4mmol)氯化钯和0.125g(2.9mmol)氯化锂的混合物加热至60℃。
然后连续加入包括10l/h氮气和0.1mol/h亚硝酸甲酯的气体物流。
15分钟后，滴加溶解于20ml甲醇中的8.4g(0.046mol)乙烯基磺酸苯酯。
然后的2小时中，将亚硝酸甲酯通入混合物中，以致总共消耗约0.2mol亚硝酸甲酯。
当加完亚硝酸甲酯时，将混合物在氮气氛下搅拌1小时。
从溶液中蒸馏出甲醇，并将剩余物在真空下蒸馏，得到9.1g(理论值的81％)2，2-二甲氧基乙基磺酸苯酯。
沸点：135℃/0.5mbar。
实施例3
将400mg(2.3mmol)氯化钯和200mg(4.7mmol)氯化锂于60℃加热溶解于240ml甲醇中。
然后连续加入包括10l/h氮气和0.2mol/h亚硝酸甲酯的气体物流。
15分钟后，滴加30g(0.18mol)苯基乙烯基砜在60ml甲醇中形成的溶液。
将更多的亚硝酸甲酯通入混合物2小时，以致总共消耗约0.4mol亚硝酸甲酯。
从溶液中蒸馏出甲醇并将剩余物在真空中蒸馏，得到31.6g(0.14mol)(理论值的77％)2，2-二甲氧基乙基苯基砜。沸点：139-140C/0.7mbar。
Claims (10)
1.制备下式杂取代的乙缩醛类化合物的方法：
其中：
R1代表直链或支链C1-C8烷基，和
A1代表杂原子，其选自硅、氧、硫、硒、碲、氮和磷，所述杂原子在其键合能力的范围内带有一个或多个相同或不同的取代基，这些取代基选自双键氧、C1-C8烷氧基、C1-C8烷基、芳氧基、取代的芳氧基、芳基和取代的芳基，这些杂原子可另外带有正电荷，其特征在于，在金属或键合形式的钯存在下和在作反应介质的醇类或醚类或其两者或多者的混合物中，在0至120℃下，使式(II)乙烯基化合物：
CH2＝CH-A1 (II)其中：A1具有上述定义，与式(III)的亚硝酸烷基酯反应：
R1-ONO (III)其中：R1具有上述定义。
2.根据权利要求1的方法，其特征在于使用下式的乙烯基化合物：
CH2＝CH-A2 (IV)其中A2代表选自硅、氧、硫、氮和磷的被取代的杂原子，其可另外带有正电荷。
3.根据权利要求1的方法，其特征在于使用选自下列的乙烯基化合物：
CH2＝CH-O-R2 
CH2＝CH-S-R2 其中R2、R3和R4彼此独立地代表直链或支链C1-C8烷氧基、C1-C8烷基、C6-C12芳氧基、取代的C6-C12芳氧基、C6-C12芳基或取代的C6-C12芳基，和X-为氯、溴、1/2硫酸根、硝酸根、乙酸根、三氟乙酸根、甲酸根、丙酸根或苯甲酸根。
4.根据权利要求3的方法，其特征在于使用选自下列的乙烯基化合物：其中R5和R6彼此独立地为甲基、乙基或苯基。
5.根据权利要求1的方法，其特征在于R1代表C1-C2烷基。
6.根据权利要求5的方法，其特征在于R1代表甲基。
7.根据权利要求1的方法，其特征在于所述反应在40-80℃下进行。
8.根据权利要求1的方法，其特征在于使用键合形式的钯，其通过加入另外的盐可转化为复合物的形式。
9.根据权利要求8的方法，其特征在于所述钯以卤化钯形式使用。
10.根据权利要求9的方法，其特征在于所述卤化钯为氯化钯。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4410867A DE4410867A1 (de) | 1994-03-29 | 1994-03-29 | Verfahren zur Herstellung von heterosubstituierten Acetalen |
| DEP4410867.2 | 1994-03-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1118784A CN1118784A (zh) | 1996-03-20 |
| CN1051556C true CN1051556C (zh) | 2000-04-19 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN95103771A Expired - Fee Related CN1051556C (zh) | 1994-03-29 | 1995-03-29 | 杂取代的乙缩醛类化合物的制备方法 |
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| Country | Link |
|---|---|
| US (1) | US5478960A (zh) |
| EP (1) | EP0675129B1 (zh) |
| JP (1) | JPH07300440A (zh) |
| KR (1) | KR100346318B1 (zh) |
| CN (1) | CN1051556C (zh) |
| CA (1) | CA2145498A1 (zh) |
| DE (2) | DE4410867A1 (zh) |
| ES (1) | ES2150511T3 (zh) |
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| US7133845B1 (en) * | 1995-02-13 | 2006-11-07 | Intertrust Technologies Corp. | System and methods for secure transaction management and electronic rights protection |
| US6948070B1 (en) | 1995-02-13 | 2005-09-20 | Intertrust Technologies Corporation | Systems and methods for secure transaction management and electronic rights protection |
| US7095854B1 (en) * | 1995-02-13 | 2006-08-22 | Intertrust Technologies Corp. | Systems and methods for secure transaction management and electronic rights protection |
| CN1183841A (zh) | 1995-02-13 | 1998-06-03 | 英特特拉斯特技术公司 | 用于安全交易管理和电子权利保护的系统和方法 |
| FR3057467B1 (fr) * | 2016-10-17 | 2018-12-07 | IFP Energies Nouvelles | Procede de purification d'une solution aqueuse comprenant du diethylacetal |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0055108A1 (en) * | 1980-12-23 | 1982-06-30 | Ube Industries, Ltd. | Process for producing an acetal |
| EP0359118A2 (de) * | 1988-09-15 | 1990-03-21 | BASF Aktiengesellschaft | Verfahren zur Herstellung von 1,1,2-Trialkoxyethanen |
-
1994
- 1994-03-29 DE DE4410867A patent/DE4410867A1/de not_active Withdrawn
-
1995
- 1995-03-16 EP EP95103819A patent/EP0675129B1/de not_active Expired - Lifetime
- 1995-03-16 DE DE59508615T patent/DE59508615D1/de not_active Expired - Fee Related
- 1995-03-16 ES ES95103819T patent/ES2150511T3/es not_active Expired - Lifetime
- 1995-03-22 US US08/408,240 patent/US5478960A/en not_active Expired - Fee Related
- 1995-03-24 CA CA002145498A patent/CA2145498A1/en not_active Abandoned
- 1995-03-27 JP JP7091963A patent/JPH07300440A/ja active Pending
- 1995-03-29 CN CN95103771A patent/CN1051556C/zh not_active Expired - Fee Related
- 1995-03-29 KR KR1019950006816A patent/KR100346318B1/ko not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0055108A1 (en) * | 1980-12-23 | 1982-06-30 | Ube Industries, Ltd. | Process for producing an acetal |
| EP0359118A2 (de) * | 1988-09-15 | 1990-03-21 | BASF Aktiengesellschaft | Verfahren zur Herstellung von 1,1,2-Trialkoxyethanen |
Also Published As
| Publication number | Publication date |
|---|---|
| US5478960A (en) | 1995-12-26 |
| DE4410867A1 (de) | 1995-10-05 |
| ES2150511T3 (es) | 2000-12-01 |
| KR100346318B1 (ko) | 2003-05-01 |
| EP0675129B1 (de) | 2000-08-09 |
| DE59508615D1 (de) | 2000-09-14 |
| EP0675129A1 (de) | 1995-10-04 |
| CN1118784A (zh) | 1996-03-20 |
| JPH07300440A (ja) | 1995-11-14 |
| KR950032107A (ko) | 1995-12-20 |
| CA2145498A1 (en) | 1995-09-30 |
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