EP2544819A2 - Solutions d'acides de lewis dans un solvant ou mélange de solvants contenant des donneurs d'oxygène - Google Patents
Solutions d'acides de lewis dans un solvant ou mélange de solvants contenant des donneurs d'oxygèneInfo
- Publication number
- EP2544819A2 EP2544819A2 EP11708050A EP11708050A EP2544819A2 EP 2544819 A2 EP2544819 A2 EP 2544819A2 EP 11708050 A EP11708050 A EP 11708050A EP 11708050 A EP11708050 A EP 11708050A EP 2544819 A2 EP2544819 A2 EP 2544819A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- asymmetrically substituted
- solution according
- lewis acid
- hydrocarbons
- oxygen donor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
- 239000002841 Lewis acid Substances 0.000 title claims abstract description 47
- 150000007517 lewis acids Chemical class 0.000 title claims abstract description 47
- 239000002904 solvent Substances 0.000 title claims description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims description 20
- 229910052760 oxygen Inorganic materials 0.000 title claims description 20
- 239000001301 oxygen Substances 0.000 title claims description 20
- 239000011877 solvent mixture Substances 0.000 title abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 229930195733 hydrocarbon Chemical class 0.000 claims abstract description 23
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 23
- 150000002170 ethers Chemical class 0.000 claims abstract description 12
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 230000000737 periodic effect Effects 0.000 claims abstract description 4
- -1 methoxy, methylmethoxy, ethyl Chemical group 0.000 claims description 34
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 125000006017 1-propenyl group Chemical group 0.000 claims description 2
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000005427 anthranyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- KSCFJBIXMNOVSH-UHFFFAOYSA-N dyphylline Chemical group O=C1N(C)C(=O)N(C)C2=C1N(CC(O)CO)C=N2 KSCFJBIXMNOVSH-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003136 n-heptyl 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])* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
- 229940078552 o-xylene Drugs 0.000 claims description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 2
- 125000005561 phenanthryl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 claims description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 125000005023 xylyl group Chemical group 0.000 claims description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims 1
- 229960002089 ferrous chloride Drugs 0.000 claims 1
- 239000012535 impurity Substances 0.000 claims 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 125000002524 organometallic group Chemical group 0.000 abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 150000002483 hydrogen compounds Chemical class 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005698 Diels-Alder reaction Methods 0.000 description 2
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 2
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000010933 acylation Effects 0.000 description 2
- 238000005575 aldol reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- TYZYNGFWGHGRBZ-REOHCLBHSA-N (2s)-2-(chloroamino)propanoic acid Chemical class ClN[C@@H](C)C(O)=O TYZYNGFWGHGRBZ-REOHCLBHSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- FCYRSDMGOLYDHL-UHFFFAOYSA-N chloromethoxyethane Chemical compound CCOCCl FCYRSDMGOLYDHL-UHFFFAOYSA-N 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005859 coupling reaction 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
- 238000004090 dissolution Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000006478 transmetalation reaction Methods 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0204—Ethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/06—Boron halogen compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/10—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/04—Halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
- B01J2231/326—Diels-Alder or other [4+2] cycloadditions, e.g. hetero-analogues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
- B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/90—Catalytic systems characterized by the solvent or solvent system used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
Definitions
- the invention relates to Lewis acid solutions in asymmetrically substituted ethers or in solvent mixtures containing asymmetrically substituted ethers and hydrocarbons, the preparation of the solutions according to the invention and the use of the solutions in the inorganic, organic and organometallic synthesis.
- the invention furthermore relates to solutions of the halide compounds of elements from the 8th and 13th group of the Periodic Table of the Elements in asymmetrically substituted ethers or in mixtures of asymmetrically substituted ethers and hydrocarbons.
- Lewis acids find numerous applications in the field of chemical synthesis. By adding Lewis acids, for example in Diels-Alder reactions, radical-mediated reactions, Friedel-Crafts alkylations or acylations or aldol reactions, the yield of a synthesis reaction can be increased and optionally the regio-, enantio- or diastereoselectivity of the corresponding reaction can be controlled ( Yamamoto, Lewis Acids in Organic Synthesis, Wiley-VCH, 2000, Volume 1 and 2, and citations therein).
- Lewis acids find applications in the preparation of organometallic compounds, elemental hydrogen compounds (EH X ), elemental hydrogen compounds, metal element hydrides, and complex metal hydrides, such as in the preparation of copper or organozinc compounds, alan (AIH 3 ), chloralanines (AIH X CI (3 -X )) zinc borohydride or lithium aluminum hydride (P. Knöchel, P. Jones in Organozinc Reagents (editors: LM Harwwod, CJ Moody), Oxford University Press Inc., New York, 1999, and citations therein; C. Eischenbroich, A.
- a further area of application is CC coupling reactions catalyzed by Lewis acids (M.Nakamura, S. Ito, K. Matsuo, E. Nakamura, Synlett., 2005, 11, 1794; A. Mariestner, G. Seidel, DE-A-10355169).
- Solid halogen-containing Lewis acids are usually extremely corrosive and hygroscopic. The problem is therefore the dosage of these solids in the chemical synthesis, since this must be done with exclusion of air and moisture. The adhesion of these compounds to the materials used is also problematic because it causes corrosion and wear.
- the Lewis acids are hydrolyzed on contact with water or atmospheric moisture to release hydrogen halide. The hydrolysis reduce the yield of the reactions, interfere with subsequent reactions, for example by reducing the stereoselectivity, and must be separated consuming. Another disadvantage is that the finely powdered solids can cause burns to the mucous membranes and respiratory tract of the staff.
- halogen-containing Lewis acids dissolve in diethyl ether in high concentrations.
- solubility of aluminum trichloride in diethyl ether at 25 ° C about 55 weight percent (wt .-%), of zinc dichloride, the solubility at 25 ° C is about 50 wt .-%.
- diethyl ether on an industrial scale is due to its low boiling point (34.6 ° C) and the associated high vapor pressure (443 mm Hg, 20 ° C), the low flash point (-40 ° C), the low ignition temperature (1 60 ° C) and the high explosiveness (lower explosion limit 1, 8%, upper explosion limit 48%) problematic.
- a further disadvantage is that diethyl ether is highly prone to the formation of highly explosive peroxides.
- THF tetrahydrofuran
- the solubility of halogen-containing Lewis acids is often low. Very large volumes must be used for a reaction which minimize the space-time yield and render the synthesis uneconomical. For example, the solubility of zinc dichloride at 25 ° C in THF is only about 20% by weight.
- Lewis acids form poorly soluble chelate complexes or decompose with solvents containing more than one donor atom.
- aluminum trichloride with 1,2-dimethoxyethane (1,2-DME) forms an insoluble complex of the composition [(1,2-DME) 3 Al] [CI] 3.
- Attempts to dissolve aluminum trichloride in diethoxymethane result in decomposition of the solvent to form ethoxychloromethane.
- 1,2-DME the solubility of zinc dichloride at 25 ° C is only about 1% by weight.
- the object of the present invention is to overcome the disadvantages of the prior art.
- the object of the present invention is to provide concentrated solutions of Lewis acids in an aprotic, oxygen donor-containing solvent, or mixtures thereof with hydrocarbons, which overcome the disadvantages of the prior art.
- Another object of the invention is to provide solutions of Lewis acids in aprotic, oxygen donor-containing solvents, or mixtures thereof with hydrocarbons, in which these compounds are predominantly monomeric to a high percentage.
- Another object of the invention is to provide solutions of Lewis acids in oxygen donor-containing solvents, or their mixtures with hydrocarbons, which have poor miscibility with water.
- the object is surprisingly achieved by Lewis acids which are dissolved in aprotic, asymmetrically substituted, oxygen donor-containing solvents of the general formula I.
- R 1 R 2 and R 1 , R 2 u ntig each other H, or a functionalized or an unfunctionalized branched or unbranched alkyl, alkyloxy, cycloalkyl, cycloalkyloxy group having 1 to 20 carbon atoms or an aryl or a Aryloxy be used with 1 -12 C-atoms.
- R 1 H, R 2 ⁇ H.
- R 1 and R 2 are: H, methyl, methoxy, methylmethoxy, ethyl, ethoxy, methylethoxy, n-propyl, propoxy, methylpropoxy, iso-propyl, n-butyl, 2-butyl, isobutyl, terf- Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl, hexyl, n-heptyl, iso-heptyl, n -octyl, isooctyl, 2-ethyl-1-hexyl, 2,2,4- Trimethylpentyl, nonyl, decyl, dodecyl, n-dodecyl, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, vinyl, 1-propenyl, 2-propen
- Lewis acids are also present in mixtures of solvents according to the invention with hydrocarbons, for example benzene, toluene, ethylbenzene, m-xylene, p-xylene, o-xylene, cyclohexane, heptane, n-hexane, methylcyclohexane or cumene, preferably toluene , solve in high concentration.
- hydrocarbons for example benzene, toluene, ethylbenzene, m-xylene, p-xylene, o-xylene, cyclohexane, heptane, n-hexane, methylcyclohexane or cumene, preferably toluene , solve in high concentration.
- aprotic, asymmetrically substituted, oxygen donor-containing solvents according to the invention or their mixtures with hydrocarbons are distinguished by excellent solubility for Lewis acids, in particular halogen-containing Lewis acids.
- Lewis acids within the meaning of the invention are molecules, salts or ions which can act as electron pair acceptor with respect to other particles to form a covalent bond.
- Preferred are halides of the 8th, 12th and 1 3rd group of the Periodic Table of the Elements, particularly preferred are the chlorides of boron, zinc and iron.
- the aprotic, asymmetrically substituted, oxygen donor-containing solvents according to the invention are also characterized by a higher boiling point compared with diethyl ether.
- the danger of forming an explosive atmosphere on an industrial scale is thus reduced.
- tetrahydro-2-methylfuran has a boiling point of 77 to 79 ° C.
- a further advantage of the solutions according to the invention of Lewis acids in aprotic, asymmetrically substituted, oxygen donor-containing solvents or in mixtures with hydrocarbons is that, for example, lithium halides or even magnesium halides are poorly soluble in these solvents.
- the solubility of lithium chloride in tetrahydro-2-m ethylfu ran at 25 ° C n u r 0, 05 mmol / g.
- the aprotic, asymmetrically substituted, oxygen donor-containing solvent or mixtures of inventive aprotic, asymmetrically substituted, oxygen donor-containing solvent with Coals of hydrogen are placed in a reactor.
- a Lewis acid is introduced either in one portion or in several portions or by continuous conveyance, for example via a screw conveyor with stirring. The mixture is then stirred until the required amount of Lewis acid is dissolved or until it has completely dissolved.
- a Lewis acid is initially charged and the aprotic, asymmetrically substituted, oxygen donor Lettele or their M ischung m with hydrocarbons - or separated from each other an aprotic, asymmetrically substituted, oxygen donor solvent and hydrocarbons - added and stirred until the desired amount of Lewis acid has dissolved or it has completely dissolved.
- undissolved solid content is separated by decantation, centrifugation or filtration.
- the process is preferably carried out at temperatures between -78 ° C and the boiling point of the solvent or the solvent mixture.
- the proportion of hydrocarbon in the product solution is preferably between 0.1% by weight and 70% by weight.
- the manipulations preferably take place in the absence of air in an inert gas atmosphere, preferably in an Ar or N 2 atmosphere.
- solutions according to the invention are suitable for use in synthetic chemistry, organic chemistry and organometallic chemistry, in particular for: - Lewis acid catalyzed reactions;
- the solvent is introduced into a reactor under an inert gas atmosphere.
- the addition of the Lewis acidic salt is carried out under stirring due to the exothermic nature of the dissolution process in portions under inert gas conditions at the indicated temperatures.
- Technical salts and solvents were used.
- the slightly cloudy solution is clear filtered.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
L'invention concerne des solutions d'acides de Lewis sélectionnés parmi les acides de Lewis halogénés des éléments du 12ème et 13ème groupe de la classification périodique des éléments ou des mélanges de ces acides de Lewis dans des éthers aprotiques à substitution asymétrique ou des mélanges de solvants contenant des éthers à substitution asymétrique et des hydrocarbures. Cette invention concerne également la production des solutions selon l'invention et leur utilisation en synthèse inorganique, organique et organométallique.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102010002811 | 2010-03-12 | ||
| PCT/EP2011/053788 WO2011110691A2 (fr) | 2010-03-12 | 2011-03-14 | Solutions d'acides de lewis dans un solvant ou mélange de solvants contenant des donneurs d'oxygène |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2544819A2 true EP2544819A2 (fr) | 2013-01-16 |
Family
ID=44359823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP11708050A Ceased EP2544819A2 (fr) | 2010-03-12 | 2011-03-14 | Solutions d'acides de lewis dans un solvant ou mélange de solvants contenant des donneurs d'oxygène |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20130142721A1 (fr) |
| EP (1) | EP2544819A2 (fr) |
| CN (1) | CN102939156A (fr) |
| DE (1) | DE102011005499A1 (fr) |
| WO (1) | WO2011110691A2 (fr) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3089938B1 (fr) * | 2014-01-03 | 2018-07-25 | Albemarle Germany GmbH | Procédé de préparation de solutions aprotiques contenant du bromure de zinc et du bromure de lithium |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100827257B1 (ko) * | 2002-01-10 | 2008-05-07 | 다케다 야쿠힌 고교 가부시키가이샤 | 융합 이미다졸 화합물의 제조 방법, 안정한 형태의레포르마츠키 시약 및 이의 제조 방법 |
| DE10355169A1 (de) | 2003-11-26 | 2005-06-23 | Studiengesellschaft Kohle Mbh | Verfahren zur Herstellung von substituierten Arylverbindungen |
| EP1902061B1 (fr) * | 2005-07-01 | 2009-12-30 | Dr Reddy's Laboratories (Eu) Limited | Procédé servant à fabriquer des complexes diphosphine-ruthénium-diamine |
| EP1924524B1 (fr) * | 2005-09-01 | 2012-11-14 | Chemetall GmbH | Procédé de préparation de solutions d'hydrure d'aluminium et de lithium |
| WO2009114313A2 (fr) * | 2008-03-14 | 2009-09-17 | International Partnership For Microbicides | Procédés de synthèse de composés antiviraux |
| CN101643439A (zh) * | 2008-08-07 | 2010-02-10 | 浙江九洲药业股份有限公司 | 一种乙基甲基胺甲酰氯的制备方法 |
-
2011
- 2011-03-14 US US13/634,327 patent/US20130142721A1/en not_active Abandoned
- 2011-03-14 EP EP11708050A patent/EP2544819A2/fr not_active Ceased
- 2011-03-14 CN CN2011800136044A patent/CN102939156A/zh active Pending
- 2011-03-14 DE DE102011005499A patent/DE102011005499A1/de not_active Withdrawn
- 2011-03-14 WO PCT/EP2011/053788 patent/WO2011110691A2/fr not_active Ceased
Non-Patent Citations (2)
| Title |
|---|
| None * |
| See also references of WO2011110691A2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102939156A (zh) | 2013-02-20 |
| WO2011110691A3 (fr) | 2011-11-10 |
| WO2011110691A2 (fr) | 2011-09-15 |
| US20130142721A1 (en) | 2013-06-06 |
| DE102011005499A1 (de) | 2011-09-15 |
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