EP1114054A1 - Verfahren zur herstellung von mono- oder di-organo-boranen - Google Patents
Verfahren zur herstellung von mono- oder di-organo-boranenInfo
- Publication number
- EP1114054A1 EP1114054A1 EP99969417A EP99969417A EP1114054A1 EP 1114054 A1 EP1114054 A1 EP 1114054A1 EP 99969417 A EP99969417 A EP 99969417A EP 99969417 A EP99969417 A EP 99969417A EP 1114054 A1 EP1114054 A1 EP 1114054A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- formula
- compound
- trimethylbenzene
- independently
- group
- 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.)
- Withdrawn
Links
- 229910000085 borane Inorganic materials 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 21
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 18
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 10
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 10
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 10
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 claims description 10
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 9
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 9
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 9
- 150000003254 radicals Chemical class 0.000 claims description 9
- 230000000737 periodic effect Effects 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 229910052796 boron Chemical group 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- MQXCDPDLPMAEIE-UHFFFAOYSA-N bis(2,3,4,5,6-pentafluorophenyl)borinic acid Chemical compound FC=1C(F)=C(F)C(F)=C(F)C=1B(O)C1=C(F)C(F)=C(F)C(F)=C1F MQXCDPDLPMAEIE-UHFFFAOYSA-N 0.000 claims description 6
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- SGVYKUFIHHTIFL-UHFFFAOYSA-N Isobutylhexyl Natural products CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 claims description 5
- -1 di-2-methoxyethyl Chemical compound 0.000 claims description 5
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 5
- VKPSKYDESGTTFR-UHFFFAOYSA-N isododecane Natural products CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 claims description 5
- 229940078552 o-xylene Drugs 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 125000005915 C6-C14 aryl group Chemical group 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 4
- 125000003106 haloaryl group Chemical group 0.000 claims description 4
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 claims description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 3
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- VASOMTXTRMYSKD-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)boronic acid Chemical compound OB(O)C1=C(F)C(F)=C(F)C(F)=C1F VASOMTXTRMYSKD-UHFFFAOYSA-N 0.000 claims description 2
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 2
- TWHSZJXHGGRWTP-UHFFFAOYSA-N 1-[amino-(2,3,4,5,6-pentafluorophenyl)boranyl]-2,3,4,5,6-pentafluorobenzene Chemical compound FC1=C(C(=C(C(=C1B(N)C1=C(C(=C(C(=C1F)F)F)F)F)F)F)F)F TWHSZJXHGGRWTP-UHFFFAOYSA-N 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000012038 nucleophile Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- NPCGBGCBMXKWIH-UHFFFAOYSA-N chloro-bis(2,3,4,5,6-pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(Cl)C1=C(F)C(F)=C(F)C(F)=C1F NPCGBGCBMXKWIH-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000004293 19F NMR spectroscopy Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- DNGCVNLAPRZOAM-UHFFFAOYSA-N dimethyl-bis(2,3,4,5,6-pentafluorophenyl)stannane Chemical compound FC=1C(F)=C(F)C(F)=C(F)C=1[Sn](C)(C)C1=C(F)C(F)=C(F)C(F)=C1F DNGCVNLAPRZOAM-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- VIGVRXYWWFPORY-UHFFFAOYSA-N diphenylborinic acid Chemical compound C=1C=CC=CC=1B(O)C1=CC=CC=C1 VIGVRXYWWFPORY-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- LOOIBNGLXZDUKT-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)tin Chemical compound FC1=C(F)C(F)=C([Sn])C(F)=C1F LOOIBNGLXZDUKT-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ZFMOJHVRFMOIGF-UHFFFAOYSA-N 2,4,6-trimethoxy-1,3,5,2,4,6-trioxatriborinane Chemical compound COB1OB(OC)OB(OC)O1 ZFMOJHVRFMOIGF-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HXLSIFPWUAFXOF-UHFFFAOYSA-N NCCOB(C1=CC=CC=C1)C1=CC=CC=C1.C(O)CN Chemical compound NCCOB(C1=CC=CC=C1)C1=CC=CC=C1.C(O)CN HXLSIFPWUAFXOF-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000004639 Schlenk technique Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- YMEKEHSRPZAOGO-UHFFFAOYSA-N boron triiodide Chemical compound IB(I)I YMEKEHSRPZAOGO-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- RBMCKUNBFWVWQJ-UHFFFAOYSA-N dichloro-(2,3,4,5,6-pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(B(Cl)Cl)C(F)=C1F RBMCKUNBFWVWQJ-UHFFFAOYSA-N 0.000 description 1
- DOHQOGRRQASQAR-UHFFFAOYSA-L dimethyltin(2+);dibromide Chemical compound C[Sn](C)(Br)Br DOHQOGRRQASQAR-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZDNZXKMCNCTLGN-UHFFFAOYSA-N methyl-tris(2,3,4,5,6-pentafluorophenyl)stannane Chemical compound FC=1C(F)=C(F)C(F)=C(F)C=1[Sn](C=1C(=C(F)C(F)=C(F)C=1F)F)(C)C1=C(F)C(F)=C(F)C(F)=C1F ZDNZXKMCNCTLGN-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KSBKVGFAMLUKFL-UHFFFAOYSA-N tetrakis(2,3,4,5,6-pentafluorophenyl)stannane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1[Sn](C=1C(=C(F)C(F)=C(F)C=1F)F)(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F KSBKVGFAMLUKFL-UHFFFAOYSA-N 0.000 description 1
- GABHTFORECKGBB-UHFFFAOYSA-N trimethyl-(2,3,4,5,6-pentafluorophenyl)silane Chemical compound C[Si](C)(C)C1=C(F)C(F)=C(F)C(F)=C1F GABHTFORECKGBB-UHFFFAOYSA-N 0.000 description 1
- CMBHQACAYHEMEZ-UHFFFAOYSA-N trimethyl-(2,3,4,5,6-pentafluorophenyl)stannane Chemical compound C[Sn](C)(C)C1=C(F)C(F)=C(F)C(F)=C1F CMBHQACAYHEMEZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
Definitions
- the present invention relates to a new process for the preparation of perhalogenated mono- or di-organoboranes which makes these compounds accessible under conditions which are technically feasible.
- diorgano-hydroxy-boranes Various methods for the preparation of diorgano-hydroxy-boranes are described in the prior art. For example, Davidson et al. the preparation of diorgano-hydroxy boranes from dioxy organoboranes with Grignard compounds (J.M. Davidson et al., French Soc, 1960, 191). The production of diorgano-hydroxyboranes from Lewis base diorgano-oxyboranes is also known. For this purpose, diaryl-hydroxyboranes with the connection of 2-aminoethanol are prepared as salts with the aid of aqueous mineral acids. Acid hydrolysis gives the desired diorganohydroxyboranes (R.L. Letsinger, I. Skoog, J. Am. Chem. Soc, 77, 1955, 2491).
- di (pentafluorophenyl) hydroxy borane can be prepared by hydrolysis of di (pentafluorophenyl) chloroborane in acetone (R.D. Chambers, T. Chivers, J. Chem. Soc, 1965, 3933). The production of
- Organoboron compounds are distinguished as effective co-catalysts in the polymerization of olefins with metallocenes (M. Bochmann, J. Chem. Soc, Dalton Trans, 1996, 255-270). Partially or perhalogenated diorganohydroxy boranes, in particular, serve as precursors for the production of corresponding co-catalysts.
- the present invention relates to a process for the preparation of compounds of the formula (I)
- R 1 independently of one another, the same or different, represents a hydrogen atom, a halogen atom, a C 1 -C 8 -carbon-containing group such as (C x -C 2 o) alkyl, (C 6 -C 4 ) aryl, (Cj-Cio) alkoxy, (C 2 -C ⁇ o) alkenyl, ' (C 7 -C 20 ) arylalkyl, (C 7 -C 20 ) alkylaryl, (C 6 -C ⁇ 0 ) aryloxy, (Ci-Cio) haloalkyl, (C ⁇ -Cio) haloaryl, (C 2 -C ⁇ o) alkynyl or C 3 -C 20 alkylsilyl,
- M is an element of the III main group of the Periodic Table of the Elements, preferably aluminum and boron, very particularly preferably boron, X independently of one another, the same or different, and for an element of V. or VI.
- Main group of the Periodic Table of the Elements preferably oxygen and nitrogen
- R 9 is a hydrogen atom or a C 1 -C 2 -carbon-containing group such as (C 1 -C 0 ) alkyl or (C 6 -C 3.4 ) aryl,
- p is an integer 1 or 2
- 1 is an integer 0 or 1
- R 1 represents the radicals listed under formula (I),
- M 1 represents an element of the IV main group of the Periodic Table of the Elements, preferably silicon and tin, very particularly preferably tin,
- R 2 is, independently of one another, identical or different, a hydrogen atom, a halogen atom, a C 1 -C 8 -carbon-containing group such as (C 1 -C 20 ) alkyl or (C 6 -Ci 4 ) aryl, and
- n is an integer from 0 to 3
- R 3 , R, R 5, independently of one another, the same or different, represent a hydrogen atom, a halogen atom, a
- -C-C 2 o _ carbon-containing group such as (-C-C 2 o) -alkyl, (C 6 -C ⁇ 4 ) aryl, (C1-C10) -alkoxy, (C 2 -C10) -alkenyl, (C 7 - C 2 o) arylalkyl, (C 7 -C 20 ) alkylaryl, (C 6 -C ⁇ 0 ) aryloxy, (C 1 -C 10 ) haloalkyl, (Ce-Cio) haloaryl,
- R 6 is a C ⁇ -C 2 o ⁇ carbon - containing group such as (-C-C 20 ) alkyl or (C 6 -C 14 ) aryl, or one or more radicals R 3 , R 4 , R 5 are a -NR 7 2 group, wherein R 7 is a hydrogen atom , a halogen atom, a C ⁇ -C 2 o-carbon-containing group such as
- R 1 represents the radicals listed under formula (I),
- M represents an element of the III main group of the Periodic Table of the Elements, preferably aluminum and boron, very particularly preferably boron,
- R 8 independently of one another, the same or different, is preferred for a hydrogen atom or a halogen atom
- Bromine or chlorine, particularly preferably chlorine, is and
- n is an integer 0 or 1
- Nucleophile such as, for example, a compound of the formula H-XR 9 p , where X and R 9 are the radicals listed under the formula (I) and p is 1 or 2, in an organic medium, after the compound has been split off HR 8 the compound of formula (I) is obtained,
- Preferred compounds of the formula (II) are pentafluorophenyltrimethylstannane, bis (pentafluorophenyl) dimethylstannane, tris (pentafluorophenyl) methylstannane, tetrakis (pentafluorophenyl) stannane, pentafluorophenyltrimethylsilane and bis (pentafluoromethylstannane).
- Preferred compounds of the formula (III) are boron trifluoride, boron trichloride, boron tribromide, boron triiodide.
- Donor complexes such as boron trifluoride-diethyl ether complex or boron trichloride-diethyl ether complex are also preferred.
- the compounds bis (pentafluorophenyl) -hydroxyborane, pentafluorophenyl-dihydroxyborane and bis (pentafluorophenyl) aminoborane described by the formula (I) are particularly accessible in industrial quantities.
- one or more compounds of the formula (III) are placed in a reaction vessel.
- the compounds can either be dissolved or suspended in a solvent, or else be in bulk.
- Aliphatic or aromatic hydrocarbons such as n-pentane, isopentane, n-hexane, n-heptane, cyclohexane, isododecane, n-octane, n-nonane, n-decane, petreleomether, toluene, benzene, o-xylene, m- Xylene, p-xylene, 1, 2, 3-trimethylbenzene, 1, 2, 4-trimethylbenzene, 1,2,5-trimethylbenzene, 1,3, 5-trimethylbenzene, ethylbenzene, propylbenzene, etc as well as mixtures of these.
- Solvents with donor molecules can also be used, e.g. Diethyl ether, diisopropyl ether, dibuthyl ether, diisoamyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, di-2-methoxyethyl, tetrahydrfuron,
- the solvents are preferably aprotic.
- One or more compounds of the formula (III) are initially introduced at temperatures between -100 ° C. and 200 ° C. Temperatures between -80 ° C and 40 ° C are preferred. Temperatures between -80 ° C and 0 ° C are particularly preferred.
- the compound of formula (III) should be in the liquid phase.
- one or more compounds of the formula (II) are added. These can also be dissolved or suspended in a solvent, but can also be in substance.
- the solvents already described above are used as solvents, preferably the same solvent is used.
- the addition takes place over a period of 1 minute to 96 hours. An addition time of 10 minutes to 8 hours is preferred.
- the temperature of the sample is between -100 ° C and 200 ° C when added. Temperatures between -80 ° C and 40 ° C are preferred. Temperatures between -80 ° C and 0 ° C are particularly preferred.
- the Temperature is chosen so that at least one reactant is in the liquid phase. Furthermore, the reaction is carried out at normal pressure.
- cooling is carried out with an intensive cooler, which is optionally operated with refrigerants.
- an intensive cooler which is optionally operated with refrigerants.
- a cooler is operated at -20 ° C., so that the boron trichloride does not escape.
- the stoichiometric ratio between compounds of the formula (III) and compounds of the formula (II) is between 1000: 1 and 1: 100.
- a stoichiometric ratio between compounds of the formula (III) and compounds of the formula (II) is between 100: 1 and 1:10.
- the reaction temperature is between -100 ° C and 200 ° C.
- a reaction temperature between 0 ° C. and 150 ° C. is preferred.
- a reaction temperature between 50 ° C. and 150 ° C. is particularly preferred.
- At least one reactant is preferably in the liquid phase.
- the reaction is particularly preferably carried out under reflux. It is also advantageous if the bath temperature of the heating bath is between 50 ° C and 200 ° C, so that the reaction time is considerably shortened. Depending on the reaction temperature chosen, the reaction time is between 1 minute and up to 96 hours. A reaction time of 10 minutes to 8 hours is preferred.
- Suitable extractants are, for example, n-pentane, isopentane, n-hexane, n-heptane, cyclohexane, isododecane, n-octane, n-nonane, n-decane, petreleomether, toluene, benzene, o-xylene, m-xylene, p-xylene, 1, 2, 3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2, 5-trimethylbenzene, 1, 3, 5-trimethylbenzene, ethylbenzene, propylbenzene and mixtures of these.
- a compound of formula (IV) is dissolved or suspended in an organic medium (step C).
- Aprotic, aliphatic or aromatic hydrocarbons such as n-pentane, isopentane, n-hexane, n-heptane, cyclohexane, isododecane, n-octane, n-nonane, n-decane, petroleum ether, toluene, benzene, o-xylene are used as the organic medium , m-xylene, p-xylene, 1,2, 3-trimethylbenzene, 1, 2, 4-trimethylbenzene, 1,2, 5-trimethylbenzene, 1, 3, 5-trimethylbenzene, ethylbenzene, propylbenzene and mixtures thereof.
- agents with donor properties such as diethyl ether, diisopropyl ether, dibuthyl ether, diisoamyl ether, 1, 2-dimethoxyethane, 1,2-diethoxyethane, di-2-methoxyethyl, tetrahydrofuron, tetrahydropyran, 1,4-dioxane can be used.
- the subsequent reaction with compounds of the formula H-XR p 9 with elimination of a compound of the formula HR 8 gives the corresponding compounds of the formula (I).
- the reaction can be carried out in bulk or in an organic medium described above, and the reagents can be added suspended or dissolved. The addition takes place over a period of 1 minute to 96 hours. An addition time of 10 minutes to 8 hours is preferred.
- the temperature of the sample is between -100 ° C and 200 ° C when added. Temperatures between -10 ° C and 40 ° C are preferred.
- the reagents used such as water, ammonia, primary amines, secondary amines, alcohols or thiols, can be used stoichiometrically or in excess.
- step D) The resulting compounds of formula (I) can be obtained in step D) using known technologies such as e.g. Distillation, recrystallization, extraction or sublimation can be isolated.
- known technologies such as e.g. Distillation, recrystallization, extraction or sublimation can be isolated.
- the following examples serve to explain the invention in more detail.
- the ammonium chloride solution was slowly added dropwise, a gray, black precipitate separating out.
- the mixture is stirred for half an hour and then the organic phase from the precipitate and the aqueous phase separates.
- the precipitate and aqueous phase are shaken out with 200 ml of n-heptane.
- the combined organic phases are distilled with 50 ml. H 2 0 shaken and dried over 100g MgSÜ 4 . After the desiccant has been separated off, the solvent is drawn off in an oil pump vacuum and the remaining dark brown solution is fractionally distilled. The overall yield is 93%.
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Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE19843055 | 1998-09-19 | ||
DE1998143055 DE19843055A1 (de) | 1998-09-19 | 1998-09-19 | Verfahren zur Herstellung von Mono- oder Di-organo-boranen |
PCT/EP1999/006861 WO2000017208A1 (de) | 1998-09-19 | 1999-09-16 | Verfahren zur herstellung von mono- oder di-organo-boranen |
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EP1114054A1 true EP1114054A1 (de) | 2001-07-11 |
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EP99969417A Withdrawn EP1114054A1 (de) | 1998-09-19 | 1999-09-16 | Verfahren zur herstellung von mono- oder di-organo-boranen |
Country Status (5)
Country | Link |
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EP (1) | EP1114054A1 (de) |
JP (1) | JP2002526503A (de) |
AU (1) | AU5978899A (de) |
DE (1) | DE19843055A1 (de) |
WO (1) | WO2000017208A1 (de) |
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IL146684A0 (en) | 2000-11-29 | 2002-07-25 | Nippon Catalytic Chem Ind | Method for purifying fluoroaryl metal compound |
IL146683A (en) | 2000-11-29 | 2005-07-25 | Nippon Catalytic Chem Ind | Method for producing fluoroaryl metal compound |
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DE19632558A1 (de) * | 1996-08-13 | 1998-02-19 | Hoechst Ag | Geträgerte chemische Verbindung |
DE19733017A1 (de) * | 1997-07-31 | 1999-02-04 | Hoechst Ag | Chemische Verbindung |
ATE243700T1 (de) * | 1998-02-20 | 2003-07-15 | Dow Global Technologies Inc | Expandierte anionen enthaltende katalysatoraktivatoren |
-
1998
- 1998-09-19 DE DE1998143055 patent/DE19843055A1/de not_active Withdrawn
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1999
- 1999-09-16 AU AU59788/99A patent/AU5978899A/en not_active Abandoned
- 1999-09-16 WO PCT/EP1999/006861 patent/WO2000017208A1/de not_active Application Discontinuation
- 1999-09-16 JP JP2000574117A patent/JP2002526503A/ja active Pending
- 1999-09-16 EP EP99969417A patent/EP1114054A1/de not_active Withdrawn
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See references of WO0017208A1 * |
Also Published As
Publication number | Publication date |
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JP2002526503A (ja) | 2002-08-20 |
WO2000017208A1 (de) | 2000-03-30 |
AU5978899A (en) | 2000-04-10 |
DE19843055A1 (de) | 2000-03-23 |
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