CN1140533C - 磷杂苯类化合物的制备 - Google Patents
磷杂苯类化合物的制备 Download PDFInfo
- Publication number
- CN1140533C CN1140533C CNB988096943A CN98809694A CN1140533C CN 1140533 C CN1140533 C CN 1140533C CN B988096943 A CNB988096943 A CN B988096943A CN 98809694 A CN98809694 A CN 98809694A CN 1140533 C CN1140533 C CN 1140533C
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- CN
- China
- Prior art keywords
- reaction
- hydrogen
- crust
- alkyl
- phenyl
- 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.)
- Expired - Fee Related
Links
- UNQNIRQQBJCMQR-UHFFFAOYSA-N phosphorine Chemical class C1=CC=PC=C1 UNQNIRQQBJCMQR-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical class C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 18
- -1 hydrosulfate Chemical compound 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 16
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 239000011541 reaction mixture Substances 0.000 claims description 10
- 229910052728 basic metal Inorganic materials 0.000 claims description 5
- 150000003818 basic metals Chemical class 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 abstract description 9
- 125000005842 heteroatom Chemical group 0.000 abstract description 4
- 125000002877 alkyl aryl group Chemical group 0.000 abstract description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 125000003277 amino group Chemical group 0.000 abstract 1
- 150000001450 anions Chemical group 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 239000003085 diluting agent Substances 0.000 abstract 1
- 125000000592 heterocycloalkyl group Chemical group 0.000 abstract 1
- 125000004043 oxo group Chemical group O=* 0.000 abstract 1
- 125000004354 sulfur functional group Chemical group 0.000 abstract 1
- 239000002585 base Substances 0.000 description 12
- 238000007037 hydroformylation reaction Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CFEYBLWMNFZOPB-UHFFFAOYSA-N Allylacetonitrile Natural products C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 2
- PYFVRMNFLPOIHE-UHFFFAOYSA-N 1-phenylethanone;sodium Chemical compound [Na].CC(=O)C1=CC=CC=C1 PYFVRMNFLPOIHE-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- LIINGNMKNRSOGW-UHFFFAOYSA-N oct-7-enal Chemical compound C=CCCCCCC=O LIINGNMKNRSOGW-UHFFFAOYSA-N 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- ZOLLIQAKMYWTBR-MOLCZBCNSA-N (1z,5z,9z)-cyclododeca-1,5,9-triene Chemical compound C\1C\C=C/CC\C=C/CC\C=C/1 ZOLLIQAKMYWTBR-MOLCZBCNSA-N 0.000 description 1
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 1
- UVKXJAUUKPDDNW-NSCUHMNNSA-N (e)-pent-3-enenitrile Chemical compound C\C=C\CC#N UVKXJAUUKPDDNW-NSCUHMNNSA-N 0.000 description 1
- VCHOFVSNWYPAEF-UHFFFAOYSA-N 1-(3-acetylphenyl)ethanone Chemical compound CC(=O)C1=CC=CC(C(C)=O)=C1 VCHOFVSNWYPAEF-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical group CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- SPVWSVYJPGRPFL-UHFFFAOYSA-N 2,4,6-triphenylphosphinine Chemical compound C1=CC=CC=C1C1=CC(C=2C=CC=CC=2)=PC(C=2C=CC=CC=2)=C1 SPVWSVYJPGRPFL-UHFFFAOYSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical class CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- XGCGBERCJBVJJA-UHFFFAOYSA-N P.C(O)O Chemical compound P.C(O)O XGCGBERCJBVJJA-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- MNZMECMQTYGSOI-UHFFFAOYSA-N acetic acid;hydron;bromide Chemical compound Br.CC(O)=O MNZMECMQTYGSOI-UHFFFAOYSA-N 0.000 description 1
- NENDHUHGFRLXEN-UHFFFAOYSA-N acetic acid;rhodium Chemical compound [Rh].CC(O)=O NENDHUHGFRLXEN-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- ZIQCCIAIROIHHR-UHFFFAOYSA-N benzene;boric acid Chemical compound OB(O)O.C1=CC=CC=C1 ZIQCCIAIROIHHR-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 1
- JMXMXKRNIYCNRV-UHFFFAOYSA-N bis(hydroxymethyl)phosphanylmethanol Chemical compound OCP(CO)CO JMXMXKRNIYCNRV-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- DJAVXMMLFOAEMI-UHFFFAOYSA-N ethene 2-methylpropylbenzene Chemical compound C(C(C)C)C1=CC=CC=C1.C=C DJAVXMMLFOAEMI-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910021472 group 8 element Inorganic materials 0.000 description 1
- 229910001689 halotrichite Inorganic materials 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 235000015598 salt intake Nutrition 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- AKXUUJCMWZFYMV-UHFFFAOYSA-M tetrakis(hydroxymethyl)phosphanium;chloride Chemical compound [Cl-].OC[P+](CO)(CO)CO AKXUUJCMWZFYMV-UHFFFAOYSA-M 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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Abstract
本发明涉及一种制备式I和II所示磷杂苯类化合物的方法,其中R1-R6彼此独立地是氢、COOM、SO3M、NR3X、NR2、OR、COOR或SR,其中M是氢、NH4或碱金属,X是阴离子,R是氢或C1-6-烷基,或R1-R6彼此独立地是C1-12-烷基、C6-12-芳基、C7-12-芳烷基或具有1-3个杂原子的C3-6杂环烷基,并且它们可以被上述基团取代或连接形成稠环,-W-是选自共价键、氧基、硫基、氨基、二-C1-6-烷基硅基或C1-16-基团的桥连单元,该桥连单元可以是一个或多个相连环状或芳香环的组成部分且可以间隔有1-3个杂原子,其中所述磷杂苯环中的、未与所述桥连单元相键合的邻位或间位可以带有基团R1-R6之一,但不包括双-3,3’-(2,4,6-三苯基-3-磷杂苯)-1,1-联苯,该方法是使相应的吡喃鎓盐在催化量的酸和有或没有溶剂或稀释剂存在下与PH3反应,其中该吡喃鎓盐在0℃以上与PH3混合且在0℃-200℃和压力大于1巴的条件下反应。
Description
磷杂苯类化合物在烯烃的加氢甲酰化合成中可以用作过渡金属配合物的配体。在标题为“加氢甲酰化方法及其含有适合作为配体的磷化合物的催化剂”的DE-A 196 21 967中,描述了相应的配合物及其制备方法,该申请具有在先的优先权日,但在本申请的优先权日之前未公开。根据其中的一种制备方法,双-3,3’-(2,4,6-三苯基-3-磷杂苯)-1,1’-联苯可以由相应的吡喃鎓盐与膦反应制得。
DE-A 1 618 668公开了一种取代磷杂苯的制备方法,其中吡喃鎓盐是与三羟甲基膦、四羟甲基氯化膦或四羟甲基氢氧化膦反应。但膦类化合物难以制备,所以该方法是不经济的。
F.Lieb在“膦类化合物的合成和反应,对制备含有砷-碳双键体系的研究”(开幕式论文,伍兹堡,1969,106-107页)中公开了2,4,6-三苯基磷苯(2,4,6-三苯基磷杂苯)的制备方法,其中2,4,6-三苯基吡喃鎓四氟硼酸盐在正丁醇中与溶于稀释剂中的-78℃的PH3反应。当反应容器被密封后,该反应是在110℃和自生压力的条件下进行41小时。
在自生压力条件下进行反应的缺点在于,反应物的浓度不断改变,并且反应花费较长的时间。在-78℃下引入PH3需要使用相应的冷却设备。在密闭反应容器中进行的该制备方法难以或无法控制。
本发明的一个目的是,提供一种经济且能避免现有技术方法所存缺陷的制备磷杂苯类化合物的方法。
其中R1-R6彼此独立地是氢、COOM、SO3M、NR3X、NR2、OR、COOR或SR,其中M是氢、NH4或碱金属,X是阴离子,R是氢或C1-6-烷基,或R1-R6彼此独立地是C1-12-烷基、C6-12-芳基、C7-12-芳烷基或具有1-3个杂原子的C3-6杂环烷基,并且它们可以被上述基团取代或连接形成稠环;
W是选自共价键、氧基、硫基、氨基、二-C1-6-烷基硅基或C1-16-基团的桥连单元,该桥连单元可以是一个或多个相连环状或芳香环的组成部分并可以间隔有1-3个杂原子,其中所述磷杂苯环中的、未与所述桥连单元相键合的邻位或间位可以带有基团R1-R6之一,但不包括双-3,3’-(3-甲基(2,4,6-三苯基磷杂苯))-1,1’-联苯,该方法是使相应的吡喃鎓盐在催化量的酸和有或没有溶剂或稀释剂存在下与PH3反应。在新的制备方法中,吡喃鎓盐在高于0℃的温度下与PH3混合,并且在0℃-200℃和压力大于1巴的条件下反应。
现已发现,按照本发明所述,如果维持所定的工艺条件不变,则使相应的吡喃鎓盐、即其中式I和II的磷被带有相应抗衡离子的O+所替代的化合物与PH3反应,可以获得上式所示的磷杂苯类化合物。所述吡喃鎓盐可以购得或易于制备。PH3是市售产品。
所述反应适宜在0.1-100巴,优选5-35巴,更优选20-30巴的PH3分压下进行。体系的总压力取决于所用的具体溶剂。通过注入PH3或惰性气体可以提高总压力。
在一个优选制备方法中,PH3是在反应期间通入反应混合物内,以保持PH3的分压基本恒定。该方法特别经济且迅速反应,得到预期的磷杂苯化合物。产物高度纯净且转化率高。这种新方法适用于多种不同的产物。该方法可以连续或分批进行,更优选分批进行。
在一个较优选的制备方法中,吡喃鎓盐在室温下与PH3混合,所得混合物被加热至110℃-130℃,以便进行反应。
反应期间的温度更优选是115-125℃。该反应适宜在高压反应釜内进行。除PH3之外,另外也可以使用惰性气体来达到预定的总压。但是,优选单独使用PH3。
所述反应是在溶剂或稀释剂存在或不存在的条件下进行。优选在溶剂或稀释剂存在下进行。适用的溶剂或稀释剂例如是低级脂肪醇,如甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、叔丁醇或戊醇异构体;优选乙醇、丙醇或丁醇,更优选正丁醇。
所述反应适宜在酸催化剂的存在下进行。适用的酸催化剂是无机酸,如HI、HCl或HBr。具体而言,可以用溶于醋酸或醋酸酐中的氢溴酸作为酸催化剂。
反应之后,将反应混合物适当减压,并且,如果需要,可以用惰性气体冲洗。为的是以液态形式除去未反应的PH3,将从反应混合物逸出的气体冷却并通过一个分离器,以使被分离的PH3再次加入到反应中。
因此,一个特别经济且生态可接受的方法是,将PH3通入反应器,进行反应,气流经另一途径通过任何按需设计的冷凝器,其中PH3被冷凝出来。在任意按需设计的分离器的下游,PH3被分离且再次加入到反应中,例如在泵的辅助下重新加入反应。为了能够脱气,特别是PH3中较低量的气体,优选使用二级下游冷凝器和分离器。鉴于PH3的毒性,为了使反应器的气体空间和所用装置完全没有PH3,应提供惰性气体如氮气的冲洗管。冲洗气体应通过冷凝器和分离器的组合装置。
反应所需的时间取决于吡喃鎓盐的种类和性质。根据吡喃鎓盐的不同,反应适宜进行1-4小时。以所用吡喃鎓盐计,溶剂的比例优选5-50%(重量),更优选15-35%(重量)。以吡喃鎓盐计,酸催化剂的用量优选0.01-1%(重量),更优选0.03-0.1%(重量)。在反应使用了溶剂的情况中,PH3在溶剂中的浓度取决于PH3的分压和溶剂的性质;特别是在连续进行反应的情况中,应保持PH3在溶剂中的高浓度。
为了在较短的反应时间中获得高转化率,优选采用高PH3分压并令PH3连续后加压回流。
所述新方法可以选用多种不同的吡喃鎓盐。该方法一般不局限在某类化合物。例如,吡喃鎓盐可以是高铁酸盐、锌酸盐、盐酸盐、硼酸盐,必要时带有一个C1-6烷基、三氟酸盐(triflate)、三氟醋酸盐或优选的四氟硼酸盐、高氯酸盐、硫酸氢盐、溴化物、碘化物或其混合物。优选四氟硼酸盐。本发明所用吡喃鎓盐中的有机基团将在下文中参考其制备的磷杂苯化合物作详细描述。
在上式I的化合物中,基团R1-R5彼此独立地是氢、COOM、SO3M、NR3X、NR2、OR、COOR或SR,其中M是氢、NH4或碱金属,X是阴离子,R是氢、C1-6-烷基,或R1-R5彼此独立地是C1-12-烷基、C6-12-芳基、C7-12-芳烷基或具有1-3个杂原子的C3-6-杂环烷基,其中所述烷基、芳基和芳烷基可以被上述基团取代或连接形成稠环。R1-R5可以相同或不同。R1-R5优选是烷基、芳基或芳烷基,它们可以被取代。
如果两个或多个基团相连形成稠环,所述化合物可以是磷杂萘或更高级的芳香化合物。所述基团优选是C6-12-芳基,具体优选苯基,或是C7-12-芳烷基,具体优选苄基。
特别优选那些其中邻位和/或对位被取代或未取代苯基取代的式I化合物。特别是,邻位和对位全部被苯基取代。如果希望是盐的形式,这些取代基适宜是酸基或胺基,特别是在对位取代。此外,一个或两个间位可以被苄基取代。
在式II的化合物中,R1-R6如上述定义。-W-代表选自共价键、氧基、硫基、氨基、二-C1-6-烷基硅基或C1-16-基团、优选C1-6-基团的桥连单元,该桥连单元可以是一个或多个相连的环状或芳香环的组成部分并可以间隔有1-3个杂原子,其中各磷杂苯环的未与所述桥连单元相键合的邻位或间位可以带有基团R1-R6之一。
例如,桥连单元W可以是如式CR7R8所示的取代或未取代亚甲基,其中R7和R8可以相同或不同,并且可以是氢或碳原子总数为1-15的烷基或苯基,或碳原子不超过16个的烷芳基或芳烷基。
此外,-W-可以是氧基(-O-)、硫基(-S-)、二-C1-6烷基硅基(-Si(烷基)2-)或氨基-NR9-,其中R9是C1-6-烷基、C6-12-芳基或C7-15-芳烷基,具体如苄基。
-W-可以含有一个或多个相连的环状或芳香环,更优选一个或两个环状或芳香环。例如,W可以是邻-、间-或对-亚苯基。其他的适用基团是环烷二基,具体如环戊二基和环己二基。适用的芳二基例如是1,1’-联苯二基、萘二基、联苯醚二基、二苯甲二基、二苯乙二基、二苯丙二基和铁茂二基。适用的磷杂苯化合物的例子在上述DE-A 196 21 967中提及:
ph=phenyl X=C,Si X=C,Si
X=CH2,(CH2)2,SiMe2
用于直接与PH3反应的吡喃鎓盐可按照例如在Houben-Weyl,杂芳烯类II,第2部,R.Kreher编辑,第E7b卷,第755ff页,(Thiene出版社,斯图加特)中所述的内容来获得。
本发明制备的化合物可以用来制备元素周期表中第VIII副族金属的配合物。这些配合物在加氢甲酰化反应中可用作助催化剂。在DE-A196 21 967中描述了适当的反应条件。
活性催化剂是如式M(L)n(CO)m所示的那些物质,其中M是至少一种元素周期表第VIII族元素的中心原子,L是至少一种式I-IV所示的配体,n和m分别至少是1,其中例如,对于每1当量的M来说,n和m分别为1和3,并且n+m之和为2-5,并且其中其它基团如氢、烷基或酰基可以作为配体存在。
通常,活化羰基配合物是由金属M的盐或化合物、配体和一氧化碳就地制成,即在加氢甲酰化反应釜中制成;而且,它也可以单独制备并使用。
所述配合物催化剂适宜由与羰基和氢、烷基或酰基以及作为配体的本发明优选单齿配体或多齿配体磷杂苯类化合物相配合的中心原子M构成,M选自过渡金属钴、钌、铑、钯和铂,但更优选钴和铑。如果所述配合物催化剂是就地生成,则令前体配合物,如乙酰基醋酸双羰基铑或醋酸铑,直接在相应配体的存在下处于反应条件下;或向前体配合物中加入活化添加剂,例如布朗斯特或路易斯酸或路易斯碱。
对于在反应混合物中就地生成的催化剂,配体与铑的摩尔比为1∶1-1000∶1(以当量的磷计算),另外还采用惰性溶剂。特别优选的溶剂是不同烯烃通过反应形成的醛类化合物,以及合成中固有的高沸点化合物,它们是由各种醛在加氢甲酰化过程中进一步反应生成的。在通过适当取代、将配体亲水化处理的情况中,优选水、醇或其它极性溶剂。
加氢甲酰化新方法中所用的合成气体CO/H2的组成可以在较宽范围内变化。例如,采用CO/H2摩尔比为5∶95-70∶30的合成气体就很成功。优选合成气体的CO/H2摩尔比是40∶60-60∶40。更优选的CO/H2比例约是1∶1。
采用催化剂的加氢甲酰化反应适宜在20-180℃,优选50-150℃内进行。但是,最佳的温度应根据各个催化剂体系通过试验测定。反应压力可以在常压至700巴内变化,这取决于助催化剂、即配体和底物,优选至多300巴;术语“低压反应”一般是指反应在至多约30巴的压力下进行,术语“中压反应”一般是指反应在至多约100巴的压力下进行,术语“高压反应”一般表示反应是在高于100巴的压力下进行。
通常,反应是在催化剂均匀溶解在反应介质的条件下进行;催化剂被从加氢甲酰化反应产物中分离出来,并且再次加入到加氢甲酰化步骤中。
一般地,相应的醛事实上是以优异的收率唯一地获得。
可以在本发明中被加氢甲酰化的烯烃是α-烯烃、内烯烃或支链内烯烃。例如,可具体提及下列烯烃:乙烯、丙烯、1-丁烯、1-辛烯、C5-20-α-烯烃、直链内C5-20-烯烃、2-丁烯;支链内辛烯混合物;支链内壬烯混合物;支链内十二碳烯混合物;环己烯、α-蒎烯、苯乙烯、4-异丁基苯乙烯、3-戊烯酸甲酯、4-戊烯酸甲酯、油酸甲酯、3-戊烯腈、4-戊烯腈、2,7-辛二烯-1-醇、7-辛烯醛、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯腈、醋酸乙烯酯、二醋酸乙烯乙二醇酯、乙烯基甲基醚、聚丙烯和聚异丁烯。其它适用的底物是含有分立的或共轭的双键的二烯类化合物和多烯烃。例如1,3-丁二烯、1,5-己二烯、乙烯基环己烯、双环戊二烯、1,5,9-环辛三烯、丁二烯均聚物和-共聚物,以及聚异丁烯。
此外,加氢甲酰化反应是以已知方式进行。Beller等人在《分子催化杂志》A:104(1995)17-85页中和Falbe编辑的《采用一氧化碳的新合成方法》(Springer,柏林)1980,第5页中详细描述了这种反应方法。
本发明将参考下列实施例更详细地举例说明。
实施例1-62,4,6-三苯基磷杂苯
2,4,6-三苯基磷杂苯是由市售的2,4,6-三苯基吡喃鎓四氟硼酸盐(Aldrich)和PH3制得。盐的用量分别是4mmol或63mmol。全部实验是在容量为300ml的高压反应釜(材料HC)中进行。向高压反应釜中分别加入100g或150g的正丁醇作为溶剂,并分别加入0.5g或1.0g溶于醋酸中的氢溴酸(30%重量,Aldrich)作为催化剂且通入5巴的氮气。随后将气体空间用PH3冲洗1次。此后在室温下通入5巴的PH3,并使PH3连续通入直至压力稳定在5巴。进而将反应混合物加热至110℃的反应温度,并用气体扩散搅拌器剧烈搅动该溶液。压力自动变成12巴。反应随后在12巴的压力下进行,利用压力调节器反复通气来使反应釜中的压力在反应过程中维持在预定的压力水平。反应完毕后,冷却该高压反应釜,减压,在搅拌的同时用氮气彻底冲洗,并且卸开设备。将高压反应釜中的产物蒸发至半,并在冰箱中过夜结晶。抽滤出结晶,用戊烷洗涤3次并干燥。将结晶和母液称重,通过气相色谱、用内标和校正系数测定磷杂苯的比例。结果如下表所示:
实施例 | 量g(mmol) | 时间小时 | 压力巴 | 固体中配体的含量%(重量) | 固体的重量g | 固体的收率% | 固体+母液的收率% |
1 | 1.58(4) | 1 | 10.8 | 99.8 | 0.78 | 60 | 68 |
2 | 1.58(4) | 4 | 10.4 | 100.0 | 0.91 | 70 | 78 |
3 | 1.58(4) | 41 | 10.5 | 99.9 | 0.92 | 71 | 78 |
4 | 1.58(4) | 1 | 20 | 99.9 | 1.00 | 77 | 86 |
5 | 1.58(4) | 1 | 30 | 99.9 | 1.00 | 77 | 82 |
6 | 25(63) | 4 | 30 | 99.9 | 16.6 | 77 | 79 |
结果表明,反应迅速且完全。在较短时间内,较高的PH3压力是适宜的。
实施例7用于制备2,4,6-三苯基-3-苄基磷杂苯的吡喃鎓盐
由1,3-二苯基-3-氧代丙烯(查耳酮),按照Houben-Weyl,E7b卷,855页中所述的用于制备2,4,6-三苯基吡喃鎓四氟硼酸盐的方法、但不加入苯乙酮,合成2,4,6-三苯基-3-苄基吡喃鎓四氟硼酸盐。
实施例8用于制备1,3-双(2,2’-4,6-二苯基磷杂苯基)苯的吡喃鎓盐
将1,3-二乙酰基苯(1.00g,6.17mmol)和查耳酮(5.10g,24.7mmol)溶解在10ml 1,2-二氯乙烷中,将该混合物升温至70℃。加入四氟硼酸二乙基醚化物(4.02g,24.7mmol),将所得溶液回流2小时。令反应混合物冷却至室温并过滤,在滤液中加入20ml乙醚。将沉淀的固体溶解在少量二氯甲烷中并用乙醇沉淀。合并的固体由乙醇中重结晶。收率:35-40%。
实施例9用于制备2,6-(4-磺酸根合苯基)-4-苯基磷杂苯的吡喃鎓盐
2,6-(4-磺酸根合苯基)-4-吡喃鎓四氟硼酸盐的合成分以下两步进行:步骤1:3-(4-磺酸根合苯基)-3-氧代-1-苯基丙烯的制备
将4-乙酰基苯磺酸钠(22.2g,0.1mol)溶解在100ml的水中,将混合物加热至50℃。加入0.2g氢氧化钠在100ml甲醇中的溶液和苯甲醛(10.6g,0.1mol)。沉淀出固体,并且当在室温下搅拌3小时后,抽滤出固体。用乙醚洗涤固体。收率:77%。步骤2:2,6-(4-磺酸根合苯基)-4-苯基吡喃鎓四氟硼酸盐的合成
将3-(4-磺酸根合苯基)-3-氧代-1-苯基丙烯(3.1g,0.01mol)和乙酰基苯磺酸钠(2.22g,0.01mol)混合,向混合物中加入2ml水。随后滴加高氯酸(10ml)。生成强黄色的混悬液。将该混悬液加热至90℃并搅拌2小时,其间形成均匀溶液。当混合物冷却至室温后,一些产物以固体形式沉淀出来,通过过滤分离,用冷的正丁醇洗涤3次并在80℃和6毫巴下干燥。将上清液滴加到冷却的正丁醇中,由此进一步沉淀出产物,过滤分离并按照上述第1个馏分进行处理。产量:3.1g黄绿色水溶性固体。
实施例10-14PH3的反应
所有实验均是在300ml的高压反应釜(材料HC)中进行。向高压反应釜中进料(溶剂:正丁醇,100g;催化剂:溶于醋酸中的氢溴酸(30%重量,Aldrich))并用5巴的氮气冲洗。气体空间用PH3冲洗1次。在室温下通入5巴的PH3,并且反复加入PH3直至压力稳定维持在5巴。将反应混合物加热至反应温度,用气体分散搅拌器剧烈搅动该溶液。反应釜中的压力变为10.5巴。随后反应在此压力下进行,或,如果需要,通过注入PH3使反应在更高的压力下进行。利用压力调节器反复通气来使反应釜中的压力在反应过程中维持在预定的压力水平。反应之后,冷却该高压反应釜,减压,在搅拌下用氮气彻底冲洗并拆卸装置。
实施例 | 吡喃鎓盐 | 用量g | 时间小时 | 温度℃ | 压力 巴 | 磷杂苯收率 |
10 | 2,4,6-三苯基吡喃鎓硫酸氢盐(Aldrich) | 1.6 | 1 | 110 | 10.5 | 63 |
11 | 2,4,6-三苯基-3-苄基吡喃鎓四氟硼酸盐 | 1.9 | 1 | 110 | 10.5 | 63 |
12 | 2,4,6-三苯基-3-苄基吡喃鎓四氟硼酸盐 | 1.5 | 4 | 120 | 30 | 72 |
13 | 1,3-双(2,2’-4,6-二苯基吡喃鎓四氟硼酸盐苯 | 2.5 | 4 | 120 | 30 | 65 |
14 | 2,6-(4-磺酸根合苯基)-4-苯基-吡喃鎓四氟硼酸盐 | 1.3 | 4 | 110 | 10.5 | 水溶液31P-NMR 185ppm |
Claims (10)
1.一种制备式I和II所示磷杂苯类化合物的方法,
其中R1-R6彼此独立地是氢、C6-12-芳基或C7-12-芳烷基,并且它们可以被SO3M取代,M是氢、NH4或碱金属,
W是亚苯基,
该方法是使相应的吡喃鎓盐在催化量的酸和有或没有溶剂或稀释剂存在下与PH3反应,其中该吡喃鎓盐在高于0℃的温度下与PH3混合,并且在0℃-200℃和压力大于1巴的条件下反应。
2.如权利要求1所述的方法,其特征在于,该反应是在0.1-100巴的PH3分压下进行。
3.如权利要求1所述的方法,其特征在于,该反应是在5-35巴的PH3分压下进行。
4.如权利要求1-3任一项所述的方法,其特征在于,在反应期间将PH3通入反应混合物中,以使PH3的分压维持基本恒定。
5.如权利要求1-3任一项所述的方法,其特征在于,所述吡喃鎓盐在室温下与PH3混合,并且将所得混合物加热至110℃-130℃,以进行反应。
6.如权利要求1-3任一项所述的方法,其特征在于,式I和II所示化合物中的基团R1-R6是苯基或苄基,它们可以被SO3M取代。
7.如权利要求1-3任一项所述的方法,其特征在于,所述吡喃鎓盐是四氟硼酸盐、高氯酸盐、硫酸氢盐、溴化物、碘化物或其混合物。
8.如权利要求1-3任一项所述的方法,其特征在于,在反应后,反应混合物被减压,并且,如果需要,可以用惰性气体冲洗,将从反应混合物逸出的气体冷却并通过分离器,由此以液态形式除去未反应的PH3,并且将分离出的PH3再次加回到反应中。
10.如权利要求9所示化合物的用途,用于制备与元素周期表的第VIII族金属形成的配合物。
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