EP0000757B1 - Process for the preparation of triarylphosphites - Google Patents
Process for the preparation of triarylphosphites Download PDFInfo
- Publication number
- EP0000757B1 EP0000757B1 EP78100550A EP78100550A EP0000757B1 EP 0000757 B1 EP0000757 B1 EP 0000757B1 EP 78100550 A EP78100550 A EP 78100550A EP 78100550 A EP78100550 A EP 78100550A EP 0000757 B1 EP0000757 B1 EP 0000757B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- salts
- process according
- atoms
- aryl
- acids
- 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
Links
- 238000000034 method Methods 0.000 title claims description 24
- 238000002360 preparation method Methods 0.000 title description 4
- -1 a-thiopicoanilide Chemical compound 0.000 claims description 35
- 239000003054 catalyst Substances 0.000 claims description 24
- 125000003118 aryl group Chemical group 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 150000001408 amides Chemical class 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 8
- 150000003863 ammonium salts Chemical class 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 150000003003 phosphines Chemical group 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 125000004434 sulfur atom Chemical group 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 150000001409 amidines Chemical class 0.000 claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 5
- 150000003009 phosphonic acids Chemical class 0.000 claims description 5
- 150000003462 sulfoxides Chemical class 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 5
- 150000003566 thiocarboxylic acids Chemical class 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 150000002357 guanidines Chemical class 0.000 claims description 4
- 150000004694 iodide salts Chemical class 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 150000003457 sulfones Chemical class 0.000 claims description 4
- 150000001805 chlorine compounds Chemical class 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 claims description 3
- 150000002926 oxygen Chemical class 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 150000003335 secondary amines Chemical group 0.000 claims description 3
- WSANLGASBHUYGD-UHFFFAOYSA-N sulfidophosphanium Chemical class S=[PH3] WSANLGASBHUYGD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- WCQOBLXWLRDEQA-UHFFFAOYSA-N ethanimidamide;hydrochloride Chemical compound Cl.CC(N)=N WCQOBLXWLRDEQA-UHFFFAOYSA-N 0.000 claims description 2
- VFJYIHQDILEQNR-UHFFFAOYSA-M trimethylsulfanium;iodide Chemical compound [I-].C[S+](C)C VFJYIHQDILEQNR-UHFFFAOYSA-M 0.000 claims description 2
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims 3
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims 2
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims 1
- MNOILHPDHOHILI-UHFFFAOYSA-N Tetramethylthiourea Chemical compound CN(C)C(=S)N(C)C MNOILHPDHOHILI-UHFFFAOYSA-N 0.000 claims 1
- 150000001491 aromatic compounds Chemical class 0.000 claims 1
- 229940043279 diisopropylamine Drugs 0.000 claims 1
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 13
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 12
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 6
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000006267 biphenyl group Chemical group 0.000 description 3
- 235000013877 carbamide Nutrition 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- KATOLVAXCGIBLO-UHFFFAOYSA-N 1,3-dibenzylurea Chemical compound C=1C=CC=CC=1CNC(=O)NCC1=CC=CC=C1 KATOLVAXCGIBLO-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000000052 comparative effect Effects 0.000 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 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 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 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 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 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000005027 hydroxyaryl group Chemical group 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- FXJRXJXSLXNGBY-UHFFFAOYSA-N 1,1,3,3-tetrabutylguanidine Chemical compound CCCCN(CCCC)C(=N)N(CCCC)CCCC FXJRXJXSLXNGBY-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- TUMNHQRORINJKE-UHFFFAOYSA-N 1,1-diethylurea Chemical compound CCN(CC)C(N)=O TUMNHQRORINJKE-UHFFFAOYSA-N 0.000 description 1
- UUZJJNBYJDFQHL-UHFFFAOYSA-N 1,2,3-triazolidine Chemical compound C1CNNN1 UUZJJNBYJDFQHL-UHFFFAOYSA-N 0.000 description 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- NLCAUVFHXKUYMZ-UHFFFAOYSA-N 1,3-dioctylurea Chemical compound CCCCCCCCNC(=O)NCCCCCCCC NLCAUVFHXKUYMZ-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- OGYGFUAIIOPWQD-UHFFFAOYSA-N 1,3-thiazolidine Chemical compound C1CSCN1 OGYGFUAIIOPWQD-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- MHQSQCVXHDWARZ-UHFFFAOYSA-N 1-phenylpyrazolidine Chemical compound C1CCNN1C1=CC=CC=C1 MHQSQCVXHDWARZ-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- HVFKKINZIWVNQG-UHFFFAOYSA-N 2,4,6-tri(propan-2-yl)phenol Chemical compound CC(C)C1=CC(C(C)C)=C(O)C(C(C)C)=C1 HVFKKINZIWVNQG-UHFFFAOYSA-N 0.000 description 1
- BPRYUXCVCCNUFE-UHFFFAOYSA-N 2,4,6-trimethylphenol Chemical compound CC1=CC(C)=C(O)C(C)=C1 BPRYUXCVCCNUFE-UHFFFAOYSA-N 0.000 description 1
- CELSEOKAEJGADX-UHFFFAOYSA-N 2,6-dimethyl-4-octylphenol Chemical compound CCCCCCCCC1=CC(C)=C(O)C(C)=C1 CELSEOKAEJGADX-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- CDMGNVWZXRKJNS-UHFFFAOYSA-N 2-benzylphenol Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1 CDMGNVWZXRKJNS-UHFFFAOYSA-N 0.000 description 1
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 1
- DGXRGGUNBXNJRI-UHFFFAOYSA-N 2-methyl-4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C(C)=C1 DGXRGGUNBXNJRI-UHFFFAOYSA-N 0.000 description 1
- SRJCJJKWVSSELL-UHFFFAOYSA-N 2-methylnaphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(C)=CC=C21 SRJCJJKWVSSELL-UHFFFAOYSA-N 0.000 description 1
- WCRKLZYTQVZTMM-UHFFFAOYSA-N 2-octadecylphenol Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1O WCRKLZYTQVZTMM-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- ZLCSFXXPPANWQY-UHFFFAOYSA-N 3-ethyltoluene Chemical compound CCC1=CC=CC(C)=C1 ZLCSFXXPPANWQY-UHFFFAOYSA-N 0.000 description 1
- MCGBIXXDQFWVDW-UHFFFAOYSA-N 4,5-dihydro-1h-pyrazole Chemical compound C1CC=NN1 MCGBIXXDQFWVDW-UHFFFAOYSA-N 0.000 description 1
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical group CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 1
- JPCITNVIXXYRQK-UHFFFAOYSA-N 4-benzyl-2-methylphenol Chemical compound C1=C(O)C(C)=CC(CC=2C=CC=CC=2)=C1 JPCITNVIXXYRQK-UHFFFAOYSA-N 0.000 description 1
- SNKLPZOJLXDZCW-UHFFFAOYSA-N 4-tert-butyl-2-methylphenol Chemical compound CC1=CC(C(C)(C)C)=CC=C1O SNKLPZOJLXDZCW-UHFFFAOYSA-N 0.000 description 1
- DGGKXQQCVPAUEA-UHFFFAOYSA-N 8-azabicyclo[3.2.1]octane Chemical compound C1CCC2CCC1N2 DGGKXQQCVPAUEA-UHFFFAOYSA-N 0.000 description 1
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000251730 Chondrichthyes Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 1
- 125000001204 arachidyl 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])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])[H] 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical compound C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 description 1
- RQBJDYBQTYEVEG-UHFFFAOYSA-N benzylphosphane Chemical compound PCC1=CC=CC=C1 RQBJDYBQTYEVEG-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- DQTRYXANLKJLPK-UHFFFAOYSA-N chlorophosphonous acid Chemical class OP(O)Cl DQTRYXANLKJLPK-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 1
- 150000003950 cyclic amides Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- ZQBJYMGLPSURKJ-UHFFFAOYSA-N diaminophosphorylmethane Chemical compound CP(N)(N)=O ZQBJYMGLPSURKJ-UHFFFAOYSA-N 0.000 description 1
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- AAKDVDDBABPPKC-UHFFFAOYSA-N dodecylphosphane Chemical compound CCCCCCCCCCCCP AAKDVDDBABPPKC-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- GWJBMEMOPTZCIG-UHFFFAOYSA-N ethene;urea Chemical compound C=C.NC(N)=O.NC(N)=O GWJBMEMOPTZCIG-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- VUWLQNLERCCXNN-UHFFFAOYSA-N ethyl-iodo-dimethyl-$l^{4}-sulfane Chemical compound CCS(C)(C)I VUWLQNLERCCXNN-UHFFFAOYSA-N 0.000 description 1
- JLHMVTORNNQCRM-UHFFFAOYSA-N ethylphosphine Chemical compound CCP JLHMVTORNNQCRM-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- CHXARDKIHSVFDK-UHFFFAOYSA-N hexylphosphane Chemical compound CCCCCCP CHXARDKIHSVFDK-UHFFFAOYSA-N 0.000 description 1
- GJWAEWLHSDGBGG-UHFFFAOYSA-N hexylphosphonic acid Chemical compound CCCCCCP(O)(O)=O GJWAEWLHSDGBGG-UHFFFAOYSA-N 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- LPAGFVYQRIESJQ-UHFFFAOYSA-N indoline Chemical compound C1=CC=C2NCCC2=C1 LPAGFVYQRIESJQ-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- SAWKFRBJGLMMES-UHFFFAOYSA-N methylphosphine Chemical compound PC SAWKFRBJGLMMES-UHFFFAOYSA-N 0.000 description 1
- 125000001421 myristyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WUQAXJAVUGHZGD-UHFFFAOYSA-N n'-butylpropanimidamide Chemical compound CCCCNC(=N)CC WUQAXJAVUGHZGD-UHFFFAOYSA-N 0.000 description 1
- NKQBQVNKUQULLD-UHFFFAOYSA-N n'-methylethanimidamide Chemical compound CNC(C)=N NKQBQVNKUQULLD-UHFFFAOYSA-N 0.000 description 1
- KBZUICKSJWHZIF-UHFFFAOYSA-N n,n-diphenylaniline;hydrochloride Chemical compound [Cl-].C1=CC=CC=C1[NH+](C=1C=CC=CC=1)C1=CC=CC=C1 KBZUICKSJWHZIF-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 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 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- DTHHUAXKOMWYBI-UHFFFAOYSA-N oxadiazolidine Chemical compound C1CONN1 DTHHUAXKOMWYBI-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- USPWKWBDZOARPV-UHFFFAOYSA-N pyrazolidine Chemical compound C1CNNC1 USPWKWBDZOARPV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl 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])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])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- RABUZJZUBFMWSH-UHFFFAOYSA-N sulfane;hydroiodide Chemical class [SH3+].[I-] RABUZJZUBFMWSH-UHFFFAOYSA-N 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- RLTPJVKHGBFGQA-UHFFFAOYSA-N thiadiazolidine Chemical compound C1CSNN1 RLTPJVKHGBFGQA-UHFFFAOYSA-N 0.000 description 1
- BUGOPWGPQGYYGR-UHFFFAOYSA-N thiane 1,1-dioxide Chemical compound O=S1(=O)CCCCC1 BUGOPWGPQGYYGR-UHFFFAOYSA-N 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- LKDQWVKWYGOVJW-UHFFFAOYSA-M triethylsulfanium;iodide Chemical compound [I-].CC[S+](CC)CC LKDQWVKWYGOVJW-UHFFFAOYSA-M 0.000 description 1
- BPLKQGGAXWRFOE-UHFFFAOYSA-M trimethylsulfoxonium iodide Chemical compound [I-].C[S+](C)(C)=O BPLKQGGAXWRFOE-UHFFFAOYSA-M 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/145—Esters of phosphorous acids with hydroxyaryl compounds
Definitions
- the present invention relates to a process for the preparation of triaryl phosphites from phosphorus trihalides and hydroxyaromatics using certain compounds containing phosphorus, nitrogen and / or sulfur as catalysts.
- triaryl phosphites have been widely used as stabilizers or costabilizers in the processing of, in particular, thermoplastics.
- the aryl groups can be substituted or unsubstituted. They are generally prepared by reacting phosphorus trihalides with hydroxyaromatics. In this reaction, high temperatures have to be used in order to achieve the most complete conversion possible, in particular when the aryl groups are substituted and the reactivity of the hydroxyl groups is hindered. However, the high temperatures and relatively long reaction times are often not sufficient to achieve complete conversion, but rather a mixture is obtained which essentially consists of mono- and diaryloxyphosphorus halides and triarylphosphites.
- catalysts include alkali and alkaline earth metal halides such as LiCl, MgCl 2 or CaCl 2 , metals such as Mg or Zn, Lewis acids such as ZnCl 2 or AICI 3 and aromatic heterocycles containing nitrogen as organic compounds such as pyridine, cf. Russian Patent No. 488 821. These solutions are not yet satisfactory and still require heating times that are too long at too high temperatures.
- the quaternary phosphonium bases proposed as suitable catalysts in Russian Patent No. 488 821 are distinguished by an increased reactivity, but are not sufficiently specific. Especially when using substituted hydroxylaryls, only mixtures of predominantly diarylchlorophosphites and triarylphosphites are obtained.
- the object of the present invention is to provide a process for the preparation of triaryl phosphites from phosphorus trihalides and hydroxyaromatics which, by using reactive and selective catalysts, enables high yields at lower temperatures and shorter reaction times, especially when using substituted hydroxyaromatics.
- the present invention relates to a process for the preparation of triaryl phosphites according to claim 1.
- R in the formula (RO) 3 P in its meaning as aryl is, for example, naphthyl and in particular phenyl, which can be substituted as indicated.
- the substituents can be in any position on the aryl. Preferably there are no more than three substituents.
- the substituents are preferably in the 2-, 4- and / or 6-positions.
- the 2,4-position is particularly preferred. If there are substituents in the 2,6 positions, they should not be those with strong space filling, e.g. tertiary alkyl groups. According to the process according to the invention, reaction mixtures are also obtained in which predominantly undesired chlorophosphites are found.
- the aryl can be substituted with linear or branched alkyl. This preferably contains 1 to 18, in particular 1 to 12, carbon atoms. Examples include methyl, ethyl, n-propyl, iso-propyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, heptyl, n-octyl, t-octyl, n-nonyl, i-nonyl, decyl , called n-dodecyl, tetradecyl, hexadecyl, octadecyl and eicosyl.
- the alkyl can also be substituted or interrupted by cycloalkyl, e.g. Cyclohexylmethyl or methylcyclohexylethyl.
- the aryl can also be substituted by cycloalkyl, preferably having 5 or 6 ring carbon atoms, which can also be substituted by alkyl. Examples are: cyclopentyl, cyclohexyl, methylcyclohexyl, ethylcyclohexyl, octylcyclohexyl, cyclooctyl.
- the aryl can also be substituted by aryl, preferably phenyl and aralkyl, preferably benzyl, ⁇ - or ⁇ -phenylethyl.
- the aryl group can be substituted by alkyl groups with preferably 1 to 8 carbon atoms. Examples are methylphenyl, ethylphenyl, methylbenzyl.
- hydroxyaromatic compounds of the formula ROH are phenol, Y t - or ⁇ -naphthol, methylnaphthol, 2- or 4-methylphenol, 2-or 4-ethylphenol, 2- or 4-propyl- and isopropylphenol, 2-or 4-n Butyl, i-butyl and t-butylphenol, pentyl, hexyl, heptyl, n-octyl, tert-octyl, nonyl, decyl, dodecyl, octadecylphenol, cyclohexyl, phenyl or benzylphenol, 2,4- or 2,6-dimethyl, diethyl, dipropyl, diisopropyl, di-n-butyl, di-i-butylphenol, 2,4-di-tert-butylphenol, 2-methyl 4-ethylbenzene, 2-methyl-4-tert-
- phosphorus halides used as starting compounds in the implementation of the phosphor trichloride is particularly preferred. Stoichiometric amounts of the reactants are preferably used in order to avoid additional cleaning operations. Sometimes, however, it can be advantageous if a slight excess, for example up to 10%, of the hydroxyaryles is used.
- the catalyst is preferably used in amounts of 0.05 to 5 mol%, in particular 0.1 to 2 mol%.
- the inventive method can be at temperatures from 10 ° C to preferably 150 ° C. be carried out in particular 20 to 130 ° C. Higher temperatures are generally not required, which is particularly advantageous.
- Suitable solvents are e.g. Ethers such as diethyl ether, tetrahydrofuran and dioxane, aliphatic and aromatic hydrocarbons such as hexane, heptane, petroleum ether, cyclohexane, methylcyclohexane, benzene, toluene and xylene, chlorinated hydrocarbons such as methylene chloride, chloroform, dichloroethane and carbon tetrachloride.
- Ethers such as diethyl ether, tetrahydrofuran and dioxane
- aliphatic and aromatic hydrocarbons such as hexane, heptane, petroleum ether, cyclohexane, methylcyclohexane, benzene, toluene and xylene
- chlorinated hydrocarbons such as methylene chloride, chloroform, dichloroethane and carbon tetrachlor
- the process is carried out in the presence of selected catalysts.
- the N atoms of the amines and ammonium salts, the amides and the nitrogen-containing heterocycles, the guanidines, amidines and azomethines and their salts, the sulfones, sulfoxides, sulfonium compounds, phosphines, phosphine oxides and phosphine sulfides can optionally alkyl, cycloalkyl interrupted by oxygen or sulfur atoms, Aryl, here especially phenyl, alkaryl, here especially alkylated phenyl, aralkyl, here especially benzyl or alkaralkyl, here especially alkylated benzyl, which preferably have 1 to 18, in particular 1 to 12, carbon atoms.
- the alkyl contains especially 1 to 6 carbon atoms and cycloalkyl is especially cyclopentyl and cyclohexyl.
- the catalysts to be used according to the invention as salts are preferably the halides and especially the chlorides.
- the salts can also be formed in situ by the hydrogen halide formed in the process. Nevertheless, in some cases it is advantageous to use the salts themselves as catalysts.
- the amines and ammonium salts are a catalyst group. These can be primary, secondary and tertiary amines and their salts.
- the salts also include the quaternary ammonium salts.
- the secondary amines, their salts and the quaternary ammonium salts are preferred.
- the alkyl and cycloalkyl substituted amines such as the cyclic amines, which are assigned to the non-aromatic heterocycles.
- Examples are: methyl, ethyl, propyl, n-butyl, t-butyl, pentyl, octyl, dodecyl, phenyl, benzyl, dimethyl, diethyl, methylethyl, methylbutyl, methyloctyl, methylphenyl -, ethylbenzyl, trimethyl, triethyl, tributyl, octyldimethyl, dimethylphenylamine and tetramethyl, trimethylethyl, triethylmethyl, tributylmethyl, tetrabutyl, trimethyloctyl, triphenylmethyl and tribenzylmethylammonium chloride or bromide or bromide.
- ammonium salts examples include methyl, octyl, dimethyl, methylcyclohexyl, dibenzyl, diphenyl, trimethyl, tributyl, tribenzyl and triphenylammonium chloride, bromide and iodide.
- the amines and ammonium salts can also contain aromatic N-heterocyclic radicals, e.g. Pyridyl. These amines are more effective than the pure aromatic N-heterocycles.
- Another group of catalysts are the amides of carboxylic and thiocarboxylic acids and the oxygen acids of phosphorus.
- This group also includes ureas, thioureas and their bis-urea derivatives.
- the amides can be derived from polyfunctional, preferably monofunctional, carboxylic acids or thiocarboxylic acids, which in particular contain 1 to 14 carbon atoms.
- the acids can also be derived from aromatic N-heterocycles. It has been found that these amides are significantly more effective than the underlying aromatic N-heterocycles. Cyclic amides such as, for example, s-caprolacetam are also suitable.
- Examples are formamide, oxalic acid diamide, dimethylformamide, acetamide, thioacet amide, N, N-dimethylacetamide or thioacetamide, picoanilide, thiopicoanilide, benzoic acid amide, terephthalic acid diamide, trimellitic acid triamide.
- the phosphoric oxygen acids from which the amides can be derived are e.g. phosphoric acid, phosphorous acid, hypophosphorous acid, phosphonic acid or phosphinic acid.
- Phosphoric acid and phosphonic acids are preferred.
- Examples of such amides are phosphoric acid triamide, hexamethylphosphoric acid triamide, methylphosphonic acid diamide, phenylphosphonic acid N, N-tetramethyldiamide, N, N '- (dimethyl) phenylphosphonic acid diamide.
- Examples of the amides of carbonic acid and thionocarbonic acid include urea and thiourea: tetramethylurea or thiourea, diphenyl or dibenzylurea or thiourea, diethylurea, di-n-octylurea or thiourea and bis-urea derivatives such as e.g. Ethylene bisurea, N, N-tetramethylphenylene thiourea.
- Examples of cyclic ureas are hydantoin and benzimidazolone.
- Non-aromatic N-heterocycles These can contain more than one N atom as well as 0 and S atoms. They can also be unsaturated. They can be in the form of salts, also in the form of quaternary ammonium bases, and the N atoms can be substituted, preferably with alkyl groups of 1 to 12 carbon atoms. Examples are:
- the guanides themselves include N-alkylated, benzylated and phenylated derivatives, e.g. Tetramethyl or tetrabutylguanidine, N, N'-bisphenylguanidine.
- the halides are mainly considered as salts.
- catalysts are the azomethines and amidines and their salts, preferably the halides. They can be represented by the following formulas: wherein R 4 is phenyl, benzyl, cyclohexyl, a hydrogen atom or alkyl having 1 to 8, preferably 1 to 4 C atoms and R 5 is a hydrogen atom or phenyl, benzyl, cyclohexyl or alkyl having 1 to 18, preferably 1 to 8 C atoms are. Examples include:
- Acetamidine hydrochloride N-methylacetamidine, benzylidene anilide, N-butylpropionamidine.
- the sulfones and sulfoxides used as catalysts can be linear or cyclic and they can contain further functional groups, e.g. Ester groups. Examples are: dimethyl sulfone, dimethyl sulfoxide, tetra- or pentamethylene sulfone, tetramethylene xulfoxide, bis-carboisooctyloxidi-. methyl sulfoxide.
- the sulfonium iodides are preferred, e.g. Trimethylsulfonium iodide, dimethylethylsulfonium iodide, triethylsulfonium iodide.
- the salts, especially the iodides of the sulfoxides, are also suitable, e.g. Trimethylsulfoxonium iodide.
- catalysts to be used according to the invention are the primary, secondary and tertiary phosphines, their salts, oxides and sulfides.
- the tertiary phosphines, their salts, oxides and sulfides are preferred and among the salts the hydrohalides, especially the chlorides, bromides and iodides.
- the phosphorus atom can contain phenyl, benzyl, cyclohexyl and alkyl having 1 to 12, preferably 1 to 6, carbon atoms.
- Examples are: methylphosphine, ethylphosphine, hexylphosphine, dodecylphosphine, dimethyl-, ethylmethyl-, diphenyl-, dicyclohexyl-, dibenzyl-, phenylmethylphosphine, triphenyl-, tribenzyl-, tricyclohexyl-, trimethyl-, triethyl-, tripropyl-, tri-pyl-, tri- -, Tripentyl, trihexyl, dimethylphenylphosphine, their hydrochlorides, bromides and iodides as well as oxides and sulfides.
- the alcohol residues of the esters of phosphonic acids and phosphoric acid are preferably derived from phenols and especially C 1 -C 1s- alkanols and cycloalkanols, for example phenol, 2-methylphenol, cyclohexanol, methanol, ethanol, propanol, butanol, hexanol, octanol, i-octanol , Dodecanol, octadecanol.
- Examples of phosphonic acids are: phenyl, benzyl, cyclohexyl, methyl, ethyl, propyl, butyl, pentyl and hexylphosphonic acid.
- the method according to the invention is carried out in devices known for this.
- the hydroxyaryl, optionally together with a solvent, the phosphorus trihalide is added and, after the catalyst has been added, the reaction mixture is stirred until the reaction is complete. Stirring is preferably carried out with heating to accelerate the reaction.
- the hydrogen halide formed is advantageously removed continuously during the reaction, vacuum being able to be used for complete separation.
- the desired triaryl phosphite is isolated by known methods by distillation or crystallization, if appropriate after removing the solvent.
- triaryl phosphites are surprisingly obtained under mild conditions in relatively short reaction times in high purity and excellent yields. It is particularly advantageous in this process that this also applies to the production of substituted hydroxyaromatics as reactants, particularly those in which the reactivity of the hydroxyl group is impaired by steric hindrance.
- the triaryl phosphites produced according to the invention are suitable as stabilizers or costabilizers together with e.g. phenolic antioxidants for processing thermoplastic polymers, e.g. Polyolefins.
- the acidity of the initial charge is then determined by titration with 0.1 N sodium hydroxide solution.
- reaction mixture is diluted with isopropanol.
- the crystallized tris (2,4-di-tert-butylphenyl) phosphite is filtered off, washed with isopropanol and dried. 221 g of product (85.4% yield) with a melting point of 186-187 ° C. are obtained.
- the phosphite is very pure and only contains traces of 2,4-di-tert-butylphenol.
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Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Triarylphosphiten aus Phosphortrihalogeniden und Hydroxyaromaten unter Verwendung bestimmter Phosphor, Stickstoff und/oder Schwefel enthaltender Verbindungen als Katalysatoren.The present invention relates to a process for the preparation of triaryl phosphites from phosphorus trihalides and hydroxyaromatics using certain compounds containing phosphorus, nitrogen and / or sulfur as catalysts.
Es ist bekannt, dass Triarylphosphite als Stabilisatoren bzw. Kostabilisatoren eine breite Anwendung bei der Verarbeitung von insbesondere thermoplastischen Kunststoffen gefunden haben. Die Arylgruppen können hierbei substituiert oder unsubstituiert sein. Ihre Herstellung erfolgt im allgemeinen durch die Umsetzung von Phosphortrihalogeniden mit Hydroxyaromaten. Bei dieser Reaktion müssen hohe Temperaturen angewendet werden, um einen möglichst vollständigen Umsatz zu erzeilen, insbesondere dann, wenn die Arylgruppen substituiert sind und die Reaktivität der Hydroxylgruppen behindert wird. Oft reichen jedoch die hohen Temperaturen und relativ langen Reaktionszeiten nicht aus, um eine vollständige Umsetzung zu erzielen, sondern man erhält ein Gemisch, das im wesentlichen aus Mono- und Diaryloxyphosphorhalogeniden sowie Triarylphosphiten besteht.It is known that triaryl phosphites have been widely used as stabilizers or costabilizers in the processing of, in particular, thermoplastics. The aryl groups can be substituted or unsubstituted. They are generally prepared by reacting phosphorus trihalides with hydroxyaromatics. In this reaction, high temperatures have to be used in order to achieve the most complete conversion possible, in particular when the aryl groups are substituted and the reactivity of the hydroxyl groups is hindered. However, the high temperatures and relatively long reaction times are often not sufficient to achieve complete conversion, but rather a mixture is obtained which essentially consists of mono- and diaryloxyphosphorus halides and triarylphosphites.
Es wurde daher schon vorgeschlagen, diese Reaktion in Gegenwart von Katalysatoren durchzuführen. Als mögliche Katalysatoren sind Alkali- und Erdalkalihalogenide wie z.B. LiCI, MgCI2 oder CaCl2, Metalle wie z.B. Mg oder Zn, Lewissäuren wie z.B. ZnCI2 oder AICI3 sowie als organische Verbindungen sitckstoffhaltige aromatische Heterocyclen wie Pyridin genannt, vgl. russisches Patent Nr. 488 821. Diese Lösungen sind noch nicht befriedigend und erfordern immer noch zu lange Erwärmungszeiten bei zu hohen Temperaturen.It has therefore already been proposed to carry out this reaction in the presence of catalysts. Possible catalysts include alkali and alkaline earth metal halides such as LiCl, MgCl 2 or CaCl 2 , metals such as Mg or Zn, Lewis acids such as ZnCl 2 or AICI 3 and aromatic heterocycles containing nitrogen as organic compounds such as pyridine, cf. Russian Patent No. 488 821. These solutions are not yet satisfactory and still require heating times that are too long at too high temperatures.
Die in dem russischen Patent Nr. 488 821 als geeignete Katalysatoren vorgeschlagenen quartären Phosphoniumbasen zeichnen sich zwar durch eine erhöhte Reaktivität aus, sind aber nicht ausreichend spezifisch. Besonders bei Verwendung substituierter Hydroxylaryle werden nur Gemische aus überwiegend Diarylchlor- und Triarylphosphiten erhalten.The quaternary phosphonium bases proposed as suitable catalysts in Russian Patent No. 488 821 are distinguished by an increased reactivity, but are not sufficiently specific. Especially when using substituted hydroxylaryls, only mixtures of predominantly diarylchlorophosphites and triarylphosphites are obtained.
Aufgabe vorliegender Erfindung ist es, ein Verfahren zur Herstellung von Triarylphosphiten aus Phosphortrihalogeniden und Hydroxyaromaten bereitzustellen, das durch den Einsatz reaktiver und selektiver wirkender Katalysatoren hohe Ausbeuten bei niedrigeren Temperaturen und verkürzten Reaktionszeiten ermöglicht, besonders beim Einsatz substituierter Hydroxyaromaten.The object of the present invention is to provide a process for the preparation of triaryl phosphites from phosphorus trihalides and hydroxyaromatics which, by using reactive and selective catalysts, enables high yields at lower temperatures and shorter reaction times, especially when using substituted hydroxyaromatics.
Gegenstand vorliegender Erfindung ist ein Verfahren zur Herstellung von Triarylphosphiten gemäß Patentanspruch 1.The present invention relates to a process for the preparation of triaryl phosphites according to claim 1.
R in der Formel (RO)3P in seiner Bedeutung als Aryl ist beispielsweise Naphthyl und insbesondere Phenyl, die wie angegeben substituiert sein können. Die Substituenten können sich in beliebiger Position des Aryls befinden. Vorzugsweise sind nicht mehr als drei Substituenten vorhanden.R in the formula (RO) 3 P in its meaning as aryl is, for example, naphthyl and in particular phenyl, which can be substituted as indicated. The substituents can be in any position on the aryl. Preferably there are no more than three substituents.
Im Falle der Phenylgruppen befinden sich die Substituenten vorzugsweise in den 2-, 4- und/oder 6-Stellungen. Besonders bevorzugt ist die 2,4-Stellung. Sofern sich Substituenten in den 2,6-Positionen befinden, soll es sich nicht um jene mit starker Raumerfüllung handeln, z.B. tertiär-Alkylgruppen. Gemäss dem erfindungsgemässen Verfahren werden auch hierbei Reaktionsgemische erhalten, in denen sich überwiegend unerwünschte Chlorphosphite finden. Es ist also beim erfindungsgemässen Verfahren ausgeschlossen, dass sich zwei Substituenten mit einem tertiären a-C-Atom in den 2,6-Stellungen befinden; wenn sich also in 2-Stellung eine Gruppe mit einem tertiären a-C-Atome gebunden ist, ist in 6-Stellung eine Gruppe mit einem sekundären, vorzugsweise primären C-Atom gebunden.In the case of the phenyl groups, the substituents are preferably in the 2-, 4- and / or 6-positions. The 2,4-position is particularly preferred. If there are substituents in the 2,6 positions, they should not be those with strong space filling, e.g. tertiary alkyl groups. According to the process according to the invention, reaction mixtures are also obtained in which predominantly undesired chlorophosphites are found. In the process according to the invention, it is therefore impossible for two substituents with a tertiary a-C atom to be in the 2,6 positions; if a group with a tertiary a-C atom is bonded in the 2-position, a group with a secondary, preferably primary C-atom is bonded in the 6-position.
Das Aryl kann mit linearem oder verzweigtem Alkyl substituiert sein. Dieses enthält bevorzugt 1 bis 18, insbesondere 1 bis 12 C-Atome. Als Beispiele seien Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, i-Butyl, t-Butyl, Pentyl, Hexyl, Heptyl, n-Octyl, t-Octyl, n-Nonyl, i-Nonyl, Decyl, n-Dodecyl, Tetradecyl, Hexadecyl, Octadecyl und Eicosyl genannt. Das Alkyl kann auch durch Cycloalkyl substituiert oder unterbrochen sein, z.B. Cyclohexylmethyl oder Methylcyclohexyläthyl.The aryl can be substituted with linear or branched alkyl. This preferably contains 1 to 18, in particular 1 to 12, carbon atoms. Examples include methyl, ethyl, n-propyl, iso-propyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, heptyl, n-octyl, t-octyl, n-nonyl, i-nonyl, decyl , called n-dodecyl, tetradecyl, hexadecyl, octadecyl and eicosyl. The alkyl can also be substituted or interrupted by cycloalkyl, e.g. Cyclohexylmethyl or methylcyclohexylethyl.
Das Aryl kann auch durch Cycloalkyl mit vorzugsweise 5 oder 6-Ringskohlenstoffatomen substituiert sein, das auch durch Alkyl substituiert sein kann. Beispiele sind: Cyclopentyl, Cyclohexyl, Methylcyclohexyl, Ethylcyclohexyl, Octylcyclohexyl, Cyclooctyl.The aryl can also be substituted by cycloalkyl, preferably having 5 or 6 ring carbon atoms, which can also be substituted by alkyl. Examples are: cyclopentyl, cyclohexyl, methylcyclohexyl, ethylcyclohexyl, octylcyclohexyl, cyclooctyl.
Das Aryl kann auch durch Aryl, vorzugsweise Phenyl und Aralkyl, vorzugsweise Benzyl, α- oder β-Phenylethyl, substituiert sein. Die Arylgruppe kann hierbei durch Alkylgruppen mit vorzugsweise 1 bis 8 C-Atomen substituiert sein. Beispiele sind Methylphenyl, Ethylphenyl, Methylbenzyl.The aryl can also be substituted by aryl, preferably phenyl and aralkyl, preferably benzyl, α- or β-phenylethyl. The aryl group can be substituted by alkyl groups with preferably 1 to 8 carbon atoms. Examples are methylphenyl, ethylphenyl, methylbenzyl.
Einige Beispiele für Hydroxyaromaten der Formel ROH sind Phenol, tY- oder β-Naphthol, Methylnaphthol, 2- oder 4-Methylphenol, 2-oder 4-Ethylphenol, 2- oder 4-Propyl- sowie Isopropylphenol, 2-oder 4-n-Butyl-, i-Butyl- sowie t-Butylphenol, Pentyl-, Hexyl-, Heptyl-, n-Octyl-, tert-Octyl-, Nonyl-, Decyl, Dodecyl-, Octadecylphenol, Cyclohexyl-, Phenyl- oder Benzylphenol, 2,4- oder 2,6-Dimethyl-, Diethyl-, Dipropyl-, Diisopropyl-, Di-n-butyl-, Di-i-Butylphenol, 2,4-Di-tert-Butyl-phenol, 2-Methyl-4-Aethylbenzol, 2-Methyl-4-tert-Butylphenol, 2-tert-Butyl-4-Methylphenol, 2-Methyl-4-n-Octylphenol, 2,4,6-Trimethylphenol, 2,4,6-Triisopropylphenol, 2,6-Dimethyl-4-Octylphenol, 2-Methyl-4-Benzylphenol.Some examples of hydroxyaromatic compounds of the formula ROH are phenol, Y t - or β-naphthol, methylnaphthol, 2- or 4-methylphenol, 2-or 4-ethylphenol, 2- or 4-propyl- and isopropylphenol, 2-or 4-n Butyl, i-butyl and t-butylphenol, pentyl, hexyl, heptyl, n-octyl, tert-octyl, nonyl, decyl, dodecyl, octadecylphenol, cyclohexyl, phenyl or benzylphenol, 2,4- or 2,6-dimethyl, diethyl, dipropyl, diisopropyl, di-n-butyl, di-i-butylphenol, 2,4-di-tert-butylphenol, 2-methyl 4-ethylbenzene, 2-methyl-4-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-methyl-4-n-octylphenol, 2,4,6-trimethylphenol, 2,4,6-triisopropylphenol, 2,6-dimethyl-4-octylphenol, 2-methyl-4-benzylphenol.
Unter den Phosphorhalogeniden, die als Ausgangsverbindungen bei der Durchführung des erfindungsgemässen Verfahrens verwendet werden, ist Phosphortrichlorid besonders bevorzugt. Vorzugsweise werden stöchiometrische Mengen der Reaktanden eingesetzt, um zusätzliche Reinigungsoperationen zu vermeiden. Mitunter kann es aber von Vorteil sein, wenn ein geringer Ueberschuß, z.B. bis 10%, des Hydroxyaryles eingesetzt wird. Der Katalysator wird vorzugsweise in Mengen von 0,05 bis 5 Mol-%, insbesondere 0,1 bis 2 Mol-% eingesetzt.Among the phosphorus halides used as starting compounds in the implementation of the phosphor trichloride is particularly preferred. Stoichiometric amounts of the reactants are preferably used in order to avoid additional cleaning operations. Sometimes, however, it can be advantageous if a slight excess, for example up to 10%, of the hydroxyaryles is used. The catalyst is preferably used in amounts of 0.05 to 5 mol%, in particular 0.1 to 2 mol%.
Das erfindungsgemässe Verfahren kann bei Temperaturen von 10°C bis vorzugsweise 150°C, be- . sonders 20 bis 130°C durchgeführt werden. Höhere Temperaturen sind im allgemeinen nicht erforderlich, was als besonders vorteilhaft anzusehen ist.The inventive method can be at temperatures from 10 ° C to preferably 150 ° C. be carried out in particular 20 to 130 ° C. Higher temperatures are generally not required, which is particularly advantageous.
Das erfindungsgemässe Verfahren kann ohne Lösungsmittel durchgeführt werden. Die Mitverwendung eines Lösungsmittels hat sich jedoch als vorteilhaft erwiesen. Geeignete Lösungsmittel sind z.B. Aether wie Diethyläther, Tetrahydrofuran und Dioxan, aliphatische und aromatische Kohlenwasserstoffe wie Hexan, Heptan, Petroläther, Cyclohexan, Methylcyclohexan, Benzol, Toluol und Xylol, chlorierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform, Dichloräthan und Tetrachlorkohlenstoff.The process according to the invention can be carried out without a solvent. However, the use of a solvent has proven to be advantageous. Suitable solvents are e.g. Ethers such as diethyl ether, tetrahydrofuran and dioxane, aliphatic and aromatic hydrocarbons such as hexane, heptane, petroleum ether, cyclohexane, methylcyclohexane, benzene, toluene and xylene, chlorinated hydrocarbons such as methylene chloride, chloroform, dichloroethane and carbon tetrachloride.
Erfindungsgemäss wird das Verfahren in Gegenwart ausgewählter Katalysatoren durchgeführt. Die N-Atome der Amine und Ammoniumsalze, der Amide und der stickstoffhaltigen Heterocyclen, der Guanidine, Amidine und Azomethine sowie deren Salze, die Sulfone, Sulfoxide, Sulfoniumverbindungen, Phosphine, Phosphinoxide und Phosphinsulfide können gegebenenfalls durch Sauerstoff-oder Schwefelatome unterbrochenes Alkyl, Cycloalkyl, Aryl, hier besonders Phenyl, Alkaryl, hier besonder alkyliertes Phenyl, Aralkyl, hier besonders Benzyl oder Alkaralkyl, hier besonders alkyliertes Benzyl enthalten, die vorzugsweise 1 bis 18, insbesondere 1 bis 12 C-Atome aufweisen. Das Alkyl enthält besonders 1 bis 6 C-Atome und bei Cycloalkyl handelt es sich besonders um Cyclopentyl und Cyclohexyl.According to the invention, the process is carried out in the presence of selected catalysts. The N atoms of the amines and ammonium salts, the amides and the nitrogen-containing heterocycles, the guanidines, amidines and azomethines and their salts, the sulfones, sulfoxides, sulfonium compounds, phosphines, phosphine oxides and phosphine sulfides can optionally alkyl, cycloalkyl interrupted by oxygen or sulfur atoms, Aryl, here especially phenyl, alkaryl, here especially alkylated phenyl, aralkyl, here especially benzyl or alkaralkyl, here especially alkylated benzyl, which preferably have 1 to 18, in particular 1 to 12, carbon atoms. The alkyl contains especially 1 to 6 carbon atoms and cycloalkyl is especially cyclopentyl and cyclohexyl.
Bei den erfindungsgemäss als Salze zu verwendenden Katalysatoren handelt es sich bevorzugt um die Halogenide und besonders um die Chloride. Die Salze können auch in situ durch den beim Verfahren entstehenden Halogenwasserstoff gebildet werden. Gleichwohl ist es in einigen Fällen vorteilhaft, die Salze selbst als Katalysatoren einzusetzen.The catalysts to be used according to the invention as salts are preferably the halides and especially the chlorides. The salts can also be formed in situ by the hydrogen halide formed in the process. Nevertheless, in some cases it is advantageous to use the salts themselves as catalysts.
Eine Katalysatorgruppe sind die Amine und Ammoniumsalze. Es kann sich hierbei um primäre, sekundäre und tertiäre Amine sowie deren Salze handeln. Zu den Salzen zählen auch die quartären Ammoniumsalze. Bevorzugt sind die sekundären Amine, deren Salze und die quartären Ammoniumsalze. Ebenfalls bevorzugt sind die Alkyl- und Cycloalkylsubstituierten Amine, wie die cyclischen Amine, die den nichtaromatischen Heterocyclen zugerechnet werden.The amines and ammonium salts are a catalyst group. These can be primary, secondary and tertiary amines and their salts. The salts also include the quaternary ammonium salts. The secondary amines, their salts and the quaternary ammonium salts are preferred. Also preferred are the alkyl and cycloalkyl substituted amines, such as the cyclic amines, which are assigned to the non-aromatic heterocycles.
Beispiele sind: Methyl-, Ethyl-, Propyl-, n-Butyl-, t-Butyl-, Pentyl-, Octyl-, Dodecyl-, Phenyl-, Benzyl-, Dimethyl-, Diäthyl-, Methylethyl, Methylbutyl, Methyloctyl, Methylphenyl-, Ethylbenzyl-, Trimethyl-, Triethyl-, Tributyl-, Octyldimethyl-, Dimethylphenylamin sowie Tetramethyl-, Trimethylethyl-, Triethylmethyl-, Tributylmethyl-, Tetrabutyl-, Trimethyloctyl-, Triphenylmethyl- und Tribenzylmethylammoniumchlorid, -bromid oder -jodid. Beizpiele für weitere Ammoniumsalze sind Methyl-, Octyl-, Dimethyl-, Methylcyclohexyl-, Dibenzyl-, Diphenyl-, Trimethyl-, Tributyl-, Tribenzyl- und Triphenylammoniumchlorid, -bromid und -jodid. Die Amine und Ammoniumsalze können auch aromatische N-heterocyclische Reste enthalten, z.B. Pyridyl. Diese Amine sind wirksamer als die reinen aromatischen N-Heterocyclen.Examples are: methyl, ethyl, propyl, n-butyl, t-butyl, pentyl, octyl, dodecyl, phenyl, benzyl, dimethyl, diethyl, methylethyl, methylbutyl, methyloctyl, methylphenyl -, ethylbenzyl, trimethyl, triethyl, tributyl, octyldimethyl, dimethylphenylamine and tetramethyl, trimethylethyl, triethylmethyl, tributylmethyl, tetrabutyl, trimethyloctyl, triphenylmethyl and tribenzylmethylammonium chloride or bromide or bromide. Examples of other ammonium salts are methyl, octyl, dimethyl, methylcyclohexyl, dibenzyl, diphenyl, trimethyl, tributyl, tribenzyl and triphenylammonium chloride, bromide and iodide. The amines and ammonium salts can also contain aromatic N-heterocyclic radicals, e.g. Pyridyl. These amines are more effective than the pure aromatic N-heterocycles.
Eine weitere Gruppe an Katalysatoren sind die Amide der Carbon- und Thiocarbonsäuren sowie der Sauerstoffsäuren des Phosphors. Zu dieser Gruppe zählen auch die Harnstoffe, Thioharnstoffe und ihre Bisharnstoffderivate. Die Amide können sich von mehrfunktionellen, vorzugsweise monofunktionellen Carbonsäuren oder Thiocarbonsäuren ableiten, die insbesondere 1 bis 14 C-Atome enthalten. Die Säuren können auch von aromatischen N-Heterocyclen abgeleitet sein. Es wurde gefunden, dass diese Amide wesentlich wirksamer sind als die zu Grunde liegenden aromatischen N-Heterocyclen. Femer sind auch cyclische Amide wie z.B. s-Caprolacetam geeignet. Die von Carbonsäuren und Thiocarbonsäuren abgeleiteten Amide entsprechen bevorzugt der Formel
Bei den Phosphorsauerstoffsäuren, von denen sich die Amide ableiten können, handelt es sich z.B. um Phosphorsäure, phosphorige Säure, hypophosphorige Säure, Phosphonsäure oder Phosphinsäure. Bevorzugt sind Phosphorsäure und Phosphonsäuren. Beispiele für solche Amide sind Phosphorsäuretriamid, Hexamethylphosphorsäuretriamid, Methylphosphonsäurediamid, Phenylphosphonsäure-N,N-tetramethyldiamid, N,N'-(Dimethyl)phenylphosphonsäurediamid.The phosphoric oxygen acids from which the amides can be derived are e.g. phosphoric acid, phosphorous acid, hypophosphorous acid, phosphonic acid or phosphinic acid. Phosphoric acid and phosphonic acids are preferred. Examples of such amides are phosphoric acid triamide, hexamethylphosphoric acid triamide, methylphosphonic acid diamide, phenylphosphonic acid N, N-tetramethyldiamide, N, N '- (dimethyl) phenylphosphonic acid diamide.
Als Beispiele für die Amide der Kohlensäure bzw. Thionokohlensäure seien neben Harnstoff und Thioharnstoff genannt: Tetramethylharnstoff oder -thioharnstoff, Diphenyl-oder Dibenzylharnstoff oder -thioharnstoff, Diethylharnstoff, Di-n-octylharnstoff oder -thioharnstoff sowie Bisharnstoffderivate wie z.B. Ethylenbisharnstoff, N,N-Tetramethyl-phenylenthioharnstoff. Beispiele für cylclische Harnstoffe sind Hydantoin und Benzimidazolon.Examples of the amides of carbonic acid and thionocarbonic acid include urea and thiourea: tetramethylurea or thiourea, diphenyl or dibenzylurea or thiourea, diethylurea, di-n-octylurea or thiourea and bis-urea derivatives such as e.g. Ethylene bisurea, N, N-tetramethylphenylene thiourea. Examples of cyclic ureas are hydantoin and benzimidazolone.
Eine weitere Gruppe für das erfindungesgemässe Verfahren geeigneter Katalysatoren sind nichtaromatische N-Heterocyclen. Diese können mehr als ein N-Atom sowie auch 0- und S-Atome enthalten. Sie können auch ungesättigt sein. Sie können in Form von Salzen vorliegen, auch in Form von quartären Ammoniumbasen und die N-Atome können substituiert sein, vorzugsweise mit Alkylgruppen von 1 bis 12 C-Atomen. Beispiele sind:Another group of catalysts suitable for the process according to the invention are non-aromatic N-heterocycles. These can contain more than one N atom as well as 0 and S atoms. They can also be unsaturated. They can be in the form of salts, also in the form of quaternary ammonium bases, and the N atoms can be substituted, preferably with alkyl groups of 1 to 12 carbon atoms. Examples are:
Pyrrolidin, ti3-Pyrrolin, N-Methylpyrrolidin, Dihydroindol, Pyrazolidin, Imidazolidin, Δ2-Pyrazolin, 1-Phenylpyrazolidin, Oxazolidin, Thiazolidin, Oxazolin, Triazolidin, Oxadiazolidin, Thiadiazolidin, Piperridin, Morpholin, N-Methylmorpholin, Chinolidin, 1,2-Dihydropurin, 8-Aza-bicyclo-(3,2,1)-octan.Pyrrolidine, ti3-pyrroline, N-methylpyrrolidine, dihydroindole, pyrazolidine, imidazolidine, Δ 2 -pyrazoline, 1-phenylpyrazolidine, oxazolidine, thiazolidine, oxazoline, triazolidine, oxadiazolidine, thiadiazolidine, piperridine, morpholine, morpholine, morpholine, morpholine -Dihydropurine, 8-aza-bicyclo- (3,2,1) -octane.
Unter den Guaniden sind neben dem Guanidin selbst N-alkylierte, benzylierte und phenylierte Derivate zu nennen, z.B. Tetramethyl- oder Tetrabutylguanidin, N,N'-Bisphenylguanidin. Als Salze kommen hauptsächlich die Halogenide in Frage.In addition to guanidine, the guanides themselves include N-alkylated, benzylated and phenylated derivatives, e.g. Tetramethyl or tetrabutylguanidine, N, N'-bisphenylguanidine. The halides are mainly considered as salts.
Eine weitere Katalysatorengruppe sind die Azomethine und Amidine sowie deren Salze, bevorzugt die Halogenide. Sie können durch folgende Formeln dargestellt werden:
Acetamidinhydrochlorid, N-Methylacetamidin, Benzylidenanilid, N-Butylpropionamidin.Acetamidine hydrochloride, N-methylacetamidine, benzylidene anilide, N-butylpropionamidine.
Die als Katalysatoren verwendeten Sulfone und Sulfoxide können linear oder cyclisch sein und sie können weitere funktionelle Gruppen enthalten, z.B. Estergruppen. Beispiele sind: Dimethylsulfon, Dimethylsulfoxid, Tetra- oder Pentamethylensulphon, Tetramethylenxulfoxid, Bis-carboisooctyloxidi-. methylsulfoxid.The sulfones and sulfoxides used as catalysts can be linear or cyclic and they can contain further functional groups, e.g. Ester groups. Examples are: dimethyl sulfone, dimethyl sulfoxide, tetra- or pentamethylene sulfone, tetramethylene xulfoxide, bis-carboisooctyloxidi-. methyl sulfoxide.
Von den Sulfoniumsalzen sind die Sulfoniumjodide bevorzugt, z.B. Trimethylsulfoniumjodid, Dimethyläthylsulfoniumjodid, Triäthylsulfoniumjodid. Auch die Salze, besonders die Jodide der Sulfoxide sind geeignet, z.B. Trimethylsulfoxoniumjodid.Of the sulfonium salts, the sulfonium iodides are preferred, e.g. Trimethylsulfonium iodide, dimethylethylsulfonium iodide, triethylsulfonium iodide. The salts, especially the iodides of the sulfoxides, are also suitable, e.g. Trimethylsulfoxonium iodide.
Eine weitere Gruppe erfindungsgemäss zu verwendender Katalysatoren sind die primären, sekundären und tertiären Phosphine, deren Salze, Oxide und Sulfide. Bevorzugt sind die tertiären Phosphine, ihre Salze, Oxide und Sulfide und unter den Salzen die Hydrohalogenide, besonders die Chloride, Bromide und Jodide. Das Phosphoratom kann Phenyl, Benzyl, Cyclohexyl und Alkyl mit 1 bis 12, vorzugsweise 1 bis 6 C-Atome enthalten. Beispiele sind: Methylphosphin, Ethylphosphin, Hexylphosphin, Dodecylphosphin, Dimethyl-, Ethylmethyl-, Diphenyl-, Dicyclohexyl-, Dibenzyl-, Phenylmethylphosphin, Triphenyl-, Tribenzyl-, Tricyclohexyl-, Trimethyl-, Triethyl-, Tripropyl-, Tributyl-, Triisobutyl-, Tripentyl-, Trihexyl-, Dimethylphenylphosphin, ihre Hydrochloride, -bromide und -jodide sowie -oxide und -sulfide.Another group of catalysts to be used according to the invention are the primary, secondary and tertiary phosphines, their salts, oxides and sulfides. The tertiary phosphines, their salts, oxides and sulfides are preferred and among the salts the hydrohalides, especially the chlorides, bromides and iodides. The phosphorus atom can contain phenyl, benzyl, cyclohexyl and alkyl having 1 to 12, preferably 1 to 6, carbon atoms. Examples are: methylphosphine, ethylphosphine, hexylphosphine, dodecylphosphine, dimethyl-, ethylmethyl-, diphenyl-, dicyclohexyl-, dibenzyl-, phenylmethylphosphine, triphenyl-, tribenzyl-, tricyclohexyl-, trimethyl-, triethyl-, tripropyl-, tri-pyl-, tri- -, Tripentyl, trihexyl, dimethylphenylphosphine, their hydrochlorides, bromides and iodides as well as oxides and sulfides.
Die Alkoholreste der Ester von Phosphonsäuren und Phosphorsäure leiten sich bevorzugt von Phenolen und besonders C1-C1s-Alkanolen sowie Cycloalkanolen ab, z.B. Phenol, 2-Methylphenol, Cyclohexanol, Methanol, Ethanol, Propanol, Butanol, Hexanol, Octanol, i-Octanol, Dodecanol, Octadecanol. Beispiele für Phosphonsäuren sind: Phenyl-, Benzyl-, Cyclohexyl-, Methyl-, Ethyl-, Propyl-, Butyl-, Pentyl- und Hexylphosphonsäure.The alcohol residues of the esters of phosphonic acids and phosphoric acid are preferably derived from phenols and especially C 1 -C 1s- alkanols and cycloalkanols, for example phenol, 2-methylphenol, cyclohexanol, methanol, ethanol, propanol, butanol, hexanol, octanol, i-octanol , Dodecanol, octadecanol. Examples of phosphonic acids are: phenyl, benzyl, cyclohexyl, methyl, ethyl, propyl, butyl, pentyl and hexylphosphonic acid.
Das erfindungsgemässe Verfahren wird in hierfür bekannten Vorrichtungen durchgeführt. Im allgemeinen wird das Hydroxyaryl, gegebenenfalls zusammen mit einem Lösungsmittel vorgelegt, das Phosphortrihalogenid zugegeben und nach Zugabe des Katalysators das Reaktionsgemisch bis zur vollständigen Reaktion gerührt. Das Rühren erfolgt zur Beschleunigung der Reaktion bevorzugt unter Erwärmen.The method according to the invention is carried out in devices known for this. In general, the hydroxyaryl, optionally together with a solvent, the phosphorus trihalide is added and, after the catalyst has been added, the reaction mixture is stirred until the reaction is complete. Stirring is preferably carried out with heating to accelerate the reaction.
Es ist jedoch auch möglich den Hydroxyaromaten, gegebenenfalls ein Lösungsmittel und den Katalysator vorzulegen und das Phosphortrihalogenid langsam zuzugeben. In einigen Fällen hat es sich als vorteilhaft erwiesen, hierzu das vorgelegte Gemisch leicht zu erwärmen, z.B. bis zu 60°C, vorzugsweise bis zu 40°C. Nach Zugabe des gesamten Phosphorhaiogehides wird zur Vervollständigung gegebenenfalls unter Erwärmen bis zu 150°C nachgerührt.However, it is also possible to introduce the hydroxyaromatic compounds, if appropriate a solvent and the catalyst, and to add the phosphorus trihalide slowly. In some cases it has proven to be advantageous to heat the mixture initially, for example up to 60 ° C., preferably up to 40 ° C. After addition of the entire phosphorus shark, the mixture is optionally stirred with heating up to 150 ° C.
Der entstehende Halogenwasserstoff wird vorteilhaft während der Reaktion laufend entfernt, wobei zur vollständigen Abtrennung Vakuum verwendet werden kann. Die Isolierung des gewünschten Triarylphosphites erfolgt nach bekannten Methoden durch Destillation oder Kristallisation, gegebenenfalls nach Entfernen des Lösungsmittels.The hydrogen halide formed is advantageously removed continuously during the reaction, vacuum being able to be used for complete separation. The desired triaryl phosphite is isolated by known methods by distillation or crystallization, if appropriate after removing the solvent.
Mit dem erfindungsgemässen Verfahren werden überraschend unter schonenden Bedingungen Triarylphosphite innerhalb relativ kurzer Reaktionszeiten in hoher Reinheit und hervorragenden Ausbeuten erhalten. Besonders vorteilhaft ist bei diesem Verfahren, dass dies auch für die Herstellung von substituierten Hydroxyaromaten als Reaktanden, gilt insbesondere jenen, in denen die Reaktivität der Hydroxylgruppe durch sterische Hinderung beeinträchtigt ist.With the process according to the invention, triaryl phosphites are surprisingly obtained under mild conditions in relatively short reaction times in high purity and excellent yields. It is particularly advantageous in this process that this also applies to the production of substituted hydroxyaromatics as reactants, particularly those in which the reactivity of the hydroxyl group is impaired by steric hindrance.
Die erfindungsgemäss hergestellten Triarylphosphite sind geeignet als Stabilisatoren oder Costabilisatoren zusammen mit z.B. phenolischen Antioxidantien für die Verarbeitung von thermoplastischen Polymeren, z.B. Polyolefinen.The triaryl phosphites produced according to the invention are suitable as stabilizers or costabilizers together with e.g. phenolic antioxidants for processing thermoplastic polymers, e.g. Polyolefins.
Die nachfolgenden Beispiele erläutern die Erfindung naher.The following examples explain the invention in more detail.
In einem 250 ml-Dreihalsrundkolben mit Thermometer, Magnetrührer und angeschlossenem Gasableitungsrohr, werden 61,91 g (0,3 Mol) 2,4-Di-tert.-butylphenol in 135 ml Toluol vorgelegt, 13,73 g (0,1 Mol) Phosphortrichlorid zugesetzt und nach Zugabe von 0.003 Mol des jeweiligen Katalysators 7 h bei 2226°C gerührt. Der freigesetzte Chlorwasserstoff wird über das Gasableitungsrohr und einen kleinen angeschlossenen Blasenzähler in eine Absorptionsvorlage geleitet und mit ca. 300 ml Wasser absorbiert.61.91 g (0.3 mol) of 2,4-di-tert-butylphenol in 135 ml of toluene, 13.73 g (0.1 mol ) Added phosphorus trichloride and, after adding 0.003 mol of the respective catalyst, stirred at 2226 ° C. for 7 h. The released hydrogen chloride is passed through the gas discharge pipe and a small connected bubble counter into an absorption receiver and absorbed with approx. 300 ml of water.
Der Säuregehalt der Vorlage wird danach durch Titration mit 0,1 N-Natronlauge ermittelt.The acidity of the initial charge is then determined by titration with 0.1 N sodium hydroxide solution.
Die in der nachstehenden Tabelle 1 zusammengefassten Versuchergebnisse zeigen die überraschend hohe Wirksamkeit der Katalysatorsysteme.
Die Umsetzung mit Phosphortrichlorid und 2,4-Di-tert.-butylphenol wird gemäss Beispiel 1 durchgeführt. An Stelle von Toluol wird Chloroform als Lösungsmittel verwendet.The reaction with phosphorus trichloride and 2,4-di-tert-butylphenol is carried out according to Example 1. Instead of toluene, chloroform is used as the solvent.
Die Ergebnisse der Versuche sind in der nachstehenden Tabelle 2 zusammengefasst.
Für Vergleichszwecke wird 2.4-Ditert.-Butylphenol mit Phosphortrichlorid gemäss Beispiel 1 umgesetzt, wobei als Katalysatoren verschiedene bekannte Produkte Verwendung finden. Die Ergebnisse sind in Tabelle 3 zusammengestellt.
Die Ergebnisse der Vergleichsversuche zeigen, das durch die bislang bekannten Katalysatoren nur eine geringe Steigerung der Reaktionsgeschwindigkeit bei der Umsetzung von Phosphortrichlorid mit sterisch gehinderten Phenolen erzielt werden kann.The results of the comparative experiments show that only a slight increase in the reaction rate in the reaction of phosphorus trichloride with sterically hindered phenols can be achieved by the catalysts known to date.
In einem 500 ml-Rundkolben werden 247,6 g 2.4-Di-tert.-butylphenol (1,2 Mol), 39 g Xylol und 0,8 g Dimethylformamid (0,011 Mol) vorgelegt und auf 40°C erwärmt. Innerhalb von 15 Minuten werden 54,9 g Phosphortrichlorid (0,4 Mol) zugetropft. Das Gemisch wird noch 1 Std. bei 40-50°C gerührt, auf 130°C erhitzt und 1 Std. bei 130°C gerührt. Anschliessend wird zur Entfernung des im Reaktionsgemisch noch enthaltenen Chlorwasserstoffs 1 Std. bei 120-130°C unter vermindertem Druck (ca. 267 m bar) gerührt, wobei auch ein Teil des Lösungsmittels mitentfernt wird.247.6 g of 2,4-di-tert-butylphenol (1.2 mol), 39 g of xylene and 0.8 g of dimethylformamide (0.011 mol) are placed in a 500 ml round-bottomed flask and heated to 40.degree. 54.9 g of phosphorus trichloride (0.4 mol) are added dropwise within 15 minutes. The mixture is stirred for a further 1 hour at 40-50 ° C., heated to 130 ° C. and stirred for 1 hour at 130 ° C. The mixture is then stirred for 1 hour at 120-130 ° C. under reduced pressure (approx. 267 m bar) to remove the hydrogen chloride still present in the reaction mixture, with part of the solvent also being removed.
Zur Isolierung des Produktes wird das Reaktionsgemisch mit Isopropanol verdünnt. Das auskristallisierte Tris(2.4-di-tert.-butylphenyl)-phosphit wird abfiltriert, mit Isopropanol gewaschen und getrocknet. Es werden 221 g Produkt (85,4% Ausbeute) mit einem Schmelzpunkt von 186-187°C erhalten. Das Phosphit ist sehr rein und enthält nur noch Spuren 2.4-Di-tert.-butylphenol.To isolate the product, the reaction mixture is diluted with isopropanol. The crystallized tris (2,4-di-tert-butylphenyl) phosphite is filtered off, washed with isopropanol and dried. 221 g of product (85.4% yield) with a melting point of 186-187 ° C. are obtained. The phosphite is very pure and only contains traces of 2,4-di-tert-butylphenol.
Claims (8)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH969177 | 1977-08-08 | ||
| CH9691/77 | 1977-08-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000757A1 EP0000757A1 (en) | 1979-02-21 |
| EP0000757B1 true EP0000757B1 (en) | 1981-08-05 |
Family
ID=4354605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100550A Expired EP0000757B1 (en) | 1977-08-08 | 1978-07-31 | Process for the preparation of triarylphosphites |
Country Status (4)
| Country | Link |
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| US (1) | US4312818A (en) |
| EP (1) | EP0000757B1 (en) |
| JP (1) | JPS5430140A (en) |
| DE (1) | DE2860898D1 (en) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4492661A (en) * | 1977-08-08 | 1985-01-08 | Ciba-Geigy Corporation | Process for producing triarylphosphites |
| US4440696A (en) * | 1977-08-08 | 1984-04-03 | Ciba-Geigy Corporation | Process for producing triarylphosphites |
| DE2940620A1 (en) * | 1979-10-06 | 1981-04-16 | Hoechst Ag, 6000 Frankfurt | Tri:aryl phosphite prodn. from phosphorus tri:halide - and aromatic hydroxy cpd. in presence of nitrogen heterocycle as catalyst |
| DE3029176C2 (en) * | 1980-08-01 | 1995-02-02 | Hoechst Ag | Migration-resistant, polymeric, aromatic phosphites |
| EP0159294B1 (en) * | 1984-04-17 | 1988-11-17 | Ciba-Geigy Ag | Process for preparing cyclic phosphorous-acid esters |
| JPS61225191A (en) * | 1985-03-29 | 1986-10-06 | Adeka Argus Chem Co Ltd | Production of diarylpentaerythritol diphosphite |
| US4894481A (en) * | 1988-07-05 | 1990-01-16 | Ethyl Corporation | Method of making cyclic aryl chlorophosphites |
| AU3788189A (en) * | 1988-07-25 | 1990-01-25 | Borg-Warner Specialty Chemicals, Inc. | 3, 9-diphosphaspiroundecanes and process for making3, 9-diphosphaspiroundecanes |
| US5023285A (en) * | 1988-07-25 | 1991-06-11 | G E Specialty Chemicals | Bis (tri-tertiary-alkylphenoxy) diphosphaspiroundecanes |
| US5308901A (en) * | 1988-07-25 | 1994-05-03 | General Electric Company | 3-9-diphosphaspiroundecane-stabilized polymer compositions |
| EP0413661B1 (en) * | 1989-08-15 | 1995-06-14 | Ciba-Geigy Ag | Process for preparing tris (2,4-di-tert-butyl-phenyl) phosphite |
| US5235086A (en) * | 1989-08-15 | 1993-08-10 | Ciba-Geigy Corporation | Process for the preparation of tris(2,4-ditert-butylphenyl)phosphite |
| DE69012835T2 (en) * | 1989-12-08 | 1995-02-16 | Uniroyal Chem Co Inc | METHOD FOR PRODUCING STERICALLY HIDDEN ARYLPHOSPHITES. |
| US5254709A (en) * | 1989-12-08 | 1993-10-19 | Uniroyal Chemical Company, Inc. | Method for preparing stearically hindered aryl phosphites |
| DE3942787A1 (en) * | 1989-12-23 | 1991-06-27 | Hoechst Ag | PROCESS FOR PREPARING HYDROLYSESTABLIC ORGANIC PHOSPHITE |
| US5103035A (en) * | 1990-04-05 | 1992-04-07 | Ethyl Corporation | Process for preparing bis(alkylphenyl)pentaerythritol diphosphites |
| AU7015294A (en) * | 1993-08-30 | 1995-03-22 | Dover Chemical Corporation | Hydrolytically stable pentaerythritol diphosphites |
| US5786497A (en) * | 1997-08-29 | 1998-07-28 | General Electric Company | Process for the preparation of phosphites |
| US5919966A (en) * | 1998-03-26 | 1999-07-06 | General Electric Company | Process for the preparation of spiro bis-phosphites |
| US5917076A (en) * | 1998-04-16 | 1999-06-29 | General Electric Company | Process for the preparation of spiro bis-phosphites using finely ground pentaerythritol |
| US6426429B1 (en) | 2000-08-11 | 2002-07-30 | General Electric Company | Process for the preparation of hindered phosphites |
| US6504065B1 (en) | 2000-09-29 | 2003-01-07 | General Electric Company | Method of making metal salts of 2,4,6-tri-t-butylphenol |
| US6653494B2 (en) | 2001-11-26 | 2003-11-25 | Strides Inc. | Processes for producing triaryl phosphite |
| WO2018215509A1 (en) | 2017-05-24 | 2018-11-29 | Basf Se | Alkylated triphenyl phosphorothionates as selective metal sulphide collectors |
| CN110323142B (en) * | 2018-03-29 | 2021-08-31 | 台达电子工业股份有限公司 | Power module and method for manufacturing the same |
| GB2591482A (en) * | 2020-01-29 | 2021-08-04 | Si Group Switzerland Chaa Gmbh | Non-dust blend |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3463838A (en) * | 1965-12-09 | 1969-08-26 | Chemagro Corp | Chloro and nitro containing phenyl phosphites |
| DE1493613B2 (en) * | 1965-12-18 | 1974-02-14 | Dynamit Nobel Ag, 5210 Troisdorf | Process for the preparation of halogenated esters of phosphorus |
| US3558554A (en) * | 1966-06-09 | 1971-01-26 | Yoshitomi Pharmaceutical | Oxidatively stable polyolefin composition |
| US3533989A (en) * | 1967-03-15 | 1970-10-13 | Exxon Research Engineering Co | Phosphite antioxidants in polyolefins |
| US3489826A (en) * | 1967-03-15 | 1970-01-13 | Exxon Research Engineering Co | Bis(2-t-butyl-4-methyl-6-chlorophenyl) phenyl phosphite |
| DE1668883A1 (en) * | 1968-01-25 | 1971-02-11 | Dynamit Nobel Ag | Process for the preparation of halogenated esters of phosphoric acids |
| US3772414A (en) * | 1971-01-05 | 1973-11-13 | Monsanto Co | Preparation of esters of phosphorus acids |
| US3773866A (en) * | 1971-06-24 | 1973-11-20 | Monsanto Co | Preparation of esters of phosphorus acids |
| US3751529A (en) * | 1971-06-24 | 1973-08-07 | Monsanto Co | Preparation of esters of phosphorus acids |
| GB1414478A (en) * | 1972-03-23 | 1975-11-19 | Albright & Wilson | Phosphorylation of alkylated phenols |
| JPS5311226B2 (en) * | 1972-06-20 | 1978-04-20 | ||
| JPS519735A (en) * | 1974-07-08 | 1976-01-26 | Sunstar Inc | Kihoofukumanai kihatsuseiseibunganjuhamigakino seizoho |
| CA1078991A (en) * | 1975-02-20 | 1980-06-03 | Hans J. Lorenz | Stabilization systems from triarylphosphites and phenols |
| JPS5242857A (en) * | 1975-09-29 | 1977-04-04 | Sumitomo Chem Co Ltd | Synthetic method of diphenyl phosphite |
| JPS5839158B2 (en) * | 1976-03-29 | 1983-08-27 | 四日市合成株式会社 | Production method of halogen-containing phosphite ester |
| US4237075A (en) * | 1979-06-05 | 1980-12-02 | Mobil Oil Corporation | Formamide catalysts for reacting phosphorus halides with thiols |
-
1978
- 1978-07-31 DE DE7878100550T patent/DE2860898D1/en not_active Expired
- 1978-07-31 EP EP78100550A patent/EP0000757B1/en not_active Expired
- 1978-08-08 JP JP9657978A patent/JPS5430140A/en active Granted
-
1979
- 1979-12-13 US US06/103,132 patent/US4312818A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| US4312818A (en) | 1982-01-26 |
| EP0000757A1 (en) | 1979-02-21 |
| JPS6317080B2 (en) | 1988-04-12 |
| JPS5430140A (en) | 1979-03-06 |
| DE2860898D1 (en) | 1981-11-05 |
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