CA2023164C - Process for the preparation of tris-(2,4-ditert-butylphenyl)phosphite - Google Patents
Process for the preparation of tris-(2,4-ditert-butylphenyl)phosphite Download PDFInfo
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- CA2023164C CA2023164C CA002023164A CA2023164A CA2023164C CA 2023164 C CA2023164 C CA 2023164C CA 002023164 A CA002023164 A CA 002023164A CA 2023164 A CA2023164 A CA 2023164A CA 2023164 C CA2023164 C CA 2023164C
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- reaction
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- ditert
- reaction mixture
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- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 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 title claims description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 239000011541 reaction mixture Substances 0.000 claims abstract description 33
- 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 claims abstract description 15
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 230000035484 reaction time Effects 0.000 claims description 8
- AZSKHRTUXHLAHS-UHFFFAOYSA-N tris(2,4-di-tert-butylphenyl) phosphate Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(=O)(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 AZSKHRTUXHLAHS-UHFFFAOYSA-N 0.000 abstract 2
- -1 nitrogen-containing heterocyclic compounds Chemical class 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 150000001408 amides Chemical class 0.000 description 7
- 230000011514 reflex Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 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 4
- 150000003003 phosphines Chemical group 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- CMIAIUZBKPLIOP-YZLZLFLDSA-N methyl (1r,4ar,4br,10ar)-7-(2-hydroperoxypropan-2-yl)-4a-methyl-2,3,4,4b,5,6,10,10a-octahydro-1h-phenanthrene-1-carboxylate Chemical compound C1=C(C(C)(C)OO)CC[C@@H]2[C@]3(C)CCC[C@@H](C(=O)OC)[C@H]3CC=C21 CMIAIUZBKPLIOP-YZLZLFLDSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 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
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical class Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-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
- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical compound CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 150000003840 hydrochlorides Chemical class 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-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
- NLCAUVFHXKUYMZ-UHFFFAOYSA-N 1,3-dioctylurea Chemical compound CCCCCCCCNC(=O)NCCCCCCCC NLCAUVFHXKUYMZ-UHFFFAOYSA-N 0.000 description 1
- GWEHVDNNLFDJLR-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1=CC=CC=C1 GWEHVDNNLFDJLR-UHFFFAOYSA-N 0.000 description 1
- OGYGFUAIIOPWQD-UHFFFAOYSA-N 1,3-thiazolidine Chemical compound C1CSCN1 OGYGFUAIIOPWQD-UHFFFAOYSA-N 0.000 description 1
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-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
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-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
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- KXDMPSYVRRXXGP-UHFFFAOYSA-N C1NC=c2[nH]cnc2=N1 Chemical compound C1NC=c2[nH]cnc2=N1 KXDMPSYVRRXXGP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-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
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- XTUVJUMINZSXGF-UHFFFAOYSA-N N-methylcyclohexylamine Chemical compound CNC1CCCCC1 XTUVJUMINZSXGF-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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000003950 cyclic amides Chemical class 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
- 238000010586 diagram Methods 0.000 description 1
- SBWJERDWKYNUFP-UHFFFAOYSA-N dibenzylphosphane Chemical compound C=1C=CC=CC=1CPCC1=CC=CC=C1 SBWJERDWKYNUFP-UHFFFAOYSA-N 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- HDULBKVLSJEMGN-UHFFFAOYSA-N dicyclohexylphosphane Chemical compound C1CCCCC1PC1CCCCC1 HDULBKVLSJEMGN-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-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
- YOTZYFSGUCFUKA-UHFFFAOYSA-N dimethylphosphine Chemical compound CPC YOTZYFSGUCFUKA-UHFFFAOYSA-N 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- BXDCELKJGGVUHD-UHFFFAOYSA-N ethyl(methyl)phosphane Chemical compound CCPC BXDCELKJGGVUHD-UHFFFAOYSA-N 0.000 description 1
- ZUTJDJAXWKOOOI-UHFFFAOYSA-N ethylene diurea Chemical compound NC(=O)NCCNC(N)=O ZUTJDJAXWKOOOI-UHFFFAOYSA-N 0.000 description 1
- JLHMVTORNNQCRM-UHFFFAOYSA-N ethylphosphine Chemical compound CCP JLHMVTORNNQCRM-UHFFFAOYSA-N 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- CHXARDKIHSVFDK-UHFFFAOYSA-N hexylphosphane Chemical compound CCCCCCP CHXARDKIHSVFDK-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
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 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
- 239000011872 intimate mixture Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- SAWKFRBJGLMMES-UHFFFAOYSA-N methylphosphine Chemical compound PC SAWKFRBJGLMMES-UHFFFAOYSA-N 0.000 description 1
- MXHTZQSKTCCMFG-UHFFFAOYSA-N n,n-dibenzyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)CC1=CC=CC=C1 MXHTZQSKTCCMFG-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
- HVAAHUDGWQAAOJ-UHFFFAOYSA-N n-benzylethanamine Chemical compound CCNCC1=CC=CC=C1 HVAAHUDGWQAAOJ-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-O octylazanium Chemical compound CCCCCCCC[NH3+] IOQPZZOEVPZRBK-UHFFFAOYSA-O 0.000 description 1
- DTHHUAXKOMWYBI-UHFFFAOYSA-N oxadiazolidine Chemical compound C1CONN1 DTHHUAXKOMWYBI-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229940100684 pentylamine Drugs 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 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
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 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
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- RLTPJVKHGBFGQA-UHFFFAOYSA-N thiadiazolidine Chemical compound C1CSNN1 RLTPJVKHGBFGQA-UHFFFAOYSA-N 0.000 description 1
- IFXORIIYQORRMJ-UHFFFAOYSA-N tribenzylphosphane Chemical compound C=1C=CC=CC=1CP(CC=1C=CC=CC=1)CC1=CC=CC=C1 IFXORIIYQORRMJ-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- FPZZZGJWXOHLDJ-UHFFFAOYSA-N trihexylphosphane Chemical compound CCCCCCP(CCCCCC)CCCCCC FPZZZGJWXOHLDJ-UHFFFAOYSA-N 0.000 description 1
- IWPNEBZUNGZQQQ-UHFFFAOYSA-N tripentylphosphane Chemical compound CCCCCP(CCCCC)CCCCC IWPNEBZUNGZQQQ-UHFFFAOYSA-N 0.000 description 1
- KCTAHLRCZMOTKM-UHFFFAOYSA-N tripropylphosphane Chemical compound CCCP(CCC)CCC KCTAHLRCZMOTKM-UHFFFAOYSA-N 0.000 description 1
- DAGQYUCAQQEEJD-UHFFFAOYSA-N tris(2-methylpropyl)phosphane Chemical compound CC(C)CP(CC(C)C)CC(C)C DAGQYUCAQQEEJD-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A process far the preparation of tris-(2,4-ditert-butylphenyl) phosphate from 2,4-ditert-butylphenol and phosphorus trichloride in the presence of catalysts, which comprises carrying out the reaction in an at least three-stage process in which the 2,4-ditert-butylphenol and 40 - 100 % of the catalyst are combined in a preliminary stage and are brought together with the phosphorus trichloride in a first stage, these being allowed to react under normal pressure and at temperatures of 55 to 70°C for a dwell time of 15 to 40 minutes, the reaction mixture is then reacted in a second stage under normal pressure and at temperatures of over 140°C, remaining amounts of catalyst being added to the first and/or second reaction stage, the reaction mixture is then kept under reduced pressure at temperatures of at least 186°C in a third reaction stage, and the tris-(2,4-ditert-butylphenyl) phosphate is then isolated from the reaction mixture, the process being carried out in the absence of solvents.
Description
A-176>6/=/CGM 341 Process for the preparation of tris-(2L4-diten-butvlnhenyl~phosphite The invention relates to a process for the preparation of tris-(2,4-ditert-butylphenyl) phosphite from 2,4-ditert-butylphenol and phosphorus trichloride in the presence of a catalyst.
It is known from DE-A 2,007,070 to prepare triaryl phosphites from phenols and phosphorus trichloride, the reaction taking place in three stages in successive sections of equipment. The process can be operated in the absence of solvent, but problems then arise with the formation of foam in the reaction mixture to the point where the orderly course of the reaction is interfered with. A process is known from EP-A 0,000,757 for the preparation of triaryl phosphites by reacting phosphorus trihalides with hydroxyaromatic compounds in the presence of catalysts. According to Example 4 of EP-A
0,000,757 tris-(2,4-ditert-butylphenyl) phosphite can be prepared with the concomitant use of a solvent. Working with a solvent has the advantage that the course of the reaction and hence also the undesirable foam formation can be controlled, but has, in turn, the obvious disadvantage that the solvent, by its volume, reduces the space/time yield and has to be heated and cooled with the reactants and, at the end of the process, removed and worked up.
The object of the present invention was to avoid the said disadvantages and to provide a process which makes it possible to prepare tris-(2,4-ditert-butylphenyl) phosphite in a simple manner and in high space/time yields.
In accordance with the invention this is achieved by means of a process which comprises carrying out the reaction in an at least three-stage process in which the 2,4-ditert-butylphenol and 40 - 100 % of the catalyst are combined in a preliminary stage and are brought together with the phosphorus trichloride in a first stage, these being allowed to react under normal pressure and at temperatures of 55 to 70°C for a dwell time of 15 to 40 minutes, the reaction mixture is then reacted in a second stage under normal pressure and at temperatures of over 140°C, remaining amounts of catalyst being added to the first and/or second reaction stage, the reaction mixture is then kept under reduced pressure at temperatures of at least 186°C in a third reaction stage, and the tris-(2,4-ditert-butylphenyl) phosphite is then isolated from the reaction mixture, the process being carried out in the absence of solvents.
The following embodiments, independently of one another, are preferred: for example, that the reaction mixture is subjected to a fourth stage, the reaction mixture being kept in the fourth stage at at least 186°C and under reduced pressure, preferably a pressure of 6 to 20 hPa; that a reaction time of 45 to 75 minutes is maintained in the second stage; that a reaction time of 1.5 to 2.5 hours is maintained in the third stage; that a reaction time of 20 to 120 minutes is maintained in the fourth stage; and that a temperature of 190 to 195° is maintained in the fourth stage.
In a preferred embodiment of the process the 2,4-ditert-butylphenol is added in a 1-fold to 1.1-fold stoichiometric amount, relative to phosphorus trichloride.
Examples of catalysts available for the process according to the invention are those described in EP-A 0,000,757.
Examples of catalysts of this type are compounds belonging to the group comprising amines or ammoninium salts, amides of carboxylic acids or of carbonic acid, non-aromatic N-containing heterocyclic compounds and salts thereof, primary, secondary and tertiary phosphines and salts thereof or esters of phosphoric acids and phosphonic acids.
The amines and ammonium salts, amides and nitrogen-containing heterocyclic compounds or phosphines can contain, as substituents, alkyl, cycloalkyl, aryl;
particularly phenyl, alkaryl, particularly alkylated phenyl, aralkyl, particularly benzyl, or alkaralkyl, particularly alkylated benzyl, groups which preferably contain 1 to 18 C
atoms, particularly 1 to 12 C atoms, and are interrupted, if appropriate, by oxygen or sulfur atoms.
Alkyl contains especially 1 to 6 C atoms and cycloalkyl is especially cyclopentyl and cyclohexyl.
The catalysts to be used in the form of salts are preferably the halides and particularly the chlorides. The salts can also be formed in situ by means of the hydrogen halide formed in the course of the process: Nevertheless, it is advantageous in certain cases to employ the salts themselves as catalysts.
T
It is known from DE-A 2,007,070 to prepare triaryl phosphites from phenols and phosphorus trichloride, the reaction taking place in three stages in successive sections of equipment. The process can be operated in the absence of solvent, but problems then arise with the formation of foam in the reaction mixture to the point where the orderly course of the reaction is interfered with. A process is known from EP-A 0,000,757 for the preparation of triaryl phosphites by reacting phosphorus trihalides with hydroxyaromatic compounds in the presence of catalysts. According to Example 4 of EP-A
0,000,757 tris-(2,4-ditert-butylphenyl) phosphite can be prepared with the concomitant use of a solvent. Working with a solvent has the advantage that the course of the reaction and hence also the undesirable foam formation can be controlled, but has, in turn, the obvious disadvantage that the solvent, by its volume, reduces the space/time yield and has to be heated and cooled with the reactants and, at the end of the process, removed and worked up.
The object of the present invention was to avoid the said disadvantages and to provide a process which makes it possible to prepare tris-(2,4-ditert-butylphenyl) phosphite in a simple manner and in high space/time yields.
In accordance with the invention this is achieved by means of a process which comprises carrying out the reaction in an at least three-stage process in which the 2,4-ditert-butylphenol and 40 - 100 % of the catalyst are combined in a preliminary stage and are brought together with the phosphorus trichloride in a first stage, these being allowed to react under normal pressure and at temperatures of 55 to 70°C for a dwell time of 15 to 40 minutes, the reaction mixture is then reacted in a second stage under normal pressure and at temperatures of over 140°C, remaining amounts of catalyst being added to the first and/or second reaction stage, the reaction mixture is then kept under reduced pressure at temperatures of at least 186°C in a third reaction stage, and the tris-(2,4-ditert-butylphenyl) phosphite is then isolated from the reaction mixture, the process being carried out in the absence of solvents.
The following embodiments, independently of one another, are preferred: for example, that the reaction mixture is subjected to a fourth stage, the reaction mixture being kept in the fourth stage at at least 186°C and under reduced pressure, preferably a pressure of 6 to 20 hPa; that a reaction time of 45 to 75 minutes is maintained in the second stage; that a reaction time of 1.5 to 2.5 hours is maintained in the third stage; that a reaction time of 20 to 120 minutes is maintained in the fourth stage; and that a temperature of 190 to 195° is maintained in the fourth stage.
In a preferred embodiment of the process the 2,4-ditert-butylphenol is added in a 1-fold to 1.1-fold stoichiometric amount, relative to phosphorus trichloride.
Examples of catalysts available for the process according to the invention are those described in EP-A 0,000,757.
Examples of catalysts of this type are compounds belonging to the group comprising amines or ammoninium salts, amides of carboxylic acids or of carbonic acid, non-aromatic N-containing heterocyclic compounds and salts thereof, primary, secondary and tertiary phosphines and salts thereof or esters of phosphoric acids and phosphonic acids.
The amines and ammonium salts, amides and nitrogen-containing heterocyclic compounds or phosphines can contain, as substituents, alkyl, cycloalkyl, aryl;
particularly phenyl, alkaryl, particularly alkylated phenyl, aralkyl, particularly benzyl, or alkaralkyl, particularly alkylated benzyl, groups which preferably contain 1 to 18 C
atoms, particularly 1 to 12 C atoms, and are interrupted, if appropriate, by oxygen or sulfur atoms.
Alkyl contains especially 1 to 6 C atoms and cycloalkyl is especially cyclopentyl and cyclohexyl.
The catalysts to be used in the form of salts are preferably the halides and particularly the chlorides. The salts can also be formed in situ by means of the hydrogen halide formed in the course of the process: Nevertheless, it is advantageous in certain cases to employ the salts themselves as catalysts.
T
The amines and ammonium salts comprise one catalyst group. These can be primary, secondary and tertiary amines and also salts thereof. The salts also include the quaternary ammonium salts. The secondary amines, their salts and the quaternary ammonium salts are preferred. The alkyl-substituted and cycloalkyl-substituted amines or ammonium salts are preferred.
The following are examples: methylamine, ethylamine, propylamine, n-butylamine, t-butylamine, pentylamine, octylamine, dodecylamine, phenylamine, benzylamine, dimethylamine, diethylamine, methylethylamine, methylbutylamine, methyoctylamine, methylphenylamine, ethylbenzylamine, trimethylamine, triethylamine, tributylamine, octyldirnethylamine and dimethylphenylamine and also tetramethylamonium, trimethylethylamonium, triethylmethylamonium, tributylmethylamonium, tetrabutylamonium, trimethyloctylamonium, triphenylmethylamonium and tribenzylmethylammonium chloride, bromide or iodide. Examples of other ammonium salts are methylammonium, octylammonium, dimethylammonium, methylcyclohexylammonium, dibenzylammonium, diphenylammonium, trimethylammonium, tributylammonium, tribenzylammonium and triphenylammonium chloride, bromide and iodide. The amines and ammonium salts can also contain aromatic N-heterocyclic radicals, for example pyridyl. These amines are more effective than the purely aromatic N-heterocyclic compounds.
The amides of carboxylic acids constitute another group of catalysts. This group also includes the areas and their bisurea derivatives. The amides can be derived from polyfunctional, preferably monofunctional, carboxylic acids containing, in particular, 1 to 14 C atoms. The amides can also be derived from aromatic N-heterocyclic compounds.
Cyclic amides, for example ~-caprolactam, are also suitable. The amides derived from carboxylic acids preferably have the formula ~R3 n in which, if n = l, Rt is phenyl, benzyl, naphthyl, cyclohexyl, cyclopentyl, pyridyl, hydrogen or alkyl having 1 to 13, preferably 1 to 6, C atoms, if n = 2, Rt is phenylene, naphthylene, cyclohexylene or alkylene having 1 to 12, preferably 1 to 6, C
atoms or a d~'~ r~3W ~. id direct bond, and R2 and R3 independently of one another are a hydrogen atom, phenyl, benzyl, cyclohexyl and alkyl having 1 to 12, preferably 1 to 6, C atoms or R2 and R3 together are alkylene which preferably has 4-7 C atoms and, if appropriate, is interrupted by O or S atoms. Examples are formamide, oxamide, dimethylfonnamide, acetamide, N,N-dimethylacetarnide, picoanilide, benzamide, terephthalamide and trimellitamide.
Dimethylformamide is very particularly preferred as the catalyst in the present process.
The .Following, besides urea, may be mentioned as examples of amides of carbonic acid:
tetramethylurea, diphenylurea, dibenzylurea, diethylurea, di-n-octylurea and bisurea derivatives, for example ethylenebisurea. Examples of cyclic ureas are hydantoin and benzimidazolone.
Non-aromatic N-heterocyclic compounds constitute another group of catalysts suitable for the process according to the invention. These can contain 1 to 3 N atoms and, if appropriate, one or 2 O and S atoms. They can also be unsaturated. They can be present in the form of salts and also in the form of quaternary ammonium bases, and the N
atoms can be substituted, preferably by alkyl groups having 1 to 12 C atoms. The following are examiples: pyrrolidine, D3-pyrroline, N-methylpyrrolidine, dihydroindole, pyrazolidine, imidazolidine, a2-pyrazoline, 1-phenylpyrazolidine, oxazolidine, thiazolidine, oxazoline, triazolidine, oxadiazolidine, thiadiazolidine, piperidine, morpholine, N-methylmorpholine, quinolidine, 1,2-dihydropurine, 8-aza-bicyclo-(3,2,1)-octane, piperazine and N-methylpiperazine.
The primary, secondary and tertiary phosphines and salts thereof constitute another group of catalysts to be used in accordance with the invention. The tertiary phosphines and their salts are preferred, amongst the salts the hydrohalides, preferably the hydrochlorides, hydrobromides and hydriodides. The phosphorus atom can be unsubstituted or substituted by phenyl, benzyl, cyclohexyl and/or alkyl having 1 to l2, preferably 1 to 6, C atoms. The following are examples:
methylphosphine, ethylphosphine, hexylphosphine, dadecylphosphine, dimethylphosphine, ethylmethylphosphine, diphenylphosphine, dicyclohexylphosphine, dibenzylphosphine, phenylmethylphosphine, triphenylphosphine, tribenzylphosphine, tricyclohexylphosphine, trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, triisobutylphosphine, tripentylphosphine, trihexylphosphine and dimethylphenylphosphine and hydrochlorides, hydrobromides and hydiodides thereof.
The following are examples: methylamine, ethylamine, propylamine, n-butylamine, t-butylamine, pentylamine, octylamine, dodecylamine, phenylamine, benzylamine, dimethylamine, diethylamine, methylethylamine, methylbutylamine, methyoctylamine, methylphenylamine, ethylbenzylamine, trimethylamine, triethylamine, tributylamine, octyldirnethylamine and dimethylphenylamine and also tetramethylamonium, trimethylethylamonium, triethylmethylamonium, tributylmethylamonium, tetrabutylamonium, trimethyloctylamonium, triphenylmethylamonium and tribenzylmethylammonium chloride, bromide or iodide. Examples of other ammonium salts are methylammonium, octylammonium, dimethylammonium, methylcyclohexylammonium, dibenzylammonium, diphenylammonium, trimethylammonium, tributylammonium, tribenzylammonium and triphenylammonium chloride, bromide and iodide. The amines and ammonium salts can also contain aromatic N-heterocyclic radicals, for example pyridyl. These amines are more effective than the purely aromatic N-heterocyclic compounds.
The amides of carboxylic acids constitute another group of catalysts. This group also includes the areas and their bisurea derivatives. The amides can be derived from polyfunctional, preferably monofunctional, carboxylic acids containing, in particular, 1 to 14 C atoms. The amides can also be derived from aromatic N-heterocyclic compounds.
Cyclic amides, for example ~-caprolactam, are also suitable. The amides derived from carboxylic acids preferably have the formula ~R3 n in which, if n = l, Rt is phenyl, benzyl, naphthyl, cyclohexyl, cyclopentyl, pyridyl, hydrogen or alkyl having 1 to 13, preferably 1 to 6, C atoms, if n = 2, Rt is phenylene, naphthylene, cyclohexylene or alkylene having 1 to 12, preferably 1 to 6, C
atoms or a d~'~ r~3W ~. id direct bond, and R2 and R3 independently of one another are a hydrogen atom, phenyl, benzyl, cyclohexyl and alkyl having 1 to 12, preferably 1 to 6, C atoms or R2 and R3 together are alkylene which preferably has 4-7 C atoms and, if appropriate, is interrupted by O or S atoms. Examples are formamide, oxamide, dimethylfonnamide, acetamide, N,N-dimethylacetarnide, picoanilide, benzamide, terephthalamide and trimellitamide.
Dimethylformamide is very particularly preferred as the catalyst in the present process.
The .Following, besides urea, may be mentioned as examples of amides of carbonic acid:
tetramethylurea, diphenylurea, dibenzylurea, diethylurea, di-n-octylurea and bisurea derivatives, for example ethylenebisurea. Examples of cyclic ureas are hydantoin and benzimidazolone.
Non-aromatic N-heterocyclic compounds constitute another group of catalysts suitable for the process according to the invention. These can contain 1 to 3 N atoms and, if appropriate, one or 2 O and S atoms. They can also be unsaturated. They can be present in the form of salts and also in the form of quaternary ammonium bases, and the N
atoms can be substituted, preferably by alkyl groups having 1 to 12 C atoms. The following are examiples: pyrrolidine, D3-pyrroline, N-methylpyrrolidine, dihydroindole, pyrazolidine, imidazolidine, a2-pyrazoline, 1-phenylpyrazolidine, oxazolidine, thiazolidine, oxazoline, triazolidine, oxadiazolidine, thiadiazolidine, piperidine, morpholine, N-methylmorpholine, quinolidine, 1,2-dihydropurine, 8-aza-bicyclo-(3,2,1)-octane, piperazine and N-methylpiperazine.
The primary, secondary and tertiary phosphines and salts thereof constitute another group of catalysts to be used in accordance with the invention. The tertiary phosphines and their salts are preferred, amongst the salts the hydrohalides, preferably the hydrochlorides, hydrobromides and hydriodides. The phosphorus atom can be unsubstituted or substituted by phenyl, benzyl, cyclohexyl and/or alkyl having 1 to l2, preferably 1 to 6, C atoms. The following are examples:
methylphosphine, ethylphosphine, hexylphosphine, dadecylphosphine, dimethylphosphine, ethylmethylphosphine, diphenylphosphine, dicyclohexylphosphine, dibenzylphosphine, phenylmethylphosphine, triphenylphosphine, tribenzylphosphine, tricyclohexylphosphine, trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, triisobutylphosphine, tripentylphosphine, trihexylphosphine and dimethylphenylphosphine and hydrochlorides, hydrobromides and hydiodides thereof.
In the case of the esters of phosphoric acid and phosphonic acid the alcohol radicals are preferably derived from phenols, and especially, Ct-CtBalkanols and cycloalkanols, for example from phenol, 2-methylphenol, cyclohexanol, methanol, ethanol, propanol, butanol, hexanol, octanol, i-octanol, dodecanol and octadecanol. The following are examples of phosphonic acids: phenylphosphonic, benzylphosphonic, cyclohexylphosphonic, methylphosphonic, ethylphosphonic, propylphosphonic, butylphosphonic, pentylphosphonic and hexylphos,phonic acid.
The catalyst can be employed in amounts of, for example, 0.005 to 10 mol-%, appropriately in amounts of 0.05 to 8 mol % and preferably of 4 to 6 mol %, in each case relative to the phosphorus trichloride.
The process according to the invention is carried out in apparatus known per se. Reaction vessels in the form of stirred kettles are particularly appropriate and reaction vessels in the form of reaction columns, particularly with inserts which force intimate mixture on the reactants by means of circuitous paths are also possible.
A heatalile reaction vessel eqiupped with at least two inlets, one outlet and a stirring device are appropriately envisaged for carrying out the first stage of the process. The phosphorus trichloride is preferably introduced directly into the reaction vessel via one inlet, the 2,4-ditert-butylphenol through a column, for example a packed column, and through the second inlet. Depending on its nature, the catalyst can be introduced into the reaction vessel in part separately via a third inlet. 40 - 100 % of the catalyst are put into the second inlet, also via the packed column. The streams of starting materials are appropriately controlled in such a way that the phosphorus trichloride is taken initially and the catalyst and the phenol compound reach the reaction vessel via the packed column.
The HCl formed during the reaction which sets in escapes through the packed column countercurrent to the phenol compound. Entrained phosphorus trichloride is absorbed by the phenol compound and recycled into the reaction vessel. The reaction is already catalysed by the catalyst which is present in the column at the same time, and the escaping phosphorus trichloride reacts with the phenol compound which flows through the column.
Thus a preliminary step already takes place in the column. The reaction mixture then flows into the first reaction vessel. The reactants can be intimately mixed in the reaction vessel by means of a stirring device. At the same time the reaction mixture is heated to temperatures of 55° to 70°C. Temperatures of 60 to 70°C
are preferred. The HCl formed in the reaction is removed via the packed column and is disposed of. The first stage of the reaction is complete after 15 to 40 minutes. It is then possible to carry out the second stage of the reaction in the first reaction vessel, but preferably the contents of the reaction vessel from the first stage are transferred into a second reaction vessel, preferably a heatable stirred kettle. This stirred kettle preferably has feed inlets for the reaction mixture from the vessel of the first stage and, if appropriate, for the addition of a second part amount of the catalyst, and also has a gas outlet equipped with a reflex condenser for discharging the I-ICl formed during second reaction stage. The second stirred kettle is also preferably equipped with a stirring device. When the second stage starts the reaction mixture is immediately heated to over 140°C, for example 145 to 200°C, preferably 150 to 170°C
and particularly preferably about 160°C, and is preferably kept at these elevated temperatures for 45 minutes to 75 minutes, preferably 60 minutes. When the second stage is complete, the reaction mixture is subjected to the third stage either in the same reaction vessel or, preferably, in another reaction vessel. The heatable reaction vessel for the third stage is preferably equipped with an inlet for the reaction mixture, an outlet for reactants which escape in the form of gas, an outlet for the reaction mixture and, preferably, a stirring device. The outlet for the reactants which are evolved, in particular HCI, can have a reflex condenser and, if appropriate, also a desublimer in order to separate the escaping reactants. Furthermore, since the third stage is carried out under reduced pressure, appropriate arrangements are provided, such as a vacuum pump and appropriate seals and valves. The third stage of the reaction is carried out at at least 186°C, appropriately at 186°C to 210°C and preferably at 190 to 195°C, under a reduced pressure of, appropriately, 10 to 60 hPa, in particular 10 to 20 hPa and preferably 15 hPa.
The reaction time for the third stage is, for example, 1 to 2.5 hours, preferably 2 hours.
After the expiry of the reaction time the reaction mixture is, if desired, subjected to the fourth stage. This is effected either by bringing the reaction mixture into the reaction vessel of the third stage or, preferably, bringing it into another reaction vessel and subjecting it to the conditions of the fourth stage in this other xeaction vessel, which can be heated and evacuated. The reaction mixture is also preferably stirred in the fourth stage. The xeaction vessel of the fourth stage should therefore contain not only an inlet for the reaction mixture but also a stirring device and a suitable outlet fox removing, in particular, the gaseous products of the reaction, preferably an oulet containing a reflex condenser and a desublimer.
Finally, a suitable outlet should be provided at this reaction vessel for discharging the reaction material. Since the fourth stage is to be carried out under reduced pressure, appropriate means of producing a vacuum and seals should be provided. The reaction mixture is appropriately subjected to the fourth stage for 20 to 120 minutes, preferably 60 minutes.
Meanwhile the pressure can be, for example, 6 to 20 hPa, appropriately 10 to 15 hPa and _7_ preferably 10 hPa. The temperature in this fourth stage is at least 186°C, appropriately 186°C to 210°C and especially 190 to 195°C.
It is possible to distill off the 2,4-ditert-butylphenol which may be used in excess from the reaction vessel of the third stage or, if used, the fourth stage, and, if desired, to recycle it to the reaction. The excess 2,4-ditert-butylphenol can also be disposed of from the reaction mixture of the third stage or, if used, the fourth stage.
A preferred embodiment consists in carrying out the process of the present invention in a three-stage kettle cascade.
The particularly preferred embodiments of the present invention include carrying out the process in a four-stage kettle cascade.
Another preferred embodiment is to stir the reaction mixture in at least one stage.
It is very particularly preferable to stir in all four stages.
It is also preferable in the present process to maintain a temperature of 170 to 190°C in the second stage.
Another preference in the process of the invention is to maintain a temperature of 190 to 195°C in the third and the fourth stage, independently of one another.
In the process according to the invention the amount of catalyst envisaged is added to the reaction to the exent of 40 to 100 % through the packed column in which the preliminary stage described above is earned out. It is appropriate to add 50 to 100 %, preferably 70 to 100 % and especially 90 to 100 %, of the catalyst to the reaction via the packed column.
Remaining amounts of catalyst, insofar as not fed in via the packed column, are added in the first and/or second stage of the reaction.
Remaining amounts of catalyst, unless 100 % of the catalyst are added to the reaction via the packed column, are preferably added to the first reaction stage.
It is very particularly preferable to add the whole amount of catalyst, i.e.
100 % of the _g-catalyst, to the reaction via the packed column. All percentage figures relate to weight.
The continuous mode of operation is particularly preferred for the process according to the invention.
The present process according to the invention has the advantage that tris-(2,4-ditert-butylphenyl) phosphite, which, in terms of processes, can only be obtained with difficulty, can be obtained in a high space/time yield. As a result of dispensing with a solvent more reaction volume is available in the present process, which makes higher reaction temperatures and hence higher reaction rates possible, and the heating up times and the time needed for distilling off the solvent prior to the further working up, in particular the crystallization, of the product are omitted.
The processes of the state of the art quoted initially are incapable of giving satisfaction in this respect, since it is absolutely necessary to use a solvent for the compound of present interest, tris-(2,4-ditert-butylphenyl) phosphite, by virtue of its high melting point.
Example: The following flows of materials:
Addition of ~ g/hour ~ Addition to 2,4-ditert-butylphenol, 994 via packed column (F) into 98.9% pure [1] i I reactor (A) Phosphorus trichloride (3] I 216.2 ~ Reactor (A) Dimethylformamide (2] ~ ( ~ via packed column (F) into (catalyst) reactor (A) are set up in a four-stage stirred kettle cascade such as can be seen from the diagram (Figure 1), composed of a) a reactor (A) having a packed column F for the first stage, b) a main reactor (B) equipped with a reflux condenser (Kl) for the second stage, c) a second main reactor (C) equipped with a reflux condenser (K2) and after that a desublimer (S1) for the third stage, and finally d) an after-reactor (D) equipped with a reflux condenser (K3) and a desublimer (S2).
a) Conditions in reactor (A):
Normal pressure, temperature 65°C, dwell time 30 minutes, discharge of 89.8 g/hour of HCI (4] via the packed column (F) to waste disposal and discharge of 1126.4 g/hour of reaction mixture [5] via the bottom valve to the first main reactor (B).
b) Conditions in the first main reactor (B):
Normal pressure, temperature 16S°C, dwell time 1 hour, discharge of 64 g/hour of I-ICl [7]
via a reflex condensder (K1) and discharge of 1062.4 g/hour of reaction mixture [8] via the bottom valve to the second main reactor (C).
c) Conditions in the second main reactor (C):
Reduced pressure 15 hPa, temperature 190°C, dwell time 2 hours, discharge of I3 g/hour of HCl [9] via a reflex condenser (K2) and a desublimer (S 1) and discharge of 1049.4 g/hour of reaction mixture [ 10] via the bottom valve into the after-reactor (D).
d) Conditions in the after-reactor (D):
Reduced pressure 10 hPa, temperature 190°C, dwell time 60 minutes, discharge of 5.4 g/hour of HCl [I 1] via a reflex condensder (K3) and a desublimer (S2) and discharge of 1045 g/hour of reaction mixture [12], containing 1003.2 g/hour of tris-(2,4-ditert-butylphenyl) phosphite, to be crystallized.
The end product is of high purity, and virtually no content of monochloro and dichloro compounds or unreacted PC13 could be detected.
Figure 2 shows an alternative embodiment differing from the embodiment described above in that the reflex condenser (K3) also constitutes a distillation device in which the excess 2,4-ditert-butylphenol can be removed. This 2,4-ditert-butylphenol can be recycled to the reaction via the feed inlet [I].
The catalyst can be employed in amounts of, for example, 0.005 to 10 mol-%, appropriately in amounts of 0.05 to 8 mol % and preferably of 4 to 6 mol %, in each case relative to the phosphorus trichloride.
The process according to the invention is carried out in apparatus known per se. Reaction vessels in the form of stirred kettles are particularly appropriate and reaction vessels in the form of reaction columns, particularly with inserts which force intimate mixture on the reactants by means of circuitous paths are also possible.
A heatalile reaction vessel eqiupped with at least two inlets, one outlet and a stirring device are appropriately envisaged for carrying out the first stage of the process. The phosphorus trichloride is preferably introduced directly into the reaction vessel via one inlet, the 2,4-ditert-butylphenol through a column, for example a packed column, and through the second inlet. Depending on its nature, the catalyst can be introduced into the reaction vessel in part separately via a third inlet. 40 - 100 % of the catalyst are put into the second inlet, also via the packed column. The streams of starting materials are appropriately controlled in such a way that the phosphorus trichloride is taken initially and the catalyst and the phenol compound reach the reaction vessel via the packed column.
The HCl formed during the reaction which sets in escapes through the packed column countercurrent to the phenol compound. Entrained phosphorus trichloride is absorbed by the phenol compound and recycled into the reaction vessel. The reaction is already catalysed by the catalyst which is present in the column at the same time, and the escaping phosphorus trichloride reacts with the phenol compound which flows through the column.
Thus a preliminary step already takes place in the column. The reaction mixture then flows into the first reaction vessel. The reactants can be intimately mixed in the reaction vessel by means of a stirring device. At the same time the reaction mixture is heated to temperatures of 55° to 70°C. Temperatures of 60 to 70°C
are preferred. The HCl formed in the reaction is removed via the packed column and is disposed of. The first stage of the reaction is complete after 15 to 40 minutes. It is then possible to carry out the second stage of the reaction in the first reaction vessel, but preferably the contents of the reaction vessel from the first stage are transferred into a second reaction vessel, preferably a heatable stirred kettle. This stirred kettle preferably has feed inlets for the reaction mixture from the vessel of the first stage and, if appropriate, for the addition of a second part amount of the catalyst, and also has a gas outlet equipped with a reflex condenser for discharging the I-ICl formed during second reaction stage. The second stirred kettle is also preferably equipped with a stirring device. When the second stage starts the reaction mixture is immediately heated to over 140°C, for example 145 to 200°C, preferably 150 to 170°C
and particularly preferably about 160°C, and is preferably kept at these elevated temperatures for 45 minutes to 75 minutes, preferably 60 minutes. When the second stage is complete, the reaction mixture is subjected to the third stage either in the same reaction vessel or, preferably, in another reaction vessel. The heatable reaction vessel for the third stage is preferably equipped with an inlet for the reaction mixture, an outlet for reactants which escape in the form of gas, an outlet for the reaction mixture and, preferably, a stirring device. The outlet for the reactants which are evolved, in particular HCI, can have a reflex condenser and, if appropriate, also a desublimer in order to separate the escaping reactants. Furthermore, since the third stage is carried out under reduced pressure, appropriate arrangements are provided, such as a vacuum pump and appropriate seals and valves. The third stage of the reaction is carried out at at least 186°C, appropriately at 186°C to 210°C and preferably at 190 to 195°C, under a reduced pressure of, appropriately, 10 to 60 hPa, in particular 10 to 20 hPa and preferably 15 hPa.
The reaction time for the third stage is, for example, 1 to 2.5 hours, preferably 2 hours.
After the expiry of the reaction time the reaction mixture is, if desired, subjected to the fourth stage. This is effected either by bringing the reaction mixture into the reaction vessel of the third stage or, preferably, bringing it into another reaction vessel and subjecting it to the conditions of the fourth stage in this other xeaction vessel, which can be heated and evacuated. The reaction mixture is also preferably stirred in the fourth stage. The xeaction vessel of the fourth stage should therefore contain not only an inlet for the reaction mixture but also a stirring device and a suitable outlet fox removing, in particular, the gaseous products of the reaction, preferably an oulet containing a reflex condenser and a desublimer.
Finally, a suitable outlet should be provided at this reaction vessel for discharging the reaction material. Since the fourth stage is to be carried out under reduced pressure, appropriate means of producing a vacuum and seals should be provided. The reaction mixture is appropriately subjected to the fourth stage for 20 to 120 minutes, preferably 60 minutes.
Meanwhile the pressure can be, for example, 6 to 20 hPa, appropriately 10 to 15 hPa and _7_ preferably 10 hPa. The temperature in this fourth stage is at least 186°C, appropriately 186°C to 210°C and especially 190 to 195°C.
It is possible to distill off the 2,4-ditert-butylphenol which may be used in excess from the reaction vessel of the third stage or, if used, the fourth stage, and, if desired, to recycle it to the reaction. The excess 2,4-ditert-butylphenol can also be disposed of from the reaction mixture of the third stage or, if used, the fourth stage.
A preferred embodiment consists in carrying out the process of the present invention in a three-stage kettle cascade.
The particularly preferred embodiments of the present invention include carrying out the process in a four-stage kettle cascade.
Another preferred embodiment is to stir the reaction mixture in at least one stage.
It is very particularly preferable to stir in all four stages.
It is also preferable in the present process to maintain a temperature of 170 to 190°C in the second stage.
Another preference in the process of the invention is to maintain a temperature of 190 to 195°C in the third and the fourth stage, independently of one another.
In the process according to the invention the amount of catalyst envisaged is added to the reaction to the exent of 40 to 100 % through the packed column in which the preliminary stage described above is earned out. It is appropriate to add 50 to 100 %, preferably 70 to 100 % and especially 90 to 100 %, of the catalyst to the reaction via the packed column.
Remaining amounts of catalyst, insofar as not fed in via the packed column, are added in the first and/or second stage of the reaction.
Remaining amounts of catalyst, unless 100 % of the catalyst are added to the reaction via the packed column, are preferably added to the first reaction stage.
It is very particularly preferable to add the whole amount of catalyst, i.e.
100 % of the _g-catalyst, to the reaction via the packed column. All percentage figures relate to weight.
The continuous mode of operation is particularly preferred for the process according to the invention.
The present process according to the invention has the advantage that tris-(2,4-ditert-butylphenyl) phosphite, which, in terms of processes, can only be obtained with difficulty, can be obtained in a high space/time yield. As a result of dispensing with a solvent more reaction volume is available in the present process, which makes higher reaction temperatures and hence higher reaction rates possible, and the heating up times and the time needed for distilling off the solvent prior to the further working up, in particular the crystallization, of the product are omitted.
The processes of the state of the art quoted initially are incapable of giving satisfaction in this respect, since it is absolutely necessary to use a solvent for the compound of present interest, tris-(2,4-ditert-butylphenyl) phosphite, by virtue of its high melting point.
Example: The following flows of materials:
Addition of ~ g/hour ~ Addition to 2,4-ditert-butylphenol, 994 via packed column (F) into 98.9% pure [1] i I reactor (A) Phosphorus trichloride (3] I 216.2 ~ Reactor (A) Dimethylformamide (2] ~ ( ~ via packed column (F) into (catalyst) reactor (A) are set up in a four-stage stirred kettle cascade such as can be seen from the diagram (Figure 1), composed of a) a reactor (A) having a packed column F for the first stage, b) a main reactor (B) equipped with a reflux condenser (Kl) for the second stage, c) a second main reactor (C) equipped with a reflux condenser (K2) and after that a desublimer (S1) for the third stage, and finally d) an after-reactor (D) equipped with a reflux condenser (K3) and a desublimer (S2).
a) Conditions in reactor (A):
Normal pressure, temperature 65°C, dwell time 30 minutes, discharge of 89.8 g/hour of HCI (4] via the packed column (F) to waste disposal and discharge of 1126.4 g/hour of reaction mixture [5] via the bottom valve to the first main reactor (B).
b) Conditions in the first main reactor (B):
Normal pressure, temperature 16S°C, dwell time 1 hour, discharge of 64 g/hour of I-ICl [7]
via a reflex condensder (K1) and discharge of 1062.4 g/hour of reaction mixture [8] via the bottom valve to the second main reactor (C).
c) Conditions in the second main reactor (C):
Reduced pressure 15 hPa, temperature 190°C, dwell time 2 hours, discharge of I3 g/hour of HCl [9] via a reflex condenser (K2) and a desublimer (S 1) and discharge of 1049.4 g/hour of reaction mixture [ 10] via the bottom valve into the after-reactor (D).
d) Conditions in the after-reactor (D):
Reduced pressure 10 hPa, temperature 190°C, dwell time 60 minutes, discharge of 5.4 g/hour of HCl [I 1] via a reflex condensder (K3) and a desublimer (S2) and discharge of 1045 g/hour of reaction mixture [12], containing 1003.2 g/hour of tris-(2,4-ditert-butylphenyl) phosphite, to be crystallized.
The end product is of high purity, and virtually no content of monochloro and dichloro compounds or unreacted PC13 could be detected.
Figure 2 shows an alternative embodiment differing from the embodiment described above in that the reflex condenser (K3) also constitutes a distillation device in which the excess 2,4-ditert-butylphenol can be removed. This 2,4-ditert-butylphenol can be recycled to the reaction via the feed inlet [I].
Claims (15)
1. A process for the preparation of tris-(2,4-ditert-butylphenyl) phosphite from
2,4-ditert-butylphenol and phosphorus trichloride in the presence of catalysts, which comprises carrying out the reaction in an at least three-stage process in which the 2,4-ditert-butylphenol and 40 - 100 % of the catalyst are combined in a preliminary stage and are brought together with the phosphorus trichloride in a first stage, these being allowed to react under normal pressure and at temperatures of 55 to 70°C for a dwell time of 15 to 40 minutes, the reaction mixture is then reacted in a second stage under normal pressure and at temperatures of over 140°C, remaining amounts of catalyst being added to the first and/or second reaction stage, the reaction mixture is then kept under reduced pressure at temperatures of at least 186°C in a third reaction stage, and the tris-(2,4-ditert-butylphenyl) phosphite is then isolated from the reaction mixture, the process being carried out in the absence of solvents.
2. A process according to claim 1, wherein the reaction mixture is subjected to a fourth stage in which the reaction mixture is kept at at least 186°C and under reduced pressure in the fourth stage.
2. A process according to claim 1, wherein the reaction mixture is subjected to a fourth stage in which the reaction mixture is kept at at least 186°C and under reduced pressure in the fourth stage.
3. A process according to claim 1, wherein a reaction time of 45 to 75 minutes is maintained in the second stage.
4. A process according to claim 1, wherein a reaction time of 1.5 to 2.5 hours is maintained in the third stage.
5. A process according to claim 2, wherein a reaction time of 20 to 120 minutes is maintained in the fourth stage.
6. A process according to claim 2, wherein a temperature of 190 to 195°C is maintained in the fourth stage.
7. A process according to claim 1, wherein the 2,4-ditert-butylphenol is added in a 1-fold to 1.1-fold stoichiometric amount, relative to the phosphorus trichloride.
8. A process according to claim 1, wherein the process is carried out in a three-stage kettle cascade.
9. A process according to claim 2, wherein the process is carried out in a four-stage kettle cascade.
10. A process according to claim 1, wherein the reaction mixture is stirred in at least one stage.
11. A process according to claim 1, wherein a temperature of 150 to 170°C is maintained in the second stage.
12. A process according to claim 1, wherein a temperature of 190 to 195°C is maintained in the third stage.
13. A process according to claim 1, wherein the third stage is carried out under a reduced pressure of 10 to 60 hpa.
14. A process according to claim 1, wherein 50 - 100 % of the amount of catalyst employed and the 2,4-ditert-butylphenol are added to the reaction via a packed column in which the preliminary stage is carried out.
15. A process according to claim 1, wherein the process is carried out continuously.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH2975/89-2 | 1989-08-15 | ||
CH297589 | 1989-08-15 |
Publications (2)
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CA2023164A1 CA2023164A1 (en) | 1991-02-16 |
CA2023164C true CA2023164C (en) | 2000-06-20 |
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ID=4245844
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Application Number | Title | Priority Date | Filing Date |
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CA002023164A Expired - Fee Related CA2023164C (en) | 1989-08-15 | 1990-08-13 | Process for the preparation of tris-(2,4-ditert-butylphenyl)phosphite |
Country Status (10)
Country | Link |
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EP (1) | EP0413661B1 (en) |
JP (1) | JP2984849B2 (en) |
KR (1) | KR0147837B1 (en) |
BR (1) | BR9004018A (en) |
CA (1) | CA2023164C (en) |
CZ (1) | CZ284446B6 (en) |
DE (1) | DE59009231D1 (en) |
ES (1) | ES2073556T3 (en) |
RU (1) | RU1831485C (en) |
SK (1) | SK279179B6 (en) |
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US11612897B2 (en) | 2017-05-24 | 2023-03-28 | Basf Se | Alkylated triphenyl phosphorothionates as selective metal sulphide collectors |
CN115651012B (en) * | 2022-11-16 | 2023-04-21 | 江苏极易新材料有限公司 | Synthesis method of low acid value tri (2, 4-di-tert-butylphenyl) phosphite |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
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DE2007070C3 (en) * | 1970-02-17 | 1979-02-22 | Ciba-Geigy Ag, Basel (Schweiz) | Process and apparatus for the production of triaryl phosphites |
EP0000757B1 (en) * | 1977-08-08 | 1981-08-05 | Ciba-Geigy Ag | Process for the preparation of triarylphosphites |
DE2944254A1 (en) * | 1978-11-02 | 1980-05-08 | Gen Electric | Sterically hindered phenol-contg. phosphite derivs. - for stabilising thermoplastics, esp. aromatic polycarbonate, against heat and hydrolysis (NL 7.5.80) |
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 |
-
1990
- 1990-08-07 DE DE59009231T patent/DE59009231D1/en not_active Expired - Lifetime
- 1990-08-07 EP EP90810596A patent/EP0413661B1/en not_active Expired - Lifetime
- 1990-08-07 ES ES90810596T patent/ES2073556T3/en not_active Expired - Lifetime
- 1990-08-13 CA CA002023164A patent/CA2023164C/en not_active Expired - Fee Related
- 1990-08-14 BR BR909004018A patent/BR9004018A/en not_active IP Right Cessation
- 1990-08-14 CZ CS903990A patent/CZ284446B6/en not_active IP Right Cessation
- 1990-08-14 SK SK3990-90A patent/SK279179B6/en unknown
- 1990-08-14 RU SU904830976A patent/RU1831485C/en active
- 1990-08-14 KR KR1019900012590A patent/KR0147837B1/en not_active IP Right Cessation
- 1990-08-15 JP JP2215674A patent/JP2984849B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
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KR0147837B1 (en) | 1998-08-17 |
CA2023164A1 (en) | 1991-02-16 |
DE59009231D1 (en) | 1995-07-20 |
SK399090A3 (en) | 1998-07-08 |
EP0413661A3 (en) | 1991-09-25 |
ES2073556T3 (en) | 1995-08-16 |
RU1831485C (en) | 1993-07-30 |
SK279179B6 (en) | 1998-07-08 |
EP0413661B1 (en) | 1995-06-14 |
CZ284446B6 (en) | 1998-11-11 |
JPH03118387A (en) | 1991-05-20 |
BR9004018A (en) | 1991-09-03 |
JP2984849B2 (en) | 1999-11-29 |
EP0413661A2 (en) | 1991-02-20 |
KR910004640A (en) | 1991-03-29 |
CZ399090A3 (en) | 1998-09-16 |
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