DE4021195A1 - New 6-aryl-6H-di:benzo-(c,e)(1,2)- oxa:phosphorin(s) - prepd. by grignard reaction of aryl halide(s) and its chloro-deriv., useful as stabilisers - Google Patents
New 6-aryl-6H-di:benzo-(c,e)(1,2)- oxa:phosphorin(s) - prepd. by grignard reaction of aryl halide(s) and its chloro-deriv., useful as stabilisersInfo
- Publication number
- DE4021195A1 DE4021195A1 DE4021195A DE4021195A DE4021195A1 DE 4021195 A1 DE4021195 A1 DE 4021195A1 DE 4021195 A DE4021195 A DE 4021195A DE 4021195 A DE4021195 A DE 4021195A DE 4021195 A1 DE4021195 A1 DE 4021195A1
- Authority
- DE
- Germany
- Prior art keywords
- radical
- carbon atoms
- substituents
- dibenzo
- aryl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003381 stabilizer Substances 0.000 title description 6
- 108010025647 phosphate-binding proteolipid Proteins 0.000 title description 2
- UNQNIRQQBJCMQR-UHFFFAOYSA-N phosphorine Chemical compound C1=CC=PC=C1 UNQNIRQQBJCMQR-UHFFFAOYSA-N 0.000 title description 2
- 238000003747 Grignard reaction Methods 0.000 title 1
- 150000001502 aryl halides Chemical class 0.000 title 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- UBEUAZASIHVFOB-UHFFFAOYSA-N 6-chlorobenzo[c][2,1]benzoxaphosphinine Chemical compound C1=CC=C2P(Cl)OC3=CC=CC=C3C2=C1 UBEUAZASIHVFOB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 4
- 238000002604 ultrasonography Methods 0.000 claims abstract description 4
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 21
- -1 hydrocarbon halide Chemical class 0.000 claims description 21
- OMDCSPXITNMPHV-UHFFFAOYSA-N 2h-oxaphosphinine Chemical class O1PC=CC=C1 OMDCSPXITNMPHV-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 239000002530 phenolic antioxidant Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- 125000004957 naphthylene group Chemical group 0.000 abstract description 3
- 125000003545 alkoxy group Chemical group 0.000 abstract description 2
- 125000004414 alkyl thio group Chemical group 0.000 abstract description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 abstract description 2
- 125000004663 dialkyl amino group Chemical group 0.000 abstract description 2
- 150000008282 halocarbons Chemical class 0.000 abstract 1
- 125000001624 naphthyl group Chemical group 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical group COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VXVFHTHMLANPPL-WUKNDPDISA-N [(e)-2-diphenylphosphorylethenyl]benzene Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)\C=C\C1=CC=CC=C1 VXVFHTHMLANPPL-WUKNDPDISA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- RYIOLWQRQXDECZ-UHFFFAOYSA-N phosphinous acid Chemical class PO RYIOLWQRQXDECZ-UHFFFAOYSA-N 0.000 description 2
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- SCZXFZRJDVZMJI-UHFFFAOYSA-N 1-bromo-2,4,5-trimethylbenzene Chemical compound CC1=CC(C)=C(Br)C=C1C SCZXFZRJDVZMJI-UHFFFAOYSA-N 0.000 description 1
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 1
- WJIFKOVZNJTSGO-UHFFFAOYSA-N 1-bromo-3-methylbenzene Chemical compound CC1=CC=CC(Br)=C1 WJIFKOVZNJTSGO-UHFFFAOYSA-N 0.000 description 1
- HQJQYILBCQPYBI-UHFFFAOYSA-N 1-bromo-4-(4-bromophenyl)benzene Chemical group C1=CC(Br)=CC=C1C1=CC=C(Br)C=C1 HQJQYILBCQPYBI-UHFFFAOYSA-N 0.000 description 1
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 1
- IDRVLLRKAAHOBP-UHFFFAOYSA-N 1-bromo-4-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=C(Br)C2=C1 IDRVLLRKAAHOBP-UHFFFAOYSA-N 0.000 description 1
- XHCAGOVGSDHHNP-UHFFFAOYSA-N 1-bromo-4-tert-butylbenzene Chemical compound CC(C)(C)C1=CC=C(Br)C=C1 XHCAGOVGSDHHNP-UHFFFAOYSA-N 0.000 description 1
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 1
- MYMYVYZLMUEVED-UHFFFAOYSA-N 2-bromo-1,3-dimethylbenzene Chemical compound CC1=CC=CC(C)=C1Br MYMYVYZLMUEVED-UHFFFAOYSA-N 0.000 description 1
- QXISTPDUYKNPLU-UHFFFAOYSA-N 2-bromo-1,4-dimethylbenzene Chemical compound CC1=CC=C(C)C(Br)=C1 QXISTPDUYKNPLU-UHFFFAOYSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 1
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 1
- UZEJJDOZEUXVCW-UHFFFAOYSA-N 6-(2,3,5-trimethylphenyl)benzo[c][2,1]benzoxaphosphinine Chemical compound CC1=CC(C)=C(C)C(P2C3=CC=CC=C3C3=CC=CC=C3O2)=C1 UZEJJDOZEUXVCW-UHFFFAOYSA-N 0.000 description 1
- TUJGMAYJEAAIKO-UHFFFAOYSA-N 6-(4-tert-butylphenyl)benzo[c][2,1]benzoxaphosphinine Chemical compound C1=CC(C(C)(C)C)=CC=C1P1C2=CC=CC=C2C2=CC=CC=C2O1 TUJGMAYJEAAIKO-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical group COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5377—Phosphinous compounds, e.g. R2=P—OR'
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft neue 6-Aryl-6H-dibenzo- [c,e][1,2]-oxaphosphorine, ein Verfahren zu ihrer Herstellung sowie deren Verwendung zur Stabilisierung von Kunststoffen.The present invention relates to new 6-aryl-6H-dibenzo [c, e] [1,2] -oxaphosphorines, a process for their Production and their use for the stabilization of Plastics.
Es ist bekannt, daß synthetische Polymere gegen unerwünschte oxydative, thermische und photochemische Schädigung während der Herstellung, der Verarbeitung und des Gebrauchs durch Stabilisatoren oder Stabilisatorsysteme geschützt werden müssen. Solche Stabilisatoren bestehen beispielsweise aus einem phenolischen Antioxydans und einem oder mehreren Costabilisatoren, die teilweise auch die Wirkung der phenolischen Komponente synergistisch verstärken.It is known that synthetic polymers against undesirable oxidative, thermal and photochemical Damage during manufacture, processing and use by stabilizers or stabilizer systems must be protected. Such stabilizers exist for example from a phenolic antioxidant and one or more costabilizers, some of which are also Effect of the phenolic component synergistic reinforce.
Zu den gebräuchlichen Costabilisatoren gehören beispielsweise ortho-alkylierte Arylphosphite und Phosphonite.Common costabilizers include for example ortho-alkylated aryl phosphites and Phosphonites.
Die in der EP-PS 5 447 beschriebenen Phosphonigsäure diarylester weisen zwar für bestimmte Anwendungsbereiche ausreichende Eigenschaften als Stabilisatoren auf; deren Synthese geht jedoch von Organodichlorphosphanen aus, die technisch schwer zugänglich sind. In der Praxis steht als einziges technisch verfügbares Vorprodukt Phenyldichlor phosphan zur Verfügung, durch das ausschließlich Derivate der benzolphosphonigen Säure zugänglich werden. Zur Erzielung der angestrebten Eigenschaften ist es jedoch vielfach wünchenswert, gerade Verbindungen mit höher substituierten Arylgruppen am Phosphor zur Verfügung zu haben. The phosphonous acid described in EP-PS 5 447 diarylesters indicate certain areas of application sufficient properties as stabilizers; their However, synthesis is based on organodichlorophosphines, which are technically difficult to access. In practice it stands as only technically available intermediate phenyldichlor phosphine available through which only derivatives the benzene phosphonic acid become accessible. To However, it is achieving the desired properties often desirable, especially connections with higher substituted aryl groups on phosphorus to have.
Ein weiterer schwerwiegender Nachteil besteht in der Notwendigkeit, bei der Synthese freigesetzten Chlorwasserstoff durch eine geeignete Hilfsbase zu neutralisieren. Bei deren Recyclisierung ist der zwngsläufige Anfall von zwei Äquivalenten des entsprechenden Salzes unvermeidlich.Another serious disadvantage is that Need to be released during synthesis Hydrogen chloride through a suitable auxiliary base neutralize. When they are recycled, the inevitable occurrence of two equivalents of appropriate salt inevitable.
Die in der DE-OS 20 34 887 durch Hydrolyse, Veresterung, Umesterung, Alkylierung oder Sulfurierung von 6-Chlor dibenzo-[c,e][1,2]-oxaphosphorin hergestellten Phosphonigsäureester weisen u. a. Nachteil hinsichtlich Lagerstabilität, Farbverhalten und Hydrolysebeständigkeit auf, wie es bereits in der US-PS 41 85 006 beschrieben worden ist.The in DE-OS 20 34 887 by hydrolysis, esterification, Transesterification, alkylation or sulfurization of 6-chlorine dibenzo- [c, e] [1,2] -oxaphosphorin Phosphonous acid esters have u. a. Disadvantage with regard Storage stability, color behavior and resistance to hydrolysis on, as already described in US Pat. No. 4,185,006 has been.
Aufgabe der vorliegenden Erfindung war es daher, neue Phosphorstabilisatoren zur Verfügung zu stellen, die einerseits die hohen Anforderungen der Praxis erfüllen und insbesondere auch bei der Einwirkung von Wasser nicht in mehrere Bruchstücke und/oder saure Folgeprodukte zerfallen, gleichzeitig aber in einfacher Weise und in hoher Ausbeute durch ökologisch günstige Verfahren herstellbar sind.The object of the present invention was therefore to create new ones To provide phosphorus stabilizers that on the one hand meet the high demands of practice and especially when exposed to water not in several fragments and / or acidic secondary products disintegrate, but at the same time in a simple manner and in high yield can be produced using environmentally friendly processes.
Es wurde nun überraschend gefunden, daß cyclische Phosphinigsäureester der Formel I (siehe Patentanspruch 1) diesen Erfordernissen in hohem Maße gerecht werden.It has now surprisingly been found that cyclic Phosphinous acid esters of formula I (see claim 1) meet these requirements to a high degree.
Gegenstand der Erfindung sind daher Dibenzo-[c,e][1,2]- oxaphosphorine der Formel I, das sind Aryl-6H-dibenzo-[c,e][1,2]-oxaphosphorine mit n=1 sowie Aryl-bis-{6H-dibenzo-[c,e][1,2]-oxaphosphorine} mit n=2, in denen R¹ als einwertiger Rest einen Phenylrest, der 1 bis 3 Substituenten tragen kann oder einen Naphthylrest, der 1 bis 5 Substituenten tragen kann, wobei die Substituenten gleich oder verschieden sind und einen nicht-aromatischen Kohlenwasserstoffrest, einen Alkoxyrest, Alkylthiorest oder Dialkylaminorest mit jeweils 1 bis 8 Kohlenstoffatomen, Aryl oder Aryloxy mit jeweils 6 bis 10 Kohlenstoffatomen oder Halogen mit einer Ordnungszahl von 9 bis 35 darstellen und als zweiwertiger Rest einen Phenylen- oder Biphenylrest, der unsubstituiert ist oder mit bis zu 4 nicht-aromatischen Kohlenwasserstoffresten mit 1 bis 8 Kohlenstoffatomen substituiert ist, oder einen Naphthylenrest, der unsubstituiert ist oder 1 bis 4 nicht-aromatische Kohlenwasserstoffreste mit 1 bis 8 Kohlenstoffatomen als Substituenten trägt.The invention therefore relates to dibenzo- [c, e] [1,2] - oxaphosphorines of formula I, that are Aryl-6H-dibenzo- [c, e] [1,2] -oxaphosphorines with n = 1 as well Aryl-bis- {6H-dibenzo- [c, e] [1,2] -oxaphosphorine} with n = 2, in which R¹ as a monovalent radical is a phenyl radical, the 1st can carry up to 3 substituents or a naphthyl radical, which can carry 1 to 5 substituents, the Substituents are the same or different and have one non-aromatic hydrocarbon residue, an alkoxy residue, Alkylthio residue or dialkylamino residue each with 1 to 8 Carbon atoms, aryl or aryloxy each having 6 to 10 Carbon atoms or halogen with an atomic number of 9 to 35 and as a divalent radical a phenylene or biphenyl radical which is unsubstituted or with up to 4 non-aromatic hydrocarbon residues with 1 to 8 Carbon atoms is substituted, or a Naphthylene residue which is unsubstituted or 1 to 4 non-aromatic hydrocarbon residues with 1 to 8 Carries carbon atoms as substituents.
Im einzelnen seien für R¹ als einwertigen Rest z. B. die verschiedenen Tolylreste, Xylylreste, Mesityl, 2,4,5-Trimethylphenyl, die verschiedenen tert.-Butylphenylreste, Di-tert.-butylphenylreste, 2,4,6- Tri-tert.-butylphenyl, 2,4-Di-tert.-octylphenyl, die verschiedenen Biphenyl-, Methylnaphthyl-, Dimethylnaphthyl- sowie Trimethylnaphthylreste genannt.In particular, for R¹ as a monovalent radical z. B. the various tolyl residues, xylyl residues, mesityl, 2,4,5-trimethylphenyl, the various tert-butylphenyl, di-tert-butylphenyl, 2,4,6- Tri-tert-butylphenyl, 2,4-di-tert-octylphenyl, the various biphenyl, methylnaphthyl, dimethylnaphthyl and also called trimethylnaphthyl residues.
Für R¹ als zweiwertigen Rest seien beispielsweise genannt die verschiedenen Phenylreste, wie 1,3- und 1,4-Phenylen, die verschiedenen Biphenylenreste, wie 2′,3-, 2′,4- 3′,3-, 3′,4- und 4,4′-Biphenylen und die verschiedenen Naphthylen reste, wie 1,4- und 1,6-Naphthylen.For R¹ as a divalent radical, for example the various phenyl radicals, such as 1,3- and 1,4-phenylene, the different biphenylene residues, such as 2 ′, 3-, 2 ′, 4- 3 ′, 3-, 3 ', 4- and 4,4'-biphenylene and the various naphthylene residues such as 1,4- and 1,6-naphthylene.
Gegenstand der Erfindung ist auch ein Verfahren zur Herstellung der Phosphinigsäureester der Formel I, worin R¹ die oben angegebene Bedeutung hat, das dadurch gekennzeichnet ist, daß man zunächst in erster Stufe ein Kohlenwasserstoffhalogenid R¹-(Hal)n, worin R¹ die vorgenannte Bedeutung hat, n=1 oder 2 ist und dessen Halogen ein Atomgewicht von mindestens 35 hat, bevorzugt jedoch Chlor oder Brom ist, unter Grignard-Bedingungen, also zweckmäßig unter inniger Durchmischung, mit einer mindestens stöchiometrischen Menge feinteiligem Magnesium zu den entsprechenden Grignard-Verbindungen R¹(MgHal)n umsetzt und diese weiter in einer zweiten Stufe mit 6-Chlor-6H-dibenzo-[c,e][1,2]-oxaphosphorin umsetzt.The invention also relates to a process for the preparation of the phosphinous esters of the formula I, in which R¹ has the meaning given above, which is characterized in that firstly a hydrocarbon halide R¹- (Hal) n , in which R¹ has the abovementioned meaning, n = 1 or 2 and the halogen of which has an atomic weight of at least 35, but is preferably chlorine or bromine, under Grignard conditions, i.e. expediently with thorough mixing, with an at least stoichiometric amount of finely divided magnesium to give the corresponding Grignard compounds R¹ (MgHal ) n and reacted this further in a second stage with 6-chloro-6H-dibenzo- [c, e] [1,2] -oxaphosphorin.
Die erste Stufe des erfindungsgemäßen Verfahrens, die man an sich in jeder üblichen Weise durchführen kann, wird bevorzugt in einem aprotischen, organischen Lösungsmittel wie einem Äther, z. B. Diäthyl-, Dipropyl- oder Diisopropyl äther, Äthylenglykoldimethyl- oder -äthyläther, Diäthylen glykoldimethyl- oder -äthyläther, Methyl-tert.-butyläther, Dioxan oder Tetrahydrofuran durchgeführt.The first stage of the process according to the invention, which one can perform in any usual way preferably in an aprotic, organic solvent like an ether, e.g. B. diethyl, dipropyl or diisopropyl ether, ethylene glycol dimethyl or ethyl ether, diethylene glycol dimethyl or ethyl ether, methyl tert-butyl ether, Dioxane or tetrahydrofuran performed.
Da die Grignard-Verbindungen hydrolyse- und oxydationsempfindlich sind, kann es zweckmäig sein, unter Schutzgasatmosphäre zu arbeiten, Ein solches Vorgehen ist jedoch für das Gelingen der Reaktion keineswegs zwingend. Als Schutzgas besonders geeignet sind Stickstoff und Argon. Die Reaktionstemperatur liegt im allgemeinen zwischen 20 und 125°C, bevorzugt jedoch zwischen 30 und 70°C. Die Einwirkung von Ultraschall während der Grignardierung ist zuweilen von Vorteil.Since the Grignard compounds hydrolysis and are sensitive to oxidation, it may be appropriate to Working in a protective gas atmosphere is such a procedure however, in no way imperative for the success of the reaction. Nitrogen and argon are particularly suitable as protective gases. The reaction temperature is generally between 20 and 125 ° C, but preferably between 30 and 70 ° C. The Exposure to ultrasound during grignarding sometimes an advantage.
Zur Herstellung der Verbindungen I wird in der zweiten Stufe die Lösung bzw. Suspension des Grignard-Reagenzes zu einer Lösung von 6-Chlor-6H-dibenzo-[c,e][1,2]-oxa phosphorin unter lebhafter Durchmischung zudosiert. Als Verdünnungsmittel kommen inerte, aprotische Lösungsmittel, z. B. eine aliphatische Kohlenwasserstofffraktion, Hexan, Heptan, Cyclohexan, Toluol, Xylol oder einer der obengenannten Äther bzw. entsprechende Gemische in Frage. Die Reaktionstemperatur liegt bei diesem Schritt im allgemeinen zwischen -30 und +50°C, vorzugsweise aber zwischen -20 und +20°C. Die Umsetzung verläuft in der Regel exotherm; dementsprechend kann es zweckmäßig sein, den Reaktionsverlauf durch Kühlung zu steuern. Die günstigsten Ergebnisse werden erzielt, wenn man die Reaktionspartner in den stöchiometrischen Mengen einsetzt. Es ist jedoch auch möglich, einen Reaktionspartner im Überschuß einzusetzen; im allgemeinen sind damit aber keine besonderen Vorteile verbunden. Zweckmäßig wird gerührt, bis die Umsetzung vollständig ist, und anschließend vom ausgefallenen Magnesiumhalogenid abgetrennt. Die Lösungsmittel können aus dem Filtrat in üblicher Weise, vorteilhaft destillativ, insbesondere unter vermindertem Druck, entfernt werden.To prepare the compounds I is in the second Level the solution or suspension of the Grignard reagent a solution of 6-chloro-6H-dibenzo- [c, e] [1,2] -oxa phosphorin metered in with vigorous mixing. As Diluents come with inert, aprotic solvents, e.g. B. an aliphatic hydrocarbon fraction, hexane, Heptane, cyclohexane, toluene, xylene or one of the above ether or corresponding mixtures in question. The reaction temperature in this step is generally between -30 and + 50 ° C, but preferably between -20 and + 20 ° C. The implementation usually takes place exothermic; accordingly, it may be appropriate to Control the course of the reaction by cooling. The cheapest Results are achieved if the reactants in the stoichiometric amounts. However, it is also possible to use one reactant in excess; but in general there are no particular advantages connected. Appropriately, stirring is continued until the implementation is complete, and then from the failed Magnesium halide separated. The solvents can run out the filtrate in the usual way, advantageously by distillation, especially under reduced pressure.
Die Produkte I lassen sich nach beliebigen Verfahren, bevorzugt jedoch durch Kristallisation, aus den Rohprodukten aussondern.Products I can be made by any method, but preferably by crystallization, from the Discard raw products.
Bei der Synthese von Phosphinigsäureestern durch Umsetzung von Phosphorigsäure-ester-halogeniden mit Organomagnesiumhalogeniden läuft als ausbeutevermindernde Nebenreaktion der Austausch des OR-Restes durch die Grignard-Verbindung ab, so daß selbst in den günstigsten Fällen die erzielten Ausbeuten 60% nicht übersteigen (Houben-Weyl: "Methoden der organischen Chemie", 12/1, S. 210 (1963)).In the synthesis of phosphinous acid esters by reaction of phosphoric acid ester halides with Organomagnesium halides run as a yield-reducing Side reaction of the exchange of the OR residue by the Grignard connection off, so even in the cheapest If the yields obtained do not exceed 60% (Houben-Weyl: "Methods of Organic Chemistry", 12/1, P. 210 (1963)).
Darüber hinaus bestand in der Literatur ein Vorurteil dahingehend, daß die Umsetzung von Phosphonigsäure-halogeniden mit Organomagnesiumbromiden zunächst immer zu unlöslichen Komplexverbindungen führt, die erst durch Zugabe weiterer Hilfsstoffe (z. B. 4 Mol Pyridin) zerlegt werden müssen, um eine Isolierung der gewünschten Phosphinigsäureester zu ermöglichen (Houben-Weyl, l. c.). Daher ist es besonders überraschend, daß das Verfahren der vorliegenden Erfindung die Phosphinigsäureester I in hoher Ausbeute und Reinheit zugänglich macht, ohne daß der Einsatz von Dekomplexierungsmitteln notwendig ist.There was also prejudice in the literature in that the implementation of Phosphonous acid halides with organomagnesium bromides always leads to insoluble complex compounds, which can only be achieved by adding other auxiliary substances (e.g. 4 mol Pyridine) must be disassembled to isolate the to enable desired phosphinous acid esters (Houben-Weyl, l. C.). So it’s particularly surprising that the method of the present invention the Phosphinic acid ester I in high yield and purity makes it accessible without the use of Decomplexing agents are necessary.
Das als Vorprodukt benötigte 6-Chlor-6H-dibenzo-[c,e][1,2]- oxaphosphorin ist in einfacher Weise nach dem Verfahren der DE-OS 20 34 887 ohne Verwendung eines Lösungsmittels oder einer Hilfsbase aus Phosphortrichlorid und o-Phenylphenol zugänglich. The 6-chloro-6H-dibenzo- [c, e] [1,2] - required as a preliminary product oxaphosphorin is easily processed according to the procedure DE-OS 20 34 887 without using a solvent or an auxiliary base of phosphorus trichloride and o-phenylphenol accessible.
Gegenstand der Erfindung ist schließlich die Verwendung der Verbindungen der Formel I für sich oder in Kombination mit einem phenolischen Antioxydans zur Stabilisierung von Kunststoffen, vorzugsweise Polymerisationskunststoffen wie Polypropylen. Für diese Anwendung ist vielfach die Reinheit der anfallenden rohren Reaktionsprodukte ausreichend. Eine Isolierung in reiner Form ist dann nicht erforderlich.The invention finally relates to the use of Compounds of formula I alone or in combination with a phenolic antioxidant to stabilize Plastics, preferably polymer plastics such as Polypropylene. The purity is often for this application of the resulting tube reaction products sufficient. A Isolation in pure form is then not necessary.
Unter Stickstoffatmosphäre und Feuchtigkeitsausschluß wurde aus 300 mmol Organobromverbindung und 300 mmol (=7,3 g) Magnesiumspänen in 180 ml Tetrahydrofuran die entsprechende Grignard-Verbindung hergestellt. Anschließend wurde die erhaltene Lösung bzw. Suspension der metallorganischen Verbindung innerhalb von 30 bis 40 Minuten unter lebhaftem Rühren bei einer Innentemperatur von -20 bis -10°C zu der Lösung von 300 mmol (=70,4 g) 6-Chlor-6H-dibenzo-[c,e][1,2]-oxaphosphorin in 120 ml Tetrahydrofuran/n-Hexan (1 : 1) zudosiert. Dann ließ man die Reaktionsmischung auf Raumtemperatur erwärmen und rührte zur Vervollständigung der Umsetzung noch 2,5 Stunden. Nach Filtration vom ausgefallenen Magnesiumsalz, das mit ca. 50 ml Petroläther nachgewaschen wurde, wurde das Lösungsmittel zunächst im Vakuum der Wasserstrahlpumpe und dann im Hochvakuum abdestilliert. Der erhaltene farblose oder beige Rückstand wurde pulverisiert und im Hochvakuum getrocknet.Under a nitrogen atmosphere and excluding moisture was converted from 300 mmol organobromine compound and 300 mmol (= 7.3 g) Magnesium chips in 180 ml of tetrahydrofuran appropriate Grignard connection established. Subsequently the solution or suspension obtained organometallic compound within 30 to 40 Minutes with vigorous stirring at an internal temperature from -20 to -10 ° C to the solution of 300 mmol (= 70.4 g) 6-chloro-6H-dibenzo- [c, e] [1,2] -oxaphosphorin in 120 ml Tetrahydrofuran / n-hexane (1: 1) metered in. Then you let them Warm the reaction mixture to room temperature and stir 2.5 hours to complete the implementation. To Filtration of the precipitated magnesium salt, which with approx. 50 ml of petroleum ether was washed, the solvent became first in the vacuum of the water jet pump and then in High vacuum distilled off. The colorless or beige obtained The residue was pulverized and dried under high vacuum.
Der Produktgehalt der Rohmaterialien wurde durch ³¹P-NMR-Spektroskopie ermittelt und lag im allgemeinen zwischen 78 und 98% (von Gesamt-P).The product content of the raw materials was determined by 31 P NMR spectroscopy determined and was in general between 78 and 98% (of total P).
In den angegebenen Fällen wurde zur Charakterisierung des Produktes aus Acetonitril bzw. Aceton kristallisiert. In the given cases the characterization of the Product crystallized from acetonitrile or acetone.
Ausgehend von 47,1 g Brombenzol erhielt man 84,8 g
farbloses Harz mit einem Gehalt von 89,5% an vorstehender
Verbindung. Kristallisieren aus Acetonitril lieferte
farblose Kristalle vom Erweichungspunkt ca. 190°C;
[³¹P-NMR: δCDCl₃ = 84,1 ppm].Starting from 47.1 g of bromobenzene, 84.8 g of colorless resin with a content of 89.5% of the above compound were obtained. Crystallization from acetonitrile gave colorless crystals with a softening point of approximately 190 ° C .;
[31 P NMR: δ CDCl₃ = 84.1 ppm].
C₁₈H₁₃OP(276,27)
Ber.: C 78,25%; H 4,74%; P 11,21%;
Gef.: C 78,0%; H 4,5%; P 10,9%.C₁₈H₁₃OP (276.27)
Calc .: C 78.25%; H 4.74%; P 11.21%;
Found: C 78.0%; H 4.5%; P 10.9%.
Ausgehend von 51,3 g o-Bromtoluol erhielt man ca. 83 g
farbloses Harz mit einem Gehalt von 93,7% an vorstehender
Verbindung. Kristallisieren aus Acetonitril lieferte
farblose Kristalle vom Schmp. 100-102°C.
[³¹P-NMR: δCDCl₃ = 81,8 ppm].Starting from 51.3 g of o-bromotoluene, about 83 g of colorless resin with a content of 93.7% of the above compound were obtained. Crystallization from acetonitrile gave colorless crystals with a melting point of 100-102 ° C.
[31 P NMR: δ CDCl₃ = 81.8 ppm].
C₁₉H₁₅OP(290,29)
Ber.: C 78,61%; H 5,20%; P 10,66%;
Gef.: C 78,3%; H 5,0%; P 10,3%.C₁₉H₁₅OP (290.29)
Calcd .: C 78.61%; H 5.20%; P 10.66%;
Found: C 78.3%; H 5.0%; P 10.3%.
Ausgehend von 51,3 g m-Bromtoluol erhielt man ca. 86 g
gelbliches Harz mit einem Gehalt von 92% an vorstehender
Verbindung. Kristallisieren aus Acetonitril lieferte
farblose Kristalle vom Schmp. 70-75°C.
[³¹P-NMR: δCDCl₃ = 84,5 ppm].Starting from 51.3 g of m-bromotoluene, about 86 g of yellowish resin with a content of 92% of the above compound were obtained. Crystallization from acetonitrile gave colorless crystals with a melting point of 70-75 ° C.
[31 P NMR: δ CDCl₃ = 84.5 ppm].
C₁₉H₁₅OP(290,29)
Ber.: C 78,61%; H 5,20%; P 10,66%;
Gef.: C 78,9%; H 5,5%; P 10,4%.C₁₉H₁₅OP (290.29)
Calcd .: C 78.61%; H 5.20%; P 10.66%;
Found: C 78.9%; H 5.5%; P 10.4%.
Ausgehend von 51,3 g p-Bromtoluol erhielt man ca. 83 g
beiges Harz mit einem Gehalt von 94,4% an obiger
Verbindung. Digerieren mit Acetonitril lieferte farbloses
Pulver vom Erweichungspunkt ca. 60°C.
[³¹P-NMR: δCDCl₃ = 83,6 ppm].Starting from 51.3 g of p-bromotoluene, approximately 83 g of beige resin with a content of 94.4% of the above compound were obtained. Digestion with acetonitrile provided colorless powder with a softening point of approx. 60 ° C.
[31 P NMR: δ CDCl₃ = 83.6 ppm].
C₁₉H₁₅OP(290,29)
Ber.: C 78,61%; H 5,20%; P 10,66%;
Gef.: C 78,0%; H 5,2%; P 10,3%.
C₁₉H₁₅OP (290.29)
Calcd .: C 78.61%; H 5.20%; P 10.66%;
Found: C 78.0%; H 5.2%; P 10.3%.
Ausgehend von 63,93 g 4-Brom-tert.-butylbenzol erhielt man
ca. 100 g eines gelblichen, zähen Harzes mit einem Gehalt
von 92% an vorstehender Verbindung. Kristallisieren aus
Aceton lieferte farblose Kristalle vom Schmp. 90-92°C-
[³¹P-NMR: δCDCl₃ = 83,2 ppm].Starting from 63.93 g of 4-bromo-tert-butylbenzene, approximately 100 g of a yellowish, viscous resin with a content of 92% of the above compound were obtained. Crystallization from acetone gave colorless crystals with a melting point of 90-92 ° C.
[31 P NMR: δ CDCl₃ = 83.2 ppm].
C₂₂H₂₁OP(332,38)
Ber.: C 79,49%; H 6,36%; P 9,31%;
Gef.: C 79,1%; H 6,6%; P 9,5%.C₂₂H₂₁OP (332.38)
Calc .: C 79.49%; H 6.36%; P 9.31%;
Found: C 79.1%; H 6.6%; P 9.5%.
Ausgehend von 56,2 g 4-Bromanisol erhielt man ca. 93 g
farbloses Harz mit einem Gehalt von 78% an vorstehender
Verbindung. Kristallisieren aus Aceton lieferte Kristalle
vom Schmp. 104-106°C.-
[³¹P-NMR: δDMSO = 81,0 ppm].Starting from 56.2 g of 4-bromoanisole, about 93 g of colorless resin with a content of 78% of the above compound were obtained. Crystallization from acetone gave crystals of mp 104-106 ° C.-
[31 P NMR: δ DMSO = 81.0 ppm].
C₁₉H₁₅O₂P(306,29)
Ber.: C 74,50%; H 4,93%; P 10,11%;
Gef.: C 74,1%; H 4,7%; P 9,7%.C₁₉H₁₅O₂P (306.29)
Calc .: C 74.50%; H 4.93%; P 10.11%;
Found: C 74.1%; H 4.7%; P 9.7%.
Ausgehend von 59,73 g Brommesitylen erhielt man ca. 98 g
gelbes Pulver mit einem Gehalt von 84% an vorstehender
Verbindung und einem Erweichungspunkt von ca. 70°C.
[³¹P-NMR: δCDCl₃ = 109,9 ppm].Starting from 59.73 g of bromesitylene, about 98 g of yellow powder with a content of 84% of the above compound and a softening point of about 70 ° C. were obtained.
[31 P NMR: δ CDCl₃ = 109.9 ppm].
C₂₁H₁₉OP(318,36)C₂₁H₁₉OP (318.36)
Ausgehend von 59,73 g 5-Brom-1,2,4-trimethylbenzol erhielt
man ca. 93 g gelbes Pulver vom Erweichungspunkt ca. 70°C
und einem Gehalt von 98,3% an obiger Verbindung.
[³¹P-NMR: δCDCl₃ = 81,7 ppm].Starting from 59.73 g of 5-bromo-1,2,4-trimethylbenzene, about 93 g of yellow powder with a softening point of about 70 ° C. and a 98.3% content of the above compound were obtained.
[31 P NMR: δ CDCl₃ = 81.7 ppm].
C₂₁H₁₉OP(318,36) C₂₁H₁₉OP (318.36)
Ausgehend von 62,2 g 1-Bromnaphthalin wurden ca. 90 g
beiges Pulver vom Erweichungspunkt ca. 80°C und einem
Gehalt von 82,8% an vorstehender Verbindung erhalten.
[³¹P-NMR: δCDCl₃ = 82,0 ppm].Starting from 62.2 g of 1-bromonaphthalene, about 90 g of beige powder with a softening point of about 80 ° C. and a content of 82.8% in the above compound were obtained.
[31 P NMR: δ CDCl₃ = 82.0 ppm].
C₂₂H₁₅OP(326,33)C₂₂H₁₅OP (326.33)
Ausgehend von 66,32 g 1-Brom-4-methylnaphthalin wurden ca.
95 g farbloses Harz mit einem Gehalt von 90% an
vorstehender Verbindung erhalten. Kristallisieren aus
Aceton lieferte farblose Kristalle vom Schmp. 125-127°C.
[³¹P-NMR: δCDCl₃ = 81,7 ppm].Starting from 66.32 g of 1-bromo-4-methylnaphthalene, approximately 95 g of colorless resin with a content of 90% of the above compound were obtained. Crystallization from acetone gave colorless crystals with a mp of 125-127 ° C.
[31 P NMR: δ CDCl₃ = 81.7 ppm].
C₂₃H₁₇OP(340,37)
Ber.: C 81,16%; H 5,03%; P 9,09%;
Gef.: C 80,7%; H 4,7%; P 8,8%.C₂₃H₁₇OP (340.37)
Calc .: C 81.16%; H 5.03%; P 9.09%;
Found: C 80.7%; H 4.7%; P 8.8%.
Ausgehend von 55,5 g 1-Brom-2,6-dimethylbenzol wurden ca.
90 g farbloser Feststoff mit einem Gehalt von 82% an
vorstehender Verbindung erhalten. Kristallisieren aus
Acetonitril lieferte farblose Kristalle vom Schmp. 93-
96°C.
[³¹P-NMR: δCDCl₃ = 109,6 ppm].Starting from 55.5 g of 1-bromo-2,6-dimethylbenzene, about 90 g of a colorless solid with a content of 82% of the above compound were obtained. Crystallization from acetonitrile gave colorless crystals with a melting point of 93-96 ° C.
[31 P NMR: δ CDCl₃ = 109.6 ppm].
C₂₀H₁₇OP(304,32)
Ber.: C 78,93%; H 5,63%; P 10,17%;
Gef.: C 80,3%; H 5,9%; P 9,6%.C₂₀H₁₇OP (304.32)
Calcd .: C 78.93%; H 5.63%; P 10.17%;
Found: C 80.3%; H 5.9%; P 9.6%.
Ausgehend von 55,5 g 1-Brom-2,5-dimethylbenzol wurden ca.
88 g farbloses Harz mit einem Gehalt von 97% an
vorstehender Verbindung erhalten. Kristallisieren aus
Acetonitril lieferte farblose Kristalle vom Schmp. 70-
73°C.
[³¹P-NMR: δCDCl₃ = 82,9 ppm].Starting from 55.5 g of 1-bromo-2,5-dimethylbenzene, approximately 88 g of colorless resin with a content of 97% of the above compound were obtained. Crystallization from acetonitrile gave colorless crystals with a melting point of 70-73 ° C.
[31 P NMR: δ CDCl₃ = 82.9 ppm].
C₂₀H₁₇OP(304,32)
Ber.: C 78,93%; H 5,63%; P 10,17%;
Gef.: C 78,3%; H 5,3%; P 9,7%.
C₂₀H₁₇OP (304.32)
Calcd .: C 78.93%; H 5.63%; P 10.17%;
Found: C 78.3%; H 5.3%; P 9.7%.
Abweichend von der allgemeinen Vorschrift wurden 200 mmol
(= 62,4 g) 4,4′-Dibrombiphenyl mit 500 mmol (= 12,15 g)
Magnesiumspänen in 400 ml Tetrahydrofuran unter Einwirkung
von Ultraschall (40 kHz) grignardiert und anschließend
mit 400 mmol (= 93,9 g) 6-Chlor-6H-dibenzo-[c,e][1,2]-
oxaphosphorin in 120 ml Tetrahydrofuran/n-Hexan 1 : 1
umgesetzt. Man erhielt ca. 105 g farblosen Feststoff vom
Erweichungspunkt 68-70°C mit einem Gehalt von 73% an
vorstehender Verbindung.
[³¹P-NMR: δCDCl₃ = 83,4 ppm].Deviating from the general instructions, 200 mmol (= 62.4 g) 4,4'-dibromobiphenyl with 500 mmol (= 12.15 g) magnesium shavings in 400 ml tetrahydrofuran under the influence of ultrasound (40 kHz) were grignardized and then with 400 mmol (= 93.9 g) 6-chloro-6H-dibenzo- [c, e] [1,2] - oxaphosphorin in 120 ml tetrahydrofuran / n-hexane reacted 1: 1. About 105 g of a colorless solid with a softening point of 68-70 ° C. and a content of 73% of the above compound were obtained.
[31 P NMR: δ CDCl₃ = 83.4 ppm].
C₃₆H₂₄O₂P₂(550,52)C₃₆H₂₄O₂P₂ (550.52)
Claims (7)
Priority Applications (15)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4021195A DE4021195A1 (en) | 1990-07-02 | 1990-07-02 | New 6-aryl-6H-di:benzo-(c,e)(1,2)- oxa:phosphorin(s) - prepd. by grignard reaction of aryl halide(s) and its chloro-deriv., useful as stabilisers |
| JP3511065A JPH0832712B2 (en) | 1990-07-02 | 1991-06-22 | Novel 6-aryl-6H-dibenzo- [c, e] [1,2] -oxaphosphorine and its use for stabilizing synthetic resins, especially polyolefin molding compounds |
| PCT/EP1991/001158 WO1992000306A1 (en) | 1990-07-02 | 1991-06-22 | NEW 6-ARYL-6H-DIBENZO-[c,e][1,2]-OXAPHOSPHORINES, A METHOD FOR PREPARING THEM, AND THEIR USE FOR THE STABILIZATION OF PLASTICS, IN PARTICULAR POLYOLEFIN MOULDING MATERIALS |
| AU80779/91A AU647152B2 (en) | 1990-07-02 | 1991-06-22 | New 6-aryl-6H-dibenzo-(c,e)(1,2)-oxaphosphorines, a method for preparing them, and their use for the stabilization of plastics, in particular polyolefin moulding materials |
| BR919106637A BR9106637A (en) | 1990-07-02 | 1991-06-22 | NEW 6-ARYL-6H-DIBENZO- (C, E) (1,2) -OXAPHOSPHORINS, A PROCESS FOR ITS PREPARATION AND APPLICATION FOR PLASTIC STABILIZATION, ESPECIALLY OF POLYOLEFIN MOLDING MASSES |
| EP91911955A EP0537223B1 (en) | 1990-07-02 | 1991-06-22 | NEW 6-ARYL-6H-DIBENZO-[c,e][1,2]-OXAPHOSPHORINES, A METHOD FOR PREPARING THEM, AND THEIR USE FOR THE STABILIZATION OF PLASTICS, IN PARTICULAR POLYOLEFIN MOULDING MATERIALS |
| US07/962,187 US5356967A (en) | 1990-07-02 | 1991-06-22 | 6-aryl-6H-dibenzo[c,e][1,2]oxaphosphorine stabilizers for plastics |
| AT91911955T ATE110082T1 (en) | 1990-07-02 | 1991-06-22 | NEW 6-ARYL-6H-DIBENZO-(C,E>(1,2>-OXAPHOSPHORINES, A PROCESS FOR THEIR PRODUCTION AND THEIR USE FOR STABILIZING PLASTICS, ESPECIALLY POLYOLEFIN MOLDING COMPOUNDS. |
| DE59102579T DE59102579D1 (en) | 1990-07-02 | 1991-06-22 | NEW 6-ARYL-6H-DIBENZO- [c, e] [1,2] -OXAPHOSPHORINE, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR STABILIZING PLASTICS, IN PARTICULAR POLYOLEFINE MOLDS. |
| KR1019920703406A KR950007596B1 (en) | 1990-07-02 | 1991-06-22 | New 6-aryl-6h-dibenzo-(c,e)(1,2)-oxaphosphorines, a method for preparing them, and their use for the stabilization of plasilcs, in particular polyolefin moulding materials |
| ES91911955T ES2061254T3 (en) | 1990-07-02 | 1991-06-22 | NEW 6-ARYL-6H-DIBENZO- (C, E) (1,2) -OXAPHOSPHORINES, A PROCEDURE FOR ITS PREPARATION AND ITS USE FOR THE STABILIZATION OF SYNTHETIC MATERIALS ESPECIALLY MOLDS OF POLYOLEFIN BASED MOLDING. |
| CA002086616A CA2086616C (en) | 1990-07-02 | 1991-06-22 | 6-aryl-6h-dibenzo[c,e][1,2] oxaphosphorines, a process for their preparation, and their use for stabilizing plastics, in particular polyolefin molding compositions |
| ZA915055A ZA915055B (en) | 1990-07-02 | 1991-07-01 | Novel 6-aryl-6h-dibenzo(c,e)(1,2)oxaphosphorines,a process for their preparation,and their use for stabilizing plastics,in particular polyolefin molding compositions |
| MX919100054A MX9100054A (en) | 1990-07-02 | 1991-07-02 | NEW 6-ARYL-DIBENZO- (C, E) (1,2) -OXAPHOSPHORINES, A PROCEDURE FOR ITS PREPARATION AND ITS USE FOR THE STABILIZATION OF SYNTHETIC MATERIALS, ESPECIALLY MOLDS OF POLYOLEFIN BASED MOLDING |
| JP7261289A JP2662509B2 (en) | 1990-07-02 | 1995-10-09 | Method for producing 6-aryl-6H-dibenzo- [c, e] [1,2] -oxaphosphorin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4021195A DE4021195A1 (en) | 1990-07-02 | 1990-07-02 | New 6-aryl-6H-di:benzo-(c,e)(1,2)- oxa:phosphorin(s) - prepd. by grignard reaction of aryl halide(s) and its chloro-deriv., useful as stabilisers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE4021195A1 true DE4021195A1 (en) | 1992-01-09 |
Family
ID=6409587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE4021195A Withdrawn DE4021195A1 (en) | 1990-07-02 | 1990-07-02 | New 6-aryl-6H-di:benzo-(c,e)(1,2)- oxa:phosphorin(s) - prepd. by grignard reaction of aryl halide(s) and its chloro-deriv., useful as stabilisers |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE4021195A1 (en) |
| ZA (1) | ZA915055B (en) |
-
1990
- 1990-07-02 DE DE4021195A patent/DE4021195A1/en not_active Withdrawn
-
1991
- 1991-07-01 ZA ZA915055A patent/ZA915055B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ZA915055B (en) | 1992-04-29 |
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