US2961454A - Ester interchange - Google Patents
Ester interchange Download PDFInfo
- Publication number
- US2961454A US2961454A US4888A US488860A US2961454A US 2961454 A US2961454 A US 2961454A US 4888 A US4888 A US 4888A US 488860 A US488860 A US 488860A US 2961454 A US2961454 A US 2961454A
- Authority
- US
- United States
- Prior art keywords
- phosphite
- chlorpropyl
- tris
- alcohol
- moles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 150000002148 esters Chemical class 0.000 title description 6
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical compound [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 8
- 239000007983 Tris buffer Substances 0.000 description 40
- -1 n-hentanol Chemical compound 0.000 description 37
- SSMFJUHKXRYPMF-UHFFFAOYSA-N 2-chloropropyl dihydrogen phosphite Chemical compound CC(Cl)COP(O)O SSMFJUHKXRYPMF-UHFFFAOYSA-N 0.000 description 25
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 25
- 238000000034 method Methods 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 6
- YYTSGNJTASLUOY-UHFFFAOYSA-N 1-chloropropan-2-ol Chemical compound CC(O)CCl YYTSGNJTASLUOY-UHFFFAOYSA-N 0.000 description 5
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 4
- XCRYZUBWTDJYOO-UHFFFAOYSA-N 2-chlorobutyl dihydrogen phosphite Chemical compound CCC(Cl)COP(O)O XCRYZUBWTDJYOO-UHFFFAOYSA-N 0.000 description 3
- PYGUPHOBFHTJJF-UHFFFAOYSA-N 3-chloropropyl dihydrogen phosphite Chemical compound OP(O)OCCCCl PYGUPHOBFHTJJF-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 2
- 239000004440 Isodecyl alcohol Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- PYFRLDVYGBCYLI-UHFFFAOYSA-N decyl dihydrogen phosphite Chemical compound CCCCCCCCCCOP(O)O PYFRLDVYGBCYLI-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 1
- NDJJQUYFBKTHHM-UHFFFAOYSA-N 2-(2-chloropropoxy)-1,3,2-dioxaphospholane Chemical compound CC(Cl)COP1OCCO1 NDJJQUYFBKTHHM-UHFFFAOYSA-N 0.000 description 1
- CEIVRECSKFULMI-UHFFFAOYSA-N 2-(2-chloropropoxy)-4-methyl-1,3,2-dioxaphosphinane Chemical compound CC(Cl)COP1OCCC(C)O1 CEIVRECSKFULMI-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- BXJCEULFBLJODE-UHFFFAOYSA-N 2-chloroethyl dihydrogen phosphite Chemical compound OP(O)OCCCl BXJCEULFBLJODE-UHFFFAOYSA-N 0.000 description 1
- WUFFGJVXZCDALE-UHFFFAOYSA-N 2-ethoxy-1,3,2-dioxaphospholane Chemical compound CCOP1OCCO1 WUFFGJVXZCDALE-UHFFFAOYSA-N 0.000 description 1
- ONLIGRKGCCDLOB-UHFFFAOYSA-N 2-propoxy-1,3,2-dioxaphosphinane Chemical compound CCCOP1OCCCO1 ONLIGRKGCCDLOB-UHFFFAOYSA-N 0.000 description 1
- LAIUFBWHERIJIH-UHFFFAOYSA-N 3-Methylheptane Chemical compound CCCCC(C)CC LAIUFBWHERIJIH-UHFFFAOYSA-N 0.000 description 1
- VSOUCWIQDZWFLO-UHFFFAOYSA-N 4-methyl-1,3,2-dioxaphospholane Chemical compound CC1COPO1 VSOUCWIQDZWFLO-UHFFFAOYSA-N 0.000 description 1
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- KGQCLZJFUIPDGS-UHFFFAOYSA-N dioxaphospholane Chemical compound C1CPOO1 KGQCLZJFUIPDGS-UHFFFAOYSA-N 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- XVEOUOTUJBYHNL-UHFFFAOYSA-N heptane-2,4-diol Chemical compound CCCC(O)CC(C)O XVEOUOTUJBYHNL-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- QXLBKTGZGPVJOO-UHFFFAOYSA-N hexyl dihydrogen phosphite Chemical compound CCCCCCOP(O)O QXLBKTGZGPVJOO-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000009884 interesterification Methods 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- FXPDGSSSQUFIPW-UHFFFAOYSA-N oxaphospholane Chemical compound C1COPC1 FXPDGSSSQUFIPW-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- GTCCGKPBSJZVRZ-UHFFFAOYSA-N pentane-2,4-diol Chemical compound CC(O)CC(C)O GTCCGKPBSJZVRZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 description 1
- 229950006800 prenderol Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- PRAHMDIEZMWIRW-UHFFFAOYSA-N propyl dihydrogen phosphite Chemical compound CCCOP(O)O PRAHMDIEZMWIRW-UHFFFAOYSA-N 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- FICPQAZLPKLOLH-UHFFFAOYSA-N tricyclohexyl phosphite Chemical compound C1CCCCC1OP(OC1CCCCC1)OC1CCCCC1 FICPQAZLPKLOLH-UHFFFAOYSA-N 0.000 description 1
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 1
- QOQNJVLFFRMJTQ-UHFFFAOYSA-N trioctyl phosphite Chemical compound CCCCCCCCOP(OCCCCCCCC)OCCCCCCCC QOQNJVLFFRMJTQ-UHFFFAOYSA-N 0.000 description 1
- ILLOBGFGKYTZRO-UHFFFAOYSA-N tris(2-ethylhexyl) phosphite Chemical compound CCCCC(CC)COP(OCC(CC)CCCC)OCC(CC)CCCC ILLOBGFGKYTZRO-UHFFFAOYSA-N 0.000 description 1
- DECPGQLXYYCNEZ-UHFFFAOYSA-N tris(6-methylheptyl) phosphite Chemical compound CC(C)CCCCCOP(OCCCCCC(C)C)OCCCCCC(C)C DECPGQLXYYCNEZ-UHFFFAOYSA-N 0.000 description 1
- QEDNBHNWMHJNAB-UHFFFAOYSA-N tris(8-methylnonyl) phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OCCCCCCCC(C)C QEDNBHNWMHJNAB-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 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
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
-
- 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
- C07F9/6574—Esters of oxyacids of phosphorus
-
- 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
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
-
- 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
- C08K5/52—Phosphorus bound to oxygen only
-
- 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
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
Definitions
- Another object is to prepare such phosphites having improved physical properties and particularly having improved purity.
- A- further object is to prepare novel phosphites.
- tris 2-chlorpropyl phosphite is employed.
- tris 2-chlorpropyl phosphite less preferably there can be employed tris 2-chlorbutyl phosphite, As the' higher boiling mouohydric alcohol there are employed alcohols having higher boiling points than propylene chlorhydrin.
- alkanols and cycloalkanols such as n-hexanol, n-hentanol, n-octanol, Z-ethyl hexanol, isooctyl alcohol, octanol-2, 2- methyl heptanol-2, u-decyl alcohol, isodecyl alconol, liauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohoL-cyclehexanol, methyl cyclohexanol, alkanediols orgiycols such as ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, piuacol, 1,2- pentanediol, 2-methyl-2,4-pentan
- the transesterification between the tris 2-chlorpropyl phosphite and the alcohol can be carried out at any temperature from room temperature to the boiling point of propylene chlorhydrin, at the pressure employed.
- the reaction can be carried out at temperatures up to 133 C.
- the reaction can be carried out at atmospheric, or subatmospheric pres: sure.
- the pressure is subatmospheric, e.g., 50 mm. or less.
- the propylene chlorhydrin formed is I Patented Nov. 2 2 1960 transesterification has. a boiling point which is 50 C.
- the products can be isolated at a lower temperature than when using triphenyl phosphite as the transesterifying agent. Additionally, when using triphenyl phosphite, an alkaline catalyst is employed.
- the products obtained according to the present invention e.g., the tris higher alkyl phosphites, are water white and are of an excellent purity. In this respect they are superior to the same phosphites prepared using present commercial procedures or tri 2-chlorethyl phosphite as the transesterifying agent; 7
- R in the" formulae stands for the alkyl group. It is thus evident that the propylene oxide starting material tion, the by-product propylene chlorhydrin formed in phite, distearyl 2-.chlorpropyl phosphite, dimethyl 2 distilled oil and the desired phosphite is recovered as 2' the residue from such distillation. t It is also possible to carry out the reaction at atmos-. pheric pressure and then separate the desired phosphite ester-from the propylene chlorhydrin formed by distillation at reduced pressure, e.g.,.25.mm..or.1ess::"
- the transesterification is less toxic than the by-product ethylene chlorhydrin. Furthermore, it has been found that the products made from tris chlorpropyl phosphite interesterification are easier to control and work up and have reduced acid numbers (the acid number indicates the residual acid in the product). For example, tri n-decyl phosphite prepared from tris V2-chlorethyl phosphite and n-decyl alcohol had an acid number of 5-10, whereas when tris 2-chlorpropyl phosphite was used as the transesterifying agent, the acid number was 0.02-0.51
- R R R R R and R are hydrogen or lower alkyl and n is or 1.
- examples of such compounds are bis (4,4,6-trimethyl 1,3,2- dioxaphosphorinanoxy) 1,1,3 propane, bis(1,3',2-dioxaphospholanoxy) ethane?
- R R R R R and R are hydrogen or lower alkyl and n is either 0 or 1.
- Examples of compounds coming within this formula are 2-(2-chloro)propyl l-4,4,6- trimethyl-1,3,2 dioxaphosphorinane; 2 (2 chloro) propoxy 1,3,2 dioxaphospholane; 2 (2 chloro)pro' poxy 4 methyl 1,3,2 dioxaphospholane; 2 (2 chloro)propoxy 4,5 dimethyl 1,3,2 dioxaph'ospholane; 2-(2 chloro)propoxy 4 ethyl 1,3,2 dioxaphospholane; 2-(2 chloro)propoxy' 4,4,5,5'- tetramethyl 1,3,2 dioxaphospholane; 2 (2 chloro).propoxy 4 propyl 1,3,2 dioxaphospholane; 2-(2-chloro) propoxy 1,3,2 dioxaphosphorinane; 2 (2 chloro) propoxy 4 methyl 1,3,2 dioxaphosphorinane; 2-(
- the compounds containing a 2-chlorpropoxy group and a 5 or 6 member heterocyclic ring are new compounds as are the compounds having two heterocyclic rings joined through an oxyalkyleneoxy bridge. They are useful as stabilizers and plasticizers for vinyl chloride resins and other plastics. They are also useful as insecticides. The other tertiary phosphites disclosed likewise are useful as plasticizers and stabilizers for vinyl chloride resins.
- Example 2 Example 1 was repeated utilizing 534 grams of ndecyl alcohol in place of the isodecyl alcohol. There was obtained tri n-decyl phosphite in excellent yields.
- Example 3 Moles Tris 2-ch1orpropyl phosphit'e 1 n-oetanol 3 The process of Example 1 was repeated and there was recovered tri n-octyl phosphite of excellent purity.
- Example 2 The process of Example 1 was repeated and the tri 2- ethylhexyl phosphite recovered as a water white liquid had the following properties: N 1.4489; d 0.915.
- Example 1 The process of Example 1 was repeated and triisooctyl phosphite wasrecovered.
- Example 1 The process of Example 1 was repeated and tri n-hexyl phosphite was recovered.
- Example 1 The process of Example 1 was repeated and tricyclohexyl phosphite was recovered.
- Example 1 The process of Example 1 was repeated and trilauryl phos'phite was recovered.
- Example 1 The process of Example 1 was repeated and tristearyl phosphite was recovered.
- Example '10 Moles Tris 2-chloropropyl phosphite 2 Ethylene glycol 3
- the process of Example 1 was repeated and his (1,3,2 dioxaphospholanoxy) ethane having the formula CHz-O OCH2 was recovered.
- Example 11 Moles Tris Z-chlorpropyl phosphite 1 Decyl alcoh l 2 The proce5s of Example 1 was repeated and there was recovered di decyl 2-chlorpropyl phosphite.
- Example 12 Moles Tris 2-chlorpropyl phosphite 2 Pinacol 3 The process of Example was repeated and there was recovered bis '(4,4,5,S-tetramethyl, 1,3,2-di'oxaphospholanoxy)-1,1,2,2-tetramethylethane.
- Example 13 Moles Tris 2-chlorpropyl phosphite 2 2-methyl-2,4-pentanediol 3
- the process of Example 10 was repeated and there was recovered bis (4,4,6-trimethyl-1,3,2-dioxaphosphorinanoxy) 1,1,3-trimethylpropane.
- Example 14 Moles Tris Z-chlorpropyl phosphite 1 Decyl alcohol 1 The process of Example 1 was repeated and there was recovered decyl di-Z-chlorpropyl phosphite.
- Example 15 Moles Tris chlorpropyl phosphite l Stearyl alcohol 1 The process of Example 1 was repeated and there was recovered stearyl di-Z-chlorpropyl phosphite.
- Example 16 Moles Tris 2-chlorpropyl phosphite 1 Stearyl alcohol 2 The process of Example 1 was repeated and there was recovered di stearyl 2-chlorpropyl phosphite.
- Example 1 The process of Example 1 was repeated and there was recovered tri 2-ethy1hexy1 phosphite as the still residue.
- Example 1 The process of Example 1 was repeated and there was recovered tri decyl phosphite as the still residue.
- Example 19 Moles Tris 2-chlorpropyl phosphite 2 Pentaerythritol 1 The process of Example 1 was repeated and there was recovered bis (Z-chlorpropoxy) spiro 1,3',2phosphorinaiie having the formula: i i i cmo r tomor o' POCH281HCH:
- OCH orno t as ajvery viscous, slightly yellow liquid 5 ,1. 5012 f, d 1.355.
- ExampleZO Moles Compound of Example 19 1 Decyl alcohol 2 OCH: CH2.O/ V z where R is an alkyl group are obtained. These materials can be used as plasticizers for vinyl chloride resins.
- Example 21 Moles Tris 2-chlorpropyl phosphite 1 1,2-propanediol 1 The process of Example 1 was repeated and there was discovered 2-(2-chloro) propyl-4-methyl-1,3,2-dioxaphospholane.
- Example 22 Moles Tris 2-chlorpropyl phosphite 1 1,3-propanediol l The process of Example 1 was repeated and there was recovered 2-(2-chloro) propyl-1,3,2-dioxaphosphorinane.
- Example 23 Moles Tris Z-chlorpropyl phosphite 1 2,3 butanedinl 1 The process of Example 1 was repeated and there was recovered 2-(2-chloro) propyl-4,5-dimethyl-1,3,2-dioxaphospholane.
- Example 24 Moles Tris 2-chlorpropyl phosphite l Ethylene glycol 1 The process of Example 1 was repeated and there was recovered 2-(2-chloro) propyl-l,3,2 dioxaphospholane.
- Example 25 Moles Tris 2'chlorpropyl phosphite 1 Neopentyl glycol- 1 The process of Example 1 was repeated and there was recovered 2-(2-chloro) propyl-5,5-dimethyl-1,3,2-di'oxaphospholane.
- Example 1 The process of Example 1 was repeated and there was recovered 2-(2-chloro) propyl-4-methyl-1,3,2-dioxaphosphorinane.
- R R R R R R and R are selected from the group consisting of hydrogen and lower alkyl groups
- n is an integer of the group consisting of 0 and l.
- Cyclic phosphites having the formula wherein R and R are selected from the group consisting of alkyl having 6 to 18 carbon atoms in the alkyl group and 2 chlorpropyl.
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Description
ESTER INTERCHANGE I No Drawing. Filed Jan. 27, 1960, Ser. No. 4,888
' 6 Claims. (Cl. 260-461) -"This invention relates to the preparation of esters of phosphorous acid.
It is an object of the present invention to develop an improved process for preparing tertiary phosphites of high boiling alcohols. V
Another object is to prepare such phosphites having improved physical properties and particularly having improved purity.
. A- further object is to prepare novel phosphites.
I Still further objects and the entire scope of applicamay of the present invention will become apparent fro'rnthe detailed description given hereinafter; it should be Understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention,.are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description,
It has now been found that these objects can be attained by transesterification of tris 2-chlorpropyl phosphite with a higher boiling monohydric orpoiyhydric alcohol.
Preferably, tris 2-chlorpropyl phosphite is employed.
In place of tris 2-chlorpropyl phosphite, less preferably there can be employed tris 2-chlorbutyl phosphite, As the' higher boiling mouohydric alcohol there are employed alcohols having higher boiling points than propylene chlorhydrin. Among such alcohols are alkanols and cycloalkanols, such as n-hexanol, n-hentanol, n-octanol, Z-ethyl hexanol, isooctyl alcohol, octanol-2, 2- methyl heptanol-2, u-decyl alcohol, isodecyl alconol, liauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohoL-cyclehexanol, methyl cyclohexanol, alkanediols orgiycols such as ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, piuacol, 1,2- pentanediol, 2-methyl-2,4-pentanediol, 1,3-butyleue glycol, neopentyl glycol}2-ethyl-1,3-hexanediol, 2,4-pentanediol, 2,4-heptanediol, 2,2-diethyl-1,3-propanediol, 2- ethyl-Zn-butyl-1,3-propanediol, and also pentaer'ythritol. -"-The present invention is particularly valuable in preparing the tris alkyl phosphites from alkanols having 6 to 12 carbons.
The transesterification between the tris 2-chlorpropyl phosphite and the alcohol can be carried out at any temperature from room temperature to the boiling point of propylene chlorhydrin, at the pressure employed. Thus,.at atmospheric pressure the reaction can be carried out at temperatures up to 133 C. The reaction can be carried out at atmospheric, or subatmospheric pres: sure. Preferably, the pressure is subatmospheric, e.g., 50 mm. or less. The propylene chlorhydrin formed is I Patented Nov. 2 2 1960 transesterification has. a boiling point which is 50 C.
Lower than the boiling point of phenol. Hence, the products can be isolated at a lower temperature than when using triphenyl phosphite as the transesterifying agent. Additionally, when using triphenyl phosphite, an alkaline catalyst is employed.
The products obtained according to the present invention, e.g., the tris higher alkyl phosphites, are water white and are of an excellent purity. In this respect they are superior to the same phosphites prepared using present commercial procedures or tri 2-chlorethyl phosphite as the transesterifying agent; 7
, On a commercial basis the overall reaction is as follows:
' can be continuously regenerated.
R in the" formulae stands for the alkyl group. It is thus evident that the propylene oxide starting material tion, the by-product propylene chlorhydrin formed in phite, distearyl 2-.chlorpropyl phosphite, dimethyl 2 distilled oil and the desired phosphite is recovered as 2' the residue from such distillation. t It is also possible to carry out the reaction at atmos-. pheric pressure and then separate the desired phosphite ester-from the propylene chlorhydrin formed by distillation at reduced pressure, e.g.,.25.mm..or.1ess::"
tris .2-chlorpropylphosphite -(e.g., 3 moles? oiflel ylene V, g
the transesterification is less toxic than the by-product ethylene chlorhydrin. Furthermore, it has been found that the products made from tris chlorpropyl phosphite interesterification are easier to control and work up and have reduced acid numbers (the acid number indicates the residual acid in the product). For example, tri n-decyl phosphite prepared from tris V2-chlorethyl phosphite and n-decyl alcohol had an acid number of 5-10, whereas when tris 2-chlorpropyl phosphite was used as the transesterifying agent, the acid number was 0.02-0.51
In order to insure complete ester interchange using a monohydric alcohol there should be employed at least 3 moles of the alcohol per mole of the tris 2-chlorpropyl phosphite. Generally, from 1-15 molar excess of the alcohol is employed to insure formation of the trialkyl ester. No advantage has been found in using over 15% excess alcohol and, in general, 10-15% excess of the alcohol gives the best commercial quality product. The use of larger amounts of the alcohol means that more alcohol must be recovered in the subsequent distillation. If less than three moles of the monohydric alcoholare employed then mixed phosphites are obtained. Thus when 2 moles of the monohydric alcohol are employed per mole of tris 2-chlorpropyl phosphite there are ob-. tained compounds such as, diceryl Z-chlorpropyl' phoschlorpropyl phosphite Where one mol of monohydric phitethere are obtained compounds such as hexyl. di-2- chlorpropyl phosphite, stearyl di-Z-chlorpropyl phosphite, methyl. di-2-chlorpropyl phosphite, and decyl di-2 -chl 'or-, propyl phosphite.- p e When using 11,}? or my glycols, 'ifjone equivalentior; more) -ofpblyhydric alcohol is usedyper equivalenta'of glycol with 2 moles of 2 chlorpropyl phosphite) there are formed products of the following type:
where R R R R R and R are hydrogen or lower alkyl and n is or 1. Examples of such compounds are bis (4,4,6-trimethyl 1,3,2- dioxaphosphorinanoxy) 1,1,3 propane, bis(1,3',2-dioxaphospholanoxy) ethane? bis(4- methyl 1,3,2 dioxaphospholanoxy) 1 -;merh 1etnane; bis(4,5 dimethyl 1,3,2 dioxaph'ospholanoxy) 1 ethylethane; bis(4,4,5,5 tetramethyl 1,3,2 dioxaphospholanoxy) 1,l,2,2 tetramethylethane; bis(4 propyll,3,2 dioxaphospholanoxy) 1 proxyleth'ane; bis(l,3 ,2- dioxaphosphorinanoxy) propane; bis(4 methyl 1,3,2 dioxaphosphorinanoxy) 1 methylpropane; bis(5,5-dimethyl 1,3,2 dioxaphosphorinanoxy)-2,2:dimethylpropane; bis(4 propyl ethyl 1,3,2 diox'aphosphorinauoxy) l propyl 2 ethylpropane; bis(4 propyl 6 methyl 1,3,2 dioxaphosphorinanoxy) 1 propyl 3 methylpropane; bis(5,5-diethyl 1,3,2 dioxaphosphorinanoxy)-2,2-diethyl propane; bis(5 ethyl 5 butyl- 1,3,2 dioxaphosphorinanoxy) 2 ethyl 2 butylpropane; and bis(4-propyl 1,3,2 dioxaphosphorinanoxy)- l-propylpropane.
If less than one equivalent of diol is employed then monomeric products are formed which still have a chlorpropyl group. Thus, when reacting one mol of tris 2- chlorpropyl phosphite with one mol (or less) of a diol having 2 to 3 carbon atoms separating the hydroxyl groups, there are formed products of the formula:
where R R R R R and R are hydrogen or lower alkyl and n is either 0 or 1. Examples of compounds coming within this formula are 2-(2-chloro)propyl l-4,4,6- trimethyl-1,3,2 dioxaphosphorinane; 2 (2 chloro) propoxy 1,3,2 dioxaphospholane; 2 (2 chloro)pro' poxy 4 methyl 1,3,2 dioxaphospholane; 2 (2 chloro)propoxy 4,5 dimethyl 1,3,2 dioxaph'ospholane; 2-(2 chloro)propoxy 4 ethyl 1,3,2 dioxaphospholane; 2-(2 chloro)propoxy' 4,4,5,5'- tetramethyl 1,3,2 dioxaphospholane; 2 (2 chloro).propoxy 4 propyl 1,3,2 dioxaphospholane; 2-(2-chloro) propoxy 1,3,2 dioxaphosphorinane; 2 (2 chloro) propoxy 4 methyl 1,3,2 dioxaphosphorinane; 2-(2- chloro)-propoxy 5,5 dimethyl 1,3,2 dioxaphosphorinane; 2 (2 chloro)propoxy 4-propyl 5 ethyl- 1,3,2-dioxaphosphorinane; 2 (2 chloro)propoxy 4 propyl-6-methyl 1,3,2 dioxaphosphorinane; 2 (2 chlor)propoxy 5,5 diethyl 1,3,2 dioxaphosphorinane; 2 (2-chloro)propoxy 5 -etl1yl 5-butyl-l,3,2- dioxaphosphorinane; 2-(2-chloro)propoxy 5 ethyl 5- butyl 1,3,2 dioxaphosphorinane; 2-(2-chloro)propoxy- 4-propyl-1,3,2-dioxaphosphorinane.
The compounds containing a 2-chlorpropoxy group and a 5 or 6 member heterocyclic ring are new compounds as are the compounds having two heterocyclic rings joined through an oxyalkyleneoxy bridge. They are useful as stabilizers and plasticizers for vinyl chloride resins and other plastics. They are also useful as insecticides. The other tertiary phosphites disclosed likewise are useful as plasticizers and stabilizers for vinyl chloride resins.
When 2 mols oftn's 2-chlorpropyl phosphite are re-' acted with 1 mol of entaeryuiritol there is formed a 311 grams (1 mol) of tris 2-chlorpropyl phosphite were mixed with 534 grams (3 moles +12.7% excess) of isodecyl alcohol. The mixture was then distilled in a vacuum at 10-15 mm. until the pot temperature was C. The triisodecyl phosphite recovered from the pot was water white, had an acid number well below 0.5 an N of 1.4540 and a d of 0.898.
Example 2 Example 1 was repeated utilizing 534 grams of ndecyl alcohol in place of the isodecyl alcohol. There was obtained tri n-decyl phosphite in excellent yields.
Example 3 Moles Tris 2-ch1orpropyl phosphit'e 1 n-oetanol 3 The process of Example 1 was repeated and there was recovered tri n-octyl phosphite of excellent purity.
Example4 Moles Tris 2-chlorpropyl phosphite 1 2-ethylhexanol 3.4
The process of Example 1 was repeated and the tri 2- ethylhexyl phosphite recovered as a water white liquid had the following properties: N 1.4489; d 0.915.
Example 5 Moles Tris 2-chlorpropyl phosphite 1 Isooctyl alcoho 3.3
The process of Example 1 was repeated and triisooctyl phosphite wasrecovered.
Example 6 Moles Tris 2-chlorpropyl phosphite a ....-a..-..-- 1 n-Hexyl alcohol v 3.3
The process of Example 1 was repeated and tri n-hexyl phosphite was recovered.
Example 7 Moles Tris 2'-chlorpropyl phosphitenn l Cyclohexanol 3.2
The process of Example 1 was repeated and tricyclohexyl phosphite was recovered.
Example 8 Moles Tris 2-chlorpropylphosphite -2- 1 Lauryl alcohol 3.3
The process of Example 1 was repeated and trilauryl phos'phite was recovered.
Example 9 Mold! Tris 2-chloropropyl phosphite I Stearyl alcohol- 3.3
The process of Example 1 was repeated and tristearyl phosphite was recovered.
Example '10 Moles Tris 2-chloropropyl phosphite 2 Ethylene glycol 3 The process of Example 1 was repeated and his (1,3,2 dioxaphospholanoxy) ethane having the formula CHz-O OCH2 was recovered.
Example 11 Moles Tris Z-chlorpropyl phosphite 1 Decyl alcoh l 2 The proce5s of Example 1 was repeated and there was recovered di decyl 2-chlorpropyl phosphite.
Example 12 Moles Tris 2-chlorpropyl phosphite 2 Pinacol 3 The process of Example was repeated and there was recovered bis '(4,4,5,S-tetramethyl, 1,3,2-di'oxaphospholanoxy)-1,1,2,2-tetramethylethane.
Example 13 Moles Tris 2-chlorpropyl phosphite 2 2-methyl-2,4-pentanediol 3 The process of Example 10 was repeated and there was recovered bis (4,4,6-trimethyl-1,3,2-dioxaphosphorinanoxy) 1,1,3-trimethylpropane.
Example 14 Moles Tris Z-chlorpropyl phosphite 1 Decyl alcohol 1 The process of Example 1 was repeated and there was recovered decyl di-Z-chlorpropyl phosphite.
Example 15 Moles Tris chlorpropyl phosphite l Stearyl alcohol 1 The process of Example 1 was repeated and there was recovered stearyl di-Z-chlorpropyl phosphite.
Example 16 Moles Tris 2-chlorpropyl phosphite 1 Stearyl alcohol 2 The process of Example 1 was repeated and there was recovered di stearyl 2-chlorpropyl phosphite.
Example 17 Moles Tris 2-chlorbutyl phosphite l Z-ethylhexanol 3.3
The process of Example 1 was repeated and there was recovered tri 2-ethy1hexy1 phosphite as the still residue.
Example 18 Moles Tris 2-chlorbutyl phosphite 1 n-Decyl alcohol 3.2
The process of Example 1 was repeated and there was recovered tri decyl phosphite as the still residue.
Example 19 Moles Tris 2-chlorpropyl phosphite 2 Pentaerythritol 1 The process of Example 1 was repeated and there was recovered bis (Z-chlorpropoxy) spiro 1,3',2phosphorinaiie having the formula: i i i cmo r tomor o' POCH281HCH:
OCH: orno t as ajvery viscous, slightly yellow liquid 5 ,1. 5012 f, d 1.355.
ExampleZO Moles Compound of Example 19 1 Decyl alcohol 2 OCH: CH2.O/ V z where R is an alkyl group are obtained. These materials can be used as plasticizers for vinyl chloride resins.
Example 21 Moles Tris 2-chlorpropyl phosphite 1 1,2-propanediol 1 The process of Example 1 was repeated and there was discovered 2-(2-chloro) propyl-4-methyl-1,3,2-dioxaphospholane.
Example 22 Moles Tris 2-chlorpropyl phosphite 1 1,3-propanediol l The process of Example 1 was repeated and there was recovered 2-(2-chloro) propyl-1,3,2-dioxaphosphorinane.
Example 23 Moles Tris Z-chlorpropyl phosphite 1 2,3 butanedinl 1 The process of Example 1 was repeated and there was recovered 2-(2-chloro) propyl-4,5-dimethyl-1,3,2-dioxaphospholane.
Example 24 Moles Tris 2-chlorpropyl phosphite l Ethylene glycol 1 The process of Example 1 was repeated and there was recovered 2-(2-chloro) propyl-l,3,2 dioxaphospholane.
Example 25 Moles Tris 2'chlorpropyl phosphite 1 Neopentyl glycol- 1 The process of Example 1 was repeated and there was recovered 2-(2-chloro) propyl-5,5-dimethyl-1,3,2-di'oxaphospholane.
Example 26 Moles Tris 2-chlorpropyl phosphite 1 Butanediol-l ,3 1
The process of Example 1 was repeated and there was recovered 2-(2-chloro) propyl-4-methyl-1,3,2-dioxaphosphorinane.
Example 27 Moles Tris 2-chlorpropyl phosphite 1 2,2-dimethyl propanediol-1,3 1
Moles Tris 2-chlorpropy1 phosphite 1 2-ethyl-2-n-butyl-1,3-propanediol 1 The process of Example 1 was repeated and there was recovered 2-(2-ch1oro) propyl fi-ethyl-s-hutyl-1,3,2-dioxaphosphorinane.
What is claimed is:
1. Cyclic phosphites having the formula (RP R)h P-OCHzCHClCH:
where R R R R R and R are selected from the group consisting of hydrogen and lower alkyl groups,
8 and n is an integer of the group consisting of 0 and l.
2. Cyclic phosphites having the formula wherein R and R are selected from the group consisting of alkyl having 6 to 18 carbon atoms in the alkyl group and 2 chlorpropyl.
3. A compound according to claim 2 wherein both R and R are decyl.
4. A compound according to claim 2 wherein both R; and R are stearyl.
5. A compound according to claim 2 wherein R and R are both lauryl.
6. Bis (4,4,6-trimethy1-1,3,2-dioxaphosphorinanoxy) 1, 1,3-trimethyl propane.
References Cited in the file of this patent UNITED STATES PATENTS 2,834,798 Hechenbleikner et a1. May 13, 1958 2,841,608 Hechenbleikner et a1. July 1, 1958 2,883,411 Lanham Apr. 21, 1959 Netiee of Adverse Deeisien in Iiiterfereiiee In Interference No. 93,252 involving Patent No. 2,961,454, H. Gould and J. P. fiakus, Ester interchange, final deeislon adverse to the pa tentees was rendered Aug. 21, 1963, as to claim 3.
[Ofiioial Gazette Nowembm' 12, 1963.]
Claims (1)
- 2. CYCLIC PHOSPHITES HAVING THE FORMULA
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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US4888A US2961454A (en) | 1960-01-27 | 1960-01-27 | Ester interchange |
GB30398/62A GB943731A (en) | 1960-01-27 | 1961-01-16 | Novel tertiary spiro phosphites and their production |
GB1781/61A GB944726A (en) | 1960-01-27 | 1961-01-16 | The production of tertiary phosphites including new cyclic phosphites |
FR850582A FR1277898A (en) | 1960-01-27 | 1961-01-24 | Process for the preparation of phosphorous acid esters and phosphites obtained by this process |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US4888A US2961454A (en) | 1960-01-27 | 1960-01-27 | Ester interchange |
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US2961454A true US2961454A (en) | 1960-11-22 |
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US4888A Expired - Lifetime US2961454A (en) | 1960-01-27 | 1960-01-27 | Ester interchange |
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US (1) | US2961454A (en) |
GB (2) | GB944726A (en) |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3047608A (en) * | 1960-09-15 | 1962-07-31 | Weston Chemical Corp | Phosphites |
US3053878A (en) * | 1961-05-23 | 1962-09-11 | Weston Chemical Corp | Pentaerythritol phosphite esters |
US3081331A (en) * | 1961-08-07 | 1963-03-12 | Weston Chemical Corp | Poly phosphorus ester condensates and their preparation |
US3153036A (en) * | 1961-09-04 | 1964-10-13 | Bayer Ag | Phosphorous acid esters derived from transesterification of phosphite triesters with mono-, di-, and trisaccharides |
US3179689A (en) * | 1962-08-28 | 1965-04-20 | Union Carbide Corp | Chloro compounds prepared by reacting a trimethyloalkane and phosphorus trichloride |
US3189545A (en) * | 1965-06-15 | Lubricating composition | ||
US3192243A (en) * | 1962-04-10 | 1965-06-29 | Delaware Chemicals Inc | Phosphorous derivatives of pentaerythritol |
US3201437A (en) * | 1962-06-11 | 1965-08-17 | Union Carbide Corp | Neoalkyl phosphites |
US3205269A (en) * | 1960-05-10 | 1965-09-07 | Union Carbide Corp | Stabilization of ethers with phosphorous compounds |
US3205250A (en) * | 1961-11-20 | 1965-09-07 | Hooker Chemical Corp | 3, 9-alkoxy and 3, 9-chloropropyl-2, 4, 8, 10-tetraoxa-3, 9-phosphospiro (6, 6) hendeanes |
US3254142A (en) * | 1961-09-01 | 1966-05-31 | Bayer Ag | Phosphorous acid esters |
US4064100A (en) * | 1975-07-22 | 1977-12-20 | Weston Chemical Co., Inc. | Friable distearyl pentaerythritol diphosphite |
FR2359151A1 (en) * | 1976-07-24 | 1978-02-17 | Hoechst Ag | CYCLIC PHOSPHITES OF POLYALCOOLS, PREPARATION AND USE AS STABILIZERS OF PLASTICS |
US4290976A (en) * | 1975-03-24 | 1981-09-22 | Borg-Warner Chemicals, Inc. | Process for the preparation of phenol-free phosphites |
US4665211A (en) * | 1985-12-03 | 1987-05-12 | Borg-Warner Chemicals, Inc. | Process for preparing bis(dialkylphenyl) pentaerythritol diphosphites |
EP0685516A1 (en) | 1994-06-01 | 1995-12-06 | General Electric Company | Solid stabilizer composition with improved hydrolytic stability |
US20060116526A1 (en) * | 2003-01-06 | 2006-06-01 | Seiichi Tanabe | Process for producing pentaerythritol diphosphonates |
JP2008024667A (en) * | 2006-07-24 | 2008-02-07 | Teijin Ltd | Method for producing aliphatic phosphite ester |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS53127552A (en) * | 1977-03-14 | 1978-11-07 | Daicel Chem Ind Ltd | Cellulose organic acid ester resin composition |
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US2834798A (en) * | 1957-12-20 | 1958-05-13 | Shea Chemical Corp | Heterocyclic phosphorus compounds |
US2841608A (en) * | 1956-05-21 | 1958-07-01 | Shea Chemical Corp | Cyclic glycol phosphites |
US2883411A (en) * | 1953-06-18 | 1959-04-21 | Union Carbide Corp | Production of heterocyclic phosphoruscontaining compounds |
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- 1960-01-27 US US4888A patent/US2961454A/en not_active Expired - Lifetime
-
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- 1961-01-16 GB GB1781/61A patent/GB944726A/en not_active Expired
- 1961-01-16 GB GB30398/62A patent/GB943731A/en not_active Expired
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US2883411A (en) * | 1953-06-18 | 1959-04-21 | Union Carbide Corp | Production of heterocyclic phosphoruscontaining compounds |
US2841608A (en) * | 1956-05-21 | 1958-07-01 | Shea Chemical Corp | Cyclic glycol phosphites |
US2834798A (en) * | 1957-12-20 | 1958-05-13 | Shea Chemical Corp | Heterocyclic phosphorus compounds |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3189545A (en) * | 1965-06-15 | Lubricating composition | ||
US3205269A (en) * | 1960-05-10 | 1965-09-07 | Union Carbide Corp | Stabilization of ethers with phosphorous compounds |
US3047608A (en) * | 1960-09-15 | 1962-07-31 | Weston Chemical Corp | Phosphites |
US3053878A (en) * | 1961-05-23 | 1962-09-11 | Weston Chemical Corp | Pentaerythritol phosphite esters |
US3081331A (en) * | 1961-08-07 | 1963-03-12 | Weston Chemical Corp | Poly phosphorus ester condensates and their preparation |
US3254142A (en) * | 1961-09-01 | 1966-05-31 | Bayer Ag | Phosphorous acid esters |
US3153036A (en) * | 1961-09-04 | 1964-10-13 | Bayer Ag | Phosphorous acid esters derived from transesterification of phosphite triesters with mono-, di-, and trisaccharides |
US3205250A (en) * | 1961-11-20 | 1965-09-07 | Hooker Chemical Corp | 3, 9-alkoxy and 3, 9-chloropropyl-2, 4, 8, 10-tetraoxa-3, 9-phosphospiro (6, 6) hendeanes |
US3192243A (en) * | 1962-04-10 | 1965-06-29 | Delaware Chemicals Inc | Phosphorous derivatives of pentaerythritol |
US3201437A (en) * | 1962-06-11 | 1965-08-17 | Union Carbide Corp | Neoalkyl phosphites |
US3179689A (en) * | 1962-08-28 | 1965-04-20 | Union Carbide Corp | Chloro compounds prepared by reacting a trimethyloalkane and phosphorus trichloride |
US4290976A (en) * | 1975-03-24 | 1981-09-22 | Borg-Warner Chemicals, Inc. | Process for the preparation of phenol-free phosphites |
US4064100A (en) * | 1975-07-22 | 1977-12-20 | Weston Chemical Co., Inc. | Friable distearyl pentaerythritol diphosphite |
FR2359151A1 (en) * | 1976-07-24 | 1978-02-17 | Hoechst Ag | CYCLIC PHOSPHITES OF POLYALCOOLS, PREPARATION AND USE AS STABILIZERS OF PLASTICS |
US4665211A (en) * | 1985-12-03 | 1987-05-12 | Borg-Warner Chemicals, Inc. | Process for preparing bis(dialkylphenyl) pentaerythritol diphosphites |
EP0685516A1 (en) | 1994-06-01 | 1995-12-06 | General Electric Company | Solid stabilizer composition with improved hydrolytic stability |
US20060116526A1 (en) * | 2003-01-06 | 2006-06-01 | Seiichi Tanabe | Process for producing pentaerythritol diphosphonates |
JP2008024667A (en) * | 2006-07-24 | 2008-02-07 | Teijin Ltd | Method for producing aliphatic phosphite ester |
Also Published As
Publication number | Publication date |
---|---|
GB944726A (en) | 1963-12-18 |
GB943731A (en) | 1963-12-04 |
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