WO2010136575A1 - Method for the manufacture of dialkyl phosphites - Google Patents
Method for the manufacture of dialkyl phosphites Download PDFInfo
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- WO2010136575A1 WO2010136575A1 PCT/EP2010/057437 EP2010057437W WO2010136575A1 WO 2010136575 A1 WO2010136575 A1 WO 2010136575A1 EP 2010057437 W EP2010057437 W EP 2010057437W WO 2010136575 A1 WO2010136575 A1 WO 2010136575A1
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- WIPO (PCT)
- Prior art keywords
- accordance
- ketal
- reaction
- reaction medium
- mole
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 title claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910004856 P—O—P Inorganic materials 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 239000011800 void material Substances 0.000 claims abstract description 3
- 125000002587 enol group Chemical group 0.000 claims abstract 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 35
- 239000012429 reaction media Substances 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 2
- 150000004056 anthraquinones Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004437 phosphorous atom Chemical group 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims 2
- FOPUBNXRHRMBDX-UHFFFAOYSA-N C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C FOPUBNXRHRMBDX-UHFFFAOYSA-N 0.000 claims 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims 1
- 239000000376 reactant Substances 0.000 abstract description 10
- 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 22
- 238000004821 distillation Methods 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- 238000004679 31P NMR spectroscopy Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- NYRVXYOKUZSUDA-UHFFFAOYSA-N [dimethoxy(phenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(OC)(OC)C1=CC=CC=C1 NYRVXYOKUZSUDA-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- -1 aliphatic alcohols Chemical class 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 2
- 150000002085 enols Chemical group 0.000 description 2
- 229960003750 ethyl chloride Drugs 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 2
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical group COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 101100387923 Caenorhabditis elegans dos-1 gene Proteins 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
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- SULWMEGSVQCTSK-UHFFFAOYSA-N diethyl hydrogen phosphite Chemical class CCOP(O)OCC SULWMEGSVQCTSK-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- NFORZJQPTUSMRL-UHFFFAOYSA-N dipropan-2-yl hydrogen phosphite Chemical compound CC(C)OP(O)OC(C)C NFORZJQPTUSMRL-UHFFFAOYSA-N 0.000 description 1
- 238000007700 distillative separation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002905 orthoesters Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012619 stoichiometric conversion Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/1411—Esters of phosphorous acids with hydroxyalkyl compounds with further substituents on alkyl
Definitions
- This invention concerns a beneficial method for the manufacture of dialkyl-phosphites starting from P-O component containing from 1 to 6 P-O-P bonds in the molecule comprising the steps of reacting a mixture of an alcohol and the P-O, in specifically defined molar ratios, with a specific ketal reactant whereby the level of the ketal required for the conversion is related to the number of P-O-P bonds in the P-O compound.
- the P-O is added, simultaneously with or separately from the ketal, to a reaction medium comprising the alcohol and reacted followed by recovering the dialkyl phosphite formed in a manner known per se.
- the ketal reactant can be present during the reaction in either, with respect to the reaction medium, homogeneous form or heterogeneous form.
- the P-O is represented by liquid P 4 O 6 and compounds having from 2 to 6 P-O-P bonds.
- Dialkyl phosphites have been known for a long time and their importance as intermediates, among others, for synthesizing desirable compounds had been established accordingly.
- the art had, up to now, not offered a solution to this problem although a large variety of approaches had been investigated.
- CN 101250199 pertains to a method for preparing diisopropyl phosphite from PCI3 and isopropanol.
- DE 4121696 describes a process for the preparation of dialkyl phosphites. The treatment of a mixture of methyl- and dimethyl phosphite with acetic anhydride and methanol in benzene resulted in a product containing a high level of dimethyl phosphite.
- Several publications, HU 207334, HU 199149 and HU 196817 disclose a process for the manufacture of dialkyl phosphites starting from PCI 3 .
- DD 108755 describes the reaction of P 4 O 6 vapour and methanol vapour to thus yield a mixture of liquid monoester and gaseous diester.
- US 4,342,709 describes a process of producing diethyl phosphites by reacting an excess of triethyl phosphite with phosphorous acid.
- the triethyl reactant is usually added in excess of 7-10 % beyond stoichiometric needs.
- the process starts from a strictly anhydrous phosphorous acid.
- the phosphorous acid is added under inert gas purging.
- DD 128755 describes a continuous process for preparing dialkyl phosphites starting from phosphorus trichloride and monovalent aliphatic alcohols in the presence of an inert solvent.
- DOS 1 668 031 pertains to the manufacture, in high yields and purity, of dialkyl phosphites starting from primary or secondary linear or branched alcohols, having at least 5 carbon atoms, with phosphorous acid in an excess of at least 45 %.
- DD 116457 pertains to a continuous process for the manufacture of mono- and di-alkyl phosphites by reacting: a mixture of alcohol and alkyl phosphite or a mixture of mono- and di-alkyl phosphites to which mixture is added technical grade P(lll)-oxide containing elementary phosphorus, while purging with technical nitrogen followed by a distillative separation of the mono- and di-alkyl phosphites formed.
- DD 108755 divulges a process for the continuous preparation of mixtures of mono- and di-alkyl phosphites by reacting P 4 O6 with alcohols in the gaseous phase with high yields.
- DD 222596 concerns a method for preparing pure alkyl- or aryl-diesters of phosphorous acid starting from a mixture of mono- and di-ester phosphites. This mixture is dissolved in an inert organic solvent and the mono-species is precipitated by leading ammonia gas through the mixture.
- US 5,344,951 describes a process for preparing di-esters of phosphorous acid whereby a phosphorous acid solution is reacted with an excess of monohydric alcohol to thus yield dihydrocarbyl phosphite.
- WO 2004/024742 concerns a method for the joint manufacture of diethyl phosphite and ethylchloride whereby one reacts ethanol and phosphorous trichloride in the presence of an additive from the group of tri-ethyl phosphite, diethyl phosphite and/or ethylchloride.
- the like dialkyl phosphite preparations yield by-products including alkyl chlorides, olefins and ethers due to the presence of alcohol and HCI in the process.
- the term “percent” or “%” as used throughout this application stands, unless defined differently, for “percent by weight” or “% by weight”.
- the term “ppm” stands for “parts per million”.
- the terms “P 2 O3” and “P 4 O 6 " can be used interchangeably.
- the term homogeneous ketal means ketals adapted to form a single liquid phase in the reaction medium under the reaction conditions.
- the term heterogeneous ketal means that the ketal is substantially insoluble in the reaction medium at the reaction conditions; this insolubility can be ascertained routinely based on visible observations.
- liquid P 4 O 6 embraces neat P 4 O 6 in the liquid state, solid P 4 O 6 and gaseous P 4 O 6 , preferably liquid P 4 O 6 .
- ambient with respect to temperature and pressure generally means usually prevailing terrestrial conditions at sea level e.g. temperature is about 18°C to 25°C and pressure stands for 990-1050 mm Hg.
- PBTC phosphonobutane tricar
- the invention herein contemplates a method for the manufacture of dialkyl phosphites starting from P-O component containing from 1 to 6 P-O-P bonds in the molecule comprising the step of:
- R" is selected from alkyl groups having from 1 to 20 carbon atoms in linear or branched configuration
- the preferred ketal is one which does not contain a carbon-hydrogen bond on the ⁇ - carbon atom in the ketal structure. More generally, the ketals of this invention have a chemical structure which does not allow the formation of enol structures in accordance with Bredt's Rule associated with bridged systems. Bredt's Rule states that in small bridged systems one can not, for steric reasons, have a double bond at the bridge head position. Usually this means that the ketal is void of any carbon-hydrogen bond on the ⁇ -carbon atom in the ketal structure.
- the R"OH is represented by alcohols having an alkyl group of from Ci to C 2 o, in linear or branched structure, preferably an alkyl group having from 1 to 12 carbon atoms.
- the R"OH is used in relation to P-O in molar ratios of from R"OH: P-O of at least 1 : 1 to 6 : 1.
- the ratios R"OH : P-O of 1 : 1 to 6 : 1 are related to the number of P-O-P bonds in the P-O compound.
- the term "at least” means that the level of R"OH can be increased to e.g. 8 : 1 without adversely affecting the system. Any excess of R"OH can routinely be recycled into the system and thus doesn't affect the economics of the inventive method.
- the dialkylphosphite is prepared by adding P 4 O 6 , more preferably in liquid form, to the reaction medium simultaneously with or separately from the ketal.
- the reaction medium is generally the alcohol R"OH itself although a suitable solvent which is inert in relation to P-O, R"OH and the ketal, can be used optionally.
- Suitable solvents are preferably as follows: anisole; fluorobenzene; chlorinated hydrocarbons such as chlorobenzene, tetrachloroethane, tetrachloroethylene; polar solvents like sulfolane, diglyme, glyme, diphenyl oxide, polyalkylene glycol derivatives with capped OH groups such as OR where R is a low alkyl group; aliphatic hydrocarbons such as hexane, heptane, cyclohexane; non-cyclic ethers like dibutyl ether, diisopropyl ether, and dipentyl ether; cyclic ethers like tetrahydrofuran and dioxane; aromatic hydrocarbons like toluene, xylene; organic nitriles like acetonitrile; silicon fluids like polymethylphenyl siloxane or mixtures thereof.
- the P 4 O 6 can be represented by a substantially pure compound containing at least 85 %, preferably more than 90 %; more preferably at least 95 % and in one particular execution at least 97 % of the P 4 O 6 .
- tetraphosphorus hexa oxide suitable for use within the context of this invention, can be manufactured by any known technology, in preferred executions the hexa oxide can be prepared in accordance with the method of WO 2009/068636 and/or PCT/EP2009/064988, entitled "Process for the manufacture of P 4 O 6 with improved yield".
- oxygen, or a mixture of oxygen and inert gas, and gaseous or liquid phosphorus are reacted in essentially stoichiometric amounts in a reaction unit at a temperature in the range from 1600 to 2000 K, by removing the heat created by the exothermic reaction of phosphorus and oxygen, while maintaining a preferred residence time of from 0.5 to 60 seconds followed by quenching the reaction product at a temperature below 700 K and refining the crude reaction product by distillation.
- the hexa oxide so prepared is a pure product containing usually at least 97 % of the oxide.
- the P 4 O 6 so produced is generally represented by a liquid material of high purity containing in particular low levels of elementary phosphorus, P 4 , preferably below 1000 ppm, expressed in relation to the P 4 O 6 being 100%.
- the preferred residence time is from 5 to 30 seconds, more preferably from 8 to 30 seconds.
- the reaction product can, in one preferred execution, be quenched to a temperature below 350 K.
- liquid P 4 O 6 embraces, as spelled out, any state of the P 4 O 6 .
- the P 4 O 6 participating in a reaction at a temperature of from 70 0 C to 200 0 C is necessarily liquid or gaseous although solid species can, academically speaking, be used in the preparation of the reaction medium.
- the P-O component can be represented by P 4 O 6 , or partially hydrated species thereof, containing from 1 to 6 P-O-P bonds in the molecule.
- suitable species of the P-O component include: pyrophosphorous acid, H 4 P 2 O 5 , containing one P-O-P bond; P 4 O 6 containing six P-O-P bonds; and partially hydrated species thereof containing 2, 3, 4 and 5 P-O-P bonds respectively.
- Partially hydrated P 4 O 6 can lead to hydrolysis products containing 2, 3, 4 or 5 P-O-P bonds.
- the P-O component is preferably represented by P 4 O 6 of high purity containing very low levels of impurities, in particular elemental phosphorus, P 4 , at a level below 1000 ppm, usually below 500 ppm and preferably not more than 200 ppm, expressed in relation to the P 4 O 6 being 100%.
- the P-O component can be represented by uniform ingredients having e.g. a uniform number of P-O-P bonds or by mixtures having a distribution of P-O-P bonds as may occur in partially hydrated species of P 4 O 6 . Obviously, in such case the number of P-O-P stands for an average number of P-O-P bonds.
- Suitable P-O can also be prepared starting from PCI 3 by partial hydrolysis, or by reacting PCI 3 and phosphorous acid or by reacting P 4 O 6 and phosphorous acid or by partial hydrolysis of P 4 O 6 .
- the P-O can be represented by mixtures/combinations of different reagents e.g. PCI 3 , phosphorous acid and water subject to the presence of at least one P-O-P bond in the molecule.
- the level of water to be employed is limited (in molar terms) to 4 H 2 O or less per P 4 O 6 .
- a chlorine containing starting materials e.g. PCI 3 and combinations thereof, are used the level of chlorine shall be kept below 1000 ppm, usually below 500 ppm, preferably below 200 ppm, expressed in relation to the P-O material being 100%.
- Ketals have been known for a long time and are commodity materials. Ketals are generally formed by reaction of the corresponding ketones with alcohols in the presence of acid catalysts. As the reaction is reversible the equilibrium must be shifted, usually by removal of water. This can be done by azeotropic distillation, ordinary distillation, or the use of drying agents such as molecular sieve. Although many ketals have been synthesized in good yields from cyclic ketones, alcohols and acid catalysts, higher yields and conversions have been obtained by transacetalation whereby the ketone is reacted with e.g. an ortho ester in the presence of an acid catalyst.
- This approach can also be used to convert ketals prepared from low molecular weight alcohols by reaction with a higher molecular weight alcohols and distillation of the low molecular weight alcohol. Similar procedure can be followed up for the conversion of polymer supported ketones such as for example phenyl-CO-; naphthyl-CO- and t-butyl CO grafted onto styrene cross-linked with divinyl benzene to the corresponding ketal.
- polymer supported ketones such as for example phenyl-CO-; naphthyl-CO- and t-butyl CO grafted onto styrene cross-linked with divinyl benzene to the corresponding ketal.
- the reaction in accordance with this invention is conducted in a manner routinely known in the domain of the technology. As illustrated in the experimental showings, the method can be conducted by combining the essential reaction partners and heating the reaction mixture to a temperature usually within the range of from 70 0 C to 200 0 C, more preferably 100 ° to 160 0 C, in particular 120 to 150 0 C.
- the upper temperature aims at preventing any substantial undue decomposition of the reactants or of the intermediates formed in these reactions. It is understood and well known that the decomposition temperature of the reaction partners can vary depending upon physical parameters, such as pressure and the qualitative and quantitative parameters of the ingredients in the reaction mixture.
- the inventive reaction can be conducted at ambient, or reduced, pressure and, depending upon reaction temperature, under distillation of potential excess alcohol and alcohol formed during the reaction.
- the duration of the reaction can vary from virtually instantaneous, e.g. 10 minutes, to an extended period of e.g. 10 hours.
- the P-O, the alcohol and the ketal are added to the reactor followed by heating this mixture gradually to a temperature of from 70 ° to 150 0 C.
- This reaction can be carried out under ambient, or reduced, pressure with or without distillation of the alcohol.
- excess alcohol will be distilled, possibly under vacuum prior to the addition of the ketal and preferably of a solvent.
- the reaction can be conducted in a closed vessel under autogeneous pressure built up.
- the reaction partners in total or in part, are added to the reaction vessel at the start.
- the additional reaction partner can be added gradually, as soon as the effective reaction temperature has been reached. This set up is most advantageous inasmuch as it allows the use of low boiling solvent.
- the reaction can be conducted in a combined distillation and pressure arrangement. Specifically, the reaction vessel containing the reactant mixture is kept under ambient pressure at the selected reaction temperature.
- the mixture is then, possibly continuously circulated through a reactor operated under autogeneous (autoclave principle) pressure build up thereby gradually adding the additional reaction partners in accordance with needs.
- the reaction will preferably proceed in the autogeneous reactor.
- the reaction is substantially completed under pressure and the reaction mixture then leaves the closed vessel and is recycled to the reactor where alcohol distillation can occur.
- the foregoing process variables thus show that the reaction can be conducted by a variety of substantially complementary arrangements.
- the reaction can thus be conducted as a batch process by heating the initial reactants in a (1 ) closed vessel under autogeneous pressure built up, or (2) under distillation, to a temperature preferably in the range of from 70 0 C to 150 0 C.
- the reaction is conducted in a closed vessel at a temperature in the range of from 100 0 C to 150 0 C coinciding particularly with the gradual addition of residual ingredients.
- the reaction is conducted as a continuous process, possibly under autogeneous pressure, whereby the reactants are continuously injected into a reaction mixture at a temperature preferably in the range of from 70 0 C to 150 0 C.
- the method can be represented by a semi-continuous setup whereby the reaction is conducted continuously whereas preliminary reactions between part of the components can be conducted batch-wise e.g. between P-O and alcohol.
- the dialkyl phosphite reaction products can, if needed, be recovered from the reaction product by conventional means including, in particular, vacuum distillation.
- dialkyl phosphites can be used as intermediates, e.g. for beneficially synthesizing compounds which were known to be difficult to make.
- 2- phosphonobutyl-1 ,2,4-tricarboxylic acid can be made starting from dialkylphosphites as follows:
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Abstract
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Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MX2011012589A MX2011012589A (en) | 2009-05-28 | 2010-05-28 | Method for the manufacture of dialkyl phosphites. |
CN2010800233232A CN102448973A (en) | 2009-05-28 | 2010-05-28 | Method for the manufacture of dialkyl phosphites |
US13/322,420 US20120172614A1 (en) | 2009-05-28 | 2010-05-28 | Method for the manufacture of dialkyl phosphites |
BRPI1014930A BRPI1014930A2 (en) | 2009-05-28 | 2010-05-28 | process for the manufacture of dialkyl phosphites. |
AU2010251898A AU2010251898A1 (en) | 2009-05-28 | 2010-05-28 | Method for the manufacture of dialkyl phosphites |
RU2011150200/04A RU2011150200A (en) | 2009-05-28 | 2010-05-28 | METHOD FOR PRODUCING DIALKYL PHOSPHYFES |
EP10724398A EP2435449A1 (en) | 2009-05-28 | 2010-05-28 | Method for the manufacture of dialkyl phosphites |
JP2012512397A JP2012528128A (en) | 2009-05-28 | 2010-05-28 | Process for the production of dialkyl phosphites |
CA2760619A CA2760619A1 (en) | 2009-05-28 | 2010-05-28 | Method for the manufacture of dialkyl phosphites |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP09161390 | 2009-05-28 | ||
EP09161390.1 | 2009-05-28 |
Publications (1)
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WO2010136575A1 true WO2010136575A1 (en) | 2010-12-02 |
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Family Applications (1)
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PCT/EP2010/057437 WO2010136575A1 (en) | 2009-05-28 | 2010-05-28 | Method for the manufacture of dialkyl phosphites |
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US (1) | US20120172614A1 (en) |
EP (1) | EP2435449A1 (en) |
JP (1) | JP2012528128A (en) |
CN (1) | CN102448973A (en) |
AU (1) | AU2010251898A1 (en) |
BR (1) | BRPI1014930A2 (en) |
CA (1) | CA2760619A1 (en) |
MX (1) | MX2011012589A (en) |
RU (1) | RU2011150200A (en) |
WO (1) | WO2010136575A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012098255A1 (en) * | 2011-01-21 | 2012-07-26 | Straitmark Holding Ag | METHOD FOR THE MANUFACTURE OF COMPOUNDS CONTAINING AN α-OXY PHOSPHORUS GROUP |
EP2581378A1 (en) | 2011-10-13 | 2013-04-17 | Straitmark Holding AG | Method for the esterification of P-O components |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DD108755A1 (en) * | 1973-11-28 | 1974-10-05 | ||
DE4121696A1 (en) * | 1991-06-29 | 1993-01-07 | Wittenberg Stickstoff Ag | Novel prepn. of phosphite di:ester(s) - by reaction of phosphorous acid or its mono:ester with carboxylic anhydride and then alcohol |
-
2010
- 2010-05-28 MX MX2011012589A patent/MX2011012589A/en not_active Application Discontinuation
- 2010-05-28 AU AU2010251898A patent/AU2010251898A1/en not_active Abandoned
- 2010-05-28 CN CN2010800233232A patent/CN102448973A/en active Pending
- 2010-05-28 US US13/322,420 patent/US20120172614A1/en not_active Abandoned
- 2010-05-28 EP EP10724398A patent/EP2435449A1/en not_active Withdrawn
- 2010-05-28 WO PCT/EP2010/057437 patent/WO2010136575A1/en active Application Filing
- 2010-05-28 CA CA2760619A patent/CA2760619A1/en not_active Abandoned
- 2010-05-28 JP JP2012512397A patent/JP2012528128A/en active Pending
- 2010-05-28 RU RU2011150200/04A patent/RU2011150200A/en unknown
- 2010-05-28 BR BRPI1014930A patent/BRPI1014930A2/en not_active Application Discontinuation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DD108755A1 (en) * | 1973-11-28 | 1974-10-05 | ||
DE4121696A1 (en) * | 1991-06-29 | 1993-01-07 | Wittenberg Stickstoff Ag | Novel prepn. of phosphite di:ester(s) - by reaction of phosphorous acid or its mono:ester with carboxylic anhydride and then alcohol |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012098255A1 (en) * | 2011-01-21 | 2012-07-26 | Straitmark Holding Ag | METHOD FOR THE MANUFACTURE OF COMPOUNDS CONTAINING AN α-OXY PHOSPHORUS GROUP |
EP2581378A1 (en) | 2011-10-13 | 2013-04-17 | Straitmark Holding AG | Method for the esterification of P-O components |
WO2013053939A1 (en) | 2011-10-13 | 2013-04-18 | Straitmark Holding Ag | Method for the esterification of p-o components |
Also Published As
Publication number | Publication date |
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AU2010251898A1 (en) | 2011-11-24 |
CN102448973A (en) | 2012-05-09 |
US20120172614A1 (en) | 2012-07-05 |
JP2012528128A (en) | 2012-11-12 |
RU2011150200A (en) | 2013-07-10 |
BRPI1014930A2 (en) | 2016-04-19 |
CA2760619A1 (en) | 2010-12-02 |
EP2435449A1 (en) | 2012-04-04 |
MX2011012589A (en) | 2012-04-11 |
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