US3480701A - Process for the production of mixed phosphonic acid esters - Google Patents
Process for the production of mixed phosphonic acid esters Download PDFInfo
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- US3480701A US3480701A US535310A US3480701DA US3480701A US 3480701 A US3480701 A US 3480701A US 535310 A US535310 A US 535310A US 3480701D A US3480701D A US 3480701DA US 3480701 A US3480701 A US 3480701A
- Authority
- US
- United States
- Prior art keywords
- phosphonic acid
- mol
- methane
- ester
- bromide
- 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
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- 238000000034 method Methods 0.000 title description 13
- 150000003008 phosphonic acid esters Chemical class 0.000 title description 6
- 238000004519 manufacturing process Methods 0.000 title description 4
- -1 hydrocarbon radical Chemical class 0.000 description 32
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 18
- 238000003756 stirring Methods 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 12
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- 229940116254 phosphonic acid Drugs 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 150000003009 phosphonic acids Chemical class 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 235000009518 sodium iodide Nutrition 0.000 description 3
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- XJRIDJAGAYGJCK-UHFFFAOYSA-N (1-acetyl-5-bromoindol-3-yl) acetate Chemical compound C1=C(Br)C=C2C(OC(=O)C)=CN(C(C)=O)C2=C1 XJRIDJAGAYGJCK-UHFFFAOYSA-N 0.000 description 1
- AVMHMVJVHYGDOO-NSCUHMNNSA-N (e)-1-bromobut-2-ene Chemical compound C\C=C\CBr AVMHMVJVHYGDOO-NSCUHMNNSA-N 0.000 description 1
- AATNZNJRDOVKDD-UHFFFAOYSA-N 1-[ethoxy(ethyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(CC)OCC AATNZNJRDOVKDD-UHFFFAOYSA-N 0.000 description 1
- YXZFFTJAHVMMLF-UHFFFAOYSA-N 1-bromo-3-methylbutane Chemical compound CC(C)CCBr YXZFFTJAHVMMLF-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- AEYNBGPWSOYWSE-UHFFFAOYSA-N 2-[ethyl(propan-2-yloxy)phosphoryl]oxypropane Chemical compound CC(C)OP(=O)(CC)OC(C)C AEYNBGPWSOYWSE-UHFFFAOYSA-N 0.000 description 1
- KPJKMUJJFXZGAX-UHFFFAOYSA-N 2-chloropropan-2-ylbenzene Chemical compound CC(C)(Cl)C1=CC=CC=C1 KPJKMUJJFXZGAX-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical class NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- KNIUHBNRWZGIQQ-UHFFFAOYSA-N 7-diethoxyphosphinothioyloxy-4-methylchromen-2-one Chemical compound CC1=CC(=O)OC2=CC(OP(=S)(OCC)OCC)=CC=C21 KNIUHBNRWZGIQQ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- HZCDANOFLILNSA-UHFFFAOYSA-N Dimethyl hydrogen phosphite Chemical group COP(=O)OC HZCDANOFLILNSA-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001347 alkyl bromides Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- NKQIMNKPSDEDMO-UHFFFAOYSA-L barium bromide Chemical compound [Br-].[Br-].[Ba+2] NKQIMNKPSDEDMO-UHFFFAOYSA-L 0.000 description 1
- 229910001620 barium bromide Inorganic materials 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 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 1
- 150000005690 diesters Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- OXDOANYFRLHSML-UHFFFAOYSA-N dimethoxyphosphorylbenzene Chemical compound COP(=O)(OC)C1=CC=CC=C1 OXDOANYFRLHSML-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 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
- SVMUEEINWGBIPD-UHFFFAOYSA-N dodecylphosphonic acid Chemical compound CCCCCCCCCCCCP(O)(O)=O SVMUEEINWGBIPD-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 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
- 239000010720 hydraulic oil Substances 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical class CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical class CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 229940086542 triethylamine Drugs 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M3/00—Liquid compositions essentially based on lubricating components other than mineral lubricating oils or fatty oils and their use as lubricants; Use as lubricants of single liquid substances
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
- C10M2223/065—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
Definitions
- the present invention relates to mixed phosphonic acid esters and to a process for producing the same; more particularly it concerns a process for the production of mixed phosphonic acid esters of the general formula OR I in which R denotes a hydrocarbon radical containing 1-18 carbon atoms, while R stands for an alkyl radical containing 1-3 carbon atoms and R" for an alkyl or aralkyl radical containing 4-18 carbon atoms or for an alkenyl radical containing 318 carbon atoms, wherein phosphonic acid diesters of the general formula in which R and R have the above meaning, are reacted while heating with.
- approximately equimolar amounts of 3,480,701 Patented Nov. 25, 1969 a halide of the formula RX in which R has the above meaning and X stands for chlorine, bromine or iodine.
- this process is carried out in the presence of alkali metal, alkaline earth metal or ammonium salts of hydrohalic acids or partially esterified phosphonic acids of the general formula OH III in which R and R have the above meaning.
- Phosphonic acid diesters of the Formula II which are suitable for the process of the invention are, for example, the dimethyl, diethyl or dipropyl esters of methane-, ethane-, propane-, butane-, hexane-, heptane-, octane-, nonane-, decane, dodecane-, benzene, benzyl-, methylbenZyl-, dimethylbenZyl-, indene-(2)-, ethylene-, propylene-, butyleneor Z-phenyl-ethylene-phosphonic acid.
- Halides of the formula RX are, for example, butyl pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, allyl, crotyl, nonenyl, decenyl, dodecenyl bromide or iodide as well as benzyl, methylbenzyl or dimethylbenzyl chloride, bromide or iodide.
- the alkali metal or alkaline earth metal salts of hydrohalic acids or partially esterified phosphonic acids of the Formula III include, for example, the sodium, potassium, barium and calcium salts of hydrofluoric, hydrochloric, hydrobromic or hydroiodic acid or of the monomethyl, monoethyl and monopropyl esters of methane-, ethane-, propane-, butane-, heXane-, heptane-, octane-, nonane-, decane, dodecane-, benzene-, benzyl-, methylbenzyh, dimethylbenzyl-, indene-(2)-, ethylene-, propylene-, butyleneor Z-phenyl-ethylene-phosphonic acid.
- ammonium salts there may be mentioned the salts of these hydrohalic acids or partially esterified phosphonic acids with armmonia, pyridine or an amine, such as diethylamine and tri ethylamine; the corresponding tetraalkyl ammonium salts, such as tetraethyl ammonium bromide or the tetraethyl ammonium salts of the monomethyl, monoethyl and monopropyl esters of the mentioned phosphonic acids are also suitable.
- the amounts to be applied of these salts may vary within wide limits; in general, amounts of 1-5 mol of salt per mol phosphonic acid diester according to Formula II will prove sufficient.
- the reaction is expediently carried out at temperatures between 80 and C. While stirring; it can be performed discontinuously or continuously.
- the reaction mixture is passed through several stirring vessels connected in succession, while heating.
- the components are continuously introduced into the first stirring vessel and the reaction mixture is continuously withdrawn from the last stirring vessel and then worked up by conventional methods.
- the mixed phosphonic acid esters which can be obtained according to the invention are suitable for a variety of applications; they can be used, for example, as plasticisers for synthetic resins, as flameproofing agents, as additives to motor fuels, as hydraulic oils and as extraction agents.
- EXAMPLE 1 124 grams (1 mol) methane-phosphonic acid dimethyl ester and 137 g. (1 mol) butyl bromide are heated at 110 C. for 7 hours, while stirring, in the presence of 6.6 g. (0.05 mol) of the sodium salt of the monomethyl ester of methane-phosphonic acid, which was prepared by heating methane-phosphonic acid dimethyl ester with sodium fluoride, sodium chloride, sodium bromide or sodium iodide in a molar ratio of 1:1 at 100140 C. The reaction mixture is then subjected to a vacuum distillation. 47 grams (0.28 mol) methane-phosphonic acid-O- methyl-O-butyl ester of B.P.
- EXAMPLE 2- 124 grams (1 mol) methane-phosphonic acid dimethyl ester and 184 g, (1 mol) butyl iodide are heated at 120 C. for 7 to 10 hours, while stirring, in the presence of 6 g. sodium bromide, 3 g. ammonium chloride, 6 g. pyridine hydrochloride, 8 g. tetraethyl ammonium bromide, 4 g. diethylarnine hydrochloride, 5 g. calcium chloride, 5 g. barium bromide or 5-10 g.
- alkali metal, alkaline earth metal or ammonium salts which can be obtained from methane-phosphonic acid dimethyl ester and the above salts by heating to 100140 C.; the reaction mixture is subsequently subjected to a vacuum distillation. There are obtained 33 to 50 g. methane-phosphonic acid-O-methyl-O-butyl ester.
- EXAMPLE 4 124 grams (1 mol) methane-phosphonic acid dimethyl ester and 249 g. (1 mol) dodecyl bromide are heated at 160 C. for 5 hours, while stirring, in the presence of 6 g. of the sodium salt of the monomethyl ester of methane-phosphonic acid, which was prepared by heating methane-phosphonic acid dimethyl ester with sodium fluoride, sodium chloride, sodium bromide or sodium iodide in a molar ratio of 1:1 at 100140 C. After working up in the usual manner, there are obtained 83 g. (0.33 mol) methane-phosphonic acid-O-methyl-O-dodecyl ester of B.P. 153157 C./1.5 mm. Hg and refractive index 11 1.4410.
- EXAMPLE 7 124 grams (1 mol) methane-phosphonic acid dimethyl ester and 126.6 g. benzyl chloride are heated in the presence of 3 g. sodium chloride at 130 C. for 15 hours while stirring. After working up in the usual manner, there are obtained 60 g. (0.34 mol) methane-phosphonic acid-O-meihyl-O-benZyl ester of B.P. 215-217 C./13 mm. Hg.
- EXAMPLE 8 166 grams (1 mol) ethane-phosphonic acid diethyl ester and 137 g. (1 mol) butyl bromide are heated in the presence of 4 g. sodium bromide at C, for 12 hours while stirring. After working up in the usual manner, there are obtained 40 g. (0.2 mol) ethane-phosphonic acid-O-ethyl-O-butyl ester of B.P. Ill-113 C./13 mm. Hg and refractive index 1.4175.
- EXAMPLE 9 194 grams (1 mol) ethane-phosphonic acid diisopropyl ester and 249 g. (1 mol) dodecyl bromide are heated in the presence of 4 g. sodium bromide at 170 C. for 15 hours while stirring. After working up in the usual manner, there are obtained 20 g. (0.06 mol) ethane-phosphonic acid-O-isopropyl-O-dodecyl ester.
- EXAMPLE 10 278 grams (1 mol) dodecane-phospho-nic acid dimethyl ester and 184 g. (1 mol) butyl iodide are heated in the presence of 6 g. sodium iodide at C. for 10 hours while stirring. After working up in the usual manner, there are obtained 86 g. (0.26 mol) dodecane-phosphonic acid- O-methyl-O-butyl ester.
- EXAMPLE 1 1 186 grams (1 mol) benzene-phosphonic acid dimethyl ester and 137 g. (1 mol) butyl bromide are heated in the presence of 4 g. sodium bromide at 130 C. for 20 hours while stirring. After working up in the usual manner, there are obtained 64 g. (0.3 mol) benzene-phosphonic acid-O- methyl-O-butyl ester of refractive index n 1.4898.
- R stands for a hydrocarbon radical containing 1-18 carbon atoms
- R stands for an alkyl radical containing 1-3 carbon atoms
- R" stands for an alkyl or aralkyl radical containing 4-18 carbon atoms or for an alkenyl radical containing 318 carbon atoms comprising reacting at a temperature from 80 to C.
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Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF45585A DE1230801B (de) | 1965-03-20 | 1965-03-20 | Verfahren zur Herstellung von Phosphonsaeuremischestern |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3480701A true US3480701A (en) | 1969-11-25 |
Family
ID=7100563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US535310A Expired - Lifetime US3480701A (en) | 1965-03-20 | 1966-03-18 | Process for the production of mixed phosphonic acid esters |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US3480701A (de) |
| BE (1) | BE677973A (de) |
| DE (1) | DE1230801B (de) |
| GB (1) | GB1094435A (de) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4111882A (en) * | 1976-09-17 | 1978-09-05 | Stauffer Chemical Company | Flame retardant plasticizer formulation for polyvinyl chloride containing dimethyl methylphosphonate for haze reduction |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3138629A (en) * | 1961-01-19 | 1964-06-23 | Procter & Gamble | Process for making an omicron-higher alkyl omicron-methyl methanephosphonate |
| US3272892A (en) * | 1963-03-04 | 1966-09-13 | Stauffer Chemical Co | Method of preparing organic phosphonates by transesterification |
-
1965
- 1965-03-20 DE DEF45585A patent/DE1230801B/de active Pending
-
1966
- 1966-03-17 BE BE677973D patent/BE677973A/xx unknown
- 1966-03-18 US US535310A patent/US3480701A/en not_active Expired - Lifetime
- 1966-03-21 GB GB12415/66A patent/GB1094435A/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3138629A (en) * | 1961-01-19 | 1964-06-23 | Procter & Gamble | Process for making an omicron-higher alkyl omicron-methyl methanephosphonate |
| US3272892A (en) * | 1963-03-04 | 1966-09-13 | Stauffer Chemical Co | Method of preparing organic phosphonates by transesterification |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4111882A (en) * | 1976-09-17 | 1978-09-05 | Stauffer Chemical Company | Flame retardant plasticizer formulation for polyvinyl chloride containing dimethyl methylphosphonate for haze reduction |
Also Published As
| Publication number | Publication date |
|---|---|
| DE1230801B (de) | 1966-12-22 |
| GB1094435A (en) | 1967-12-13 |
| BE677973A (de) | 1966-09-01 |
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