CH622524A5 - Process for the preparation of alkanephosphonic esters - Google Patents
Process for the preparation of alkanephosphonic esters Download PDFInfo
- Publication number
- CH622524A5 CH622524A5 CH1436176A CH1436176A CH622524A5 CH 622524 A5 CH622524 A5 CH 622524A5 CH 1436176 A CH1436176 A CH 1436176A CH 1436176 A CH1436176 A CH 1436176A CH 622524 A5 CH622524 A5 CH 622524A5
- Authority
- CH
- Switzerland
- Prior art keywords
- reaction
- alkanephosphonic
- acid
- monoalkyl
- olefins
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 34
- 150000002148 esters Chemical class 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title claims 5
- 239000002253 acid Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 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 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 8
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 3
- OOSPDKSZPPFOBR-UHFFFAOYSA-N butyl dihydrogen phosphite Chemical compound CCCCOP(O)O OOSPDKSZPPFOBR-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims 19
- 150000001336 alkenes Chemical class 0.000 claims 13
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims 13
- 150000003254 radicals Chemical class 0.000 claims 12
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims 9
- 125000004432 carbon atom Chemical group C* 0.000 claims 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 6
- 150000007513 acids Chemical class 0.000 claims 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 6
- 150000005690 diesters Chemical class 0.000 claims 5
- 239000011261 inert gas Substances 0.000 claims 5
- 239000004711 α-olefin Substances 0.000 claims 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 4
- 150000001298 alcohols Chemical class 0.000 claims 4
- -1 alkali metal salts Chemical class 0.000 claims 4
- 125000000217 alkyl group Chemical group 0.000 claims 4
- 230000035484 reaction time Effects 0.000 claims 4
- 239000002904 solvent Substances 0.000 claims 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 3
- 229910052783 alkali metal Inorganic materials 0.000 claims 3
- 230000003197 catalytic effect Effects 0.000 claims 3
- 238000000354 decomposition reaction Methods 0.000 claims 3
- 125000004185 ester group Chemical group 0.000 claims 3
- 229910052717 sulfur Inorganic materials 0.000 claims 3
- 239000011593 sulfur Substances 0.000 claims 3
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims 2
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methyl-1-pentene Chemical compound CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 claims 2
- XTVRLCUJHGUXCP-UHFFFAOYSA-N 3-methyleneheptane Chemical compound CCCCC(=C)CC XTVRLCUJHGUXCP-UHFFFAOYSA-N 0.000 claims 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 2
- 230000002378 acidificating effect Effects 0.000 claims 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 2
- 239000003054 catalyst Substances 0.000 claims 2
- 239000000470 constituent Substances 0.000 claims 2
- 238000004821 distillation Methods 0.000 claims 2
- 229930195733 hydrocarbon Natural products 0.000 claims 2
- 150000002430 hydrocarbons Chemical class 0.000 claims 2
- 239000012442 inert solvent Substances 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000005855 radiation Effects 0.000 claims 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims 1
- RSKXYCDTGOUAKH-UHFFFAOYSA-N 2-methylpropyl dihydrogen phosphite Chemical compound CC(C)COP(O)O RSKXYCDTGOUAKH-UHFFFAOYSA-N 0.000 claims 1
- 239000004342 Benzoyl peroxide Substances 0.000 claims 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 150000005215 alkyl ethers Chemical class 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052786 argon Inorganic materials 0.000 claims 1
- 235000019400 benzoyl peroxide Nutrition 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000009835 boiling Methods 0.000 claims 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims 1
- 239000006227 byproduct Substances 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 238000005336 cracking Methods 0.000 claims 1
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 claims 1
- 230000023556 desulfurization Effects 0.000 claims 1
- 238000006471 dimerization reaction Methods 0.000 claims 1
- 230000000447 dimerizing effect Effects 0.000 claims 1
- 229940069096 dodecene Drugs 0.000 claims 1
- RSNDQTNQQQNXRN-UHFFFAOYSA-N dodecyl dihydrogen phosphite Chemical compound CCCCCCCCCCCCOP(O)O RSNDQTNQQQNXRN-UHFFFAOYSA-N 0.000 claims 1
- 230000008030 elimination Effects 0.000 claims 1
- 238000003379 elimination reaction Methods 0.000 claims 1
- 230000032050 esterification Effects 0.000 claims 1
- 238000005886 esterification reaction Methods 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- ZUNGGJHBMLMRFJ-UHFFFAOYSA-O ethoxy-hydroxy-oxophosphanium Chemical compound CCO[P+](O)=O ZUNGGJHBMLMRFJ-UHFFFAOYSA-O 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- 238000005188 flotation Methods 0.000 claims 1
- QXLBKTGZGPVJOO-UHFFFAOYSA-N hexyl dihydrogen phosphite Chemical compound CCCCCCOP(O)O QXLBKTGZGPVJOO-UHFFFAOYSA-N 0.000 claims 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- XAKRTGZVYPZHCO-UHFFFAOYSA-O hydroxy-methoxy-oxophosphanium Chemical compound CO[P+](O)=O XAKRTGZVYPZHCO-UHFFFAOYSA-O 0.000 claims 1
- OXDIZRALNSSICH-UHFFFAOYSA-N icosyl dihydrogen phosphite Chemical compound CCCCCCCCCCCCCCCCCCCCOP(O)O OXDIZRALNSSICH-UHFFFAOYSA-N 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 claims 1
- 239000013067 intermediate product Substances 0.000 claims 1
- 238000005517 mercerization Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 150000005673 monoalkenes Chemical class 0.000 claims 1
- 230000003472 neutralizing effect Effects 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 claims 1
- 239000003209 petroleum derivative Substances 0.000 claims 1
- 239000012169 petroleum derived wax Substances 0.000 claims 1
- 239000002243 precursor Substances 0.000 claims 1
- PRAHMDIEZMWIRW-UHFFFAOYSA-N propyl dihydrogen phosphite Chemical compound CCCOP(O)O PRAHMDIEZMWIRW-UHFFFAOYSA-N 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 239000012429 reaction media Substances 0.000 claims 1
- 230000009467 reduction Effects 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 238000004904 shortening Methods 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims 1
- 229940095068 tetradecene Drugs 0.000 claims 1
- NJGCRMAPOWGWMW-UHFFFAOYSA-N octylphosphonic acid Chemical class CCCCCCCCP(O)(O)=O NJGCRMAPOWGWMW-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- BVQJQTMSTANITJ-UHFFFAOYSA-N tetradecylphosphonic acid Chemical compound CCCCCCCCCCCCCCP(O)(O)=O BVQJQTMSTANITJ-UHFFFAOYSA-N 0.000 description 2
- AYIYGMYWHVTKNV-UHFFFAOYSA-N 1-dimethoxyphosphoryloctane Chemical compound CCCCCCCCP(=O)(OC)OC AYIYGMYWHVTKNV-UHFFFAOYSA-N 0.000 description 1
- YZBOVSFWWNVKRJ-UHFFFAOYSA-M 2-butoxycarbonylbenzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1C([O-])=O YZBOVSFWWNVKRJ-UHFFFAOYSA-M 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- OSPSWZSRKYCQPF-UHFFFAOYSA-N dibutoxy(oxo)phosphanium Chemical compound CCCCO[P+](=O)OCCCC OSPSWZSRKYCQPF-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000010992 reflux 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
- C07F9/28—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
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Description
Die Erfindung wird durch die nachfolgenden Beispiele erläutert. The invention is illustrated by the following examples.
Beispiel 1 example 1
200 g (2,47 Mol) phosphorige Säure und 268 g (2,47 Mol) Dimethylphosphit werden gemischt und unter Stickstoffatmo-sphäre auf 170°-175°C erhitzt. Nun wird unter lebhaftem Rühren ein Gemisch aus 545 g (4,87 Mol) Okten-1 und 6 g Di-tert.-butyl-peroxid während 2,25 Stunden eingetropft. 1 Stunde wird bei dieser Temperatur nachgerührt. In einer nachgeschalteten Kühlfalle sammeln sich 12 g Dimethyläther, 5,5 g Methanol und 1,5 g Okten-1. Es verbleiben 1000 g Oktan-phosphonsäurederivate, die aufgrund einer gaschromatogra-phischen Analyse aus 13 Gew.-% Oktanphosphonsäuredime-thylester, 55 Gew.-% Mono-methylester und 29 Gew.-% Oktanphosphonsäure bestehen und nur 0,5 Gew.-% Telomeri-sat enthalten. 200 g (2.47 mol) of phosphorous acid and 268 g (2.47 mol) of dimethyl phosphite are mixed and heated to 170 ° -175 ° C. under a nitrogen atmosphere. A mixture of 545 g (4.87 mol) of octene-1 and 6 g of di-tert-butyl peroxide is then added dropwise with vigorous stirring over a period of 2.25 hours. The mixture is stirred at this temperature for 1 hour. In a downstream cold trap, 12 g of dimethyl ether, 5.5 g of methanol and 1.5 g of octene-1 collect. There remain 1000 g of octane-phosphonic acid derivatives which, based on a gas chromatographic analysis, consist of 13% by weight of dimethyl octanephosphonate, 55% by weight of mono-methyl ester and 29% by weight of octanephosphonic acid and only 0.5% by weight. Telomeri-sat included.
Die Ausbeute beträgt somit fast 100% der Theorie an Oktanphosphonsäurederivaten. The yield is thus almost 100% of theory of octanephosphonic acid derivatives.
Beispiel 2 Example 2
250 g (3,05 Mol) phosphorige Säure, 450 g n-Butanol und 250 g (3.05 mol) of phosphorous acid, 450 g of n-butanol and
345 g Toluol werden unter Rühren zum Rückfluss erhitzt, wobei mit Hilfe eines Wasserabscheiders in etwa 4 Stunden 65 ml (3,62 Mol) Wasser abgetrennt werden. Dann wird bei 100-120 Torr bis zu einer Innentemperatur von 150°C destilliert. Der Rückstand stellt rohes Mono-n-butylphosphit dar. Er wird unter Stickstoffatmosphäre auf 180°C erhitzt. Nun wird unter lebhaftem Rühren ein Gemisch aus 342 g (3,05 Mol) Okten-1 und 3,5 g Di-tert.-butylperoxid während 3 Stunden eingetropft. 1 Stunde wird bei dieser Temperatur nachgerührt. In einer nachgeschalteten Kühlfalle sammeln sich etwa 5 g Buten-1. 345 g of toluene are heated to reflux with stirring, 65 ml (3.62 mol) of water being separated off in about 4 hours with the aid of a water separator. Then distilled at 100-120 torr to an internal temperature of 150 ° C. The residue is crude mono-n-butyl phosphite. It is heated to 180 ° C. under a nitrogen atmosphere. A mixture of 342 g (3.05 mol) of octene-1 and 3.5 g of di-tert-butyl peroxide is then added dropwise with vigorous stirring over a period of 3 hours. The mixture is stirred at this temperature for 1 hour. About 5 g of butene-1 collect in a cold trap.
Anschliessend wird das Reaktionsprodukt nach dem Verfahren der deutschen Patentanmeldung P 24 41 783.2 bei 200°C mit Wasser umgesetzt. Man erhält 592 g Oktanphosphonsäure, die nur 2 Gew.-% Telomerisat enthält. Das entspricht einer Ausbeute von 100% an Alkanphosphonsäurede-rivaten. The reaction product is then reacted with water at 200 ° C. using the process of German patent application P 24 41 783.2. 592 g of octanephosphonic acid are obtained, which contains only 2% by weight of telomerizate. This corresponds to a yield of 100% of alkanephosphonic acid derivatives.
Beispiel 3 Example 3
120 g (0,618 Mol) Di-n-butylphosphit und 50,6 g (0,618 Mol) phosphorige Säure werden gemischt und unter Stickstoffatmosphäre auf 180°C erhitzt. Nun wird unter lebhaftem Rühren während 2,5 Stunden ein Gemisch aus 139 g (1,24 Mol) Okten-1 und 1,4 g Di-tert.-butylperoxid eingetropft und das Gemisch 1 Stunde bei dieser Temperatur nachgerührt. Anschliessend wird bis zu einer Innentemperatur von 150 °C bei 1 Torr destilliert. Als Rückstand verbleiben 295 g eines Gemisches aus Oktanphosphonsäuredibutylester, Oktan-phosphonsäuremonobutylester und Oktanphosphonsäure, etwa in dem Verhältnis wie in Beispiel 1 beschrieben. 120 g (0.618 mol) of di-n-butyl phosphite and 50.6 g (0.618 mol) of phosphorous acid are mixed and heated to 180 ° C. under a nitrogen atmosphere. A mixture of 139 g (1.24 mol) of octene-1 and 1.4 g of di-tert-butyl peroxide is then added dropwise with vigorous stirring over a period of 2.5 hours, and the mixture is subsequently stirred at this temperature for 1 hour. Then distilled to an internal temperature of 150 ° C at 1 Torr. 295 g of a mixture of octanephosphonic acid dibutyl ester, octanephosphonic acid monobutyl ester and octanephosphonic acid remain in the residue, approximately in the ratio as described in Example 1.
Beispiel 4 Example 4
162 g (1,975 Mol) phosphorige Säure und 217 g (1,975 Mol) Dimethylphosphit werden gemischt und auf 155°C-160°C erhitzt. Nun wird unter Stickstoffatmosphäre unter lebhaftem Rühren während 3 Stunden ein Gemisch aus 775 g (3,95 Mol) Tetradecen-1 und 8 g Di-tert.-butylperoxid eingetropft und die Mischung bei dieser Temperatur 1 Stunde nachgerührt. In einer nachgeschalteten Kühlfalle sammeln sich 19 g Dimethyläther und Methanol. Bei Abkühlen des Reak-tionsgmisches tritt Erstarrung ein. Das erhaltene Produkt hat einen Erstarrungspunkt von 35°C. 162 g (1.975 mol) of phosphorous acid and 217 g (1.975 mol) of dimethyl phosphite are mixed and heated to 155 ° C-160 ° C. A mixture of 775 g (3.95 mol) of tetradecene-1 and 8 g of di-tert-butyl peroxide is then added dropwise under a nitrogen atmosphere with vigorous stirring and the mixture is stirred at this temperature for 1 hour. 19 g of dimethyl ether and methanol collect in a downstream cold trap. When the reaction mixture cools down, solidification occurs. The product obtained has a solidification point of 35 ° C.
Anschliessend wird das Reaktionsprodukt nach dem Verfahren der deutschen Patentanmeldung P 24 41 878.8 bei 175°C mit Wasser umgesetzt. Man erhält 1080 g Tetradecan-phosphonsäure vom Erstarrungspunkt 74° C. Das entspricht einer Ausbeute von 98,5 % der Theorie an Tetradecanphos-phonsäure. The reaction product is then reacted with water at 175 ° C. using the process of German patent application P 24 41 878.8. 1080 g of tetradecane-phosphonic acid with a solidification point of 74 ° C. are obtained. This corresponds to a yield of 98.5% of theory of tetradecane-phosphonic acid.
Beispiel 5 Example 5
200 g (2,44 Mol) phosphorige Säure und 268 g (2,44 Mol) Dimethylphosphit werden gemischt und auf 155°—160°C erhitzt. Nun wird unter Stickstoffatmosphäre unter lebhaftem Rühren während 2 Stunden ein Gemisch aus 545 g (4,87 Mol) Okten-1 und 6 g Di-tert.-butylperoxid eingetropft. 200 g (2.44 mol) of phosphorous acid and 268 g (2.44 mol) of dimethyl phosphite are mixed and heated to 155-160 ° C. A mixture of 545 g (4.87 mol) of octene-1 and 6 g of di-tert-butyl peroxide is then added dropwise under nitrogen atmosphere with vigorous stirring for 2 hours.
Es wird 1 Stunde bei dieser Temperatur nachgerührt. In einer nachgeschalteten Kühlfalle sammeln sich 8 g Dimethyläther und 1,5 g Methanol. The mixture is stirred at this temperature for 1 hour. 8 g of dimethyl ether and 1.5 g of methanol collect in a downstream cold trap.
Anschliessend wird das Reaktionsprodukt nach dem Verfahren der deutschen Patentanmeldung P 24 41 878.8 bei 170°C mit Wasser umgesetzt. Man erhält 941 g Oktanphosphonsäure vom Erstarrungspunkt 80,6°C. Das entspricht einer Ausbeute von 99% der Theorie an Oktanphosphonsäure. The reaction product is then reacted with water at 170 ° C. using the process of German patent application P 24 41 878.8. 941 g of octanephosphonic acid with a solidification point of 80.6 ° C. are obtained. This corresponds to a yield of 99% of theory of octane phosphonic acid.
s io s io
15 15
20 20th
25 25th
30 30th
35 35
40 40
45 45
50 50
55 55
60 60
65 65
B B
Claims (5)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19752551598 DE2551598C2 (en) | 1975-11-18 | Process for the preparation of alkanephosphonic acid esters |
Publications (1)
Publication Number | Publication Date |
---|---|
CH622524A5 true CH622524A5 (en) | 1981-04-15 |
Family
ID=5961953
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CH1436176A CH622524A5 (en) | 1975-11-18 | 1976-11-15 | Process for the preparation of alkanephosphonic esters |
Country Status (8)
Country | Link |
---|---|
BE (1) | BE848498A (en) |
CH (1) | CH622524A5 (en) |
DK (1) | DK516876A (en) |
FR (1) | FR2332283A1 (en) |
GB (1) | GB1559883A (en) |
IT (1) | IT1063803B (en) |
LU (1) | LU76203A1 (en) |
NL (1) | NL7612608A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7208452B2 (en) | 2003-05-16 | 2007-04-24 | Afton Chemical Intangibles, Llc | Process for manufacturing alkylphosphonate monoesters |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3517676A (en) * | 1967-10-25 | 1970-06-30 | Caterpillar Tractor Co | Quench apparatus for providing pulsating and sweeping flow of quench fluid |
IL35844A (en) * | 1969-12-16 | 1973-11-28 | Hoechst Ag | Process for the manufacture of alkane phosphonic acid diesters |
-
1976
- 1976-11-12 NL NL7612608A patent/NL7612608A/en not_active Application Discontinuation
- 1976-11-15 CH CH1436176A patent/CH622524A5/en not_active IP Right Cessation
- 1976-11-15 IT IT2937176A patent/IT1063803B/en active
- 1976-11-16 LU LU76203A patent/LU76203A1/xx unknown
- 1976-11-17 GB GB4790976A patent/GB1559883A/en not_active Expired
- 1976-11-17 DK DK516876A patent/DK516876A/en unknown
- 1976-11-18 BE BE172488A patent/BE848498A/en unknown
- 1976-11-18 FR FR7634716A patent/FR2332283A1/en active Granted
Also Published As
Publication number | Publication date |
---|---|
DK516876A (en) | 1977-05-19 |
GB1559883A (en) | 1980-01-30 |
LU76203A1 (en) | 1977-06-06 |
IT1063803B (en) | 1985-02-18 |
BE848498A (en) | 1977-05-18 |
FR2332283A1 (en) | 1977-06-17 |
NL7612608A (en) | 1977-05-23 |
FR2332283B1 (en) | 1980-11-28 |
DE2551598B1 (en) | 1977-04-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE1543471A1 (en) | Process for the production of aldehydes and / or alcohols | |
DE1107665B (en) | Process for the production of olefin-free pure aluminum trialkyls | |
EP0008654A1 (en) | Process for obtaining pure 2-(perfluoroalkyl)-ethanols from their mixtures with 2-(perfluoroalkyl)-ethylenes and optionally 2-(perfluoroalkyl)-ethyl esters | |
DE2612642C2 (en) | Process for the preparation of alkali metal alcoholates free from crystalline alcohol which are soluble in inert solvents or solvent mixtures | |
DE69810931T2 (en) | METHOD FOR PRODUCING RIGHT-CHAIN ALDEHYDES | |
DE2361402C3 (en) | Process for the preparation of polyol esters of carboxylic acids | |
DE2551598C2 (en) | Process for the preparation of alkanephosphonic acid esters | |
CH622524A5 (en) | Process for the preparation of alkanephosphonic esters | |
EP0728176B1 (en) | Method of producing lower-alkyl esters of fatty acids | |
DE1902444C3 (en) | Process for the preparation of tertiary phosphine oxides | |
DE2851515A1 (en) | METHOD FOR DEGRADING ACID ESTERS | |
DE2127821C3 (en) | Process for the production of acyloxyalkanephosphonic acid diesters or acyloxyalkanephosphinic acid esters | |
DE2513838C2 (en) | Process for the preparation of polyol ester mixtures | |
DE2937840C2 (en) | Process for the production of diols, triols or tetrols by hydroxylation of aliphatic mono- or diolefins | |
DE2737633C2 (en) | Process for the production of aldehydes | |
EP1047658A1 (en) | Method for producing alkoxylated dimer fatty acids | |
DE1963014B2 (en) | Process for the preparation of alkane phosphonic acid diesters | |
DE2527650C3 (en) | Process for the preparation of phenylthiophosphonyl dichloride | |
EP0511982B1 (en) | Saturated, branched fatty acids with 21 to 28 carbon atoms or esters of the same with c1-c36 alkanols, process for producing them and their use | |
DE2447770A1 (en) | PROCESS FOR THE POLYMERIZATION OF UNSATATURATED FATTY ACIDS AND THEIR DERIVATIVES | |
DE681078C (en) | Process for the production of mercaptans and organic sulfides | |
DE1064941B (en) | Process for the preparation of mixtures of saturated aliphatic or cycloaliphatic monocarboxylic acid alkyl esters | |
DE4445825C2 (en) | Monoalkylphosphine and method of making the same | |
DE3011687C2 (en) | Process for the separation of a cobalt component from a reaction mixture of a hydroesterification | |
DE1793209A1 (en) | Branched chain aliphatic esters and processes for their preparation |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PL | Patent ceased |