DE2222578C3 - Process for the preparation of O1O-dialkyl-O-phenylthionophosphoric acid esters - Google Patents
Process for the preparation of O1O-dialkyl-O-phenylthionophosphoric acid estersInfo
- Publication number
- DE2222578C3 DE2222578C3 DE19722222578 DE2222578A DE2222578C3 DE 2222578 C3 DE2222578 C3 DE 2222578C3 DE 19722222578 DE19722222578 DE 19722222578 DE 2222578 A DE2222578 A DE 2222578A DE 2222578 C3 DE2222578 C3 DE 2222578C3
- Authority
- DE
- Germany
- Prior art keywords
- formula
- group
- compounds
- radical
- carbon atoms
- 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
Links
- 150000002148 esters Chemical class 0.000 title claims description 9
- 239000002253 acid Substances 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 6
- 239000000460 chlorine Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- YDOLGQNXROBHNZ-UHFFFAOYSA-N hydroxy-diphenoxy-sulfanylidene-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1OP(=S)(O)OC1=CC=CC=C1 YDOLGQNXROBHNZ-UHFFFAOYSA-N 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000000575 pesticide Substances 0.000 claims 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims 1
- 230000000895 acaricidal effect Effects 0.000 claims 1
- 239000000642 acaricide Substances 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 239000002917 insecticide Substances 0.000 claims 1
- 239000000543 intermediate Substances 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000012230 colorless oil Substances 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007858 starting material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- OJZGWRZUOHSWMB-UHFFFAOYSA-N ethoxy-dihydroxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCOP(O)(O)=S OJZGWRZUOHSWMB-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- -1 triethylamine Chemical class 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
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/18—Esters of thiophosphoric acids with hydroxyaryl compounds
-
- 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
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4084—Esters with hydroxyaryl compounds
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
R1O-PSR 1 O-PS
— O- O
(V)(V)
mit einem Alkohol der Formelwith an alcohol of the formula
R1OH (VI)R 1 OH (VI)
in Gegenwart von starken Basen umesterttransesterified in the presence of strong bases
Die Erfindung betrifft ein Verfahren zur Herstellung von Verbindungen der FormelThe invention relates to a method of manufacture of compounds of the formula
RiORiO
R2OR 2 O
in derin the
Ri einen Alkylrest mit 1 bis 12 Kohlenstoffatomen, der durch Sauerstoff unterbrochen oder durch die COOR-Gruppe (mit R gleich niederes Alkyl) substituiert sein kann, oder einen Alkenylrest mit 3 bis 12 Kohlenstoffatomen bedeutet,Ri is an alkyl radical having 1 to 12 carbon atoms, the interrupted by oxygen or by the COOR group (with R being lower alkyl) can be substituted, or denotes an alkenyl radical having 3 to 12 carbon atoms,
X, Y und Z, die gleich oder verschieden sein können, für Wasserstoff, Chlor, Brom, Jod, eine niedere Alkyl- oder die Nitrogruppe stehen und in der Z außerdem für die Nitril-, die Acetylgruppe oder die Gruppe -S(O)nRj stehen kann, in der R3 einen niederen Alkylrest und η0,1 oder 2 bedeutet.X, Y and Z, which can be the same or different, stand for hydrogen, chlorine, bromine, iodine, a lower alkyl or the nitro group and in which Z also stands for the nitrile, the acetyl group or the group -S (O) n Rj can be in which R3 is a lower alkyl radical and η is 0, 1 or 2.
RO SRO S
\y\ y
R"OR "O
ClCl
(R' und R" = gleiche oder verschiedene Alkylreste) mit einem Phenol und einem säurebindenden Mittel zur Reaktion gebracht(R 'and R "= identical or different alkyl radicals) with a phenol and an acid-binding agent for Brought reaction
Der Nachteil dieses Verfahrens ist daß die in technischem Maßstab zum Teil schwer zugänglichen Säurechloride der Formel II als Ausgangsstoffe benötigt werdea Bei der Herstellung dieser Verbindungen — insbesondere, wenn R' und R" verschieden sind — ist die Ausbeute schlecht Die technischen Produkte fallen in mangelhafter Reinheit an und sind, besonders für R' oder R" gleich Methyl, thermisch labil. Als Nebenprodukt bildet sich immer ein störender Anteil von Thiophosphorsäuretrialkylester, während ein Teil des Ausgangsmaterials unverändert bleibt Die Auftrennung der so entstehenden Gemische ist schwierig und mit erheblichen Verlusten verbunden. Die schlechte Zugänglichkeit der Ausgangsstoffe der Formel II dürfte der Grund dafür sein, daß bisher noch keine 0,0-Dialkyl-O-phenylthionophosphorsäureester mit verschiedenen Alkylgruppen in den Handel gekommen sind, obwohl ihre gute Wirksamkeit erUnnt istThe disadvantage of this process is that it is difficult to access on an industrial scale Acid chlorides of the formula II are required as starting materials a In the production of these compounds - especially if R 'and R "are different - the yield is poor. The technical products fall in poor purity and are, especially when R 'or R "is methyl, thermally labile. As a by-product always forms a troublesome proportion of thiophosphoric acid trialkyl ester, while part of the The starting material remains unchanged. The separation of the resulting mixtures is difficult and with associated significant losses. The poor accessibility of the starting materials of the formula II is likely be the reason that so far no 0,0-dialkyl-O-phenylthionophosphoric acid ester with various alkyl groups have come onto the market, although their effectiveness has been recognized
Wie nun gefunden wurde, erhält man die Verbindungen der Formel I in guter Ausbeute und hoher Reinheit, indem man ei.i Thionophosphorsäuredichlorid der FormelAs has now been found, the compounds of the formula I are obtained in good yield and high purity, by ei.i thionophosphoric acid dichloride of the formula
R1O-PSCI2 (ID)R 1 O-PSCI 2 (ID)
zunächst mit einem Phenol bzw. Phenolat der Formelfirst with a phenol or phenolate of the formula
M-OM-O
(IV)(IV)
umsetzt, worin M Wasserstoff oder ein Äquivalent eines Kations, vorzugsweise eines Alkalikations, bedeutet,converts, in which M is hydrogen or an equivalent of a cation, preferably an alkali cation,
und indem man dann die erhaltenen ThJonophosphorsäurediphenylester der Formeland then by using the diphenyl thionophosphorate obtained the formula
R1O-PSR 1 O-PS
—O-O
mit dem Alkohol der Formel
R2OHwith the alcohol of the formula
R 2 OH
(V)(V)
(VD(VD
1010
1515th
in Gegenwart von starken Basen umesterttransesterified in the presence of strong bases
Dabei wird dann die eine Phenoxygruppe durch den Rest R2O ersetzt Als Katalysator dienen vorzugsweise die Alkalialkoholate des betreffenden Alkohols R2OH, gelöst in diesem Alkohol, sowie Lösungen von Alkalihydroxiden Ln Wasser oder in dem Alkohol R2OH. Auch starke organische Basen, etwa Triäthylamin, katalysieren die Umesterung. Das Alkalialkoholat oder Alkalihydroxid wird in molarer Menge eingesetzt Überraschenderweise führt die Umesterung zum Austausch nur einer Phenoxygruppe gegen eine R2O-GmPPe, selbst wenn der Alkohol R2OH in großem Überschuß zugegen ist Die Umesterung kann sowohl in der Warme als auch in der Kälte erfolgen. Vorzugsweise arbeitet man bei Temperaturen unterhalb Raumtemperatur. Selbst bei - 1O0C ist die Umesterung in etwa 2 bis 4 Stunden beendet Dem Reaktionsgemisch kann gewünschtenfaUs ein inertes organisches Lösungsmittel, beispielsweise Benzol, Toluol, tin Ätht., ein Keton oder ein Halogenkohlenwasserstoff zugesetzt werden.One phenoxy group is then replaced by the radical R 2 O. The catalyst used is preferably the alkali metal alcoholates of the alcohol in question R 2 OH, dissolved in this alcohol, and solutions of alkali metal hydroxides Ln water or in the alcohol R 2 OH. Strong organic bases, such as triethylamine, also catalyze the transesterification. The alkali alcoholate or alkali hydroxide is used in molar amounts. Surprisingly, the transesterification leads to the exchange of only one phenoxy group for one R 2 O-GmPPe, even if the alcohol R 2 OH is present in large excess. The transesterification can take place both in the warm and in the cold take place. It is preferred to work at temperatures below room temperature. Even at - 1O 0 C, the transesterification is approximately 2 to 4 hours completed the reaction mixture may gewünschtenfaUs an inert organic solvent, for example benzene, toluene, tin Ätht, a ketone or a halogenated hydrocarbon may be added..
Im einzelnen verfährt man im allge leinen so, daß man die Ausgangsverbindung der Formel V in dem zur Alkohoty.se vorgesehenen Alkohol, gewünschtenfaUs unter Zugabe eines weiteren Lösungsmittels, löst und unter Rühren bei Raumtemperatur oder tieferer Temperatur die molare Menge Alkalialkoholat in dem betreffenden Alkohol oder Alkalihydroxid in dem Alkohol oder in Wasser zutropftIn detail one proceeds in general linen so that the starting compound of formula V in the for Alkohoty.se provided alcohol, if desired with the addition of another solvent, dissolves and with stirring at room temperature or lower temperature, the molar amount of alkali metal alcoholate in the relevant alcohol or alkali hydroxide in the alcohol or in water is added dropwise
Der Fortgang der Reaktion kann dünnschichtchromatographisch (auf Kieselgelplatten mit Leuchtstoff, Laufmittel Toluol + n-Heptan + Chloroform 2:2:1) und durch Titration der nicht verbrauchten Alkalimenge verfolgt werden. Nach Beendigung der Reaktion wird schwach angesäuert und im Vakuum eingedampft Der Rückstand wird in einem geeigneten Lösungsmittel aufgenommen und das abgespaltene Phenol durch Ausschütteln mit Natronlauge abgetrennt und zurückgewonnen. Der aus der organischen Lösung isolierte Ester wird je nach seinen Eigenschaften durch Umkristallisieren oder durch Destillation gereinigt Das Ausgangsmateria! III der Synthese wird nach bekannten Verfahren (Kosolapoff, Organophosphorus Compounds, 2. Auflage, London 1958, Seite 241/242) hergestelltThe progress of the reaction can be monitored by thin-layer chromatography (on silica gel plates with fluorescent material, solvent toluene + n-heptane + chloroform 2: 2: 1) and tracked by titration of the unused amount of alkali. After the reaction is finished weakly acidified and evaporated in vacuo. The residue is dissolved in a suitable solvent added and the split off phenol separated by shaking with sodium hydroxide solution and recovered. The ester isolated from the organic solution is, depending on its properties, through Recrystallize or purified by distillation The starting material! III the synthesis is known according to Process (Kosolapoff, Organophosphorus Compounds, 2nd edition, London 1958, page 241/242) manufactured
Thiophosphorsäure-0-äthyl-O-raethyl-O-(4-brom-2^-dichlorphenyI)-ester Thiophosphoric acid 0-ethyl-O-raethyl-O- (4-bromo-2 ^ -dichlorophenyI) ester
a)Thionophosphorsäure-0-äthyl-0,0-di-(4-brom-2i5-dichlorphenyl)-ester a) Thionophosphoric acid 0-ethyl-0,0-di- (4-bromo-2i5-dichlorophenyl) ester
Zu einer Lösung von 36 g Thiophosphorsäure-O-äthylester-dichlorid (0,2 Mol) und 102 g 4-Brom-2£-dichlorphenol (0,42 Mol) in 100 ml Äthylenchlorid tropft man unter Rühren bei 20 bis 300C eine Lösung von 17 g Ätznatron (0,42 MoI) in 40 ml Wasser. Der Ansatz wird zunächst 30 Minuten bei 20 bis 30° C und dann noch eine Stunde bei 70 bis 8O0C nachgerührt Dann läßt man abkühlen, trennt die organische Lösung ab und schüttelt sie mit 1 η Natronlauge und Wasser aus. Nach dem Trocknen und Einengen der Lösung erhält man 108 g (91% dTh.) eines farblosen, öligen Rückstandes, der beim Stehen erstarrt Nach Umkristallisieren aus Benzin schmilzt das Produkt bei 59 bis 62° C.To a solution of 36 g thiophosphoric acid O-ethyl ester dichloride (0.2 mol) and 102 g of 4-bromo-2 £ -dichlorphenol (0.42 mol) in 100 ml of ethylene chloride is added dropwise with stirring at 20 to 30 0 C. a solution of 17 g of caustic soda (0.42 mol) in 40 ml of water. The mixture is then allowed first for 30 minutes at 20 to 30 ° C and then for another hour at 70 to 8O 0 C. for a further cooling, the organic solution is separated off and shakes them with 1 η sodium hydroxide solution and water. After drying and concentrating the solution, 108 g (91% of theory) of a colorless, oily residue which solidifies on standing are obtained. After recrystallization from gasoline, the product melts at 59 to 62 ° C.
b)Thiophosphorsäure-0-äthyl-0-methyl-0-(4-brom-2£-dichlorphenyl)-ester b) Thiophosphoric acid 0-ethyl-0-methyl-0- (4-bromo-2 £ -dichlorophenyl) ester
96 g Thiophosphorsäure-0-äthyI-0,0-di-(4-brom-2,5-dichlorphenyQ-ester
(0,162 MoI) werden in 200 ml Äthylenchlorid gelöst Bei 00C wird unter Rühren eine
Lösung von 4,1g Natrium in 100 ml Methanol eingetropft Man läßt den Ansatz 1 Stunde bei 00C
nachrühren und gießt ihn dann auf 1 Ltr. Eiswasser, das mit 25 ml konzentrierter Salzsäure angesäuert worden
ist Nach gutem Durchmischen wird itte organische
Schicht abgetrennt und mit 250 ml 1 η Natronlauge und Wasser ausgeschüttelt getrocknet und eingeengt Man
erhält 61 g (99% Rohausbeute) eines öligen Rückstandes, der durch Destillation gereinigt wird. Bei 150 bis
152°C/0,01 Torr destillieren 49 g (80%) des Produkts als
farbloses Ol über; n?: 1.5674.
Analyse:96 g of thiophosphoric acid-0-äthyI-0,0-di- (4-bromo-2,5-dichlorphenyQ ester (0.162 MoI) are dissolved in 200 ml of ethylene chloride at 0 0 C is added a solution of 4.1 g of sodium in 100 ml of methanol is added dropwise the mixture is allowed 1 hour at 0 0 C stirred and then poured over 1 l. of ice water, which was acidified with 25 ml concentrated hydrochloric acid After thorough mixing itte organic layer is separated and washed with 250 ml 1 η sodium hydroxide and water, extracted, dried and concentrated. 61 g (99% crude yield) of an oily residue, which is purified by distillation, are obtained. n?: 1.5674.
Analysis:
gef.: Gesamthalogen: 39,4%, P 8,04%.found: total halogen: 39.4%, P 8.04%.
Entsprechend dem vorstehenden Beispiel werden auch folgende Verbindungen hergestellt:According to the example above, the following connections are also made:
SCH3 SCH 3
Kp001: 150-160 C farbloses Öl
<: 1,5804Bp 001 : 150-160 C colorless oil
<: 1.5804
Cl ber.: 20,5% gef.: 22,6%
P ber.: 8,9% gef.: 8,7%Cl ber .: 20.5% found: 22.6%
P calc .: 8.9% found: 8.7%
farbloses Öl, <: 1,5580colorless oil, <: 1.5580
Cl ber.: 31,6% gef.: 30,7%Cl ber .: 31.6% found: 30.7%
P ber.: 9,22% gef.: 8,9%P calc .: 9.22% found: 8.9%
1Cl
1
\ J : 4 Hj0 s
\ J
ber.:found:
ber .:
CHjO O —/ \
CHjO O -
7,57%,35.0%,
7.57%,
C2HjOC 2 HjO
farbloses Öl, n$: 1,5432 Cl ber.: 23,6% gef.: 24,0%colorless oil, n $: 1.5432 Cl calc .: 23.6% found: 24.0%
C2H5O SC 2 H 5 OS
\y\ y
CH3O 0CH 3 O 0
ClCl
ClCl
farbloses Öl, n%: 1,>ί38 Cl ber.: 23,6% gef.: 22,5%colorless oil, n%: 1,> ί38 Cl calc .: 23.6% found: 22.5%
farbloses Öl, <: 1,5581 Halogen ber.: 38,2% gef.: 38,5%colorless oil, <: 1.5581 halogen calc .: 38.2% found: 38.5%
C2H5OOCCH2O SC 2 H 5 OOCCH 2 OS
farbloses Ölcolorless oil
Cl ber.: 17,5% gef.: 16,9%Cl ber .: 17.5% found: 16.9%
C2H5OC2H4O SC 2 H 5 OC 2 H 4 OS
SCH3 Cl 'Der.: 18,2% gef.: 17,5%SCH 3 Cl 'Der .: 18.2% found: 17.5%
CjH5Q-C3H4O §CjH 5 QC 3 H 4 O §
farbloses Öl, »*: 1,5568colorless oil, »*: 1.5568
Claims (1)
s Der Rest Ri enthält bevorzugt 1 bis 8, vor allem 1 bis 4, Kohlenstoffatome.Those compounds of the formula I in which Rt and Rj are different should be emphasized. These compounds can only be prepared in moderate yields by the methods known up to now,
s The radical Ri preferably contains 1 to 8, especially 1 to 4, carbon atoms.
Priority Applications (14)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19722222578 DE2222578C3 (en) | 1972-05-09 | 1972-05-09 | Process for the preparation of O1O-dialkyl-O-phenylthionophosphoric acid esters |
| AT73573A AT321943B (en) | 1972-02-07 | 1973-01-29 | Process for the preparation of thionophosphorus or thionophosphonic acid esters |
| IT48083/73A IT977220B (en) | 1972-02-07 | 1973-02-06 | PROCEDURE FOR THE PRODUCTION OF THYONOPHORIC AND THIOPHOSPHONIC ACID ESTERS |
| NL7301632A NL7301632A (en) | 1972-02-07 | 1973-02-06 | |
| JP1509373A JPS5652913B2 (en) | 1972-02-07 | 1973-02-06 | |
| CH165773A CH576990A5 (en) | 1972-02-07 | 1973-02-06 | |
| CA163,046A CA1011754A (en) | 1972-02-07 | 1973-02-06 | Process for production of thionophosphorates and thionophosphonates |
| IL41470A IL41470A (en) | 1972-02-07 | 1973-02-06 | The production of thionophosphoric and thionophosphonic acid esters |
| BE795039D BE795039A (en) | 1972-02-07 | 1973-02-06 | METHOD FOR MANUFACTURING ESTERS OF THIONOPHOSPHORIC AND THIONOPHOSPHONIC ACIDS |
| FR7304355A FR2177738B1 (en) | 1972-02-07 | 1973-02-07 | |
| GB607073A GB1400903A (en) | 1972-02-07 | 1973-02-07 | Process for the preparation of sulphur-containing phosphorus esters |
| BE134047A BE803000R (en) | 1972-02-07 | 1973-07-30 | Thiophosphoric - and thiophosphonic esters - by transesterification using a weak base as catalyst |
| US385065A US3896192A (en) | 1972-02-07 | 1973-08-02 | Process for the preparation of thionophosphoric and thionophosphonic acid esters |
| FR7328513A FR2239475A2 (en) | 1972-02-07 | 1973-08-03 | Thiophosphoric - and thiophosphonic esters - by transesterification using a weak base as catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19722222578 DE2222578C3 (en) | 1972-05-09 | 1972-05-09 | Process for the preparation of O1O-dialkyl-O-phenylthionophosphoric acid esters |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE2222578A1 DE2222578A1 (en) | 1973-11-22 |
| DE2222578B2 DE2222578B2 (en) | 1980-06-19 |
| DE2222578C3 true DE2222578C3 (en) | 1981-02-26 |
Family
ID=5844412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19722222578 Expired DE2222578C3 (en) | 1972-02-07 | 1972-05-09 | Process for the preparation of O1O-dialkyl-O-phenylthionophosphoric acid esters |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE2222578C3 (en) |
-
1972
- 1972-05-09 DE DE19722222578 patent/DE2222578C3/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2222578A1 (en) | 1973-11-22 |
| DE2222578B2 (en) | 1980-06-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| OD | Request for examination | ||
| C3 | Grant after two publication steps (3rd publication) | ||
| 8339 | Ceased/non-payment of the annual fee |