DE1159935B - Process for the production of Arylthiolphosphorsäuredichloriden - Google Patents
Process for the production of ArylthiolphosphorsäuredichloridenInfo
- Publication number
- DE1159935B DE1159935B DEF35915A DEF0035915A DE1159935B DE 1159935 B DE1159935 B DE 1159935B DE F35915 A DEF35915 A DE F35915A DE F0035915 A DEF0035915 A DE F0035915A DE 1159935 B DE1159935 B DE 1159935B
- Authority
- DE
- Germany
- Prior art keywords
- acid
- production
- dichloride
- arylthiolphosphorsäuredichloriden
- acid dichloride
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- WVTOJNFZIVWNIY-UHFFFAOYSA-N (4-chlorophenyl) thiohypochlorite Chemical compound ClSC1=CC=C(Cl)C=C1 WVTOJNFZIVWNIY-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- -1 pentachlorophenyl Chemical group 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- YVDBISQMWKWRBX-UHFFFAOYSA-N (2,3,4,5,6-pentachlorophenyl) thiohypochlorite Chemical compound ClSC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl YVDBISQMWKWRBX-UHFFFAOYSA-N 0.000 description 1
- GOFWOVUVYQPHFC-UHFFFAOYSA-N 3,3-dimethylbutan-2-yl dihydrogen phosphite Chemical compound CC(C)(C)C(C)OP(O)O GOFWOVUVYQPHFC-UHFFFAOYSA-N 0.000 description 1
- GFMYEVPBEJFZHH-UHFFFAOYSA-N CP(O)(O)O Chemical compound CP(O)(O)O GFMYEVPBEJFZHH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- DGVNWNYQSOYWKZ-UHFFFAOYSA-N methyl dihydrogen phosphite Chemical compound COP(O)O DGVNWNYQSOYWKZ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000003107 substituted aryl group Chemical group 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
- C07F9/20—Esters of thiophosphoric acids containing P-halide groups
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
Verfahren zur Herstellung von Arylthiolphosphorsäurediehloriden Die Herstellung von Arylthiolphosphorsäuredichloriden der allgemeinen Formel in welcher Ar für einen beliebig substituierten Arylrest steht, ist aus der Literatur bekannt. Man erhält diese Verbindungsklasse aber in sehr schlechten Ausbeuten durch langes Erwärmen von Phosphoroxychlorid mit Thiophenolen. Da die obigen Arylthiolphosphorsäuredichloride wichtige Zwischenprodukte zur Herstellung von Schädlingsbekämpfungsmitteln sind, ist ein technisch leicht ausführbares Verfahren zu ihrer Herstellung von vordringlichem Interesse.Process for the preparation of arylthiolphosphoric acid dichlorides The preparation of arylthiolphosphoric acid dichlorides of the general formula in which Ar stands for any substituted aryl radical is known from the literature. However, this class of compounds is obtained in very poor yields by prolonged heating of phosphorus oxychloride with thiophenols. Since the above arylthiolphosphoric acid dichlorides are important intermediate products for the production of pesticides, a technically easily feasible process for their production is of primary interest.
Es wurde gefunden, daß überraschenderweise die leicht herstellbaren Alkylphosphorigsäuredichloride mit Arylsulfensäurechloriden reagieren, wobei sich zunächst ein Trichlorid vom Typ I bildet: Ar hat die oben angegebene Bedeutung, und RO ist der Rest eines beliebigen Alkohols.It has been found that, surprisingly, the easily prepared alkylphosphorous acid dichlorides react with arylsulfenic acid chlorides, initially forming a type I trichloride: Ar has the meaning given above and RO is the remainder of any alcohol.
Diese Verbindungen der Formel 1 sind aber nicht beständig. Unter Entwicklung eines Mols Alkylchlorid zerfällt I spontan in das gewünschte Arylthiophosphorsäuredichlorid (II): Diese Reaktion ist in ihrem Verlauf überraschend und konnte nicht vorausgesehen werden.However, these compounds of formula 1 are not stable. I decompose spontaneously into the desired arylthiophosphoric acid dichloride (II) with development of one mole of alkyl chloride: This reaction is surprising in its course and could not be foreseen.
Vorteilhaft läßt man die geschilderte Reaktion bei tiefer Temperatur (0 bis +30"C) und in Gegenwart geeigneter Lösemittel ablaufen. The reaction described is advantageously left at low temperature (0 to +30 "C) and in the presence of suitable solvents.
Die folgenden Beispiele geben einen Überblick über das erfindungsgemäße Verfahren. The following examples give an overview of that according to the invention Procedure.
Beispiel 1 179 g (1 Mol) 4-Chlorphenylsulfensäurechlorid werden in 100 ccm Benzol gelöst. Diese Lösung tropft man unter Rühren bei 0°C zu 133 g O-Methylphosphorigsäuredichlorid, gelöst in 500 ccm Benzol.example 1 179 g (1 mol) of 4-chlorophenylsulfenic acid chloride are dissolved in 100 cc of benzene. This solution is added dropwise with stirring at 0 ° C. to 133 g of O-methylphosphorous acid dichloride, dissolved in 500 cc of benzene.
Nach dem Abklingen der stark exothermen Reaktion wird fraktioniert. Man erhält 160 g S-(p-Chlorphenyl) - thiolphosphorsäuredichlorid vom Kp.s = C. Beim längeren Stehen erstarrt das Dichlorid kristallin und zeigt dann einen Schmelzpunkt von 66"C. Ausbeute: 610/0 der Theorie.After the strongly exothermic reaction has subsided, it is fractionated. 160 g of S- (p-chlorophenyl) thiolphosphoric acid dichloride with a boiling point of C. Standing for a longer period of time, the dichloride solidifies in crystalline form and then shows a melting point of 66 "C. Yield: 610/0 of theory.
Beispiel 2 102 g (0,5 Mol) O-Pinacolylphosphorigsäuredichlorid (Kp.3 = 52"C) werden in einem Rührkolben vorgelegt. Dann tropft man unter gutem Rühren bei 0 bis 10"C 90 g 4-Chlorphenylsulfensäurechlorid hinzu. Nach dem Abklingen der stark exothermen Reaktion wird fraktioniert. Man erhält 80 g S-(4-Chlorphenyl-thiolphosphorsäuredichlorid vom Kp.2 = 142°C. F. = 63°C. Ausbeute: 610/0 der Theorie.Example 2 102 g (0.5 mol) of O-pinacolylphosphorous acid dichloride (boiling point 3 = 52 "C) are placed in a stirred flask. 90 g of 4-chlorophenylsulfenic acid chloride are then added dropwise with thorough stirring at 0 to 10" C. After the strongly exothermic reaction has subsided, it is fractionated. 80 g of S- (4-chlorophenyl-thiolphosphoric acid dichloride with a boiling point of 142 ° CF = 63 ° C.) are obtained. Yield: 610/0 of theory.
Beispiel 3 80 g (0,25 Mol) Pentachlorphenylsulfensäurechlorid (F. = 99 bis 100°C) werden in 100 ccm Benzol gelöst. Unter gutem Rühren tropft man zu dieser Lösung bei 20 bis 30°C 38 g SMethylphosphorigsäuredichlorid. Nach dem Abklingen der Reaktion läßt man noch 1 Stunde bei Zimmertemperatur weiterrühren. Beim Abdestillieren des Lösemittels im Vakuum bleibt das S-(Pentachlorphenyl)-thiolphosphorsäuredichloridkristallin zurück.Example 3 80 g (0.25 mol) of pentachlorophenylsulfenic acid chloride (melting point = 99 to 100 ° C.) are dissolved in 100 cc of benzene. 38 g of methylphosphorous acid dichloride are added dropwise to this solution at 20.degree. To 30.degree. C. with thorough stirring. After the reaction has subsided, stirring is continued for a further hour at room temperature. When the solvent is distilled off in vacuo, the S- (pentachlorophenyl) -thiolphosphoric acid dichloride crystalline remains.
Man erhält 51 g des Dichlorids, entsprechend einer Ausbeute von 51 0/o der Theorie. Aus Petroläther umkristallisiert zeigt das S-(Pentachlorphenyl)-thiolphosphorsäuredichlorid einen Schmelzpunkt von 98°C. Beispiel 4 139 g (0,5 Mol) O-(1,1-Dimethyl-3,3,3-trichlorpropyl)-phosphorigsäuredichlorid (Kp.3 = 92° C) werden in 100 com Methylenchlorid gelöst. Unter Rühren tropft man bei 20 bis 30°C 90g 4-Chlorphenylsulfensäurechlorid hinzu. Man läßt noch 1 Stunde rühren und fraktioniert dann. Es werden auf diese Weise 97 gS-(p-Chlorphenyl)-thiolphosphorsäuredichlorid vom F. = 63 bis 650 C erhalten.51 g of the dichloride are obtained, corresponding to a yield of 51% of theory. Recrystallized from petroleum ether, the S- (pentachlorophenyl) -thiolphosphoric acid dichloride has a melting point of 98 ° C. Example 4 139 g (0.5 mol) of O- (1,1-dimethyl-3,3,3-trichloropropyl) -phosphorous acid dichloride (boiling point 3 = 92 ° C.) are dissolved in 100 com of methylene chloride. 90 g of 4-chlorophenylsulfenic acid chloride are added dropwise at 20 ° to 30 ° C. with stirring. The mixture is left to stir for 1 hour and then fractionated. In this way, 97 g of S- (p-chlorophenyl) thiolphosphoric acid dichloride with a melting point of 63 to 650 ° C. are obtained.
Ausbeute: 74% der Theorie.Yield: 74% of theory.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF35915A DE1159935B (en) | 1962-02-03 | 1962-02-03 | Process for the production of Arylthiolphosphorsäuredichloriden |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF35915A DE1159935B (en) | 1962-02-03 | 1962-02-03 | Process for the production of Arylthiolphosphorsäuredichloriden |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1159935B true DE1159935B (en) | 1963-12-27 |
Family
ID=7096222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF35915A Pending DE1159935B (en) | 1962-02-03 | 1962-02-03 | Process for the production of Arylthiolphosphorsäuredichloriden |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1159935B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4290978A (en) * | 1979-04-19 | 1981-09-22 | Nihon Tokushu Noyasu Seizo K.K. | Production of phosphoro chloride thiolates |
-
1962
- 1962-02-03 DE DEF35915A patent/DE1159935B/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4290978A (en) * | 1979-04-19 | 1981-09-22 | Nihon Tokushu Noyasu Seizo K.K. | Production of phosphoro chloride thiolates |
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