DE1129959B - Process for the preparation of nucleus-substituted phosphorus (on, in-) acidic phenyl esters or the corresponding thiono compounds - Google Patents
Process for the preparation of nucleus-substituted phosphorus (on, in-) acidic phenyl esters or the corresponding thiono compoundsInfo
- Publication number
- DE1129959B DE1129959B DEF30862A DEF0030862A DE1129959B DE 1129959 B DE1129959 B DE 1129959B DE F30862 A DEF30862 A DE F30862A DE F0030862 A DEF0030862 A DE F0030862A DE 1129959 B DE1129959 B DE 1129959B
- Authority
- DE
- Germany
- Prior art keywords
- nucleus
- phenyl
- preparation
- phenyl esters
- compounds
- 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 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title claims description 7
- 150000001875 compounds Chemical class 0.000 title claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 title claims description 5
- 239000011574 phosphorus Substances 0.000 title claims description 5
- 150000003017 phosphorus Chemical class 0.000 title claims description 3
- 230000002378 acidificating effect Effects 0.000 title 1
- 239000000460 chlorine Substances 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- -1 methyl mercapto-phenyl-phosphorus Chemical compound 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 238000005660 chlorination reaction Methods 0.000 description 5
- 235000019256 formaldehyde Nutrition 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical group 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- YCWBNIVSNFOFBQ-UHFFFAOYSA-N trichloro(trichloromethylsulfanyl)methane Chemical class ClC(Cl)(Cl)SC(Cl)(Cl)Cl YCWBNIVSNFOFBQ-UHFFFAOYSA-N 0.000 description 1
- PXIIUHJVQVAEEM-UHFFFAOYSA-N trichloromethylsulfanylbenzene Chemical compound ClC(Cl)(Cl)SC1=CC=CC=C1 PXIIUHJVQVAEEM-UHFFFAOYSA-N 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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3282—Esters 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric 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
- C07F9/06—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)
Description
Verfahren zur Herstellung von kernsubstituierten Phosphor- (on-, in-) säurephenylestern bzw. den entsprechenden Thionoverbindungen Aus der belgischen Patentschrift 556 009 sind Methylmercapto-phenyl-phosphorsäureester bekannt. Process for the production of nuclear-substituted phosphorus (on-, in) acid phenyl esters or the corresponding thiono compounds From the Belgian Patent 556 009 discloses methyl mercapto-phenyl-phosphoric acid esters.
Nach dem belgischen Patent 579 006 sind Methylmercapto-phenyl-phosphorsäureester zugänglich, die im Phenylkern weiter durch eine CH3-Gruppe substituiert sind.According to Belgian patent 579 006, methyl mercapto-phenyl-phosphoric acid esters are used accessible, which are further substituted by a CH3 group in the phenyl nucleus.
Es wurde nun gefunden, daß die Chlorierung der genannten Methylmercapto-phenyl-phosphorsäureester zu den hisher noch nicht beschriebenen Trichlormethylmercaptophenyl-phosphorsäureestern führt : [R und R'stehen für Reste, die zusammen mit dem verbleibenden Molekülrest ein Derivat einer Phosphor-(on-, in-) säure bilden. Auch in den folgenden Formeln sei die Bedeutung dieser Reste dieselbe, wenn nicht ausdrücklich etwas anderes festgestellt wird.] Diese Reaktion ist in ihrem einheitlichen Verlauf überraschend und konnte nicht vorausgesehen werden.It has now been found that the chlorination of the methyl mercapto-phenyl-phosphoric acid esters mentioned leads to the trichloromethyl mercaptophenyl-phosphoric acid esters not yet described: [R and R 'stand for radicals which, together with the remainder of the molecule, form a derivative of a phosphoric (on, in) acid. The meaning of these radicals is also the same in the following formulas, unless expressly stated otherwise.] This reaction is surprising in its uniform course and could not be foreseen.
Derselben Chlorierungsreaktionmgänglich sind nicht nur Methylmercapto-phenyl-phosphorsäureester, sondern auch die entsprechenden Methylmercapto-phenylthionophosphorsäureester. Bei schonender Chlorierung (Temperatur bei 0 bis +5°C) erhält man auf diese Weise Trichlormethylmercapto-phenyl-thionophosphorsäureester. Es ist erstaunlich, daß unter den gewählten Bedingungen der Thionoschwefel am Phosphor nicht angegriffen wird. The same chlorination reactions are possible not only for methyl mercapto-phenyl-phosphoric acid esters, but also the corresponding methyl-mercapto-phenylthionophosphoric acid esters. With gentle chlorination (temperature from 0 to + 5 ° C.), trichloromethylmercapto-phenyl-thionophosphoric acid ester is obtained in this way. It is astonishing that the thionosulfur on the phosphorus is not attacked under the selected conditions.
Derselben Reaktion können schließlich auch solche Verbindungen unterworfen werden, die im Phenylring durch eine Alkylgruppe substituiert sind. Such compounds can ultimately also undergo the same reaction substituted in the phenyl ring by an alkyl group.
Schließlich können außer Alkylgruppen auch noch weitere Substituenten, wie Halogen-, Nitro-oder Alkoxygruppen, im Phenylrest enthalten sein. Finally, in addition to alkyl groups, other substituents can also be used, such as halogen, nitro or alkoxy groups, may be contained in the phenyl radical.
Nach der genannten Reaktion sind neuartige Stoffklassen zugänglich, die als Zwischenprodukte für Insektizide und als Fungizide Verwendung finden sollen bzw. als solche selbst verwendet werden können. After the mentioned reaction, new classes of substances are accessible, which are to be used as intermediates for insecticides and as fungicides or can be used as such.
Aus der deutschen Patentschrift 895 151 ist bereits ein Verfahren zur Herstellung von Chlormethyl-, insbesondere Trichlormethylsulfiden aromatischer, cycloaliphatischer oder heterocyclischer Verbindungen bekannt. From the German patent specification 895 151 there is already a method for the production of chloromethyl, especially trichloromethyl sulfides of aromatic, cycloaliphatic or heterocyclic compounds known.
So wird in der genannten deutschen Patentschrift die Gewinnung von Trichlormethylphenylsulfid durch Einwirkung von elementarem Chlor auf Methylphenylsulfid im Licht unter Kühlung des Reaktionsgemisches sowie in Gegenwart eines chlorierten Kohlenwasserstoffs (Chloroform) beschrieben. So in the aforementioned German patent, the extraction of Trichloromethylphenylsulphide due to the action of elemental chlorine on methylphenylsulphide in the light with cooling of the reaction mixture and in the presence of a chlorinated one Hydrocarbon (chloroform).
Zwar sind nach den Angaben der deutschen Patentschrift 895 151 auch solche Methylphenylsulfide der vorgenannten Reaktion zugänglich, die im Phenylkern Substituenten wie Halogenatome, Nitro-, Cyanogruppen u. ä. enthalten ; doch wird weder erwähnt, daß sich die Methylgruppe von Methylmercapto-phenylphosphor-(on-, in-) säureestern bzw. der entsprechenden Thionoverbindungen ebenfalls in dieser Weise chlorieren läßt, noch war diese Tatsache dem genannten Schrifttum ohne weiteres zu entnehmen. According to the information in German patent specification 895 151, there are also those methylphenyl sulfides accessible to the aforementioned reaction, those in the phenyl nucleus Contain substituents such as halogen atoms, nitro, cyano groups and the like; but will neither mentions that the methyl group of methylmercapto-phenylphosphor- (on-, in) acid esters or the corresponding thiono compounds also in this Chlorinated wise, nor was this fact obvious to the literature mentioned refer to.
Der glatte Verlauf der Chlorierung der Methylgruppe ist auch insofern überraschend, als durch den Eintritt des (Thio-) Phosphor- (on-, in-) säurerestes in das Methylphenylsulfidmolekiil letzteres zweifellos reaktionsfähiger wird und insbesondere die in Nachbarstellung zum Phosphorsäureesterrest stehenden Wasserstoffatome des Phenylkerns stark aktiviert werden. The smooth course of the chlorination of the methyl group is insofar as well surprisingly than through the entry of the (thio) phosphorus (on, in-) acid residue in the methylphenyl sulfide molecule, the latter is undoubtedly more reactive and in particular those in the vicinity of the phosphoric acid ester residue Hydrogen atoms of the phenyl nucleus are strongly activated.
Man müßte daher erwarten, daß bei dem erfindungsgemäßen Verfahren ein Austausch des zum Phosphorsäureesterrest o-ständigen Wasserstoffs gegen Chlor erfolgt. Um so erstaunlicher ist, daß bei der verfahrensgemäßen Umsetzung nur der Wasserstoff der Methylgruppe durch Chlor ersetzt wird und keine Kernchlorierung eintritt.One would therefore have to expect that in the process according to the invention an exchange of the hydrogen in the o-position to the phosphoric acid ester residue for chlorine he follows. It is all the more astonishing that in the process according to the implementation only the Hydrogen of the methyl group is replaced by chlorine and no nuclear chlorination entry.
Die folgenden Beispiele geben eine Erläuterung des Verfahrens : Beispiel 1 In eine Lösung von 55 g (0, 2 Mol) O, O-Diäthylp-methylmercapto-phenyl-phosphorsäureester in 400ml Tetrachlorkohlenstoff leitet man bei 5°C unter Rühren etwa 85 g Chlor ein, während man das Reaktionsgemisch mit W-Licht bestrahlt. Dann wird noch 1 Stunde bei 20°C nachgerührt und das Lösungsmittel im Vakuum entfernt. Man erhält 67g des neuen Esters. Ausbeute 90 °/0 der Theorie.The following examples provide an explanation of the procedure: Example 1 About 85 g of chlorine are introduced into a solution of 55 g (0.2 mol) of O, O-diethylp-methylmercapto-phenyl-phosphoric acid ester in 400 ml of carbon tetrachloride at 5 ° C. with stirring, while the reaction mixture is irradiated with UV light. The mixture is then stirred for a further 1 hour at 20 ° C. and the solvent is removed in vacuo. 67 g of the new ester are obtained. Yield 90% of theory.
Berechnet für Mol 379, 5.. P 8,16%, S 8,42%, Cl28,0%; gefunden....... P 7, 98 °/0, S 8, 05 Cl 27, 91 Beispiel 2 In eine Lösung von 58 g (0, 2 Mol) O, O-Diäthyl-O-p-methylmercapto-phenyl-thionophosphorsäureester in 300 ml Tetrachlorkohlenstoff leitet man bei 5°C unter Bestrahlung mit UV-Licht überschüssiges Chlor ein und rührt danach noch 30 Minuten bei 0 bis +5°C. Die Lösung wird anschließend filtriert und das Lösungsmittel im Vakuum entfernt. Es hinterbleiben 62 g des neuen Esters. Ausbeute 80% der Theorie.Calculated for Mol 379.5 .. P 8.16%, S 8.42%, Cl28.0%; found ....... P 7.98 ° / 0, S 8.05 Cl 27.91 Example 2 Excess chlorine is passed into a solution of 58 g (0.2 mol) of O, O-diethyl-Op-methylmercapto-phenyl-thionophosphoric acid ester in 300 ml of carbon tetrachloride at 5 ° C. while irradiating with UV light and then stirred for a further 30 minutes at 0 to + 5 ° C. The solution is then filtered and the solvent is removed in vacuo. There remain 62 g of the new ester. Yield 80% of theory.
Berechnet für Mol 395 .. P 7,8%, S 16,4%, Cl 27,0% ; gefunden ...... P 8, 6 S 20, 2%, Cl 31,2%. Calculated for moles 395 .. P 7.8%, S 16.4%, Cl 27.0%; found ...... P 8, 6 S 20, 2%, Cl 31.2%.
Beispiel 3 Aus O, O-Diäthyl-4-methylmercapto-3-chlorphenylphosphorsäureester erhält man, wie in den vorstehenden Beispielen beschrieben, 38 g des neuen Esters, entsprechend einer Ausbeute von 91% der Theorie.Example 3 As described in the preceding examples, 38 g of the new ester are obtained from O, O-diethyl-4-methylmercapto-3-chlorophenylphosphoric acid ester, corresponding to a yield of 91% of theory.
Berechnet für Mol 414.. P 7, 5°/0, S 7, 7%, Cl 34, 4"/. ; gefunden... P 7,7%, S 8,5%, Cl 31,4%. Calculated for mol 414 .. P 7.5 / 0, S 7.7%, Cl 34.4 "/.; Found ... P 7.7%, S 8.5%, Cl 31.4%.
Beispiel 4 Der Ester wird analog den vorstehenden Beispielen aus O, O-Diäthyl-4-methylmercapto-3-chlorphenylthionophosphorsäureester dargestellt. Ausbeute 58 g, entsprechend 81 % der Theorie.Example 4 The ester is prepared analogously to the above examples from O, O-diethyl-4-methylmercapto-3-chlorophenylthionophosphoric acid ester. Yield 58 g, corresponding to 81% of theory.
Berechnet für Mol 430.. P 7, 2 °/o, S 14, 9 %, Cl 33, 0 °/o ; gefunden...... P 8, 1%, S 12, 5%, Cl 34, 7 %. Calculated for moles 430 .. P 7.2%, S 14.9%, Cl 33.0%; found...... P 8.1%, S 12.5%, Cl 34.7%.
Beispiel 5 Wie vorstehend beschrieben, erhält man aus 29 g (0, 1 Mol) O, O-Diäthyl-4-methylmercapto-3-methylphenyl-phosphorsäureester den trichlorierten Ester in einer Ausbeute von 35 g, entsprechend 89% der Theorie.Example 5 As described above, the trichlorinated ester is obtained from 29 g (0.1 mol) of O, O-diethyl-4-methylmercapto-3-methylphenyl-phosphoric acid ester in a yield of 35 g, corresponding to 89% of theory.
Berechnet für Mol 393 .. P 7,9%, S 8,15%, Cl 27,0% ; gefunden.. P 8,7%, S 7,24%, Cl 27,8%. Calculated for moles 393 .. P 7.9%, S 8.15%, Cl 27.0%; found .. P 8.7%, S 7.24%, Cl 27.8%.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF30862A DE1129959B (en) | 1960-03-29 | 1960-03-29 | Process for the preparation of nucleus-substituted phosphorus (on, in-) acidic phenyl esters or the corresponding thiono compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF30862A DE1129959B (en) | 1960-03-29 | 1960-03-29 | Process for the preparation of nucleus-substituted phosphorus (on, in-) acidic phenyl esters or the corresponding thiono compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1129959B true DE1129959B (en) | 1962-05-24 |
Family
ID=7093954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF30862A Pending DE1129959B (en) | 1960-03-29 | 1960-03-29 | Process for the preparation of nucleus-substituted phosphorus (on, in-) acidic phenyl esters or the corresponding thiono compounds |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1129959B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3162672A (en) * | 1961-11-22 | 1964-12-22 | Bayer Ag | Omicron-trifluoromethylmercaptophenyl esters of pentavalent phosphorus acids |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE895151C (en) * | 1951-07-29 | 1953-11-02 | Robert Dr Pfleger | Process for the production of chloromethyl sulfides |
-
1960
- 1960-03-29 DE DEF30862A patent/DE1129959B/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE895151C (en) * | 1951-07-29 | 1953-11-02 | Robert Dr Pfleger | Process for the production of chloromethyl sulfides |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3162672A (en) * | 1961-11-22 | 1964-12-22 | Bayer Ag | Omicron-trifluoromethylmercaptophenyl esters of pentavalent phosphorus acids |
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