DE1197883B - Process for the production of phosphonic acid esters - Google Patents
Process for the production of phosphonic acid estersInfo
- Publication number
- DE1197883B DE1197883B DEF41825A DEF0041825A DE1197883B DE 1197883 B DE1197883 B DE 1197883B DE F41825 A DEF41825 A DE F41825A DE F0041825 A DEF0041825 A DE F0041825A DE 1197883 B DE1197883 B DE 1197883B
- Authority
- DE
- Germany
- Prior art keywords
- phosphonic acid
- acid esters
- general formula
- production
- alkenyl
- 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 12
- 150000003008 phosphonic acid esters Chemical class 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title description 3
- -1 Alkenyl radicals Chemical class 0.000 claims description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- RMRFFCXPLWYOOY-UHFFFAOYSA-N allyl radical Chemical compound [CH2]C=C RMRFFCXPLWYOOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- AVTAIKNWAIKGEV-UHFFFAOYSA-N 1,1,1-trichloro-3,3,3-trifluoropropan-2-one Chemical compound FC(F)(F)C(=O)C(Cl)(Cl)Cl AVTAIKNWAIKGEV-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DOJXGHGHTWFZHK-UHFFFAOYSA-N Hexachloroacetone Chemical compound ClC(Cl)(Cl)C(=O)C(Cl)(Cl)Cl DOJXGHGHTWFZHK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- UTZAXPKCGJZGLB-UHFFFAOYSA-N diethyl methyl phosphite Chemical group CCOP(OC)OCC UTZAXPKCGJZGLB-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- KJWHEZXBZQXVSA-UHFFFAOYSA-N tris(prop-2-enyl) phosphite Chemical group C=CCOP(OCC=C)OCC=C KJWHEZXBZQXVSA-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 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
Verfahren zur Herstellung von Phosphonsäureestern Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Phpsphonsäureestern der allgemeinen Formel in der die Reste R1 und R2 gleiche oder verschiedene, gegebenenfalls halogensubstituierte ALkyl- bzw. Alkenylreste, vorzugsweise mit 1 bis 4 Kohlenstoffatomen bedeuten, während X-für Chlor- und/oder Fluoratome steht. Das Verfahren ist dadurch gekennzeichnet, daß man Di- oder TriåLkylt bzw. -alkenylphosphite der allgemeinen Formel in der R1 und R2 die vorstehend angegebene Bedeutung haben und R3 für ein Wasserstoffatom, den Allylrest Die Umsetzung gehorcht dem Reaktionsschema: oder eine niedere Alkylgruppe steht; mit HexahálogenJ acetonen der allgemeinen Formel in der X die vorstehend angegebene Bedeutung hat, bei Temperaturen von 0 bis +100"C umsetzt. Process for the production of phosphonic acid esters The invention relates to a process for the production of phosphonic acid esters of the general formula in which the radicals R1 and R2 are identical or different, optionally halogen-substituted alkyl or alkenyl radicals, preferably with 1 to 4 carbon atoms, while X- stands for chlorine and / or fluorine atoms. The process is characterized in that di- or tri-alkyl or alkenyl phosphites of the general formula are used in which R1 and R2 have the meanings given above and R3 represents a hydrogen atom, the allyl radical. The reaction obeys the reaction scheme: or represents a lower alkyl group; with hexahallogenic acetones of the general formula in which X has the meaning given above, is reacted at temperatures from 0 to +100 ° C.
In letztgenannten Formeln haben die Symbole R1, R2, R8 und X die vorstehend angegebene Bedeutung. In the latter formulas, the symbols R1, R2, R8 and X have the meaning given above.
Die Umsetzung erfolgt vorzugsweise bei 20 bis 80ob.The reaction is preferably carried out at 20 to 80ob.
Da die Reaktion meist mehr oder minder stark exotherm verläuft, arbeitet man zwecks Abführung der entstehenden Wärme vorteilhafterweise in einem inerten organischen Lösungs- bzw. Verdünnungsmittel wie Benzol, Dioxan oder Chlorbenzol. Since the reaction is usually more or less exothermic, it works for the purpose of dissipating the heat produced, it is advantageously in an inert organic solvents or diluents such as benzene, dioxane or chlorobenzene.
Als Ausgangsmaterialien für das erfindungsgemäße Verfahren geeignete Hexahalogenacetone sind beispielsweise Hexachlor-, Monofluorpentachlor-, Difluortetrachlor-, Trifluortrichlor- und Tetrafluordichloraceton. Suitable starting materials for the process according to the invention Hexahalogenacetones are, for example, hexachloro, monofluoropentachloro, difluorotetrachloro, Trifluorotrichloroacetone and tetrafluorodichloroacetone.
An Phosphiten können gemäß der Erfindung z. B. umgesetzt werden: Di- und Trimethyl-, Triäthyl-, Tri-(p-chloräthyl)-, Methyldiäthyl-, Triallyl- und Tributylphosphit. On phosphites according to the invention, for. B. implemented: Di- and trimethyl-, triethyl-, Tri- (p-chloroethyl), methyl diethyl, triallyl and Tributyl phosphite.
Die nach den erfindungsgemäßen Verfahren herstellbaren Phosphonsäureester dienen als Zwischenprodukte für weitere Synthesen. Darüber hinaus finden sie auf Grund ihrer hervorragenden insektiziden Eigenschaften als Schädlingsbekämpfungsmittel vor allem im Pflanzenschutz Verwendung. The phosphonic acid esters which can be prepared by the process according to the invention serve as intermediates for further syntheses. They can also be found on Because of their excellent insecticidal properties as pesticides mainly used in crop protection.
Der glatte und einheitliche Verlauf des erfindungsgemäßen Verfahrens ist völlig überraschend und konnte in keiner Weise vorausgesehen werden, da im Hinblick auf den durch Houben-Weyl, »Methoden der organischen Chemie«, Bd. 12/1 (1963), S. 490, 491, gegebenen Stand der Technik die Entstehung von 0, O-Dialkylphosphorsäure-O-vinylestern erwartet werden mußte. Aus dem Infrarotspektrum der verfahrensgemäß herstellbaren Verbindungen geht jedoch eindeutig hervor, daß diesen die oben angegebene Struktur zukommt. The smooth and uniform course of the method according to the invention is completely surprising and could in no way be foreseen as in view on the by Houben-Weyl, "Methods of Organic Chemistry", Vol. 12/1 (1963), p. 490, 491, given prior art, the formation of 0, O-dialkylphosphoric acid O-vinyl esters expected had to become. From the infrared spectrum of the compounds that can be produced according to the method However, it is clear that these have the structure indicated above.
Beispiel 1 Zu einer Lösung von 40 g synunetrischem Tetrafluordichloraceton in 150 mol Benzol werden unter Außenkühlung bei Temperaturen unterhalb von 40"C 22 g Dimethylphosphit getropft. Hierbei entwickelt sich fortlaufend Chlorwasserstoff. Man engt die Mischung im Vakuum ein und erhält nach Verdampfen des Lösungsmittels durch Destillation 47 g des Phosphonsäureesters obiger Konstitution vom Kr.1 48 bis 52"C.example 1 22 g of dimethyl phosphite are added dropwise to a solution of 40 g of synunetric tetrafluorodichloroacetone in 150 mol of benzene with external cooling at temperatures below 40 ° C. During this process, hydrogen chloride is continuously evolved. The mixture is concentrated in vacuo and, after evaporation of the solvent by distillation, 47 g are obtained of the phosphonic acid ester of the above constitution from Kr.1 48 to 52 "C.
In analoger Weise können die folgenden Verbindungen hergestellt werden:
Unter gleichen Bedingungen wird die Verbindung folgender Konstitution vom Kp.12 80 bis 84"C erhalten: Under the same conditions the compound of the following constitution is obtained from bp 12 80 to 84 "C:
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF41825A DE1197883B (en) | 1964-01-24 | 1964-01-24 | Process for the production of phosphonic acid esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF41825A DE1197883B (en) | 1964-01-24 | 1964-01-24 | Process for the production of phosphonic acid esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1197883B true DE1197883B (en) | 1965-08-05 |
Family
ID=7098825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF41825A Pending DE1197883B (en) | 1964-01-24 | 1964-01-24 | Process for the production of phosphonic acid esters |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1197883B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4541858A (en) * | 1983-04-12 | 1985-09-17 | Bayer Aktiengesellschaft | Chlorinated phosphorylmethylcarbonyl derivative plant protection agents |
-
1964
- 1964-01-24 DE DEF41825A patent/DE1197883B/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4541858A (en) * | 1983-04-12 | 1985-09-17 | Bayer Aktiengesellschaft | Chlorinated phosphorylmethylcarbonyl derivative plant protection agents |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1139117B (en) | Process for the preparation of thiophosphorus, thiophosphonic and thiophosphinic acid esters | |
| DE1131671B (en) | Process for the production of vinyl phosphines | |
| DE1197883B (en) | Process for the production of phosphonic acid esters | |
| DE2417615A1 (en) | CYCLIC KETONES AND THE METHOD OF MANUFACTURING THEM | |
| EP0090213A1 (en) | Process for the preparation of derivatives of vinylphosphonic or vinylpyrophosphonic acids | |
| DE2129583C3 (en) | Process for the production of phosphinic anhydrides | |
| DE1138049B (en) | Process for the preparation of dithiophosphonic acid esters | |
| EP0130439B1 (en) | Process for the preparation of vinylphosphonic acid or vinylpyrophonic acid | |
| CH615438A5 (en) | ||
| DE1153746B (en) | Process for the preparation of thiophosphorus - (- phosphon, -phosphine) - or dithiophosphorus - (- phosphon, -phosphine) acid esters | |
| EP0122587A2 (en) | Process for preparing organic chlorophosphanes | |
| DE1276633B (en) | Process for the preparation of esters of certain acids of phosphorus | |
| DE1252680B (en) | Process for the preparation of phosphinic acid esters | |
| DE2702363C2 (en) | Process for the preparation of organotin trihalides | |
| DE2133198C3 (en) | Process for the preparation of O- (2,2-dichlorovinyl) thionophosphoric acid ester dichloride | |
| DE1054453B (en) | Process for the production of dialkyl thionophosphinic acid halides | |
| DE2514871A1 (en) | PROCESS FOR THE PRODUCTION OF CYCLIC PHOSPHIC ACID ESTERS | |
| AT229326B (en) | Process for the preparation of thiophosphonic acid esters | |
| DE1171427B (en) | Process for the preparation of thiophosphorus, -phosphonic or -phosphinic acid esters or ester amides | |
| DE1183495B (en) | Process for the production of thiol or thionothiolphosphorus (- phosphonic, -phosphine) acid esters | |
| DE1123316B (en) | Process for the preparation of dithiophosphorous acid monochlorides | |
| DE1187607B (en) | Process for the production of thiolphosphorus (- phosphono-, -phosphine-) - or thionothiol-phosphor- (- phosphon-, -phosphine-) - acid esters | |
| DE1071701B (en) | Process for the production of new dithiophosphonic acid esters | |
| DE1159935B (en) | Process for the production of Arylthiolphosphorsäuredichloriden | |
| DE1216278B (en) | Process for the production of asymmetrical phosphorus acid-O, O-diesters |