CH511897A - Insecticides containing halogenated organo phosphoric - acids - Google Patents
Insecticides containing halogenated organo phosphoric - acidsInfo
- Publication number
- CH511897A CH511897A CH1792568A CH1792568A CH511897A CH 511897 A CH511897 A CH 511897A CH 1792568 A CH1792568 A CH 1792568A CH 1792568 A CH1792568 A CH 1792568A CH 511897 A CH511897 A CH 511897A
- Authority
- CH
- Switzerland
- Prior art keywords
- sep
- chlorine
- general formula
- insecticides
- acids
- Prior art date
Links
- -1 halogenated organo phosphoric - acids Chemical class 0.000 title abstract description 9
- 239000002917 insecticide Substances 0.000 title abstract description 5
- 235000011007 phosphoric acid Nutrition 0.000 title abstract 2
- 239000000460 chlorine Chemical group 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910052794 bromium Chemical group 0.000 claims abstract 3
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 150000003015 phosphoric acid halides Chemical class 0.000 claims description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 5
- 239000000543 intermediate Substances 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 2
- 150000008282 halocarbons Chemical class 0.000 abstract description 2
- 150000007530 organic bases Chemical class 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract 6
- 235000019439 ethyl acetate Nutrition 0.000 abstract 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 1
- 239000005864 Sulphur Substances 0.000 abstract 1
- 230000000895 acaricidal effect Effects 0.000 abstract 1
- 239000000642 acaricide Substances 0.000 abstract 1
- 150000001447 alkali salts Chemical class 0.000 abstract 1
- 125000004429 atom Chemical group 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000370 acceptor Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000003139 biocide Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WPWHSFAFEBZWBB-UHFFFAOYSA-N 1-butyl radical Chemical compound [CH2]CCC WPWHSFAFEBZWBB-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- OCBFFGCSTGGPSQ-UHFFFAOYSA-N [CH2]CC Chemical compound [CH2]CC OCBFFGCSTGGPSQ-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KDPAWGWELVVRCH-UHFFFAOYSA-N bromoacetic acid Chemical class OC(=O)CBr KDPAWGWELVVRCH-UHFFFAOYSA-N 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical group C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000008096 xylene Substances 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
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/14—Esters of phosphoric acids containing P(=O)-halide groups
- C07F9/1403—Esters of phosphoric acids containing P(=O)-halide groups containing the structure Hal-P(=O)-O-unsaturated acyclic group
-
- 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)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Insecticides containing halogenated organo phosphoric acids. G5-. Cpds. of formula: (in which R is lower alkyl with 1 to 5 atoms, X is hydrogen, chlorine or bromine, Y is chlorine or bromine and Z is oxygen or sulphur). Prepd. by reacting a phosphorusoxy- or phosphorus thio-halide (a) with an acetic ester of general formula: CH3COCHXCOOR (in which R and X are as above) in presence of an acid acceptor for example an organic base such as triethylamine, if desired in presence of an inert organic solvent for example an aromatic hydrocarbon or a halogenated hydrocarbon at a temp. of -10 to + 50 degrees C. or (b) with an alkali salt of an acetic ester of the above formula. Uses: The products are suitable for uses as intermediates in the preparation of insecticides and acaricides.
Description
Verfahren zur Herstellung neuer Phosphorsäurehalogenide
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung neuer Phosphorsäurehalogenide der allgemeinen Formel I
EMI1.1
worin R eine niedere Alkylgruppe mit 1 bis 5 Kohlenstoffatomen und X ein Chlor- oder ein Bromatom bedeuten, die als Zwischenprodukte zur Herstellung von biozid, z. B. insektizid, wirkenden Phosphorsäureestern verwendet werden können.
Die Verbindungen der allgemeinen Formel I können nach dem erfindungsgemässen, in der Phosphorsäurechemie neuartigen Verfahren durch Umsetzung von Phosphorthiochlorid (PSCl:3) mit einem z-Chlor- bzw.
Brom-acetessigester der allgemeinen Formel II CH:sCOCHXCOOR II worin R eine niedere Alkylgruppe mit 1 bis 5 Kohlenstoffatomen und X ein Chlor- oder ein Bromatom bedeuten, in Gegenwart eines Säureakzeptors erhalten werden.
Die Herstellung kann wie folgt durchgeführt werden:
1 Mol Phosphorthiochlorid wird ohne Lösungsmittel oder unter Zusatz eines unter den Reaktionsbedingungen inerten Lösungsmittels, z. B. eines aromatischen Kohlenwasserstoffs, wie Toluol, Xylol etc., eines halogenierten Kohlenwasserstoffs, wie z. B. Chloroform, Trichloräthylen, eines Aethers, wie z. B. Dioxan, mit einem Mol einer Verbindung der Formel II gemischt, worauf die Mischung unter Rühren bei -100 bis +50 , vorzugsweise bei -10" bis Raumtemperatur, mit 1 Mol eines Säureakzeptors, z. B. Triäthylamin, versetzt wird. Die Reaktionstemperatur wird bei 100 bis +50 , vorzugsweise bei10 bis Raumtemperatur, gehalten.
Das Reaktionsgemisch wird etwa 1/2 Stunde zwischen -1() und t-5(), vorzugsweise bei 10 bis + 10' und noch etwa 1/4 Stunde bei Raumtemperatur gerührt. Danach wird das Reaktionsgemisch gegebenen fallssofern ohne Lösungsmittel gearbeitet wird unter Zusatz eines nicht mit Wasser mischbaren Lösungsmittels gewaschen und das Lösungsmittel nach Trocknen im Vakuum bei einer Badtemperatur von ungefähr 20 bis 50 entfernt. Anschliessend wird der flüssige Rückstand im Hochvakuum destilliert. Man erhält die reine Verbindung der allgemeinen Formel I als Ol.
Die nach dem erfindungsgemässen Verfahren erhaltenen Verbindungen der allgemeinen Formel I besitzen dann als überwiegenden Anteil die cis-Konfiguration im Crotonsäurerest, wenn als Säureakzeptoren organische Basen. z. B. Triäthylamin, eingesetzt werden. Die Zusammensetzung der stereoisomeren Formen der erhaltenen Verbindungen der allgemeinen Formel I kann auf bekannte Weise durch das NMR-Spektrum bestimmt werden.
Die nach dem erfindungsgemässen Verfahren erhaltenen Verbindungen der allgemeinen Formel I können als Zwischenprodukte fiir die Herstellung wertvoller Biozide. z. B. Insektizide. verwendet werden. Das erfindungsgemässe Verfahren. das eine in der Phosphorsäurechemie überraschende. nicht vorhersehbare Reaktion beinhaltet, bietet die Möglichkeit. die als Zwischenprodukt verwendbaren neuen Verbindungen in wirtschaftlich sehr interessanter Weise herzustellen und stellt somit einc echte Bereicherung der Technik dar.
Die neuen Verbindungen der allgemeinen Formel I reagieren beispielsweise mit einem Alkohol mit 1 bis 9 Kohlenstoffatomen und einem Säureakzeptor unter Austausch der Chloratome am Phosphoratom gegen Alkoxyreste. Die Chloratome am Phosphor können auch in zwei Stufen gegen 2 verschiedene Alkoxyreste ausgetauscht werden. In der ersten Stufe fügt man 1 Mol eines Alkohols mit beispielsweise 1 bis 5 Kohlenstoffatomen und einen Säureakzeptor hinzu, während in der zweiten Stufe 1 Mol eines Alkohols mit beispielsweise 1 bis 5 Kohlenstoffatomen, der von dem in der ersten Stufe zugefügten Alkohol verschieden ist, sowie ein Säureakzeptor zugegeben wird. Statt durch Alkoxyreste können die Chloratome am Phosphor auch durch Aminogruppen ausgetauscht werden, wobei man bei der Anwendung von 2 Mol eines Amins, z.B.
Methylamin, Dimethylamin, Diäthylamin, und einem Säureakzeptor beide Chloratome austauschen kann. Es ist auch möglich, ein Chloratom durch eine Alkoxygruppe auszutauschen, in diesem Falle arbeitet man wie oben gezeigt in 2 Stufen. In der ersten Stufe wird 1 Mol eines Amins und ein Säureakzeptor hinzugegeben, in der zweiten Stufe wird, wie oben gezeigt, 1 Mol eines Alkohols mit einem Säureakzeptor dem Säurechlorid zugefügt. Auf diese Weise ist es möglich, auf wirtschaftlichem Wege zu interessanten Bioziden, z. B. Insektiziden, zu gelangen.
Die folgenden Beispiele dienen zur Erläuterung der Herstellung der Verbindungen der allgemeinen Formel 1, sollen die Erfindung aber in keiner Weise einschränken. Die Temperaturangaben erfolgen in Celsiusgraden.
Beispiel 1 0X1 Xhlor-l -methoxycarbonyl-l -propen-2-yi)- phosphorodichloridothionat
EMI2.1
Zur Mischung von 51 g (0,3 Mol) Phosphorthiochlorid und 45 g (0,3 Mol) a-Chlor-acetessigsäuremethylester in
100 ml Toluol werden unter Rühren bei 100 innerhalb von 1 Stunde 30,5 g (0,3 Mol) Triäthylamin hinzugege ben. Anschliessend wird noch etwa 112. Stunde bei
Raumtemperatur weitergerührt. Danach wird das Reak tionsgemisch zweimal mit Eiswasser gewaschen, die
Toluol-Schicht abgetrennt, mit Na.O4 getrocknet und das Toluol abdestilliert. Man erhält das rohe O-(1 Chlor-1-methoxycarbonyl-1 -propen-2-yl)- phosphoro dichloridothionat. Die reine Verbindung siedet bei
45-48 /5.10 3 Torr.
Das Verhältnis der Isomeren cis: trans (im Crotonsäurerest) beträgt 9 1.
Analyse: C5h6Cl3O3PS Molgewicht: 283,5
C gef. 21.2 % Cl gef. 36.8 % P gef. 11,1 % S gef. 11,0 % ber. 21.2 % ber. 37,5 % ber. 10,9 % ber. 11,3 % Auf analoge Weise wie im Beispiel 1 beschrieben werden folgende Verbindungen der allg. Formel I erhalten.
EMI3.1
<SEP> Verhältnis <SEP> Analyse <SEP> %
<tb> Bei- <SEP> R <SEP> X <SEP> Bruttoformel <SEP> Molge- <SEP> Kp/Torr <SEP> cis:trans <SEP> gef.
<tb>
spiel <SEP> im <SEP> Croton- <SEP> ber.
<tb>
<SEP> säurerest <SEP> C <SEP> Cl <SEP> P <SEP> S
<tb> 2 <SEP> C2H5 <SEP> Cl <SEP> C6H8Cl3O3PS <SEP> 297,5 <SEP> 55-58 /10-2 <SEP> 9 <SEP> : <SEP> 1 <SEP> 24,8 <SEP> 35,3 <SEP> 10,5 <SEP> 10,2
<tb> <SEP> 24,2 <SEP> 35,8 <SEP> 10,4 <SEP> 10,8
<tb> 3 <SEP> n-C3H7 <SEP> Cl <SEP> C7H10Cl3O3PS <SEP> 311,5 <SEP> 60-62 /5.10-2 <SEP> 9 <SEP> : <SEP> 1 <SEP> 27,7 <SEP> 33,8 <SEP> 10,3 <SEP> 9,8
<tb> <SEP> 27,0 <SEP> 34,2 <SEP> 9,9 <SEP> 10,2
<tb> 4 <SEP> i-C3H7 <SEP> Cl <SEP> C7H10Cl3O3PS <SEP> 311,5 <SEP> 52 /10-3 <SEP> 85 <SEP> : <SEP> 15 <SEP> 27,5 <SEP> 33,8 <SEP> 9,9 <SEP> 9,7
<tb> <SEP> 27,0 <SEP> 34,2 <SEP> 9,9 <SEP> 10,2
<tb> 5 <SEP> n-C4H9 <SEP> Cl <SEP> C8H12Cl3O3PS <SEP> 315,5 <SEP> 62-64 /10-3 <SEP> 9 <SEP> :
<SEP> 1 <SEP> 30,1 <SEP> 32,2 <SEP> 9,2 <SEP> 8,9
<tb> <SEP> 29,5 <SEP> 32,7 <SEP> 9,5 <SEP> 9,8
<tb> 6 <SEP> n-C5H11 <SEP> Cl <SEP> C9H14Cl3O3PS <SEP> 339,5 <SEP> 73-75 /10-3 <SEP> 9 <SEP> : <SEP> 1 <SEP> 32,8 <SEP> 30,7 <SEP> 8,6 <SEP> 8,9
<tb> <SEP> 31,8 <SEP> 31,4 <SEP> 9,1 <SEP> 9,5
<tb>
Process for the production of new phosphoric acid halides
The present invention relates to a process for the preparation of new phosphoric acid halides of the general formula I.
EMI1.1
wherein R is a lower alkyl group having 1 to 5 carbon atoms and X is a chlorine or a bromine atom, which are used as intermediates for the preparation of biocide, e.g. B. insecticidal, phosphoric acid esters can be used.
The compounds of general formula I can be prepared by the novel process in phosphoric acid chemistry by reacting phosphorothiochloride (PSCl: 3) with a z-chlorine or
Bromo-acetic acid esters of the general formula II CH: sCOCHXCOOR II in which R is a lower alkyl group having 1 to 5 carbon atoms and X is a chlorine or a bromine atom, can be obtained in the presence of an acid acceptor.
The production can be carried out as follows:
1 mol of phosphorothiochloride is used without a solvent or with the addition of a solvent which is inert under the reaction conditions, e.g. B. an aromatic hydrocarbon such as toluene, xylene, etc., a halogenated hydrocarbon such as. B. chloroform, trichlorethylene, an ether, such as. B. dioxane, mixed with one mole of a compound of the formula II, whereupon the mixture is mixed with 1 mole of an acid acceptor, for example triethylamine, with stirring at -100 to +50, preferably at -10 "to room temperature The reaction temperature is maintained at 100 to +50, preferably at 10 to room temperature.
The reaction mixture is stirred for about 1/2 hour between -1 () and t-5 (), preferably at 10 to + 10 'and a further 1/4 hour at room temperature. Thereafter, the reaction mixture is washed with the addition of a water-immiscible solvent, provided it is carried out without a solvent, and the solvent is removed after drying in vacuo at a bath temperature of about 20 to 50. The liquid residue is then distilled in a high vacuum. The pure compound of the general formula I is obtained as an oil.
The compounds of general formula I obtained by the process according to the invention then have the predominant proportion of the cis configuration in the crotonic acid radical if organic bases are used as acid acceptors. z. B. triethylamine can be used. The composition of the stereoisomeric forms of the compounds of the general formula I obtained can be determined in a known manner by the NMR spectrum.
The compounds of general formula I obtained by the process according to the invention can be used as intermediates for the production of valuable biocides. z. B. Insecticides. be used. The method according to the invention. the one surprising thing in phosphoric acid chemistry. Unpredictable response involves the possibility. to produce the new compounds that can be used as intermediates in an economically very interesting way and thus represents a real asset to technology.
The new compounds of general formula I react, for example, with an alcohol having 1 to 9 carbon atoms and an acid acceptor, exchanging the chlorine atoms on the phosphorus atom for alkoxy radicals. The chlorine atoms on the phosphorus can also be exchanged for 2 different alkoxy radicals in two stages. In the first stage, 1 mole of an alcohol having, for example, 1 to 5 carbon atoms and an acid acceptor is added, while in the second stage, 1 mole of an alcohol having, for example, 1 to 5 carbon atoms, which is different from the alcohol added in the first stage, and an acid acceptor is added. Instead of alkoxy radicals, the chlorine atoms on the phosphorus can also be exchanged for amino groups, with the use of 2 mol of an amine, e.g.
Methylamine, dimethylamine, diethylamine, and an acid acceptor can both exchange chlorine atoms. It is also possible to replace a chlorine atom with an alkoxy group, in which case the procedure is as shown above in 2 stages. In the first stage, 1 mol of an amine and an acid acceptor is added, in the second stage, as shown above, 1 mol of an alcohol with an acid acceptor is added to the acid chloride. In this way it is possible to obtain interesting biocides such. B. insecticides to arrive.
The following examples serve to illustrate the preparation of the compounds of general formula 1, but are not intended to restrict the invention in any way. The temperatures are given in degrees Celsius.
Example 1 0X1 Xhlor-1-methoxycarbonyl-1-propene-2-yi) phosphorodichloridothionate
EMI2.1
To the mixture of 51 g (0.3 mol) of phosphorothiochloride and 45 g (0.3 mol) of a-chloro-acetic acid methyl ester in
100 ml of toluene are added 30.5 g (0.3 mol) of triethylamine with stirring at 100 within 1 hour. Then about 112th hour at
Stirring at room temperature. The reaction mixture is then washed twice with ice water, the
The toluene layer is separated off, dried with Na.O4 and the toluene is distilled off. The crude O- (1 chloro-1-methoxycarbonyl-1-propen-2-yl) phosphoro dichloridothionate is obtained. The pure connection is boiling
45-48 / 5.10 3 torr.
The ratio of the isomers cis: trans (in the crotonic acid residue) is 9 1.
Analysis: C5h6Cl3O3PS Molar weight: 283.5
C found 21.2% Cl found. 36.8% P found 11.1% S found. 11.0% calculated. 21.2% calculated. 37.5% calculated. 10.9% calculated. 11.3% In a manner analogous to that described in Example 1, the following compounds of the general formula I are obtained.
EMI3.1
<SEP> ratio <SEP> analysis <SEP>%
<tb> Bei- <SEP> R <SEP> X <SEP> Gross formula <SEP> Mol- <SEP> Kp / Torr <SEP> cis: trans <SEP> gef.
<tb>
play <SEP> in <SEP> Croton- <SEP> over.
<tb>
<SEP> acid residue <SEP> C <SEP> Cl <SEP> P <SEP> S
<tb> 2 <SEP> C2H5 <SEP> Cl <SEP> C6H8Cl3O3PS <SEP> 297.5 <SEP> 55-58 / 10-2 <SEP> 9 <SEP>: <SEP> 1 <SEP> 24.8 <SEP> 35.3 <SEP> 10.5 <SEP> 10.2
<tb> <SEP> 24.2 <SEP> 35.8 <SEP> 10.4 <SEP> 10.8
<tb> 3 <SEP> n-C3H7 <SEP> Cl <SEP> C7H10Cl3O3PS <SEP> 311.5 <SEP> 60-62 /5.10-2 <SEP> 9 <SEP>: <SEP> 1 <SEP> 27 , 7 <SEP> 33.8 <SEP> 10.3 <SEP> 9.8
<tb> <SEP> 27.0 <SEP> 34.2 <SEP> 9.9 <SEP> 10.2
<tb> 4 <SEP> i-C3H7 <SEP> Cl <SEP> C7H10Cl3O3PS <SEP> 311.5 <SEP> 52 / 10-3 <SEP> 85 <SEP>: <SEP> 15 <SEP> 27.5 <SEP> 33.8 <SEP> 9.9 <SEP> 9.7
<tb> <SEP> 27.0 <SEP> 34.2 <SEP> 9.9 <SEP> 10.2
<tb> 5 <SEP> n-C4H9 <SEP> Cl <SEP> C8H12Cl3O3PS <SEP> 315.5 <SEP> 62-64 / 10-3 <SEP> 9 <SEP>:
<SEP> 1 <SEP> 30.1 <SEP> 32.2 <SEP> 9.2 <SEP> 8.9
<tb> <SEP> 29.5 <SEP> 32.7 <SEP> 9.5 <SEP> 9.8
<tb> 6 <SEP> n-C5H11 <SEP> Cl <SEP> C9H14Cl3O3PS <SEP> 339.5 <SEP> 73-75 / 10-3 <SEP> 9 <SEP>: <SEP> 1 <SEP> 32 , 8 <SEP> 30.7 <SEP> 8.6 <SEP> 8.9
<tb> <SEP> 31.8 <SEP> 31.4 <SEP> 9.1 <SEP> 9.5
<tb>
Claims (1)
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1792568A CH511897A (en) | 1968-12-02 | 1968-12-02 | Insecticides containing halogenated organo phosphoric - acids |
| GB31237/69A GB1262760A (en) | 1968-07-15 | 1969-06-20 | Halogen containing phosphorus derivatives |
| FR6923795A FR2012980A1 (en) | 1968-07-15 | 1969-07-11 | |
| IL32608A IL32608A (en) | 1968-07-15 | 1969-07-13 | (alkoxycarbonylpropenyl)phosphoro-(and dithiophosphoro)dichloridates(and dibromidates)and their preparation |
| DE1935630A DE1935630C3 (en) | 1968-07-15 | 1969-07-14 | New phosphoric acid halides and processes for their preparation |
| ES369476A ES369476A1 (en) | 1968-07-15 | 1969-07-14 | Halogen containing phosphorus derivatives |
| BR210696/69A BR6910696D0 (en) | 1968-07-15 | 1969-07-14 | PROCESS OF MANUFACTURING NEW PHOSPHORIC ACID HALOGENETES |
| BE737270D BE737270A (en) | 1968-07-15 | 1969-08-08 | Phosphoryl halide crotonic esters - intermediates for - pesticides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1792568A CH511897A (en) | 1968-12-02 | 1968-12-02 | Insecticides containing halogenated organo phosphoric - acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH511897A true CH511897A (en) | 1971-08-31 |
Family
ID=4429131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1792568A CH511897A (en) | 1968-07-15 | 1968-12-02 | Insecticides containing halogenated organo phosphoric - acids |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH511897A (en) |
-
1968
- 1968-12-02 CH CH1792568A patent/CH511897A/en not_active IP Right Cessation
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PL | Patent ceased |