CH507990A - Insecticides containing halogenated organo phosphoric - acids - Google Patents
Insecticides containing halogenated organo phosphoric - acidsInfo
- Publication number
- CH507990A CH507990A CH1055168A CH1055168A CH507990A CH 507990 A CH507990 A CH 507990A CH 1055168 A CH1055168 A CH 1055168A CH 1055168 A CH1055168 A CH 1055168A CH 507990 A CH507990 A CH 507990A
- Authority
- CH
- Switzerland
- Prior art keywords
- general formula
- chlorine
- bromine
- formula
- acids
- Prior art date
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- -1 halogenated organo phosphoric - acids Chemical class 0.000 title claims abstract description 7
- 239000002917 insecticide Substances 0.000 title abstract 3
- 235000011007 phosphoric acid Nutrition 0.000 title abstract 2
- 239000000460 chlorine Chemical group 0.000 claims abstract description 15
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 239000011574 phosphorus Substances 0.000 claims abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910052794 bromium Chemical group 0.000 claims abstract 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract 2
- 150000001875 compounds Chemical class 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 8
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical group ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 150000003015 phosphoric acid halides Chemical class 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000003512 tertiary amines Chemical class 0.000 claims 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000543 intermediate Substances 0.000 abstract description 4
- 150000001447 alkali salts Chemical class 0.000 abstract description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 2
- 150000008282 halocarbons 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
- 125000004429 atom Chemical group 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 150000007530 organic bases Chemical class 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 15
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 4
- QXCYOZPCYNOBID-UHFFFAOYSA-N ethyl 3-dichlorophosphoryloxybut-2-enoate Chemical compound P(OC(=CC(=O)OCC)C)(=O)(Cl)Cl QXCYOZPCYNOBID-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical group C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FDFUOWSQJFQRFG-UHFFFAOYSA-N C(CC(=O)C)(=O)O.C(C)[Na] Chemical compound C(CC(=O)C)(=O)O.C(C)[Na] FDFUOWSQJFQRFG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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)
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 Phosphorsaurehalogenide
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung neuer Phosphorsäurehalogenide der allgemeinen Formel I
EMI1.1
worin R eine neidere Alkylgruppe mit 1 bis 5 Kohlenstoffatomen, X ein Wasserstoff-, Chlor- oder Bromatom und Y ein Chlor- oder Bromatom bedeuten, die als Zwischenprodukte zur Herstellung von biozid wirkenden Phosphorsäureestern verwendet werden können.
Die Verbindungen der allgemeinen Formel I können nach dem erfindungsgemässen Verfahren durch Umsetzung eines Phosphoroxyhalogenids, POY3, worin Y ein Chlor oder Bromatom bedeutet, mit einem Alkalisalz eines Acetessigesters der allgemeinen For melll CHsCOCHXCOOR II worin R eine niedere Alkylgruppe mit 1 bis 5 Kohlenstoffatomen und X ein Wasserstoff-, Chlor- oder Bromatom bedeuten, oder mit einem Acetessigester der allgemeinen Formel II, worin R und X die oben angegebenen Bedeutungen besitzen, in Gegenwart eines Säureakzeptors erhalten werden.
Die Herstellung kann wie folgt durchgeführt werden: 1 Mol Phosphoroxychlorid oder Phosphoroxybromid wird in einem unter den Reaktionsbedingungen inerten Lösungsmittel, z. B. einem aromatischen Kohlenwasserstoff wie Toluol, Xylol, etc., einem halogenierten Kohlenwasserstoff wie z. B. Chloroform, Trichlor äthylen, einem Äther wie z. B. Dioxan, bei -10 bis +500, vorzugsweise bei -100 bis Raumtemperatur, gerührt und zu dieser Lösung die Mischung von 1 Mol einer Verbindung der Formel II mit 1 Mol eines Säu- reakzeptors, z. B. Triäthylamin, hinzugeben. Sofern man ein Alkalisalz einer Verbindung der allgemeinen Formel II statt der Verbindungen der Formel II für die Reaktion verwendet, erübrigt sich die Zugabe eines Säureakzeptors.
Die Reaktionstemperatur wird bei -100 bis + 500, vorzugsweise bei -10" bis Raumtemperatur gehalten. Das Reaktionsgemisch wird etwa eine halbe Stunde zwischen -100 und +500, vorzugsweise bei 100 bis + 100, und noch etwa eine Viertelstunde bei Raumtemperatur gerührt. Danach wird von einem gegebenenfalls entstandenen Niederschlag abfiltriert und das Lösungsmittel im Filtrat 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 farbloses 01.
Die nach dem erfindungsgemässen Verfahren erhaltenen Verbindungen der allgemeinen Formel I besitzen als überwiegenden Anteil die cis-Konfiguration im Crotonsäurerest. Nur eine ganz geringe Menge der entstandenen Verbindung der allgemeinen Formel I besitzt trans-Konfiguration. 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 für die Herstellung wertvoller Biozide verwendet werden. Das erfindungsgemässe Verfahren, das eine in der Phosphorsäurechemie überraschende, nicht vorhersehbare Reaktion beinhaltet, bietet die Möglichkeit, die als Zwischenprodukte verwendbaren neuen Verbindungen in wirtschaftlich sehr interessanter Weise herzustellen, und stellt somit eine echte Bereicherung der Technik dar.
Die neuen Verbindungen der allgemeinen Formel I reagieren beispielsweise mit einem Alkohol und einem Säureakzeptor unter Austausch der Halogenatome Y am Phosphoratom gegen Alkoxyreste. Auf diese Weise ist es möglich, auf wirtschaftlichem Wege zu interessanten Phosphorsäureestern zu gelangen.
Die folgenden Beispiele dienen zur Erläuterung der Herstellung der Verbindungen der allgemeinen Formel I, sollen die Erfindung aber in keiner Weise einschränken. Die Temperaturangaben erfolgen in Celsiusgraden.
Beispiel 1
O-(1-Äthoxycarbonyl-1-propen-2-yl)- phosphorodichloridat
EMI2.1
Zu 154 g (1 Mol) Phosphoroxychlorid in 500ml Toluol werden unter Rühren bei -10 innerhalb einer halben Stunde 130 g (1 Mol) Acetessigsäureäthylester und 101 g (1 Mol) Triäthylamin hinzugegeben, wobei Triäthylaminchlorhydrat ausfällt. Anschliessend wird das Reaktionsgemisch noch eine halbe Stunde zwischen -10 und +10 und eine Viertelstunde bei 20 gerührt. Danach wird von dem entstandenen Niederschlag abfiltriert und das Lösungsmittel im Filtrat im Wasserstrahlvakuum bei 50 Badtemperatur entfernt. Man erhält 225 g (910/o der theoretischen Ausbeute) des rohen O-(1-Äthoxycarbonyl-1-propen 2-yl)-phosphorodichloridats.
Die reine Verbindung siedet bei 77-780 / 0,15 Torr und besitzt einen Brechungsindex n20D = 1,4700.
Analyse für C0H0Cl2O4P Molgewicht 247,01: berechnet: C 29,2 0/0 H 3,7 0/0 Cl 28,7 /o gefunden: C 29,8 0/0 H 3,7 0/o C1 29,4 0/0
Beispiel 2
O-(1-Äthoxycarbonyl-1-propen-2-yl)- phosphorodichloridat
11,5 g Natriummetall werden im 1,2 l Toluol bei etwa 110 mit einem Vibromischer pulverisiert. Die Natrium-Suspension wird bei 20-40 tropfenweise mit 65 g Acetessigsäureäthylester versetzt. Nach vollendeter Reaktion wird die dünnflüssige Aufschlämmung des Natriumacetessigsäureäthylesters in eine Lösung von 77 g Phosphoroxychlorid in 100 ml Toluol bei 10-20 zugetropft.
Danach wird die Reaktionsmischung noch eine halbe Stunde bei Raumtemperatur gerührt und anschliessend das Toluol im Vakuum abdestilliert. Der Rückstand wird in Ather aufgenommen, das ausgefallene Natriumchlorid abfiltriert und das Filtrat eingedampft. Die erhaltene reine Verbindung siedet bei 10-3 Torr bei 48 bis 50 . Sie besteht praktisch ausschliesslich aus der trans-Form im Crotonsäurerest.
Auf analoge Weise wie im Beispiel 1 beschrieben, werden folgende Verbindungen der allgemeinen For mehl 1 erhalten: Beispiel R X Y Bruttoformel Mol- Kp/Torr nD20 Analyse 20 gewicht gefunden berechnet
C H Cl 3 CH3 H Cl C5H7Cl2O4P 232,99 65 /0,01 1,4750 26,3 3,1 30,8
25,8 3,0 30,4 4 iC3H7 H C1 C7H11Cl2O4P 261,04 720/0,02 1,4662 32,4 4,3 26,5
32,2 4,2 27,2 5 tC4H9 H C1 C8H13Cl2O4P 275,07 43-5 /5.10-5 - 34,1 4,2 24,9
34,9 4,8 25,8 6 tCsHll H Cl C5H15C12O4P 289,09 48 /5.10-5 1,4675 36,8 4,9 23,9
37,4 5,2 24,5 7 C2H5 Cl Cl C8H0Cl5O4P 281,46 830/0,01 1,4850 26,4
3,0 36,9
25,6 2,9 37,8 8 nC3H7 C1 Cl C7H10Cl3O4P 295,49 88-9 /0,01 1,4820 28,9 3,3 35,8
28,5 3,4 36,0
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
where R is a more recent alkyl group with 1 to 5 carbon atoms, X is a hydrogen, chlorine or bromine atom and Y is a chlorine or bromine atom, which can be used as intermediates for the preparation of biocidal phosphoric acid esters.
The compounds of general formula I can be prepared by the process of the invention by reacting a phosphorus oxyhalide, POY3, in which Y is a chlorine or bromine atom, with an alkali salt of an acetoacetic ester of the general formula CHsCOCHXCOOR II in which R is a lower alkyl group having 1 to 5 carbon atoms and X is Mean hydrogen, chlorine or bromine atom, or with an acetoacetic ester of the general formula II, in which R and X have the meanings given above, can be obtained in the presence of an acid acceptor.
The preparation can be carried out as follows: 1 mol of phosphorus oxychloride or phosphorus oxybromide is dissolved in 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 z. B. dioxane, stirred at -10 to +500, preferably at -100 to room temperature, and the mixture of 1 mol of a compound of the formula II with 1 mol of an acid acceptor, for. B. triethylamine, add. If an alkali salt of a compound of the general formula II is used for the reaction instead of the compounds of the formula II, the addition of an acid acceptor is unnecessary.
The reaction temperature is kept at -100 to + 500, preferably at -10 "to room temperature. The reaction mixture is stirred for about half an hour between -100 and +500, preferably at 100 to + 100, and for about a quarter of an hour at room temperature Any precipitate that may have formed is filtered off and the solvent in the filtrate is removed in vacuo at a bath temperature of approximately 20 to 50. The liquid residue is then distilled in a high vacuum, giving the pure compound of the general formula I as colorless oil.
The compounds of general formula I obtained by the process according to the invention have the predominant proportion of the cis configuration in the crotonic acid residue. Only a very small amount of the compound of the general formula I formed has the trans configuration. 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. The process according to the invention, which includes a surprising, unforeseeable reaction in phosphoric acid chemistry, offers the possibility of producing the new compounds which can be used as intermediates in an economically very interesting manner, and thus represents a real enrichment of the technology.
The new compounds of general formula I react, for example, with an alcohol and an acid acceptor, replacing the halogen atoms Y on the phosphorus atom with alkoxy radicals. In this way it is possible to obtain interesting phosphoric acid esters in an economical way.
The following examples serve to illustrate the preparation of the compounds of general formula I, but are not intended to restrict the invention in any way. The temperatures are given in degrees Celsius.
example 1
O- (1-ethoxycarbonyl-1-propen-2-yl) phosphorodichloridate
EMI2.1
To 154 g (1 mol) of phosphorus oxychloride in 500 ml of toluene, 130 g (1 mol) of ethyl acetoacetate and 101 g (1 mol) of triethylamine are added with stirring at -10 within half an hour, with triethylamine chlorohydrate precipitating. The reaction mixture is then stirred for a further half an hour between -10 and +10 and a quarter of an hour at 20. The precipitate formed is then filtered off and the solvent in the filtrate is removed in a water jet vacuum at a bath temperature. 225 g (910 / o of the theoretical yield) of the crude O- (1-ethoxycarbonyl-1-propen 2-yl) phosphorodichloridate are obtained.
The pure compound boils at 77-780 / 0.15 Torr and has a refractive index n20D = 1.4700.
Analysis for COH0Cl2O4P molecular weight 247.01: calculated: C 29.2 0/0 H 3.7 0/0 Cl 28.7 / o found: C 29.8 0/0 H 3.7 0 / o C1 29.4 0/0
Example 2
O- (1-ethoxycarbonyl-1-propen-2-yl) phosphorodichloridate
11.5 g of sodium metal are pulverized in 1.2 l of toluene at about 110 with a vibromixer. 65 g of ethyl acetoacetate are added dropwise to the sodium suspension at 20-40. When the reaction is complete, the thin slurry of the ethyl sodium acetoacetate in a solution of 77 g of phosphorus oxychloride in 100 ml of toluene is added dropwise at 10-20.
The reaction mixture is then stirred for a further half an hour at room temperature and the toluene is then distilled off in vacuo. The residue is taken up in ether, the precipitated sodium chloride is filtered off and the filtrate is evaporated. The pure compound obtained boils at 10-3 torr at 48 to 50. It consists practically exclusively of the trans form in the crotonic acid residue.
In a manner analogous to that described in Example 1, the following compounds of general formula 1 are obtained: Example R X Y Gross formula Mol- Kp / Torr nD20 analysis 20 weight found calculated
C H Cl 3 CH 3 H Cl C5H7Cl2O4P 232.99 65 / 0.01 1.4750 26.3 3.1 30.8
25.8 3.0 30.4 4 iC3H7 H C1 C7H11Cl2O4P 261.04 720 / 0.02 1.4662 32.4 4.3 26.5
32.2 4.2 27.2 5 tC4H9 H C1 C8H13Cl2O4P 275.07 43-5 /5.10-5 - 34.1 4.2 24.9
34.9 4.8 25.8 6 tCsHll H Cl C5H15C12O4P 289.09 48 /5.10-5 1.4675 36.8 4.9 23.9
37.4 5.2 24.5 7 C2H5 Cl Cl C8H0Cl5O4P 281.46 830 / 0.01 1.4850 26.4
3.0 36.9
25.6 2.9 37.8 8 nC3H7 C1 Cl C7H10Cl3O4P 295.49 88-9 / 0.01 1.4820 28.9 3.3 35.8
28.5 3.4 36.0
Claims (1)
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1055168A CH507990A (en) | 1968-07-15 | 1968-07-15 | 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 |
| 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 |
| DE1935630A DE1935630C3 (en) | 1968-07-15 | 1969-07-14 | New phosphoric acid halides and processes for their preparation |
| ZA695031A ZA695031B (en) | 1968-07-15 | 1969-07-15 | Improvements in or relating to organic compounds |
| BE737270D BE737270A (en) | 1968-07-15 | 1969-08-08 | Phosphoryl halide crotonic esters - intermediates for - pesticides |
| US876087A US3634556A (en) | 1968-07-15 | 1969-11-12 | O-(1 - alkoxycarbonyl-1-propen-2-yl)-phosphorodihalidates and -phosphorodihalothionates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1055168A CH507990A (en) | 1968-07-15 | 1968-07-15 | Insecticides containing halogenated organo phosphoric - acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH507990A true CH507990A (en) | 1971-05-31 |
Family
ID=4364405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1055168A CH507990A (en) | 1968-07-15 | 1968-07-15 | Insecticides containing halogenated organo phosphoric - acids |
Country Status (2)
| Country | Link |
|---|---|
| CH (1) | CH507990A (en) |
| ZA (1) | ZA695031B (en) |
-
1968
- 1968-07-15 CH CH1055168A patent/CH507990A/en not_active IP Right Cessation
-
1969
- 1969-07-15 ZA ZA695031A patent/ZA695031B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ZA695031B (en) | 1971-03-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PL | Patent ceased |