IL32441A - O,o-dimethyl-o-(1-(3-methyl-1-pentyn-3-yloxycarbonyl)-1-propen-2-yl)phosphate,its preparation and use as insecticide and acaricide - Google Patents
O,o-dimethyl-o-(1-(3-methyl-1-pentyn-3-yloxycarbonyl)-1-propen-2-yl)phosphate,its preparation and use as insecticide and acaricideInfo
- Publication number
- IL32441A IL32441A IL32441A IL3244169A IL32441A IL 32441 A IL32441 A IL 32441A IL 32441 A IL32441 A IL 32441A IL 3244169 A IL3244169 A IL 3244169A IL 32441 A IL32441 A IL 32441A
- Authority
- IL
- Israel
- Prior art keywords
- compound
- formula
- yloxycarbonyl
- phosphate
- propen
- Prior art date
Links
- 229910019142 PO4 Inorganic materials 0.000 title claims description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims description 21
- 239000010452 phosphate Substances 0.000 title claims description 21
- 230000000895 acaricidal effect Effects 0.000 title claims description 4
- 239000002917 insecticide Substances 0.000 title description 2
- 238000002360 preparation method Methods 0.000 title description 2
- 239000000642 acaricide Substances 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 241000238631 Hexapoda Species 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- -1 sulphuryl Chemical group 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 239000003701 inert diluent Substances 0.000 claims description 2
- 101001053401 Arabidopsis thaliana Acid beta-fructofuranosidase 3, vacuolar Proteins 0.000 claims 1
- 229940125904 compound 1 Drugs 0.000 claims 1
- 235000021317 phosphate Nutrition 0.000 description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000012141 concentrate Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- NOSCISSLXGVNTF-UHFFFAOYSA-N 3-methylpent-1-yn-3-yl 3-oxobutanoate Chemical compound C(CC(=O)C)(=O)OC(C#C)(CC)C NOSCISSLXGVNTF-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 241001425390 Aphis fabae Species 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 230000000749 insecticidal effect Effects 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 3
- 244000046052 Phaseolus vulgaris Species 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- LNCMRASFBLBTRG-UHFFFAOYSA-N 3-methylpent-1-yn-3-yl 2-chloro-3-oxobutanoate Chemical compound CC(C#C)(CC)OC(C(C(=O)C)Cl)=O LNCMRASFBLBTRG-UHFFFAOYSA-N 0.000 description 2
- 241001143309 Acanthoscelides obtectus Species 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000239290 Araneae Species 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 241000233835 Tradescantia Species 0.000 description 2
- 240000006677 Vicia faba Species 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010410 dusting Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DTLIDVRKEFPSGM-UHFFFAOYSA-N 3-methylpent-1-yn-3-yl acetate Chemical compound CCC(C)(C#C)OC(C)=O DTLIDVRKEFPSGM-UHFFFAOYSA-N 0.000 description 1
- 241001124076 Aphididae Species 0.000 description 1
- 241000907225 Bruchidius Species 0.000 description 1
- 241000254001 Carausius Species 0.000 description 1
- 241000254000 Carausius morosus Species 0.000 description 1
- 241000122098 Ephestia kuehniella Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241001049902 Kuehniella Species 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241001454295 Tetranychidae Species 0.000 description 1
- 241001454294 Tetranychus Species 0.000 description 1
- 241001454293 Tetranychus urticae Species 0.000 description 1
- 235000010749 Vicia faba Nutrition 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000002587 enol group Chemical group 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- NBNBICNWNFQDDD-UHFFFAOYSA-N sulfuryl dibromide Chemical compound BrS(Br)(=O)=O NBNBICNWNFQDDD-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000000080 wetting agent 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
- C07F9/113—Esters of phosphoric acids with unsaturated acyclic alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
o'pin main? la B?io»a7tTi vnaan ,0R90iB m-2 'ts,nQ~i
0 O^DIMETm-Q*/i-(3^MBTHn«l^PE.lTTY ¾-5-YL0XZ0ARB0NyL)-l-PROP ^-tLPHOSPHATE, ITS PREPARATION AND USE AS
INSECTICIDE AND ACARICIDJS
SANDOZ A.G
Gi30520
WnOVDflBITO IN ΟΠ RELATING TO OnOAHIC COMTOUNBB-
The invention relates to new organic phosphates and' to
insecticidal and acaricidal compositions containing the same.
According to our invention we provide a compound of
formula I,
According to our invention we also provide processes for the production of a compound of formula I, which comprise
i) condensation of phosphorous acid trimethylester of formula II,
(CH^O)^ II
with a compound of formula III,
CH,C0CH-C00C-C H,_
3 I I 2 5
Hal CH,
in which Hal signifies bromine or chlorine,
in an organic solvent which is inert under the reaction conditions, or
ii) reaction, in a solvent, of a compound of formula V,
Hal 0 - C s CH
\ ll I
P - 0 - C = CH - COOC - C_H_
I I 2 5
Hal CH, CH,
in which Hal signifies bromine or chlorine,
with a compound of formula VI,
CH^OM VI
in which M signifies hydrogen or an alkali metal ,
with the proviso that when M signifies hydrogen the
reaction is carried out in the presence of an acid
binding agent.
The reaction of process i) may be carried out at a temperature of about 50-150°C, preferably 70-120°C. The organic solvent which is inert under the reaction conditions may be, for example benzene, toluene, xylene or chlorobenzene, and the reaction may be carried out. for from about 2 - 3 hours.
The reaction of process ii) may be carried out in a solvent which is inert under the reaction conditions, for example an aromatic hydrocarbon, e.g. toluene or xylene; a halogenated hydrocarbon, e.g. chlorobenzene or chloroform; or an ether, e.g. dioxane. Alternatively the reaction may be carried out in an excess of methanol. The reaction may be carried out at a temperature of from about -20° to +50°C, preferably from -10° to +20°C. A suitable duration for the reaction is between about 0. 5 an 2 hours .
3 1 ί£·30
It is preferred to react at least 2 mols of the compound of per
formula Vl-vdrbh-eaeh mol of the compound of formula V in order to produce as high a yield as possible and to avoid the production of unwanted by-products.
Suitable acid-binding agents include organic nitrogen bases, for example triethylamine, trimethylamine, dimethyl aniline and diethyl aniline, and inorganic bases, e.g. sodium carbonate. At least two mols of acid binding agent are preferably used for each mol of the compound of formula V.
The solvent may be removed from the reaction mixtures produced by either of processes i) and ii) by evaporation at reduced pressure and the reaction product may, if desired, be purified by distillation preferably under vacuum.
The resulting phosphoric acid ester of formula I is an oil which can be distilled in a vacuum without decomposition and may be characterized in the usual manner by its physical constants.
The compounds of formula III may be obtained by reacting the acetoacetic acid (3-methyl-l-pentyne-3-yl) ester of formula IV,
C≡CH
CH,COCH.COOC-C-H_ IV
CH3
with sulphuryl chloride or sulphuryl bromide, respectively, in a solvent which is inert under the reaction conditions, e.g. chloroform. The reaction may be carried out at room temperature or at a slightly elevated temperature, preferably at 25 - 65°C, and preferably for about 5 hours. After the reaction the solvent may be removed by evaporation at reduced pressure and the compound of formula III may
u - 32441/2
there may also exist an enol form of the compound of formula IV and . such eriol form is included within the description of the compound of formula IV.
The compound of formula IV may be bb'tained by reacting 3- methyl-l-pentyne-3-ol with diketene preferably in the presence of a condensation agent, e.g. trlethylamine, at about 6o-70°C fo a period of 1 to 2 hours.
The compounds of formula V may be made by reacting a compound of formula IV with phosphorous oxychlorlde or phosphorous bxybromide (preferably in equimolar proportions) in a solvent which is inert under the reaction conditions and in the presence of an acid acceptor (preferably using one mol of acid acceptor per mol of compound of formula IV). The inert solvent may be the same solvent us used in process ii) and the reaction may be carried out at a temperature of from -10° to +50°C conveniently for a period of 0,5 to hours.
The compound of formula I is genericaliy disclosed in the broad disclosure of US Patent 3 366 715 but is in » no way specifically disclosed or suggested therein.
While the compound of formula I possesses the advantage of insecticidal aotivlty, it is in addition characterized by a toxicity to warm blooded animals which is substantially lower than that of the compounds of substantially similar structure which are embraced by the US Patent 3 366 .715.
The new compound is therefore indicated for use as a
pesticide in,agriculture, in inhabited rooms, in cellars, attics and in stables, etc. It is also indicated for
use in protecting living organisms of the plant and .'. ·' ■! animal kingdon in their different forms of development against insects and acarids.
The combatting of insects and acarids may be carried out by conventional methods, e.g. by treating the objects to be protected with the active agent, preferably in combination with an inert diluent or carrier. For use as a plant protecting agent or as a
pesticide the compound of the invention may be prepared in the form of a dusting or spraying agent, e.g. as a solution or dispersion in water or a suitable organic solvent, e.g. alcohol, petroleum, tar distillates etc., and preferably in combination with an emulsifying agent, e.g. a liquid polyglycol ether derived from a high molecular weight alcohol, mercaptan or alkylphenol and an alkylene oxide. Suitable organic solvents, e.g. ketones, aromatic, optionally halogenated hydrocarbons, mineral oils etc., may also be added to the mixture as solution aids.
The spraying and dusting agents may contain the usual inert carrier materials, e.g. talc, diatomaceous earth, bentonite, pumice, cellulose derivatives and the like, and the usual adhesives 'and wetting agents to improve adhesiveness and wettability.
The active material of the invention may be present in the formulations as a mixture with other known active agents. Formulations suitable for use in the application of a compound of formula I to a locus generally contain between 0.01 and 0 percent, and preferably between 5 and 50$ by weight of active agent.
The invention is illustrated, but in no way limited by the following Examples In which the temperatures are indicated in degrees Centigrade and the percentages are by weight unless otherwise stated.
Example 1 : Insecticldal effect against Bruchidius obtectus
(bean weevil) - contact effect.
A concentrate is produced by mixing 25 parts by weight of 0,
0-dimethyl-O- [ l-( 3-methyl-l-pentyne-5-ylo'xy carbonyl) -l-propen-2-yl ] " phosphate with 25 parts by weight of isooctylphenyldecaglycolether
and 0 parts by weight of xylene, whereby a clear solution results,
which. is easily emulsified in water. The concentrate is then diluted
with water to the desired concentration.
0. 1 to 0.2 cc of an emulsion produced as above and
containing 0.0125$ of 0,0-dimethyl-0-[l- (3-methyl-l-pentyne-3- yloxycarbonyl) -l-propen-2-yl ] phosphate are sprayed by means of a
spraying nozzle onto Petri dishes having a diameter of 7 cm. The
emulsion in the dishes is then dried and 10 Bruchidius imagos are
counted into each dish which is then covered with a lid of fine mesh
brass gauze. The animals are kept at room temperature without food.
After lt8 hours all the imagos were dead.
Example 2; ' Insecticldal effect against Aphis fabae (black bean
aphid) - contact effect.
A concentrate is produced by mixing 25 parts by weight of 0, 0-dimethyl-O- [l-(3-methyl-l-pentyne-3-yloxycarbonyl) -l-propen-2-yl ]
phosphate with 50 parts by weight of isooctylphenyloctaglycolether
and ^ parts by weight of a petroleum fraction having a B.P. of
210-280° (Density 20°C : 0.92) . The concentrate is then diluted with
water to the desired concentration.
Hbrsebean plants (Vicia faba) are sprayed to. run off with
an emulsion produced as above and containing 0.0125$ of 0 ,0-dimethyl-
0-[l-(3-niethyl-l-pentyne-3-yloxycarbonyl)-l-propen-2-yl ] phosphate.
The horsebean plants are strongly infected with black bean aphids
(Aphis fabae) .
After k8 hours all the aphids were dead.
Example 3: Insecticidal effect against Carausius morosus
(Indian rod locust) - feed effect.
A concentrate is produced by mixing kO parts by weight of 0,0-dimethyl-0-[l-(3-methyl-l-pentyne-3-yloxycarbonyl) -l-propen-2-yl ]
phosphate with 25 parts by weight of diisohexyl/heptylphenylhexagly-colether and 35 parts by weight of acetone. The concentrate is then
diluted with water to the desired concentration.
Tradescantia branches are immersed for 3 seconds in an emulsion produced as above and containing 0.0125 of 0,0-dimethyl-O-[l-(3~methyl-l-pentyne-3-yloxycarbonyl) -l-propen-2-yl ] phosphate.
After drying each of the Tradescantia branches is inserted into a
small glass tube filled with water and this is placed in a glass dish. 10 Carausius larvae in the second stage of development are counted
into each dish which is then closed with a wire mesh lid.
After 5 days all the larvae were dead..
Example U: Insecticidal effect against Ephestla Kuehniell'a
(flour moth) - contact effect
A concentrate is produced by mixing 50. parts by weight of
0,0-dimethyl-0- [l-( 3-methyl-l-pentyne-3-yloxycarbonyl) -l-propen-2-yl ]
phosphate with 50 parts by weight of .isooctylphenyloctaglycolether.
A clear concentrate, which is easily emulsifiable in water, is obtained and is diluted with water to the desired concentration.
- 8 - 12-3230
Petri dishes having a diameter of 7 cm, each containing 10 Kuehniella caterpillars having a length of 10-12 mm, are sprayed with an emulsion produced as above and containing 0.05i¾ of 0,0-dimethyl-0-[l-(3-methyl-l-pentyne-3-yloxycarbonyl) -l-propen-2-yl ] phosphate so that each dish contains from 0.1. to 0.2 cc of emulsion. The dishes are then covered with a lid of fine mesh brass gauze.
After drying the emulsion in the dishes a wafer. is given as food and renewed as required.
After h8 hours all the caterpillars were dead.
Example = Acaricidal effect against Tetranychus telarius
(spider mite) - contact effect
A concentrate is produced by mixing JO parts by weight of
0 ,0-dirnethyl-O- [l-(3-niethyl-l-pentyne-3-yloxycarbonyl) -l-propen-2-yl ] phosphate with 5 parts by weight of laurylhexaglycolether and "+5 parts by weight of isopropyl alcohol. The concentrate is then diluted
with water to the desired concentration.
Bean plants (Phaseolus vulgaris) are sprayed to run off ■ with an emulsion produced as above and containing 0.0125$ of 0,0-dimethyl-0-[l-(3-methyl-l-pentyne-3-yloxycarbonyl) -l-p'ropen-2-yl ] phosphate. The bean plants are then strongly infected with all stages of development of the spider mite (Tetranychus* telarius).
After H8 hours all the spider mites were dead.
- 9 - 13-3¾0
Example 6: Production of 0 ,0-dimethyl-0-[l-(3-methyl-l-pentyne-3- yloxycarbonyl) -l-propen-2-yl ] phosphate (process i))
390 g of phosphorous acid trimethylester are added to 6 0 g
of 2-chloroacetoacetic acid (3-methyl-l-pentyne-3-yl) ester in 2 litres of xylene with stirring over a period of 15 minutes. The reaction mixture is subsequently stirred at a bath temperature of 1 O
to 135° f°r 3 hours. Crude 0,0-dimethyl-0-[l-(3-methyl-l-pentyne-3-yloxycarbonyl) -l-propen-2-yl ] phosphate is obtained. The pure
compound of formula I is obtained by distillation of the crude
110-112o
compound in a vacuum. B.P. /IO -3 mm of Hg.
Analysis: C^H OgP molecular weight: 290
C calculated H calculated S. P calculated 10.7$
found 1+9. found 6.6$ found 10. ¾6
The 2-chloroacetoacetic acid (3-methyl-l-pentyne-3-yl) ester (formula III) required as starting material is obtained as
follows:
I05 g of sulphuryl chloride are added to ^2 g of
acetoacetic acid (3-methyl-l-pentyne-3-yl) ester in 2 litres of chloroform with stirring over a period of 2 hours at a reaction temperature of 15 to 20°. The reaction temperature is subsequently raised to 60° for a period of 1 hour and stirring is then continued
at 60-65 for a further 3 hours. Chloroform is then' evaporated off from the reaction mixture at reduced pressure and pure 2-chloroaceto- o acetic acid (3-methyl-l-pentyne-3-yl) ester, having a B.P. of 52- /
- 10 - 13¾50
Analysis: 0-ΛΗ. -,010.. molecular weight: 216.5
15 3
C calculated 55· *$ H calculated 6.0¾ CI calculated l6.k<$ · • found 55.25^ found 6.0% found l6.7#
Acetoacetic acid (3-methyl-l-pentyne-3-yl) ester is obtained as follows:
g of triethylamine are added to 392 g of 3-methyl-l-pentyne-3-ol and the mixture is heated to 6θ° with stirring. 358 g of diketens are added to this mixture at a temperature of 60-70° over a period of 1 - 5 hours. The mixture is then stirred further r 0
at 60 for 1/2 to 1 hour, whereby a light orange coloured solution
results. Pure acetoacetic acid (3-methyl-l-pentyne-3-yl) ester, having a B. P.. of 50-51°/0.02 mm of Hg, is obtained as a colourless or slightly yellowish liquid by distillation at reduced pressure.
EXAMPLE 7 : Production of 0,0-ditnethyl-O- [l- (3-methyl-l-pentyne-3- yloxycarbonyl) -l-j>ropen -2-yl ]phosphate (process il))
I83 g (l mole) of acetoacetic acid (3-methyl-l-pentyne-3-yl) ester and 101 g (1 mole) of triethylamine are added with stirring to
153· 3 g (l mole) of phosphorous oxychloride in ¼00 ml of chlorobenzene at a temperature of -10°C over a period of 1 minutes. The reaction mixture is then stirred for a further 15 minutes at 20°C and is then
filtered. The filtrate, which contains 0- [l-(3-methyl-l-pentyne-3-yloxycarbonyl)-l-propen-2-yl] -phosphorous dichloride, is mixed with
600 ml of chlorobenzene and the mixture cooled to -5°C, 6U. g
(2 moles) of methanol and 203 g (2 moles) of triethylamine are added to this mixture over a period of 30 minutes, and the mixture stirred
for a further JO minutes at -5°C, for 1 hour at from 0-20°C and for 15 hours at 20°C. The resulting reaction mixture is filtered and the filtrate washed with water and dried over magnesium sulphate. After evaporation of the solvent the remaining crude 0,0-dimethyl-O- [l-(3-methyl-l-pentyne-3-yloxycarbonyl) -1- propen- 2-yl ]phosphate is distilled under high vacuum to give a pure material boiling at 1θ8°-110°C/10"^mm.
Claims (12)
1. A process for the production of a compound of formula I, CH,0 0 C≡CH P-0-c=CH-COOC-C_Hc I / I 2 5 CH,0 CH, 3 3 which comprises i) condensation of phosphorous acid trimethylester of formula II, (CH,0),P II 3 3 with a compound of formula III, C≡CH in which Hal signifies bromine or chlorine, in an organic solvent which is inert under the reaction conditions , or ii) reaction, in a solvent, of a compound of formula V, Hal 0 C ≡ CH \ll I P - 0 - C = CH - COOC - C_H_ V I I 2 5 Hal CH. CH. in which Hal signifies bromine or chlorine, with a compound of formula VI, CH..0M VI 3* in which M signifies hydrogen or an alkali metal, with the proviso that when M signifies hydrogen the reaction is carried out in the presence of an acid ' 3¾4l/2 - Ί3. - . ' ' ;·ΐ3-2930
2. A process as claimed in part i) of Claim 1 whenever carried o o out at a temperature of between 50 and 150 C.
J. A.process as claimed in Claim 2, wherein the temperature is between 70° and 120°C. ■,
V . A process as claimed in part ii)'of Claim 1 whenever carried out at a temperature of from -20°C to +50°C. , '
5· A process as claimed in- part ii) of Claim 1 or in Claim , wherein at least 2 mols of the compound of formula VI are used per mol of the compound of formula V.
6. A process as claimed in' part ii) of Claim 1 or in either of Claims or 5> i which,when an acid-binding agent is used, at least 2 mols of acid-binding agent are used per mol of compound1 of formula V.
7. A process according to part i) of Claim 1 or · Claim 2 or 3, wherein the compound of formula III is produced by reacting a compound · of formulq. IV, with sulphuryl c a solvent which is inert under the reaction conditions.
8. A process according to part ii) .of Claim 1 or any one of Claims 4 to 6, wherein the compound of formula V is prepared by reacting a compound .of formula IV in Claim 7 with phosphorous • . . - - 32441/2 - 14 - oxychloride or phosphorous oxybrornide "in "lin"~br anic~solvent which is ' inert under the reaction conditions and in the presence of an acid-binding agent.
9· A process for the production of a compound of formula i as defined in Claim 1 substantially as hereinbefore described in either of Examples 6 or 7.
.10. Λ process for the production of a compound of formula III as defined in Claim 1 substantially as hereinbefore described in Example 6. .. ·
11. A process for the production of a compound of formula V as defined in Claim 1 substantially as hereinbefore described in Example 7· 12. 0,0-dimethyl-0-[l-(3-methyl-l-pentyne-j5-yloxycarbonyl)-l-propen-2-yl] phosphate whenever produced by a process claimed in any of Claims 1 to 6.
12. 0,0-d.imethyl-0-[l-(3-methyl-l-pentyne-j5-yloxycarbonyl)-l-propen-2-yl ] phosphate. i 14. 'An insectlcldal or acaracidal composition comprising 0,0-dimethyl-O- [l-(j5-r"<2thyl-l-peiityne-2-yloxycarbonyl) -l-propen-2-yl ] phosphate in combination with an inert diluent or carrier. 15 14 i . A composition as claimed in Claim^6 containing between 0.01 and 90% by weight of 0 ,0-dimethyl-O- [l- (3-methyl-l-pentyne-3-yloxycarbonyl) -l-propen-2-yl ] phosphate. 16 15 · ίβ. A composition as claimed in Claim containing between 5 and 50$ by weight of 0 , 0-dimethyl-0 - [l-( methyl-l-pentyne-yloxycarbonyl)-l-propen-2-yl] phosphate. 17 14 A composition as claimed in^ Claim ffi and substantially as hereinbefore described in any one of Examples 1 to 5 · 18 ffl. A method of combatting insects or acarids, which comprises applying 0 ,0-dimethyl-O- [l-( j5-rnethyl-l-pentyne-3-yloxycarbonyl) -1-propen-2-yl] phosphate to a locus to be protected from insects or acarids. 5700/CR/SJ
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH934768A CH510696A (en) | 1968-06-21 | 1968-06-21 | Pesticide contng o, o-dimethyl-o(-1-(3-methyl- - 1-pentyne-3 yloxycarbonyl)-1-propenyl) pho- |
| CH515869 | 1969-04-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IL32441A0 IL32441A0 (en) | 1969-08-27 |
| IL32441A true IL32441A (en) | 1972-11-28 |
Family
ID=25697111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL32441A IL32441A (en) | 1968-06-21 | 1969-06-20 | O,o-dimethyl-o-(1-(3-methyl-1-pentyn-3-yloxycarbonyl)-1-propen-2-yl)phosphate,its preparation and use as insecticide and acaricide |
Country Status (5)
| Country | Link |
|---|---|
| DE (1) | DE1930751A1 (en) |
| DK (1) | DK123303B (en) |
| FR (1) | FR2011388A1 (en) |
| GB (1) | GB1265533A (en) |
| IL (1) | IL32441A (en) |
-
1969
- 1969-04-25 GB GB1265533D patent/GB1265533A/en not_active Expired
- 1969-05-30 DK DK295569AA patent/DK123303B/en unknown
- 1969-06-18 DE DE19691930751 patent/DE1930751A1/en active Pending
- 1969-06-19 FR FR6920547A patent/FR2011388A1/fr not_active Withdrawn
- 1969-06-20 IL IL32441A patent/IL32441A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE1930751A1 (en) | 1970-01-02 |
| FR2011388A1 (en) | 1970-02-27 |
| IL32441A0 (en) | 1969-08-27 |
| DK123303B (en) | 1972-06-05 |
| GB1265533A (en) | 1972-03-01 |
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