IL30804A - Phosphorus-containing oxazolidines and their use for controlling pests or weeds - Google Patents
Phosphorus-containing oxazolidines and their use for controlling pests or weedsInfo
- Publication number
- IL30804A IL30804A IL30804A IL3080468A IL30804A IL 30804 A IL30804 A IL 30804A IL 30804 A IL30804 A IL 30804A IL 3080468 A IL3080468 A IL 3080468A IL 30804 A IL30804 A IL 30804A
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- IL
- Israel
- Prior art keywords
- formula
- compound
- ethyl
- compounds
- methyl
- Prior art date
Links
- 241000607479 Yersinia pestis Species 0.000 title claims description 4
- 241000196324 Embryophyta Species 0.000 title description 23
- 229910052698 phosphorus Inorganic materials 0.000 title description 4
- 150000002917 oxazolidines Chemical class 0.000 title description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title 1
- 239000011574 phosphorus Substances 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 2
- 230000000895 acaricidal effect Effects 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 39
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 22
- 238000012360 testing method Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000007921 spray Substances 0.000 description 8
- 244000046052 Phaseolus vulgaris Species 0.000 description 7
- 239000002689 soil Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 241001414823 Lygus hesperus Species 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 6
- 208000027418 Wounds and injury Diseases 0.000 description 5
- 230000006378 damage Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000007429 general method Methods 0.000 description 5
- 239000004009 herbicide Substances 0.000 description 5
- 208000014674 injury Diseases 0.000 description 5
- 241000894007 species Species 0.000 description 5
- 238000004809 thin layer chromatography Methods 0.000 description 5
- 241001425390 Aphis fabae Species 0.000 description 4
- 241000238631 Hexapoda Species 0.000 description 4
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 241001454293 Tetranychus urticae Species 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 4
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 244000178993 Brassica juncea Species 0.000 description 3
- 244000058871 Echinochloa crus-galli Species 0.000 description 3
- 241000257159 Musca domestica Species 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 229940101209 mercuric oxide Drugs 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910052717 sulfur Chemical group 0.000 description 3
- 230000009885 systemic effect Effects 0.000 description 3
- YAXGBZDYGZBRBQ-UHFFFAOYSA-N 4,5-dihydro-1,3-oxazol-2-amine Chemical class NC1=NCCO1 YAXGBZDYGZBRBQ-UHFFFAOYSA-N 0.000 description 2
- 235000013479 Amaranthus retroflexus Nutrition 0.000 description 2
- 244000237956 Amaranthus retroflexus Species 0.000 description 2
- 235000007320 Avena fatua Nutrition 0.000 description 2
- 244000075850 Avena orientalis Species 0.000 description 2
- 235000014698 Brassica juncea var multisecta Nutrition 0.000 description 2
- 244000152970 Digitaria sanguinalis Species 0.000 description 2
- 235000010823 Digitaria sanguinalis Nutrition 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- STECJAGHUSJQJN-USLFZFAMSA-N LSM-4015 Chemical compound C1([C@@H](CO)C(=O)OC2C[C@@H]3N([C@H](C2)[C@@H]2[C@H]3O2)C)=CC=CC=C1 STECJAGHUSJQJN-USLFZFAMSA-N 0.000 description 2
- 235000015225 Panicum colonum Nutrition 0.000 description 2
- 229920001213 Polysorbate 20 Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 235000015422 Rumex crispus ssp. crispus Nutrition 0.000 description 2
- 235000015426 Rumex crispus ssp. fauriei Nutrition 0.000 description 2
- 244000207667 Rumex vesicarius Species 0.000 description 2
- 235000008515 Setaria glauca Nutrition 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- ATDGTVJJHBUTRL-UHFFFAOYSA-N cyanogen bromide Chemical compound BrC#N ATDGTVJJHBUTRL-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000005499 phosphonyl group Chemical group 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 2
- 229940116357 potassium thiocyanate Drugs 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- -1 thiophosphonyl Chemical group 0.000 description 2
- 231100000167 toxic agent Toxicity 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 241001124076 Aphididae Species 0.000 description 1
- 235000005781 Avena Nutrition 0.000 description 1
- 241001647031 Avena sterilis Species 0.000 description 1
- 235000004535 Avena sterilis Nutrition 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- 235000011332 Brassica juncea Nutrition 0.000 description 1
- 235000014700 Brassica juncea var napiformis Nutrition 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 235000017896 Digitaria Nutrition 0.000 description 1
- 241001303487 Digitaria <clam> Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000257226 Muscidae Species 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 1
- 235000011999 Panicum crusgalli Nutrition 0.000 description 1
- 244000038248 Pennisetum spicatum Species 0.000 description 1
- 235000007195 Pennisetum typhoides Nutrition 0.000 description 1
- 240000004284 Rumex crispus Species 0.000 description 1
- 235000021501 Rumex crispus Nutrition 0.000 description 1
- 235000001155 Setaria leucopila Nutrition 0.000 description 1
- 244000010062 Setaria pumila Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000208241 Tropaeolum Species 0.000 description 1
- 240000001260 Tropaeolum majus Species 0.000 description 1
- 235000005373 Uvularia sessilifolia Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- SLUNEGLMXGHOLY-UHFFFAOYSA-N benzene;hexane Chemical compound CCCCCC.C1=CC=CC=C1 SLUNEGLMXGHOLY-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KMJJJTCKNZYTEY-UHFFFAOYSA-N chloro-diethoxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCOP(Cl)(=S)OCC KMJJJTCKNZYTEY-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000002837 defoliant Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- ZBKFYXZXZJPWNQ-UHFFFAOYSA-N isothiocyanate group Chemical group [N-]=C=S ZBKFYXZXZJPWNQ-UHFFFAOYSA-N 0.000 description 1
- 150000002540 isothiocyanates Chemical class 0.000 description 1
- LGZXYFMMLRYXLK-UHFFFAOYSA-N mercury(2+);sulfide Chemical compound [S-2].[Hg+2] LGZXYFMMLRYXLK-UHFFFAOYSA-N 0.000 description 1
- 230000009526 moderate injury Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000005328 phosphinyl group Chemical group [PH2](=O)* 0.000 description 1
- 125000001863 phosphorothioyl group Chemical group *P(*)(*)=S 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical class ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 231100000208 phytotoxic Toxicity 0.000 description 1
- 230000000885 phytotoxic effect Effects 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 235000007715 potassium iodide Nutrition 0.000 description 1
- 229960004839 potassium iodide Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 208000037974 severe injury Diseases 0.000 description 1
- 230000009528 severe injury Effects 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 231100000057 systemic toxicity Toxicity 0.000 description 1
- 230000005945 translocation Effects 0.000 description 1
- 238000005303 weighing Methods 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/36—Amides thereof
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
- C07F9/653—Five-membered rings
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)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Description
Β*Ρ*Ϊ e»a»yi o» »tD tmtnV una PosphcruB-containiJig oxaaolidines and their us© for controlling peets or veerts STAUFFER CHEMICAL COMPA Ci 29031 The present invention is concerned with a novel group of thiophoephoryl, phosphonyl, thiophoaphony1, ploaphinyl and thiophoephinyl imino oxazolidines , their method of preparation, and their use as pesticides especially effective against insects, acarids and as herbicides.
The novel compounds are represented by the general formula wherein and are independently lower lkyl, lower nlkoxy or lower alk lthio; F.^ and are independently hydrogen, lower alkyl or lower alkenyl, and R¾ may also be phenyl; R_, Rg and R^ are independently hydrogen or lower i-lkyl; and X is oxygen or sulfur.
The lover rLkyl, lower ylkenyl, lower alkoxy rind lower alkylthio radicals which are suitable for ^, R3» ^ » ^5» and R are the straight rnd branched chain aliphatic radicals having from 1 to 6 carbon atoms -nd include, for example, methyl, ethyl, propyl, isopropyl, hex l and the like. 30804/2 In general, compounds of the present invention are prepared by reacting the appropriate organo substituted phosphorus chloride with an alkali metal tbiocyanate using acetone or acetonitrile as solvent. The isothiocyanate thereby produced is then reacted with the appropriate beta-hydroxy amine to give a thio urea which in the presence of mercuric ojiide undergoes cyclicization with the loss of the elements of hydrogen sulfide and yields the desired phosphoryl, thiophosphoryl, phosphonyl, thiophosphonyl, phosphinyl or thiophosphinyl imino oxazolidine. The desired product is isolated by thin layer chromatography using methods well known to those skilled in the art. The following example is illustrative of the above general method. , > EXAMPLE I Preparation of 2- fN-(0,0-Diethylphosphonothiono)-imino -3- ethyl-5-methyl-r,3-oxazolidine. To a solution of 38,8 grams (0.4 mole) of potassium thiocyanate in 395 ml. of acetone containing 6 grams of pyridine is added 75.4 grams (0.4 mole) of diethyl chlorothiophosphate over a 2 hour period. The mixture is stirred another hour at room temperature, then at 45-50 °C. for forty-five minutes. It is filtered from the precipitate of potassium chloride and the solvent removed in vacuo. The residue is taken up in benzene and the insoluble material removed. The benzene is removed in vacuo and the product distilled twice, the second time through a Vigreux column. 5.3 grams (0.025 mole) of this product is dissolved in 42 ml. of benzene 2.7 g. (0.025 mole of ethyl ^-hydroxypropylamine in 10 ml. of benzene is added over 15 minutes. After letting the mixture stand overnight, the solvent is removed in vacuo leaving a crystalline product. To a solution of 3.3 grams (0.011 mole) of the above product in 50 ml. of benzene is added 3.7 grams (0.0167 mole) of mercuric oxide.
The mixture is stirred and refluxed for 3.5 hours. The mixture is filtered and the filtrate dried over magnesium sulfate. The benzene is removed in vacuo leaving a crude viscous product. Thi product is taken up in 35 ml. of benzene and refluxed with 2.0 grams of mercuric oxide for another five hours. The mixture is again filtered, dried and the solvent removed. Pure 2-[N-(0,0-Diethyl-phosphonothiono)-imino] -3-ethyl-5-methyl-l,3-oxazolidine is isolated from the crude product by thin layer chromatography, using solvent systems 90:10 chloroform:acetone v/v on silica gel. Instrumental analysis establishes the above structure and elemental analysis shows 43.18% C, 7.53% H, 9.82% N, 11.23% P, and 11.27% S as compared with theoretical values of 43.20%, C, 7.55% H 10.00% N, 11.10% P and 11.40% S.
Another general method for the preparation of the 0,S-phos-phorylimino oxazolidines of the present invention consists of reacting the product resulting from the reaction of the appropriate 0,0-phosphorodithioic acid and cyanogen bromide in the presence of triethylamine with the appropriate beta-hydroxyamine and isolating the desired product by thin layer chromatography using methods well known to those skilled in the art. The follo ing example is illustrative of the above general method.
Example 2 Preparation of 2- [N-(Q,S-Dimethylphosphonothiolo)-imino]-3-ethyl-5-methyl-l,3-oxazolidine. To a solution of 79.0 grams (0.5 mole) of 0,0-dimethylphosphonodithioic acid in 100 ml, of benzene is added 50.5 grams (0.5 mole) of triethylamine at 15 to 2 °C. A solution of 53 grams (0.5 mole) of cyanogen bromide in 75 ml. of benzene is then added over 1.5 hours at 15°C. The reaction mixture is then stirred two more hours at room temperature, during which time the precipitate of amine hydrobromide becomes thicker. The mixture is filtered and the benzene removed from the filtrate in vacuo. The product is distilled at 55-58 °C. .75-1.0 mm. yielding 44.0 grams. 5.5 grams of this intermediate product is dissolved in 44 ml. of dry acetone and to the solution is added a solution of 3.1 grams of ethyl /$ -hydroxypropylamine i is stirred for 1.5 hours. The acetone is removed in vacuo and the residue pumped out at 0.4 mm. for 1.5 hours, yielding 8 grams. Upon standing, the product partially crystallizes. After the crystals are removed, the mixture is placed in 30 ml. of water and the mixture is extracted twice with 80 ml, portions of chloroform. The extract is dried over magnesium sulfate, filtered, and the solvent removed in vacuo. The residual oil is pumped out at 1 mm. up to 55 °C. It is then seeded with one of the spontan-eously formed crystals removed above and allowed to stand until all of the second component has crystallized out. The mixture is then filtered and the oily filtrate subjected to thin layer chromatography using 90:10 chloroform: acetone v/v and 95:5 ethanol: water v/v solvent systems on silica gel, giving pure 2- [N-(0,S-dimethylphosphonothiolo)-imino]-3-ethyl-5-methyl-l,3-oxazolidine. Instrumental analysis establishes the above structure and elemental analysis shows 12.30% P compared to 12.30¾> P theoretical.
Another general method for the preparation of the 0,S-phosphoryl imino oxazolidines of the present invention consists of reacting the appropriate 0,0-thiophosphonylimino oxazolidine with the appropriate alkyl or alkenyl iodide to form the desired product, which is isolated by thin layer chromatography using methods well known to those skilled in the art. The following example is illustrative of the above general method.
EXAMPLE 3 Preparation of 2- fN-(0, S-Dimethylphosphonothiolo)-imino'| -3-ethyl-5-me hyl-l , 3-oxazolidine. A solution of 7.6 g. (0.03 mole) of 2- [N-(0,0-dimethylphosphonothiono)-imino] -3-ethyl-5-methyl-1,3-oxazolidine and 4.4 g. (0.031 mole) of methyl iodide in a mixture of 25 ml. of hexane and 5 ml. of benzene is refluxed for 5 hours. The mixture is cooled and filtered and the solvent removed in vacuo.
EXAMPLE 4 Preparation of Diethylthiophosphinoisothiocyanatothioate. Potassium thiocyanate (65.6 g. , 0,75 mole) and a trace of potas-sium iodide are placed in 500 ml. of dry acetone and warmed to 45°. Diethylthiophosphinochloridothioate (78.3 g. , 0.5 mole) is added dropwise at 45-50°. A precipitate of potassium chloride appeared. The mixture is then refluxed for 15 minutes. It is cooled, filtered, and the solvent removed in vacuo. The residue is treated with water and the oil extracted with hexane. The extract is washed with sodium bicarbonate solution and with water, dried, and the solvent removed in vacuo. The residue is distille twice in vacuo. The product has a boiling point of 79-80°/.3 mm. Yield: 49.0 g. (55% of theory). Its IR spectrum showed a band characteristic of the isothiocyanate group at 2000-2050 cm Preparation of N-Diethylthiophosphinyl-N' -Methyl-N' -j9 -hydroxyethyl thiourea. The above-mentioned thioate (26.9 g. , .15 mole) is dissolved in 75 ml. of benzene and a solution of N-methylethanolamine (12.0 g. , .16 mole) added dropwise. The temperature increased to 33° during the addition. Stirring is continued 1 hour at room temperature, 1 hour at 65-70°. The reaction mixture is filtered through Celite and evaporated in vacuo. Upon trituation with hexane the residue solidified. It is recrystallized from benzene-hexane, and has a m.p. 68-73°. Yield: 23.4 g. (61% of theory).
Preparation of 2-(Diethylthiophosphinoimino)-3-methyl oxazolidine. The above-mentioned thiourea (15.6 g. , 0.07 mole) dissolved in 150 ml. of benzene is stirred and refluxed V7ith mercuric oxide (32.6 g. , 0,15 mole) under a Dean-Stark trap until no more water is given off (about 3 hours). Black mercuric sulfide appears. The mixture is cooled, filtered, and the filtrate dried over magnesium sulfate. Removal of the solvent left a yellow oil nj° = 1.5563. Yield: 7.8 g. (51% of theory).
The following is a table of compounds representative of those embodied in the present invention. Compound numbers have been assigned to them and are used for identification throughout the balance of the specification.
Systemic Evaluation Test. This test evaluates the j systemic toxicity by root absorption and upward translocation J of the candidate systemic compound. The two-spotted mite, j Tetranychus urticae (Koch) and the bean aphid, Aphis fabae (Scop.), j are employed in tests for systemic activity. Young pinto bean plants in the primary leaf stage are used as host plants for the two-spotted mite. The pinto bean plants are placed in bottles containing 200 ml. of the test solution and held in plac with cotton plugs. Only the roots are immersed. The solutions are prepared by dissolving the compounds to be tested in a suitable solvent, usually acetone, and then diluting with distilled water The final acetone concentration never exceeds about 1%. Immediately after the plants are placed in the test solution, they are infested with the test species. Mortalities are determined after seven days. The percentage kill is determined by comparison with control plants which are placed in distilled ater only.
The LD-50 value is calculated using well-known procedures. LD-50 values for the two-spotted mite are found in Table II under column 2SM-SYS; and for bean aphid under column BAS.
Young nasturtium plants (Tropaeolum sp.) are used as the host plants for the bean aphid. The host plants are transplanted into one pound of soil that has been treated with the candidate compound. Immediately after planting in the treated soil the plants are infested with the aphids. Concentrations of tpxiqants in the soil ranged from 10 ppm per pound of soil downward until an LD-50 value is obtained. Mortality is recorded is made with control plants placed • .*'■'¾·■' Insectlcidal Evaluation Tests* The following insect species are subjected to evaluation tests for insectlcidal activity. (1) Housefly (HF) - Musca domestica (Linn.) (2) Lygus Bug (LB) - Lygus Hesperus (Knight) Aliquots of the toxicants, dissolved in an appropriate solvent, are diluted in water containing 0.002% of a wetting agent, Sponto 221®- (a polyoxyether of alkylated phenols blended with organic sulfonates). Test concentrations range from 0.05% downward to that at which 50% mortality is obtained. In the tests, for these species, 10 one-month old nymphs of the Lygus Bug are placed in a circular cardboard cage sealed on one end with cellophane and covered by a cloth netting on the other.
Test concentrations for the Lygus Bug ranged from.0.05% downward to thaft at which 50% mortality was obtained. Each of the aqueous ί ' suspensions of the candidate compounds are sprayed onto the insects through the cloth netting by means of a hand spray gun.
Percent mortality in each case is recorded after 72 hours, and the LD-50 values expressed as percent of toxicant in the aqueous spray are recorded. The results are in Table II under Column LB. 1 The following procedure is used to test houseflies.
INSECTICIDAL EVALUATION RESUL LD-50 VALUES 6 7.5 .0005 .0003 .3 14 45.0 .0008 .0005 .05 10.0 .0008 .0003 .03 I »-» 100.0 .05 > .05 00 16 17 HOO.O .05 > 100.0 .03 .003 .8.0, 22 5.5 .00005 .0001 .008 23 85.0 .01 .05 . 5.0 24 40.0 .0005 .001 .3 40.0 .0003 .0003 .1 26 65.0 .01 .03 >10.0 37 18.0 .001 .005 8.0 8.0 > 100.0 - .005 .03 8.0 >10.0 31 5.5 .0003 .0003 .02 32 70.0 .03 .01 8.0 33 15.0 .0008 .001 .5 3.0 I 34 >100.0 > ·05 O 6.0 .0005 .0003 .3 10.0 36 ϊ ; 100.0 . .05 .03 3.0 37 18.0 .0003 .0008 .3 8.0 '3.
HF LB BA Compound BAS SYS Numbe fue/25°-) (%) I%1 -iPPm) (pom) 38 100.0 .03 .03 10.0 39 * . 30.0 .001 .001 8 _>10.0 40 ; - >ioo.o .03 .008 3.0 .0 ' .001 .003 .3 > o.o 40.0 .008 .003 1.0 > 10.0 ' 42 1 43 · 100.0 .03 .03 3.0 > io.o 44 > 100.0 .05 .03 8·°.„ ? 10.0 45 ^100.0 .003 .003 •8 >10.0 46 100.0 .03 .003 • 10.0 47 .0 . .003 . .0005 .3 8.0 48 49 > 100.0 .05 ~ .005 50 > 100.0 .01 .005 3.0 > 100.0 .01 .005 10.0 52 ' > loo. b >.05 53 > 100.0 .003 >.05 54 100.0 > .05 55 100.0 > .05 56 20.0 .0001 .0001 .03 3.0 6$ > 100.0 .05 > .05 65 . 30.0 .01 .03 1.0 10.0 66 3.7 - .001 .0003 .03 1.0 67 1.0 .0001 .00003 .005 .3 68 > 100.0 ' ·05 69 15.0 .001 .003 .08 ^10.0 . 70 70.0 .03 .008 •5 71 . 30.0 .001 .0008 .3 72 100.0 .005 .008 1.0 73 8.0 .001 .0003 As previously mentioned, the herein described compounds produced in the above described manner are phytotoxic compounds which are useful and valuable in controlling various' pla'nt species Compounds of this inventioh are tested as herbicides in the follow ing manner.
Pre-emergence herbicide test. On the, day preceding treatment, seeds of seven different weed species are planted in individual rows using one species per row across the width of the flat. The seeds used are hairy crabgrass (Digitaria sanguinatis (L.) Scop. ) , yellow foxtail (Setaria glauca (LS) Beauv.)» water-grass (Echinochloa crusgalli (L.) Beauv.)> wild oat (Avena f tua (L.))> redroot pigweed (Amaranthus retroflexus (L.))> Indian mus-tard (Brassica juncea (L.) Coss.) and curly dock (Rumex crispus (1..))· Ample seeds are planted to give about 20 to 50 seedlings per row, after emergence, depending on the size of the plants. The flats are watered after planting. The spraying solution is prepared by dissolving 50 mg. of the test compound in 3 ml. of a solvent such as acetone containing 1% Tween 20® (polyoxy-ethylene sorbitan monolaurate) and diluting with a small amount of water. The following day each flat is sprayed at the rate of 20 pounds of the candidate compound per 80 gallons of solution per acre. An atomizer is used to spray the solution on the soil sur-face. The flats are placed in a greenhouse at 80°F. and watered regularly. Two weeks later the degree of weed control is deter-mined by comparing the amount of germination and growth of each weed in the treated flats with weeds in several untreated control flats. The rating system is as follows: - = no significant injury (0-15 percent control) + = slight injury (25-35 percent control) ++ = moderate injury (55-65 percent control) .+++ = severe injury or death (85-100 percent control) An activity index is used to represent the total activity on all seven weed species. It is the sum of the number of plus marks, so that an activity index of 21 represents complete control of all seven weeds.
Post-emergence herbicide test. Seeds of five weed species including hairy crabgrass, watergrass, wild oats, Indian mustard, and curly dock and one crop pinto beans (Phaseolus vulgaris) , are planted in flats as described above for pre-emergence screening. The flats are placed in the greenhouse at 72-85 °F. and watered daily with a sprinkler. About 10 to 14 days after planting" when the primary leaves of the bean plant are almost fully expanded and the first trifoliate leaves are just starting to form, the plants are sprayed. The spray is prepared by weighing out 50 mg. of the test compound, dissolving it in 5 ml. of acetone containin 17o Tween 20® (polyoxy-ethylene sorbitan monolaurate) and then adding 5 ml. of water. The solution is sprayed on the foliage using an atomizer. The spray concentration is 0. 57o and the rate would be approximately 20 lbs. /acre if all of the spray were re-tained on the plant and the soil, but some spray is lost so it is estimated that the application rate is approximately 12. 5 lbs./ acre.
Beans are used to detect defoliants and plant growth regulators. The beans are trimmed to two or three plants per flat by cutting off the excess weaker plants several days before treat-ment. The treated plants are placed back in the greenhouse and care is taken to avoid sprinkling the treated foliage with water for three days after treatment. Water is applied to the soil by means of a slow stream from a watering hose taking care not to wet the foliage.
Injury rates are recorded 14 days after treatment. The rating system is the same as described above for the pre-emergence test where (-), (+) , (-H-) , and (+-H-) are used for the different rates of injury and control. The injury symptoms are also recorded. The maximum activity index for complete control of all the species in the post-emergence screening test is 18 which represents the sum of the plus marks obtained with the six plant species used in the test.
The concentration of a compound of the present invention constituting an effective amount and the best mode of administration to an insect or acarid pest or its habitat may be easily determined by those skilled in the art of pest control, as exemplified by the procedures described hereinabove. As shown above, the compounds of the present invention are also useful as pre-emergence or post-emergence herbicides, and can be applied in a variety of ways at various concentrations. In practice the compounds are formulated with an inert carrier utilizing methods well known to those skilled in the art, thereby making them suitable for application as dusts, sprays, drenches and the like. The amount applied depends upon the nature of the seeds or plants to be controlled and the rate of application may vary from one to 50 lbs. per acre. One particularly advantageous way of applying the compound is as a narrow band along the row crop, straddling the row.
Various changes and modifications can be made without departing from the spirit and scope of the invention described herein as will be apparent to those skilled in the art to which it pertains. It is accordingly intended that the present invention shall only be limited by the scope of the claims. 26. 30804/2
Claims (1)
1. CLAIMS Compounds of the formula wherein and independently lower lower or lover and are independently lover alkyl or lower and may also be are independently hydrogen or lower and is oxygen or of formula I in in which is lower and are lover Rg and are each is lower and X is The compound according to Claim in which is methoxy and is is ethyl and The compound according to Claim in which is 2 is is ethyl and is The compound according to Claim which is methyl is ethyl is Compounds of formula I in Claim in which nnd are each lower Rg and are and are each lower and X is The compound according to Claim in which is is methyl and and are Compounds of I in Claia in which is lower are e ch lower Rg are each and X is Compounds of I in in which and are lower and are each and is The compound according to Claim in which and are each ethyl and is acaricidal and compositione comprising an effective amount of compound having the formula I in Claim Compositions according to Claim in which in the of I is and are lower 3 4 g is lower and each and is A composition according to Claim in in the compound of formula I is is is A composition according to Claim in which in the compound of formula I is is ethyl 1 and is A composition according to in which in the of formula I is g is is ethy and is A composition according to Claim in which in the compound of formula I and are each lower and are each lower g and are is composition according to Claim in which in the of formula I is is methyl and are A ition to Claim in which in the compound of formula I is are each lower are e and X is composition to in which in the of formula I and are lower g and are and X is Λ composition according to 19 in which in the compound of formula I and ethyl is A method for controlling and applying to the of pests effective amount of a compound having the I in Claim method according to Claim in in the of formula I is and lower are ch and is method according to Claim which in the compound of formula I is and is ethyl and is A according to Claim in which in the compound of formula I is is ethylth is ethyl and is A according to Claim in which in the compound of formula I is is is ethyl and is A method according to Claim in which in the compound of formula I and are each lower and are each and are each and X ie Λ method according to Claim in which in the compound of formula I is is methyl and and g ore erch A method according to Claim in which in the compound of formula I is lower and R are lower and are each and X is according to in which in the compound of formula I each Rg and are each and is A method according to Claim in which in the of formula I and g are ethyl and is A method of controlling vegetation prising applying thereto effective amount of a having the formula I in Claim A n the of formula X io end are each lower is lower Rg and are each and X is A method according to Claim in which in the compound of formula I is methoxy and is 2 is A method according to Claim in which in the compound of formula I is g is is ethyl and is to Claim in v ich in of I in ic A to in in the I r are each lower X is recording to in in the compound of formula I is and ore netted to Claim in which in the of I ir lovrcr lower and e each X to in which in compound of formula I and are and a d X is method to C ain in the compound of fornula I R ethyl is 1 2 5 insufficientOCRQuality
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US67399367A | 1967-10-09 | 1967-10-09 | |
US70501768A | 1968-02-13 | 1968-02-13 |
Publications (2)
Publication Number | Publication Date |
---|---|
IL30804A0 IL30804A0 (en) | 1968-12-26 |
IL30804A true IL30804A (en) | 1972-05-30 |
Family
ID=27101068
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
IL30804A IL30804A (en) | 1967-10-09 | 1968-10-01 | Phosphorus-containing oxazolidines and their use for controlling pests or weeds |
Country Status (8)
Country | Link |
---|---|
BE (1) | BE722058A (en) |
CH (1) | CH502063A (en) |
DE (1) | DE1801751A1 (en) |
ES (1) | ES358861A1 (en) |
FR (1) | FR1589233A (en) |
GB (1) | GB1249343A (en) |
IL (1) | IL30804A (en) |
NL (1) | NL6814453A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3975522A (en) | 1971-12-17 | 1976-08-17 | Ciba-Geigy Corporation | Control of insects and acarids with N-phosphinylamidines |
-
1968
- 1968-10-01 IL IL30804A patent/IL30804A/en unknown
- 1968-10-05 ES ES358861A patent/ES358861A1/en not_active Expired
- 1968-10-08 FR FR1589233D patent/FR1589233A/fr not_active Expired
- 1968-10-08 CH CH1499368A patent/CH502063A/en not_active IP Right Cessation
- 1968-10-08 DE DE19681801751 patent/DE1801751A1/en active Pending
- 1968-10-09 NL NL6814453A patent/NL6814453A/xx unknown
- 1968-10-09 GB GB47836/68A patent/GB1249343A/en not_active Expired
- 1968-10-09 BE BE722058D patent/BE722058A/xx unknown
Also Published As
Publication number | Publication date |
---|---|
DE1801751A1 (en) | 1969-05-08 |
NL6814453A (en) | 1969-04-11 |
ES358861A1 (en) | 1970-12-01 |
IL30804A0 (en) | 1968-12-26 |
FR1589233A (en) | 1970-03-23 |
BE722058A (en) | 1969-04-09 |
GB1249343A (en) | 1971-10-13 |
CH502063A (en) | 1971-01-31 |
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