US3649723A - O-alkyl-s-unsaturated aliphatic hydrocarbyl phosphoroamidothioates - Google Patents
O-alkyl-s-unsaturated aliphatic hydrocarbyl phosphoroamidothioates Download PDFInfo
- Publication number
- US3649723A US3649723A US486233A US3649723DA US3649723A US 3649723 A US3649723 A US 3649723A US 486233 A US486233 A US 486233A US 3649723D A US3649723D A US 3649723DA US 3649723 A US3649723 A US 3649723A
- Authority
- US
- United States
- Prior art keywords
- phosphoroamidothioate
- phosphoroamidothioates
- propargyl
- unsaturated aliphatic
- ethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- -1 O-alkyl-s-unsaturated aliphatic hydrocarbyl phosphoroamidothioates Chemical class 0.000 title abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000749 insecticidal effect Effects 0.000 abstract description 5
- RJBIAAZJODIFHR-UHFFFAOYSA-N dihydroxy-imino-sulfanyl-$l^{5}-phosphane Chemical class NP(O)(O)=S RJBIAAZJODIFHR-UHFFFAOYSA-N 0.000 description 30
- 150000001875 compounds Chemical class 0.000 description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 241000196324 Embryophyta Species 0.000 description 6
- 241000238631 Hexapoda Species 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 241000255925 Diptera Species 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 241000238876 Acari Species 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000002917 insecticide Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 3
- 241001124076 Aphididae Species 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 150000003973 alkyl amines Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 230000009885 systemic effect Effects 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 244000045232 Canavalia ensiformis Species 0.000 description 2
- 241001454293 Tetranychus urticae Species 0.000 description 2
- SUPWBRVWHHROTG-UHFFFAOYSA-N [amino(hydroxy)phosphinothioyl]oxyethane Chemical compound CCOP(N)(O)=S SUPWBRVWHHROTG-UHFFFAOYSA-N 0.000 description 2
- WPEVVXOGSYZQDP-UHFFFAOYSA-N [amino(hydroxy)phosphinothioyl]oxymethane Chemical compound COP(N)(O)=S WPEVVXOGSYZQDP-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000003701 inert diluent Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 231100000167 toxic agent Toxicity 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- LIVCNGIOYZNYHR-UHFFFAOYSA-N 1-[amino(hydroxy)phosphinothioyl]oxybutane Chemical compound CCCCOP(N)(O)=S LIVCNGIOYZNYHR-UHFFFAOYSA-N 0.000 description 1
- ULZHPJSONPCEKP-UHFFFAOYSA-N 1-[amino(hydroxy)phosphinothioyl]oxypropane Chemical compound CCCOP(=S)(N)O ULZHPJSONPCEKP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 241001600408 Aphis gossypii Species 0.000 description 1
- 240000008067 Cucumis sativus Species 0.000 description 1
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 1
- 241000506680 Haemulon melanurum Species 0.000 description 1
- 241000257159 Musca domestica Species 0.000 description 1
- 241000257226 Muscidae Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241000258913 Oncopeltus fasciatus Species 0.000 description 1
- 235000010617 Phaseolus lunatus Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 240000003779 butterfly milkweed Species 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011593 sulfur Substances 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
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/2412—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of unsaturated acyclic alcohols
Definitions
- R is monovalent unsaturated aliphatic hydrocarbyl radical such as allyl or propargyl
- R is lower alkyl
- R" is hydrogen or lower alkyl.
- Phosphoroamidothioates of this group are insecticidal.
- This invention relates to a unique group of phosphoroamidothioates and their use as insecticides. More particularly, it concerns O-alkyl-S-unsaturated aliphatic hydrocarbyl phosphoroamidothioates and their use as contact and systemic insecticides.
- the compounds of this invention are phosphoramidothioates, wherein an unsaturated aliphatic hydrocarbyl group is bonded to the sulfur, a lower alkyl group is bonded to the oxygen which is covalently bonded to the phosphorus and the amido group is either unsubstituted or singly substituted with a lower alkyl group.
- R is a monovalent unsaturated aliphatic hydrocarbyl radical, R is lower alkyl and R" is hydrogen or lower alkyl.
- the univalent hydrocarbyl radical, R may contain single or plural sites of aliphatic unsaturation.
- the sites of unsaturation may be the same or different, that is to say, ethylenic and acetylenic sites may be present in a given radical. These sites may be located in any position within the radical. Usually there will be not more than 2 sites of unsaturation in the radical, and more usually there will be only a single site.
- the preferred compounds are those wherein R" is hydrogen and R is an aliphatic hydrocarbyl group having from 3 to 6 carbon atoms which has a single terminal site of aliphatic unsaturation. Particularly preferred compounds are those wherein R is propargyl. Lower alkyl as used herein includes alkyl groups having from 1 to 6 carbon atoms.
- Examples of the particularly preferred compounds of this invention are: O-methyl-S-propargyl phosphoroamidothioate, O-ethyLS-propargyl phosphoroamidothioate, O- butyl S propargyl phosphoroamidothioate, O-hexyl-S- propargyl phosphoroamidothioate, O-methyl-S-propargyl methylphosphoroamidothioate, O propyl S propargyl ethylphosphoroamidothioate, O i propyl 'S-propargyl butylphosphoroamidothioate, etc.
- the phosphoroamidothioates of this invention may be prepared by reacting an 0,0-dialkyl chlorophosphorothionate with ammonia or a primary alkyl amine and then heating the reaction product in the presence of an unsaturated acyclic hydrocarbon halide having from 3 to 6 carbon atoms and wherein the halogen is of atomic number 17 to 53.
- an unsaturated acyclic hydrocarbon halide having from 3 to 6 carbon atoms and wherein the halogen is of atomic number 17 to 53.
- the degree of reactivity of the bromides, and in some cases the iodides, of the unsaturated aliphatic hydrocarbons make these species particularly suitable for use in this reaction.
- the relative amounts of reactants employed must at least approximate stoichiometric proportions. Usually excess halide will be used. In terms of ratios, the mol ratio of halide to aminated phosphorothioate will be from about 1.0 to 10.
- an inert diluent such as an aromatic or paraffinic solvent.
- the ammonia and gaseous alkyl amines may be passed as such through the phosphorothionate solution.
- the liquid primary alkyl amines may be added directly to the solution.
- the inert diluent will normally be removed prior to the addition of the halide of the unsaturated aliphatic hydrocarbon. Removal of the diluent may be conveniently accomplished by stripping.
- Heating of the stripped reaction product in the presence of halide will usually take place at temperatures between about 20 to C. For convenience, reflux temperatures may be used in this step.
- Excess halide may be removed from the final product by known methods such as distillation. Further purification of the product may be achieved by dissolving it in an inert solvent, removing insoluble by-products and stripping the solvent under subatmospheric pressure.
- EXAMPLE I Into a flask were placed 10 ml. of 0,0-dimethy1 phosphoroamidothioate and 20 ml. of propargyl bromide. This mixture was refluxed for 6.5 hours, after which the contents were stripped at 70 C., 0.1 mm. Hg. An oil residue of O-methyl-S-propargyl phosphoroamidothioate was left, The structure of this product was verified by infrared and nuclear magnetic resonance analyses. Its analysis for percent P and S were, respectively: Ca1c., 18.78; found, 17.75; calc. 19.41; found, 2108.
- EXAMPLE III A reaction vessel was charged with 8 gl'IlS. of 0,0-diethyl phosphoroamidothioate and 25 mls. allyl bromide. This mixture was refluxed for 11 hours after which it was stripped at 60 C., 0.1 mm. Hg, leaving a brown oil residue which solidified on standing. The solid was broken up, slurried with hexane, filtered and washed with hexane to provide 7.9 gms. of O-ethyl-S-allyl phosphoroamidothioate. This compound was observed as a tan solid having a melting point of 32-34 C. Its analysis was: percent N--calc.: 7.74, found: 7.04; percent P-calc.: 17.10, found: 17.95.
- the phosphoroamidothioates described in Examples I through IV were evaluated as contact insecticides against aphids, flies, mites and other insects.
- the method used in the tests concerning the aphids and mites is called the Leaf Dip Method.
- 1% acetone solution of the compound to be tested is diluted with water to the desired concentration.
- Three replicate Fordhook lima bean leaves in the trifoliate stage infested with mites and 3 replicate National Pickling cucumber leaves infested with at least 20 individual aphids are used.
- l-mch leaf is dipped into the dilution of the compound, excess water is drained off and the leaf is placed in a petri dish having a piece of damp filter paper covering its bottom. The dish is allowed to dry, it is redampened with water, capped and incubated for 24 hours at 75 F. After this period, the mortality is observed and percent control is determined as compared to a standard.
- the method used in the tests on flies and milkweed bug is conducted as follows: A 1% acetone solution of the toxicant is diluted further with acetone to the desired concentration and placed in a 1 ml. syringe set to displace doses. A random mixture of male and female houseflies are anesthetized with CO and 3 replicates of 20 flies each are sorted out and placed on squares of corrugated cardboard. To each of these flies are applied directly two 0.5x doses of the acetone solution from the syringe. Each replicate is then placed in a covered onehalf pint recovery cage along with a piece of watersoaked cotton wick. The cages are placed in a recovery chamber at 75 F. and observed for mortality after 24 hours. Control is reported as the percentage of the flies 4 dead after this period. The results of this contact insecticidal testing are reported in Table I.
- F-Flies (Musca dom-estica L.)
- A-Aphids (Aphis gossypii Glover)
- M.B.-Milkweed bug (Oncopcltus facz'atus, Dal.)
- the new phosphoroamidothioates of this invention Were also tested for effectiveness as systemic insecticides.
- a soil drench method was used which employs the two-spotted mite (Tetranychus telarius L.) as the organism with 3 replica 10-14 day old Fordhook lima bean plants as the hosts.
- a 1% solution of the phosphoroamidothioate in acetone containing 12 drops of a liquid premixed emulsifier is prepared. This solution is diluted with water to the desired concentration and 25 ml. of it is applied to the soil around each plant.
- After 48 hours the plants are infested with mites by placing the plants in the mitehouse and covering them with infested leaves from the stock colony. After 48 hours the plants are inspected for mite mortality. This mortality is compared with a standard and the percent control is determined. Table 11 reports the results of these tests.
- these unique phosphoroamidothioates may be applied either directly to the organism or to any environmental area which is a host to insects or susceptible to insect attack.
- insecticidal formulations containing toxic amounts of these new phosphoroamidothioates may b sprayed directly on the insects.
- these formulations may be sprayed or otherwise applied to the plant or other host, its seed or its immediate environment, such as the soil surrounding it.
- Solid formulations will comprise a toxic amount of phosphoroamidothioate with a suitable, biologically inert solid carrier such as powder, granules or dust.
- the insecticidal compounds of this invention are, in general, water miscible and to some extent miscible in hydrocarbon solvents such as alkanes and aromatic solvents.
- hydrocarbon solvents such as alkanes and aromatic solvents.
- the solubility in hydrocarbon solvents increases. Consequently, the solvent chosen for liquid formulation will depend upon the particular compound being formulated. Also, dispensing and Wetting agents may be used in formulating these compounds.
- these compounds may not only be applied alone or in mixtures with other compounds of the disclosed class, but they may also be used in combination with other active toxicants in the making of agriculturally useful compositions for control of plant infesting insects.
- R is a monovalent aliphatic hydrocarbyl group 6 having from 3 to 6 carbon atoms and a single terminal site of aliphatic unsaturation, R is a lower alkyl group and R" is hydrogen or a lower alkyl group.
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- 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)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US48623365A | 1965-09-09 | 1965-09-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3649723A true US3649723A (en) | 1972-03-14 |
Family
ID=23931105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US486233A Expired - Lifetime US3649723A (en) | 1965-09-09 | 1965-09-09 | O-alkyl-s-unsaturated aliphatic hydrocarbyl phosphoroamidothioates |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US3649723A (enrdf_load_stackoverflow) |
| AT (2) | AT261634B (enrdf_load_stackoverflow) |
| BE (1) | BE686185A (enrdf_load_stackoverflow) |
| CH (1) | CH477478A (enrdf_load_stackoverflow) |
| DK (1) | DK122397B (enrdf_load_stackoverflow) |
| ES (1) | ES331004A1 (enrdf_load_stackoverflow) |
| GB (1) | GB1111259A (enrdf_load_stackoverflow) |
| NL (1) | NL6612670A (enrdf_load_stackoverflow) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3914417A (en) * | 1972-12-21 | 1975-10-21 | Chevron Res | Insectidical N-hydrocarboyl phosphoroamidothioates and phosphoroamidodithioates |
| US5936113A (en) * | 1997-12-10 | 1999-08-10 | Bayer Corporation | Process for making O,S-dimethyl phosphoramidothioate |
-
1965
- 1965-09-09 US US486233A patent/US3649723A/en not_active Expired - Lifetime
-
1966
- 1966-08-30 BE BE686185D patent/BE686185A/xx unknown
- 1966-09-02 CH CH1275866A patent/CH477478A/de not_active IP Right Cessation
- 1966-09-08 ES ES0331004A patent/ES331004A1/es not_active Expired
- 1966-09-08 NL NL6612670A patent/NL6612670A/xx unknown
- 1966-09-08 AT AT849466A patent/AT261634B/de active
- 1966-09-08 DK DK462866A patent/DK122397B/da unknown
- 1966-09-08 AT AT499267A patent/AT271992B/de active
- 1966-09-09 GB GB40500/66A patent/GB1111259A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3914417A (en) * | 1972-12-21 | 1975-10-21 | Chevron Res | Insectidical N-hydrocarboyl phosphoroamidothioates and phosphoroamidodithioates |
| US5936113A (en) * | 1997-12-10 | 1999-08-10 | Bayer Corporation | Process for making O,S-dimethyl phosphoramidothioate |
Also Published As
| Publication number | Publication date |
|---|---|
| ES331004A1 (es) | 1967-08-01 |
| AT271992B (de) | 1969-06-25 |
| NL6612670A (enrdf_load_stackoverflow) | 1967-03-10 |
| AT261634B (de) | 1968-05-10 |
| GB1111259A (en) | 1968-04-24 |
| BE686185A (enrdf_load_stackoverflow) | 1967-02-01 |
| DK122397B (da) | 1972-02-28 |
| CH477478A (de) | 1969-08-31 |
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