US3840361A - Herbicides - Google Patents
Herbicides Download PDFInfo
- Publication number
- US3840361A US3840361A US00266161A US26616172A US3840361A US 3840361 A US3840361 A US 3840361A US 00266161 A US00266161 A US 00266161A US 26616172 A US26616172 A US 26616172A US 3840361 A US3840361 A US 3840361A
- Authority
- US
- United States
- Prior art keywords
- carbon atoms
- group
- alkyl containing
- methyl
- compounds
- 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
- 239000004009 herbicide Substances 0.000 title abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 33
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 241000196324 Embryophyta Species 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 230000002363 herbicidal effect Effects 0.000 claims description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 4
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 4
- FKTUXVQEOXYNMO-UHFFFAOYSA-N cyanocarbamodithioic acid Chemical class SC(=S)NC#N FKTUXVQEOXYNMO-UHFFFAOYSA-N 0.000 abstract description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 6
- -1 chloro- Chemical class 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 244000046052 Phaseolus vulgaris Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229940102396 methyl bromide Drugs 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 235000007320 Avena fatua Nutrition 0.000 description 2
- 244000075850 Avena orientalis Species 0.000 description 2
- 244000056139 Brassica cretica Species 0.000 description 2
- 235000003351 Brassica cretica Nutrition 0.000 description 2
- 235000003343 Brassica rupestris Nutrition 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 235000001602 Digitaria X umfolozi Nutrition 0.000 description 2
- 235000017898 Digitaria ciliaris Nutrition 0.000 description 2
- 235000005476 Digitaria cruciata Nutrition 0.000 description 2
- 235000006830 Digitaria didactyla Nutrition 0.000 description 2
- 235000005804 Digitaria eriantha ssp. eriantha Nutrition 0.000 description 2
- 235000010823 Digitaria sanguinalis Nutrition 0.000 description 2
- 244000025670 Eleusine indica Species 0.000 description 2
- 235000014716 Eleusine indica Nutrition 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 2
- 244000207667 Rumex vesicarius Species 0.000 description 2
- 235000002905 Rumex vesicarius Nutrition 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 235000005373 Uvularia sessilifolia Nutrition 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000000262 haloalkenyl group Chemical group 0.000 description 2
- 235000010460 mustard Nutrition 0.000 description 2
- CKLNMNNPBUUYIQ-UHFFFAOYSA-M potassium;n-cyano-1-methylsulfanylmethanimidothioate Chemical compound [K+].CSC([S-])=NC#N CKLNMNNPBUUYIQ-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000006283 4-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Cl)C([H])([H])* 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 241000219053 Rumex Species 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000642 acaricide Substances 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
- 239000000443 aerosol Substances 0.000 description 1
- 239000003619 algicide Substances 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical class [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- MFVWSFXQWMYYSF-UHFFFAOYSA-L dipotassium;cyanoiminomethanedithiolate Chemical compound [K+].[K+].[S-]C([S-])=NC#N MFVWSFXQWMYYSF-UHFFFAOYSA-L 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000003324 growth hormone secretagogue Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000006277 halobenzyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000003750 molluscacide Substances 0.000 description 1
- 230000002013 molluscicidal effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000208 phytotoxic Toxicity 0.000 description 1
- 230000000885 phytotoxic effect Effects 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
-
- 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
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
Definitions
- 3,692,381 compounds are useful as herbicides.
- This invention relates to novel compositions of matter and their use as herbicides. More particularly, this invention relates to certain cyanodithioimidocarbonates, and the use of these materials in killing weeds.
- R is alkyl containing 1 through carbon atoms; R is selected from the group consisting of alkyl containing 1 through 5 carbon atoms and alkoxy containing 1 through 5 carbon atoms; X is selected from the group consisting of O and S; and R is selected from the group consisting of alkyl containing I through 5 carbon atoms; alkenyl containing 2 through 5 carbon atoms, haloalkenyl containing 2 through 5 carbon atoms; halobenzyl, benzyl, and R -S-R, wherein R is alkyl containing 1 through 4 carbon atoms, and R is selected from the group consisting of -CH CH CH
- halo used in describing the present invention encompasses the moieties chloro-, br0mo-, iodo-, and fluoro-, and includes polyas well as mono-substitution.
- the invention also comprises the use of materials having the above-described formula in novel herbicidal compositions and methods.
- the invention relates to compounds having the formula RgS.
- R is alkyl containing 1 through 5 carbon atoms; R, is selected from the group consisting of alkyl containing 1 through 5 carbon atoms and alkoxy containing 1 through 5 carbon atoms; X is selected from the group consisting ofO and S; and R is selected from the group consisting of alkyl containing 1 through 5 carbon atoms, haloalkyl containing 1 through 5 carbon atoms, alkenyl containing 2 through 5 carbon atoms, and haloalkenyl containing 2 through 5 carbon atoms, and their use as herbicides.
- the monoand disubstituted halogen compounds are favored and the halogens are selected from the group consisting of chlorine and bromine.
- the invention comprises compounds having the formula
- the method of the invention comprises contacting undesired vegetation or a locus to be protected with an effective or herbicidal amount of a composition having the formula above-indicated.
- the compounds of the invention may be prepared according to the following general reactions:
- the concentrations of the reactants employed are not particularly critical, although stoichiometry requires, e.g., in Step I, that about two mols. of KOI-l be employed per mol. of H- NCN and CS Again, bases other than KOI-I may be employed, such as NaOH or LiOI-l. In Step 2, other halides, such as R Cl or R 1 may be employed.
- the first step is preferably conducted in water, while steps 2 and 3 are carried out in a solvent such as acetone, DMF, DMSO, dioxane, or tetrahydrofuran.
- a solvent such as acetone, DMF, DMSO, dioxane, or tetrahydrofuran.
- the reaction is exothermic and thus does not require the addition of heat.
- Steps 2 and 3 may require heating, step 2 being carried out at a temperature of from about 0C. to about 40C., while step 3 is carried out at a temperature of from about 25C. to about C.
- EXAMPLE III EXAMPLE IV Preparation of the ethyl diethylphosphoro)cyanodithioimidocarbonate
- the compositions of the invention are phytotoxic compounds which are useful and valuable in controlling various plant species.
- 0,0-diethylphosphorothiono, methylcyanodithioimodocarbonate was tested as exemplary of the compounds of the invention, as follows:
- Seeds of five species including crabgrass, wild oats, mustard, curled dock, and one crop pinto beans are planted about one-half inch deep in sandy loam soil in individual rows in flats.
- Enough seeds are planted to give 30 to 50 plants of each species per flat, and the flats are watered after planting.
- the flats are placed in the greenhouse at to F. and watered daily with a sprinkler.
- the spray is prepared by weighing out 50 mg. of the test compound, dissolving it in 15 ml. of acetone containing 1 percent Tween 20-(polyoxyethylene monolaurate), and then adding 5 ml. of water.
- the solution is sprayed on the foliage using an atomizer.
- the spray concentration is 0.5 percent and the rate would be approximately 20 lb/acre if all of the spray were retained on the plant 14 and soil. However, since some spray is lost, it is estimated that the application rate is [approximately l2.5 lb/acre.
- 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.
- X is selected from the group consisting of O and S; and R is selected from the group consisting of alkyl containing 1 through 5 carbon atoms and an inert carrier.
- a herbicidal composition comprising an effective amount of a compound having the formula TABLE 11 Rate lbs/A.
- the compounds of ⁇ j the invention are useful as herbicides.
- the compounds may be applied directly to the particular undesired R1 N plant species or may be applied to a locus to be pro- 20 ms tected. In either event, it is, of course, necessary that the unwanted species receive an effective dosage of amount. i.c., an amount sufficient to kill or retard growth.
- the compounds are normally employed with a suitable carrier and may be applied as a dust, spray, drench or aerosol.
- the compounds thus may be applied in combination with solvents, diluents, various surface active agents, (for example, detergents, soaps or other emulsifying or wetting agents, surface active clays), carrier media, adhesives, spreading agents, humectants, and the like.
- surface active agents for example, detergents, soaps or other emulsifying or wetting agents, surface active clays
- carrier media for example, adhesives, spreading agents, humectants, and the like.
- Other biologically active compositions including other herbicides, fungicides, bactericides and algaecides, insecticides, growth stimulators, acaricides, molluscicides, etc., as well as with fertilizers, soil modifiers, etc.
- the compounds of the invention may be used in combination with an inert carrier and a surface active or emulsifying agent and may also be applied in combination with other biologically active materials, in conjunction with a carrier and a surface active or emulsifying agent.
- the solid and liquid formulations can be prepared by any of the conventional methods well-known by those skilled in the art. Determination of the optimum effective concentration for'a specific application is readily conducted by routine procedures, as will be apparent to those skilled in the art. As indicated, the amount applied in a given case will be an effective amount, i.e., an amount, i.e., an amount sufficient to give the type of control desired.
- a herbicidal composition comprising an effective amount of a compound having the formula wherein R is alkyl containing 1- through 5 carbon 7 atoms; R, is selected from the group consisting of alkyl containing 1 through 5 carbon atoms and alkoxy conwherein R is alkyl containing 1 through 5 carbon atoms; R is selected from the group consisting of alkyl containing 1 through 5 carbon atoms and alkoxy containing 1 through 5 carbon atoms; X is selected from the group consisting of O and S; and R is selected from the group consisting of alkyl containing '1 through 5 carbon atoms and an inert carrier.
- a method of killing weeds comprising applying to the weeds or a locus to be protected an effective amount of a compound having the formula wherein R is alkyl containing 1 through 5 carbon atoms; R is selected from the group consisting of alkyl containing 1 through 5 carbon atoms and alkoxy containing l through 5 carbon atoms; X is selected from the group consisting of O and S; and R is selected from the group consisting of alkyl containing vl'through 5 carbon atoms.
- a method of killing weeds comprising applying to the weeds or a locus to be protected an effective amount of a compound having the formula wherein R is alkyl containing 1 through 5 carbon atoms; R is selected from the 'group consisting of alkyl containing 1 through 5 carbon atoms and alkoxy containing 1 through 5 carbon atoms; X is selected from the group consisting of O and S; and R is selected from the group consisting of alkyl containing 1 through 5 carbon 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)
Abstract
Novel cyanodithioimidocarbonates are disclosed. The compounds are useful as herbicides.
Description
United States Patent [191 Gutman Oct. 8, 1974 HERBICIDES [51] Int. Cl AOln 9/36 Inventor: Arnold D. Gutman, erkeley Fleld of Search [73] Assignee: itznffelg CYhemical Company, New Primary Examiner Lewis Gotts Assistant Examiner-Catherine L. Mills [22] Filed: June 26, 1972 Attorney, Agent, or FirmAlbert J. Adamcik [2]] App]. No.: 266,161
Related US. Application Data [57]- ABSTRACT Division f No. 7, M h 7 P Novel cyanodithioimidocarbonates are disclosed. The
3,692,381 compounds are useful as herbicides.
[52] US. Cl. 71/87 10 Claims, N0 Drawings HERBICIDES This is a division, of application Ser. No. 17,954, filed Mar. 9, 1970, now US. Pat. No. 3,692,882.
BACKGROUND OF THE INVENTION This invention relates to novel compositions of matter and their use as herbicides. More particularly, this invention relates to certain cyanodithioimidocarbonates, and the use of these materials in killing weeds.
SUMMARY OF THE INVENTION The compounds of the present invention have the formula:
wherein R is alkyl containing 1 through carbon atoms; R is selected from the group consisting of alkyl containing 1 through 5 carbon atoms and alkoxy containing 1 through 5 carbon atoms; X is selected from the group consisting of O and S; and R is selected from the group consisting of alkyl containing I through 5 carbon atoms; alkenyl containing 2 through 5 carbon atoms, haloalkenyl containing 2 through 5 carbon atoms; halobenzyl, benzyl, and R -S-R, wherein R is alkyl containing 1 through 4 carbon atoms, and R is selected from the group consisting of -CH CH CH The term halo used in describing the present invention encompasses the moieties chloro-, br0mo-, iodo-, and fluoro-, and includes polyas well as mono-substitution. The invention also comprises the use of materials having the above-described formula in novel herbicidal compositions and methods.
In a preferred form, the invention relates to compounds having the formula RgS.
wherein R is alkyl containing 1 through 5 carbon atoms; R, is selected from the group consisting of alkyl containing 1 through 5 carbon atoms and alkoxy containing 1 through 5 carbon atoms; X is selected from the group consisting ofO and S; and R is selected from the group consisting of alkyl containing 1 through 5 carbon atoms, haloalkyl containing 1 through 5 carbon atoms, alkenyl containing 2 through 5 carbon atoms, and haloalkenyl containing 2 through 5 carbon atoms, and their use as herbicides. In this embodiment, where a halo-material is contemplated, the monoand disubstituted halogen compounds are favored and the halogens are selected from the group consisting of chlorine and bromine.
In its most preferred form, the invention comprises compounds having the formula In general, the method of the invention comprises contacting undesired vegetation or a locus to be protected with an effective or herbicidal amount of a composition having the formula above-indicated.
DETAILED DESCRIPTION OF THE INVENTION Broadly, the compounds of the invention may be prepared according to the following general reactions:
CNCN KBr STEP 3 R1 CNON KCI wherein R, R R and X are as indicated above.
The concentrations of the reactants employed are not particularly critical, although stoichiometry requires, e.g., in Step I, that about two mols. of KOI-l be employed per mol. of H- NCN and CS Again, bases other than KOI-I may be employed, such as NaOH or LiOI-l. In Step 2, other halides, such as R Cl or R 1 may be employed.
The first step is preferably conducted in water, while steps 2 and 3 are carried out in a solvent such as acetone, DMF, DMSO, dioxane, or tetrahydrofuran. In the case of step I, the reaction is exothermic and thus does not require the addition of heat. Steps 2 and 3 may require heating, step 2 being carried out at a temperature of from about 0C. to about 40C., while step 3 is carried out at a temperature of from about 25C. to about C.
The following examples are provided to demonstrate more fully the preparation of the compounds of the invention. The nomenclature employed is consistent with that used by Timmons et al., Journal of Organic Chemistry, Volume 37, Pages l566-1572.
EXAMPLE I Preparation of methyl, (0,0-diethylphosphorothio), cyanodithioimidocarbonate STEP I Approximately 8.4 grams (0.2 mol.) l-l NCN'dissolved in IS ml. of ethyl alcohol, and 13.4 ml. of CS zation. the product. dipotassium cyanodithioimidocarbonate, is separated and washed with alcohol. STEP II About 21.5 grams of the dipotassium salt of cyanodithioimidocarbonic acid are dissolved in 88 ml. of acetone and 98 ml. of H 0, and the solution is cooled to below C. About l4.2 grams of methyl iodide in about 44 ml. of acetone is added dropwise with rapid stirring under nitrogen atmosphere. After the addition is complete, the mixture is stirred for about'onehalf hour in the ice bath, and about three and one-half hours at room temperature. The solution is then evaporated and the residue dried at 50C. overnight. The residue is then stirred with about 232 ml. of acetone and filtered. The filtrate is evaporated and the residue washed with two 100 ml. portions of diethyl ether and the product. potassium methyl cyanodithioimidocarbonate, is recovered. STEP lll Approximately 8.5 grams (0.05 mol.) of potassium methylcyanodithioimidocarbonate, about 9.4 grams The procedure of Example I is repeated. except that ethyl iodide is employed instead of the methyl bromide. and 0,0-diethylphosphoryl chloride is employed instead of the 0.0-diethylthiophosphoryl chloride.
EXAMPLE V Preparation of allyl (0,0-diethylphosphorothiono) cyanodithioimidocarbonate The procedure ofExample I is repeated, except that allyl bromide is employed instead of the methyl bromide.
EXAMPLE VI Preparation of 4-chlorobenzyl diethylphosphorothiono)cyanodithioimidocarbonate The procedure of Example I is repeated, except that Pchlor'obenzyl chloride is employed instead of the methyl bromide.
The following is a table of preferred compounds which may be prepared according to the invention:
a mil trace of ZnCl and about 200 ml. of acetone are combined in a five hundred milliliter flask. The mixture is heated under reflux for two hours and then cooled to room temperature. About 300 ml. of benzene are added, and the mixture is washed with three 100 ml. portions of water. The benzene phase is then dried with anhydrous magnesium sulfate and is evaporated under reduced pressure to yield methyl-(0,0- diethylphosphorothiono)cyanodithioimidocarbonate. N,,"= 1.5900.
EXAMPLE ll Preparation of methyl (-0,0-diisopropyl phosphorothiono) cyanodithioimidocarbonate The procedure of Example I is repeated, except'that 0,0-diisopropylthiophosphoryl chloride is employed instead of the 0,0-diethylthiophosphoryl chloride.
EXAMPLE III EXAMPLE IV Preparation of the ethyl diethylphosphoro)cyanodithioimidocarbonate As previously indicated, the compositions of the invention are phytotoxic compounds which are useful and valuable in controlling various plant species. In order to demonstrate this valuable utility, 0,0-diethylphosphorothiono, methylcyanodithioimodocarbonate was tested as exemplary of the compounds of the invention, as follows:
Seeds of five species including crabgrass, wild oats, mustard, curled dock, and one crop pinto beans (Phaseolus vulgaris) are planted about one-half inch deep in sandy loam soil in individual rows in flats.
Enough seeds are planted to give 30 to 50 plants of each species per flat, and the flats are watered after planting. The flats are placed in the greenhouse at to 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, 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 15 ml. of acetone containing 1 percent Tween 20-(polyoxyethylene monolaurate), and then adding 5 ml. of water. The solution is sprayed on the foliage using an atomizer. The spray concentration is 0.5 percent and the rate would be approximately 20 lb/acre if all of the spray were retained on the plant 14 and soil. However, since some spray is lost, it is estimated that the application rate is [approximately l2.5 lb/acre.
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.
lnjury rates are recorded 14 days after treatment. A rating of O to is given based on estimated injury or kill. The results of this test are reported in Table ll.
taining 1 through 5 carbon atoms; X is selected from the group consisting of O and S; and R is selected from the group consisting of alkyl containing 1 through 5 carbon atoms and an inert carrier.
2. A herbicidal composition comprising an effective amount of a compound having the formula TABLE 11 Rate lbs/A.
Crabgrass Curled Dock Pinto Bean Mustard Wild Oats (Digilaris Rumex (Fhaseolus (Brarri'za (Avera Sanguinalis) Crirpus) Vulguris) .Iuncea) Fatua) As can be seen by the test results, the compounds of \j the invention are useful as herbicides. The compounds may be applied directly to the particular undesired R1 N plant species or may be applied to a locus to be pro- 20 ms tected. In either event, it is, of course, necessary that the unwanted species receive an effective dosage of amount. i.c., an amount sufficient to kill or retard growth. J
The compounds are normally employed with a suitable carrier and may be applied as a dust, spray, drench or aerosol. The compounds thus may be applied in combination with solvents, diluents, various surface active agents, (for example, detergents, soaps or other emulsifying or wetting agents, surface active clays), carrier media, adhesives, spreading agents, humectants, and the like. They may also be combined with other biologically active compositions, including other herbicides, fungicides, bactericides and algaecides, insecticides, growth stimulators, acaricides, molluscicides, etc., as well as with fertilizers, soil modifiers, etc. The compounds of the invention may be used in combination with an inert carrier and a surface active or emulsifying agent and may also be applied in combination with other biologically active materials, in conjunction with a carrier and a surface active or emulsifying agent. The solid and liquid formulations can be prepared by any of the conventional methods well-known by those skilled in the art. Determination of the optimum effective concentration for'a specific application is readily conducted by routine procedures, as will be apparent to those skilled in the art. As indicated, the amount applied in a given case will be an effective amount, i.e., an amount, i.e., an amount sufficient to give the type of control desired.
Various changes and modifications may be made without departing from the spirit and the scope of the invention described herein, as will be apparent to those skilled on the art to which it pertains.
I claim:
1. A herbicidal composition comprising an effective amount of a compound having the formula wherein R is alkyl containing 1- through 5 carbon 7 atoms; R, is selected from the group consisting of alkyl containing 1 through 5 carbon atoms and alkoxy conwherein R is alkyl containing 1 through 5 carbon atoms; R is selected from the group consisting of alkyl containing 1 through 5 carbon atoms and alkoxy containing 1 through 5 carbon atoms; X is selected from the group consisting of O and S; and R is selected from the group consisting of alkyl containing '1 through 5 carbon atoms and an inert carrier.
3. The composition of claim 2 wherein X is S, R is selected from the group consisting of alkyl containing 1 through 5 carbon atoms.
4. A method of killing weeds comprising applying to the weeds or a locus to be protected an effective amount of a compound having the formula wherein R is alkyl containing 1 through 5 carbon atoms; R is selected from the group consisting of alkyl containing 1 through 5 carbon atoms and alkoxy containing l through 5 carbon atoms; X is selected from the group consisting of O and S; and R is selected from the group consisting of alkyl containing vl'through 5 carbon atoms.
5. A method of killing weeds comprising applying to the weeds or a locus to be protected an effective amount of a compound having the formula wherein R is alkyl containing 1 through 5 carbon atoms; R is selected from the 'group consisting of alkyl containing 1 through 5 carbon atoms and alkoxy containing 1 through 5 carbon atoms; X is selected from the group consisting of O and S; and R is selected from the group consisting of alkyl containing 1 through 5 carbon atoms.
6. The method of claim 5 wherein X is S, R is selected from the group consisting of alkyl containing 1 through 5 carbon atoms.
7. The composition of claim 3 wherein R is ethyl, R 9. The method of claim 6 wherein R is ethyl, R is is ethoxy, X is S. and R is methyl. ethoxy, X is S, and R is methyl.
8. The composition of claim 3 wherein R is methyl, 10. The method of claim 6 wherein R is methyl, R R, is isopropoxy, X is S, and R is ethyl. is isopropoxy, X is S, R is ethyl.
Claims (10)
1. A HERBICIDAL COMPOSITION COMPRISING AN EFFECTIVE AMOUNT OF A COMPOUND HAVING THE FORMULA
2. A herbicidal composition comprising an effective amount of a compound having the formula
3. The composition of claim 2 wherein X is S, R2 is selected from the group consisting of alkyl containing 1 through 5 carbon atoms.
4. A method of killing weeds comprising applying to the weeds or a locus to be protected an effective amount of a compound having the formula
5. A method of killing weeds comprising applying to the weeds or a locus to be protected an effective amount of a compound having the formula
6. The method of claim 5 wherein X is S, R2 is selected from the group consisting of alkyl containing 1 through 5 carbon atoms.
7. The composition of claim 3 wherein R is ethyl, R1 is ethoxy, X is S, and R2 is methyl.
8. The composition of claim 3 wherein R is methyl, R1 is isopropoxy, X is S, and R2 is ethyl.
9. The method of claim 6 wherein R is ethyl, R1 is ethoxy, X is S, and R2 is methyl.
10. The method of claim 6 wherein R is methyl, R1 is isopropoxy, X is S, R2 is ethyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US00266161A US3840361A (en) | 1970-03-09 | 1972-06-26 | Herbicides |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US1795470A | 1970-03-09 | 1970-03-09 | |
| US00266161A US3840361A (en) | 1970-03-09 | 1972-06-26 | Herbicides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3840361A true US3840361A (en) | 1974-10-08 |
Family
ID=26690548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00266161A Expired - Lifetime US3840361A (en) | 1970-03-09 | 1972-06-26 | Herbicides |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3840361A (en) |
-
1972
- 1972-06-26 US US00266161A patent/US3840361A/en not_active Expired - Lifetime
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3325503A (en) | Polychloro derivatives of mono- and dicyano pyridines and a method for their preparation | |
| US3330641A (en) | Herbicidal composition and method | |
| US3187042A (en) | N-alkoxy benzamides | |
| US3168561A (en) | N-alkoxy 2-alkyl-4-chlorophenoxyacetamides for the control of pests | |
| US3564608A (en) | Selected n-acylsubstituted-n'-hydroxyguanidines | |
| US3187041A (en) | N-alkoxy phenylacetamides | |
| US3276855A (en) | N-alkylmercapto-ureas and a method for controlling weeds | |
| US2893855A (en) | N-1-napthylchlorophthalamic herbicides | |
| US3749747A (en) | Substituted cinnanyl thiocyanates and their isomers | |
| US3840361A (en) | Herbicides | |
| US3742005A (en) | Herbicidal thiolcarbamates | |
| US3692882A (en) | Cyanodithioimidocarbonate phosphates | |
| US3732272A (en) | Herbicidal n,n-alkyl alkyliminoalkyl thiocarbamates | |
| US3166589A (en) | Phenoxyacetamides for the control of pests | |
| US3512955A (en) | Method of protecting plant growth | |
| US3516816A (en) | Herbicidal compositions and methods utilizing alkyleneiminourea compounds | |
| US3876414A (en) | Substituted propene thiocyanate and isothiocyanate containing compositions and their use in killing weeds | |
| US3655761A (en) | Certain oxime esters | |
| US3701799A (en) | Plant growth regulators | |
| EP0206605B1 (en) | N-acyl amino acid derivative and process for production and use thereof | |
| US3632333A (en) | N-acylsubstituted-n{40 -hydroxyguanidines as herbicides | |
| US3119735A (en) | Method for combatting plant-parasitic nematodes | |
| US3497344A (en) | Herbicidal compositions and methods utilizing uramidobenzoate compounds | |
| US3352897A (en) | Nu-alkoxy amides of 4-halophenoxyalkylcarboxy acids | |
| JPS61291555A (en) | N-substituted glutamic acid and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: ICI AMERICAS INC., A DE CORP., DELAWARE Free format text: CHANGE OF NAME;ASSIGNOR:STAUFFER CHEMICAL COMPANY;REEL/FRAME:005197/0025 Effective date: 19890815 |