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Allophanimidate herbicides - Patent # 3959331 - PatentGenius
Allophanimidate herbicides
3959331 Allophanimidate herbicides
Application: 05/325,357
Filed: January 22, 1973
Inventors: Fuchs; Julius J. (Wilmington, DE)
Lin; Kang (Newark, DE)
Primary Examiner: Patten; James A.
U.S. Class: 504/303; 558/4; 558/5; 558/8; 560/115; 560/148; 560/16; 560/29; 560/30
Field Of Search: 260/471C; 260/455A
U.S Patent Documents: 3636079
Abstract: Allophanimidates and carbamates of the formulas ##EQU1## where R.sub.1 is hydrogen or alkyl;R.sub.2 is alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, benzyl or phenyl optionally substituted;R.sub.3 is SR.sub.4 or OR.sub.4 ;R.sub.4 is alkyl, cycloalkyl, alkenyl, alkynyl, phenyl, or benzyl;R.sub.5 is alkyl, alkenyl, cycloalkyl, benzyl or phenyl optionally substituted; andR.sub.6 is hydrogen or alkylX.sub.1, x.sub.2 and X.sub.3 are oxygen or sulfur,Are useful as herbicides.Exemplary of the compounds is methyl 4-tert-butyl-N-methoxycarbonyl-1-thioallophanimidate.
1. A compound of the formula ##EQU8## wherein R.sub.1 is hydrogen;
R.sub.2 is ##SPC3##
Y is hydrogen, halogen, or methyl; and
R.sub.3 is OR.sub.4 or SR.sub.4 ;
R.sub.4 is methyl or ethyl;
R.sub.5 is methyl or ethyl;
R.sub.6 is hydrogen;
X.sub.1 and X.sub.2 are oxygen; and
X.sub.3 is oxygen or sulfur.
2. The compound of claim 1 which is methyl 4-(p-chlorophenyl)-N-methoxycarbonyl allophanimidate.
3. The compound of claim 1 which is methyl 4-(p-chlorophenyl)-N-methylthiocarbonylallophanimidate.
Organic Synthesis, 42, 87, discloses preparation of methyl 4-phenyl-3-thioallophanimidate, but does not disclose any use for the compound.
We have discovered that the compounds of the following formulas I and II are useful as herbicides, i.e., they are useful as soil sterilants and as selective herbicides on crops such as corn, asparagus, pineapple and sugarcane: ##EQU2## whereinX.sub.1, X.sub.2, and X.sub.3 are oxygen or sulfur;
R.sub.1 is hydrogen or alkyl of 1 through 4 carbon atoms;
R.sub.2 is alkyl of 1 through 6 carbon atoms, cycloalkyl of 3 through 8 carbon atoms, cycloalkylalkyl of 4 through 7 carbon atoms, alkenyl of 3 through 4 carbon atoms, alkynyl of 3 through 4 carbon atoms, benzyl, or ##SPC1##
Y is hydrogen, halogen, alkyl of 1 through 4 carbon atoms, nitro, alkoxy of 1 through 4 carbon atoms, alkylthio of 1 through 4 carbon atoms, cyano, or trifluoromethyl; and
Z is hydrogen, halogen, methyl, ethyl, nitro, alkoxy of 1 through 4 carbon atoms, or alkylthio of 1 through 4 carbon atoms;
O is hydrogen, halogen, or methyl;
R.sub.3 is SR.sub.4 or OR.sub.4 ;
R.sub.4 is alkyl of 1 through 6 carbon atoms,
Cycloalkyl of 3 through 8 carbon atoms,
Alkenyl of 3 through 4 carbon atoms, alkynyl of 3 through 4 carbon atoms, benzyl or phenyl; and
R.sub.5 is alkyl of 1 through 12 carbon atoms substituted with 0-3 chlorine atoms or 0-1 methoxy group, alkenyl of 3 through 4 carbon atoms, cycloalkyl of 5 through 8 carbon atoms, benzyl, or ##SPC2##
Y and Z are as previously defined;
R.sub.6 is hydrogen or alkyl 1 through 3 carbon atoms.
Preferred within Formula I because of ease of synthesis and higher activity are those compounds where
R.sub.2 is alkyl of 1 through 6 carbon atoms, alkenyl of 3 through 4 carbon atoms, or phenyl substituted with 0-3 halogens selected from chlorine and bromine;
R.sub.4 is alkyl of 1 throughh 6 carbon atoms or allyl;
R.sub.5 is alkyl of 1 through 4 carbon atoms;
More preferred because of their highest activity are are those compounds where
R.sub.2 is alkyl of 3 through 4 carbon atoms;
Preferred compounds because of their high activity are:
methyl 4-tert-butyl-N-methoxycarbonyl-1-thioallophanimidate
methyl 4-tert-butyl-N-methylthiolcarbonyl-1-thioallophanimidate
methyl 4-isopropyl-N-methoxycarbonyl-1-thioallophanimidate
methyl 4-isopropyl-N-ethoxycarbonyl-1-thioallophanimidate
methyl 4-isopropyl-N-isopropoxycarbonyl-1-thioallophanimidate
It should be understood that tautomeric forms of the molecule are possible when R.sub.6 is hydrogen; ##EQU3## For this reason, all compounds when R.sub.6 is hydrogen are named allophanimidates according to form (A). Compounds of Form (C) arealso named as allophanimidates, while compounds of Form (D) are named as carbamates. ##EQU4##
The compounds of the invention can be made by the process illustrated by the following equations: ##EQU5## where R.sub.4, R.sub.5 and R.sub.6 are as previously defined and
R.sub.7 is R.sub.1 or R.sub.2.
In equation (1) the 2-thiopseudourea is liberated from its corresponding chloride or sulfate with one mole of base and reacted with an isocyanate in a solvent, e.g., water, aqueous methanol or aqueous acetone, at about 0.degree.C. The reactionmass is warmed to room temperature and the solvent removed by evaporation. The intermediate thioallophanimidate is collected by filtration and dried (This reaction is essentially the same method as described in Organic Synthesis, 42, 87, for thepreparation of methyl 4-phenyl-3-thioallophanimidate).
The intermediate is reacted with one equivalent of a chloroformate in methylene chloride containing one equivalent of triethylamine (equation 2). The methylene chloride solution is washed with water, dried, and stripped to afford thethioallophanimidates of this invention in good purity. The reaction product can be further purified by dissolving it in dimethylformamide and precipitating it by adding water or by recrystallization from hexane.
The same allophanimidates can also be obtained by reacting the 2-thiopseudourea first with a chloroformate and then an isocyanate as in equations 3 and 4. ##EQU6## where R.sub.4, R.sub.5, R.sub.6 and R.sub.7 are as defined for equations (1) and(2).
In Equation (3) the 2-thiopseudourea sulfate and a chloroformate in water are cooled to about 0.degree.C. and two equivalents of base are added gradually. The reaction mixture is allowed to come to room temperature and then extracted withmethylene chloride. The methylene extract is dried and evaporated to afford the intermediate alkyl N-(1-alkylamino-1-methylthiomethylene)carbamate or alkyl-(1-amino-1-methylthiomethylene)carbamate in excellent purity.
In equation (4) the intermediate is dissolved in methylene chloride and one equivalent of isocyanate is added. The mixture is stirred for several hours, and then evaporated to produce the allophanimidates in excellent yield and purity. Theproduct can be further purrified using the techniques set forth above.
To make the various analogs of the above compounds, the appropriate isothiocyanates can replace the isocyanates used in the equations (1) and (4). The useful 2-thiopseudoureas of equations (1) and (3) can be replaced by 2-alkylpseudoureas. Theuseful chloroformates of equations (2) and (4) include alkyl chloroformates, chlorothiolformates, or chlorodithioformates.
Alkoxycarbonylthioallophanimidates with 2 alkyl substituents in the 4-position can be prepared by starting with the product of reaction (3) and reacting it with a dialkylcarbamoyl chloride in the presence of triethylamine as illustrated byreaction (5). ##EQU7##
In reaction (5) the reactants are heated for 1-3 hours in the presence of triethylamine in a solvent such as benzene or toluene. After completion of the reaction, the solvent is evaporated, the residue extracted with water to dissolvewater-soluble substances, and the residue recrystallized from benzene.
To 139 parts 2-methyl-2-thiopsuedourea sulfate in 1000 parts 50% aqueous methanol at 0.degree.C. is added dropwise 88 parts 50% sodium hydroxide, followed by 90 parts tert-butylisocyanate in 200 parts tetrahydrofuran. The solution is thenstripped of most of the methanol and tetrahydrofuran on a rotary evaporator and filtered to yield after drying 90 parts methyl 4-tert-butyl-1-thioallophanimidate melting at 102.degree.-104.degree.C.
To 5.67 parts of the above compound and 4 parts triethylamine in 50 parts methylene chloride at 0.degree.C. is added dropwise 3.3 parts methyl chlorothiolformate in 5 parts methylene chloride. The solution is stirred overnight and washed oncewith water. After drying and evaporation of the solvent on a rotary evaporator, there is obtained 3.8 parts methyl 4-tert-butyl-N-methylthiolcarbonyl-1-thioallophanimidate melting at 102.degree.-105.degree.C.
4-tert-Butyl-N-methoxycarbonyl-1-thioallophanimidate
To 5.67 parts of methyl 4-tert-butyl-1-thioallophanimidate, prepared as in Example 1, and 4 parts of triethylamine in 50 parts methylene chloride at 0.degree.C. is added dropwise 2.8 parts methyl chloroformate in 5 parts methylene chloride. Thesolution is stirred overnight and washed once with water. After drying and evaporation of the solvent on a rotary evaporator, there is obtained an oil which turned crystalline. After trituration with hexane it affords 1.9 parts4-tert-butyl-N-methoxycarbonyl-1-thioallophanimidate melting at 87.degree.-90.degree.C.
To 69.5 parts 2-methyl-2-thiopseudourea sulfate and 47 parts of methyl chloroformate in 1,000 parts water at 0.degree.C is added dropwise 56.9 parts of potassium hydroxide in 200 parts of water. The reaction mixture is stirred at roomtemperature for 3 hours and then extracted with methylene chloride. The methylene chloride extract is dried and the solvent evaporated on a rotary evaporator to give 45 parts of methyl N-(1-amino-1-methylthiomethylene)carbamate melting at72.degree.-77.degree.C.
Seventy-four parts of the above compound and 47 parts of isopropyl isocyanate in 300 parts methylene chloride is stirred overnight. The solvent is evaporated on a rotary evaporator to give 113.6 parts methyl4-isopropyl-N-methoxycarbonyl-1-thioallophanimidate melting at 129.degree.-132.degree.C.
The following allophanimidates can be similarly prepared: methyl 4-cyclopentyl-2-methyl-N-methoxycarbonyl-1-thioallophanimiate, and methyl 4-cyclohexyl-2-propyl-N-methoxycarbonyl-1-thioallophanimidate.
Methyl 4-methyl-N-methylthiolcarbonyl-1-thioallophanimidate
To 69.5 parts 2-methyl-2-thiopseudourea sulfate and 110 parts methyl chlorothioformate in 500 ml. of water is added dropwise at 0.degree.-5.degree.C. 120 parts 50% sodium hydroxide. The reaction mixture is stirred at 0.degree.-5.degree.C. for1 hour and then at room temperature for 2 hours. The solution is extracted with methylene chloride. The methylene chloride extract is then dried and the solvent evaporated on a rotary evaporator to give 47 parts of methylN-(1-amino-1-methylthiomethylene)thiocarbamate melting at 75.degree.-76.degree.C.
To 8.2 parts of the above compound in 75 parts methylene chloride is added 3.1 parts methyl isocyanate. The reaction mixture is stirred at room temperature for 3 hours, and then stripped of solvent on a rotary evaporator to give 10 parts methyl4-methyl-N-methylthiocarbonyl-1-thioallophanimidate melting at 115.degree.-117.degree.C.
Methyl 4-(p-chlorophenyl)-N-methoxycarbonyl-1-thioallophanimidate
To 7.2 parts methyl N-(1-amino-1-methylthiomethylene)carbamate prepared as in Example 3 in 100 parts methylene chloride is added 8.4 parts p-chlorophenyl isocyanate. The reaction mixture is stirred overnight and the solvent evaporated on arotary evaporator. The residue is dissolved in dimethylformamide and water is added. The precipitate is collected by filtration and then dried to give 10.4 parts methyl 4-chlorophenyl)-N-methoxycarbonyl-1-thioallophanimidate melting at73.degree.-74.5.degree.C.
Methyl 4-sec-butyl-N-methoxycarbonyl-1-thioallophanimidate
To 7.2 parts methyl N-(1-amino-1-methylthiomethylene)carbamate, prepared as in Example 3, in 50 parts methylene chloride is added 5.5 parts sec-butylisocyanate. The reaction mixture is stirred overnight and the solvent is evaporated on a rotaryevaporator to give 12 parts methyl 4-sec-butyl-N-methoxycarbonyl-1-thioallophanimidate melting at 102.degree.-104.degree.C.
To 138 parts 2-methyl-2-thiopseudourea in 500 parts water at 0.degree.-10.degree.C. is added 80 parts 50% sodium hydroxide. One liter of cold acetone is added followed by dropwise addition of 85 parts isopropyl isocyanate. The mixture isallowed to stay at room temperature for 2 hours and evaporated on a rotary evaporator. The solid is collected and dried to give 150 parts methyl 4-isopropyl-1-thioallophanimidate melting at 81.degree.-85.degree.C.
To 8.8 parts of the above compound and 6.0 parts ethyl chloroformate at 0.degree.C. is added dropwise 8.4 parts triethylamine. The reaction is stirred at room temperature for 3 hours. Water is added and stirred for a while. The methylenechloride layer is dried and evaporated on a rotary evaporator to give after hexane trituration, 10.2 parts methyl 4-isopropyl-N-ethoxycarbonyl-1-thioallophanimidate melting at 90.degree.-92.degree.C.
Methyl 4-propyl-N-methoxycarbonyl-1-thioallophanimidate
To 7.4 parts of methyl N-(1-amino-1-methylthiomethylene)carbamate prepared as in Example 3 in 50 parts of methylene chloride is added 4.7 parts of propyl isocyanate. The reaction mixture is stirred overnight and the solvent is stripped on arotary evaporator to give a solid which is dissolved in benzene and precipitated by adding hexane. The solid is collected and dried to give 10 parts of methyl 4-propyl-N-methoxycarbonyl-1-thioallophanimidate melting at 68.degree.-69.degree.C.
Methyl 4-(p-chlorophenyl)-N-methoxycarbonyl allophanimidate
To 13 parts of methyl N-(1-amino-1-methoxymethylene)carbamate, m.p. 36.degree.-39.5.degree., prepared similar to the procedure in Example 3 for methyl N-(1-amino-1-methylthiomethylene)carbamate in 140 parts of methylene chloride is added 15parts of p-chlorophenyl isocyanate. The reaction mixture is stirred overnight and the solution filtered to give 10 parts of methyl 4-(p-chlorophenyl)-N-methoxycarbonylallophanimidate melting at 170.degree. dec.
Methyl 4-(p-chlorophenyl)-N-methylthiolcarbonylallophanimidate
To 9 parts by weight N-(1-amino-1-methoxymethylene)thiocarbamate, m.p. 55.degree.-57.degree., prepared similar to the procedure in Example 3 for methyl N-(1-amino-1-methylthiomethylene)carbamate in 20 parts of methylene chloride is added 9 partsof p-chlorophenyl isocyanate. The reaction mixture is stirred overnight and the solution is filtered to give 14 parts of methyl 4-(p-chlorophenyl)-N-methylthiolcarbonylallophanimidate melting at 153.degree.-155.degree..
The following allophanimidates can be prepared by the procedure of Example 2 by substituting the listed 2-substituted thiopseudoureas and pseudoureas for 2-methyl-2-thiopseudourea, by replacing tert-butylisocyanate with various isocyanates orisothiocyanates, and by using various chloroformates, chlorothiolformates, or chlorodithioformates in place of methyl chloroformate.
__________________________________________________________________________ Pseudothiourea or Isocyanate or Formate,Thiolformate Psueodurea Isothiocyanate or Dithioformate Allophanimidates __________________________________________________________________________ 2-hexyl-2-thiopseudourea methyl isocyanate methyl chloroformate hexyl 4-methyl-N-methoxycarbonyl- 2 1-thioallophanimidate 2-methyl-2-thiopseudourea hexyl isocyanate phenylchloroformate methyl 4-hexyl-N-phenoxycar- bonyl-1-thioallophanimidate 2-cyclopropyl-2-thiopseu- cyclopropyl isocyanate p-chlorophenyl cyclopropyl 4-cyclopropyl-N- dourea chloroformate (p-chlorophenoxycarbonyl)-1- thioallophanimidate 2-cyclooctyl-2-thiopseu- cyclooctyl isocyanate m-bromophenyl cyclooctyl 4-cyclooctyl-N-(m- dourea chloroformate bromophenoxycarbonyl)-1-thio- allophanimidate 2-allyl-2-thiopseudourea cyclohexylmethyl iso- o-iodophenyl chloro- allyl4-cyclohexylmethyl-N- cyanate formate (o-iodophenoxycarbonyl)-1- thioallophanimidate 2-(3-methylallyl)-2- allyl isocyanate o-fluorophenyl 3-methylallyl 4-allyl-N-(o- thiopseudourea chloroformate fluorophenoxycarbonyl)-1- thioallophanimidate 2-methylpseudourea 3-methylallyl isocyanate p-methylphenyl methyl 4-(3-methylallyl)-N- chloroformate (p-methylphenoxycarbonyl)- allophanimidate 2-hexyl-2-thiopseudourea propargyl isocyanate m-ethylphenyl hexyl 4-propargyl-N-(m-ethyl- chloroformate phenoxycarbonyl)-1-thio- allophanimidate 2-(3-methylpropargyl)- cyclopropylmethyl methyl chloroformate 3-methylpropargyl 4-cyclopropyl- 2-thiopseudourea isocyanate methyl-N-methoxycarbonyl-1- thioallophanimidate 2-cyclopropylpseudourea 3-methylpropargyl iso- p-nitrophenyl cyclopropyl 4-(3-methylpropar- cyanate chloroformate gyl)-N-(p-nitrophenoxycar- bonyl)-allophanimidate 2-cyclooctylpseudourea benzyl isocyanate p-methoxyphenyl cyclooctyl4-benzyl-N-(p- chloroformate methoxyphenoxycarbonyl)- allophanimidate 2-allylpseudourea phenyl isocyanate dodecyl chlorofor- allyl 4-phenyl-N-dodecyloxy- mate carbonyl-allophanimidate 2-(3-methylallyl)pseudo- p-chlorophenyl iso- allylchloroformate 3-methylallyl 4-(p-chlorophenyl)- urea cyanate N-allyloxycarbonyl- allophanimidate 2-methyl-2-thiopseudourea m-bromophenyl iso- 3-methylallyl methyl 4-(m-bromophenyl)-N- cyanate chloroformate (3-methylallyloxycarbonyl)- 1-thioallophanimidate 2-methyl-2-thiopseudourea o-iodophenyl isocya- cyclopentyl methyl 4-(o-iodophenyl)-N- nate chloroformate (cyclopentyloxycarbonyl)-1- thioallophanimidate 2-methyl-2-thiopseudourea o-fluorophenyl iso- cyclooctyl chloro- methyl 4-(o-fluorophenyl)-N- cyanate formate cyclooctyloxycarbonyl-1-thio- allophanimidate 2-methyl-2-thiopseudourea p-methylphenyl iso- benzyl chloroformate methyl 4-(p-methylphenyl)-N- cyanate benzyloxycarbonyl-1-thio- allophanimidate 2-methyl-2-thiopseudourea m-ethylphenyl methyl chlorothiol- methyl 4-(m-ethylphenyl)-N-methylt hiol- isocyanate formate carbonyl-1-thioallophanimidate 2-methyl-2-thiopseudourea p-nitrophenyl m-butoxyphenyl methyl 4-(p-nitrophenyl)-N-(m-buto xy- isocyanate chlorothiolformate phenylthiolcarbonyl)-1-thio- allophanimidate 2-methyl-2-thiopseudourea p-methoxyphenyl p-methylthiophenyl methyl 4-(p-methoxyphenyl)-N-(p-me thyl- isothiocyanate chlorothiolformate thiophenylthiocarbonyl)-1,3-dithi o- allophanimidate 2-methyl-2-thiopseudourea m-butyloxyphenyl m-butylthiophenyl methyl 4-(m-butoxyphenyl)-N-(m-but yl- isothiocyanate chlorothiolformate thiophenylthiolcarbonyl)-1,3-dith io- allophanimidate 2-methyl-2-thiopseudourea p-methylthiophen- m-trifluoromethyl- methyl 4-(p-methylthiophenyl)-N-(m - yl isothio- phenyl chloro- trifluoromethylphenylthiolcarbony l)- cyanate thiolformate 1,3-dithioallophanimidate 2-methyl-2-thiopseudourea m-butylthiophen- p-cyanophenyl methyl 4-(m-butylthiophenyl)-N-(p- cyano- yl isothio- chlorothiolformate phenylthiolcarbonyl)-1,3-dithio- cyanate allophanimidate 2-methyl-2-thiopseudourea m-trifluoromethyl- 3,4-dichlorophenyl methyl 4-(m-trifluoromethylphenyl) -N- phenylisothio- chlorothiolformate 3,4-dichlorophenylthiolcarbonyl)- 1,3- cyanate dithioallophanimidate 2-methyl-2-thiopseudourea p-cyanophenyl methyl dithio- methyl 4-(p-cyanophenyl)-N-(methyl thiol- isothiocyanate formatethiocarbonyl)-1,3-dithioallophani midate 2-phenyl-2-thiopseudourea 3,4-dichlorophenyl 3,5-dichlorophenyl phenyl 4-(3,4-dichlorophenyl)-N-(3 ,5- isothiocyanate chlorodithiofor- dichlorophenylthiolthiocarbonyl)- 1,3- mate dithioallophanimidate 2-benzyl-2-thiopseudourea 3,5-dichlorophenyl o-chloro-p-methyl- benzyl 4-(3,5-dichlorophenyl)-N-(o - isothiocyanate phenyl chlorodi- chloro-p-methylphenylthiolthiocar - thioformate bonyl)-1,3-dithioallophanimidate 2-propargyl-2-thio- o-chloro-p-methyl- 2,4-dinitrophenyl propargyl 4-(o-chloro-p-methylphen yl)-N- pseudourea phenyl isothio- chlorodithiofor- (2,4-dinitrophenylthiolthiocarbon yl)- cyanate mate 1,3-dithioallophanimidate 2-methylpseudourea p-chlorophenyl iso- chloroformate methyl 4-(p-chlorophenyl)-N-(2-met hoxy- cyanate methoxyethyl ethoxycarbonyl)allophanimidate 2-methylpseudourea p-chlorophenyl iso- 2,2,2-trichloroethyl methyl 4-(p-chlorophenyl)-N-(2,2,2 - cyanate chloroformate trichloroethoxycarbonyl)allophani midate 2-methylpseudourea 2-bromo-4,6-dichloro- methyl chloroformate methyl 4-(2-bromo-4,6-dichlorophen yl)-N- phenyl isocyanata methoxycarbonylallophanimidate 2-methylpseudourea 2,4,5-trichloro- methylchloroformate methyl 4-(2,4,5-trichlorphenyl)-N- phenyl methoxycarbonylallophanimidate isocyanate 2-methylpseudourea 2,4,6-trimethyl- methyl chloroformate methyl 4-(2,4,6-trimethylphenyl)-N - phenyl methoxycarbonylallophanimidate
isocyanate 2-methylpseudourea 2,4-dichloro-6- methyl chloroformate methyl 4-(2,4-dichloro-6-methylphe nyl)-N- methylphenyl methoxycarbonylallophanimidate isocyanate 2-methylpseudourea p-bromophenyl iso- methyl chloroformate methyl4-(p-bromophenyl)-N-methoxy - cyanate carbonylallophanimidate 2-methylpseudourea p-bromophenyl iso- methyl chlorothiol- methyl 4-(p-bromophenyl)-N-methylt hiol- cyanate formate carbonylallophanimidate 2-methylpseudourea p-methylphenyl iso- methyl chloroformate methyl 4-(p-methylphenyl)-N-methox y- cyanate carbonylallophanimidate 2-methylpseudourea p-methylphenyl iso- methyl chlorothiol- methyl 4-(p-methylphenyl)-N-methyl thiol- cyanate formate carbonylallophanimidate 2-methylpseudourea p-methoxyphenyl iso- methyl chloroformate methyl 4-(p-methoxyphenyl)-N-metho xy- cyanate carbonylallophanimidate 2-methylpseudourea p-methoxyphenyl iso- methyl chloroformate methyl 4-(p-methoxyphenyl)-N-methy lthiol- cyanatecarbonylallophanimidate 2-methylpseudourea p-fluorophenyl iso- methyl chloroformate methyl 4-(p-fluorophenyl)-N-methox y- cyanate carbonylallophanimidate 2-methylpseudourea p-fluorophenyl iso- methyl chlorothiol- methyl4-(p-fluorophenyl)-N-methyl thiol- cyanate formate carbonylallophanimidate 2-methylpseudourea 2,4-dichlorophenyl methyl chloroformate methyl 4-(2,4-dichlorophenyl)-N-me thoxy- isocyanate carbonylallophanimidate 2-methylpseudourea 2,4-dichlorophenyl methyl chlorothiol- methyl 4-(2,4-dichlorophenyl)-N-me thyl- isocyanate formate thiolcarbonylallophanimidate 2-methylpseudourea m-butylphenyl m-butylphenyl methyl 4-(m-butylphenyl)-N-(m-buty l- isocyanate chloroformate phenoxycarbonyl)-allophanimidate __________________________________________________________________________
Similarly, the following carbamates can be prepared.
__________________________________________________________________________ Pseudothiourea, Isocyanate or Formate, Thiolformate or Pseudourea Isothiocyanate or Dithioformate Carbamates __________________________________________________________________________ 1,2-dimethyl-2-thiopseudo- cyclopentyl iso- methyl chloroformate methyl N-(1-cyclopentylcarbamylimi no-1- urea cyanate methylthiomethyl)-N-methylcarbama te 1,2-dimethyl-2-thiopseudo- cyclohexyl iso- methyl chloroformate methyl N-(1-cyclohexylcarbamylimin o-1- urea cyanate methylthiomethyl)-N-methylcarbama te 2-methyl-1-propyl-2- cyclopentyl iso- methyl chloroformate methylN-(1-cyclopentylcarbamylimi no-1- thiopseudourea cyanate methylthiomethyl)-N-propylcarbama te 1,2-dimethyl p-chlorophenyl methyl chloroformate methyl N-(1-p-chlorophenylcarbamyl - pseudourea isocyanate imino-1-methoxymethyl)-N-methyl- carbamate __________________________________________________________________________
Methyl 4,4-dimethyl-N-methoxycarbonyl-1-thioallophanimidate
To a solution of 14.8 parts of N-(1-amino-1-methylthiomethylene)carbamate and 10.1 parts of triethylamine in 100 parts of benzene is added 11 parts dimethylcarbamoyl chloride and the reaction mixture refluxed for two hours. The reaction mixtureis then subjected to vacuum and the solvent evaporated. The residue is then triturated with 200 parts of water at room temperature. The remaining solids are then recrystallized from benzene to give pure methyl4,4-dimethyl-N-methoxycarbonyl-1-thioallophanimidate.
By using appropriate starting materials, the following compounds can be prepared in the same manner.
methyl 4,4-diethyl-N-methoxycarbonyl-thioallophanimidate
methyl 4-methyl-4-butyl-N-methoxycarbonyl-1-thioallophanimidate
The compounds of this invention are useful as herbicides. They may be used at rates of 5 to 40 kg/ha to control all vegetation in industrial sites, along rights-of-way, pipelines, tank farms, etc. At rates of 0.5 to 10 kg/ha certain of thesecompounds may be used for selective weed control in asparagus, pineapple, sugarcane, sisal, alfalfa, and corn. The precise rate of material to use in any situation will depend upon the weeds to be controlled, climatic and edaphic conditions and whetheror not selective weed control is desired.
Among the weeds that can be controlled by the compounds of the invention are chickweed (Stelaria media), henbit (Lamicum amplexicaule), mustard (Brassica spp.), wild lettuce (Lactuca spp.), dandelion (Taraxacun afficinale), crabgrass (Digitaraspp.), barnyardgrass (Echinochloa crusgalli), foxtail (Setaria spp.), fireweed (Erechtites hieracifolia), false vervain (Stachytarpheta cayannensis), richardia (Richardia scabra), pigweed (Amaranthus retroflexus), morningglory (Ipomea spp.), velvetleaf(Abutilon theophrasti), goosegrass (Eleucine indica), lambsquarters (Chenopodium album), teaweed (Sida spinosa), trumpetcreeper (Campsis radicans), Wild strawberry (Fragaria virginiana), broomsedge (Andropogon virginicus), bermudagrass (Cynodondactylon), nutsedge (Cyperus sp.), and quackgrass (Agropyron repens).
The compounds of this invention may be combined with other herbicides such as bromacil, 3-sec-butyl-5-bromo-6-methyluracil; diuron, 3-(3,4-dichlorophenyl-1,1-dimethylurea; paraquet, 1,1'-dimethyl-4,4'-bipyridinium ion;1,1-dimethyl-3,3-(N-tert-butylcarbamoyloxyphenyl)urea; 4-amino-6-tert-butyl-3-methylthio-as-triazine-5(4H)-one; and the s-triazines such as 2-chloro-4-ethylamino-6-isopropylamino-s-triazine to control a broader spectrum of weeds.
The compositions of the invention can be prepared by mixing at least one compound of either Formula (I) or (II) with a herbicidal adjuvant or modifier to provide compositions in the form of dusts, granules, pellets, water-dispersible powders,high-strength concentrates, aqueous dispersions or emulsions and solutions or dispersions in organic liquids.
Thus, the compounds of the invention can be used with herbicidal adjuvants, e.g., a carrier or diluent agent such as a finely divided solid, an organic liquid, water, a wetting agent, a dispersing agent, an emulsifying agent, or any suitablecombination of these.
Compositions of the invention, especially liquids and wettable powders, contain as a conditioning agent one or more surface-active agents, sometimes called surfactants, in amounts sufficient to render a given composition containing the compoundsof the invention readily dispersible in water or in oil.
The following paragraphs describe different types of herbicidal compositions of the compounds of the invention.
A. WETTABLE POWDERS
Wettable powders are water-dispersible compositions containing the active material, an inert solid extender, and one or more surfactants to provide rapid wetting and prevent heavy flocculation when suspended in water.
The inert extenders which are preferred for use in the wettable powders of this invention containing the compounds of the invention are of mineral origin.
The classes of extenders suitable for the wettable powder formulations of this invention are the natural clays, diatomaceous earth, and synthetic mineral fillers derived from silica and silicate. Most preferred fillers for this invention arekaolinites, attapulgite clay, montmorillonite clays, synthetic silicas, synthetic magnesium silicate and calcium sulfate dihydrate.
Suitable surfactants for use in such compositions are those listed by J. W. McCutcheon in "Detergents and Emulsifiers" 1970 Annual. Among the most preferred surfactants are the nonionic and anionic type, and those most suitable for thepreparation of the dry, wettable products of this invention are solid forms of compounds known to the art as wetters and dispersants. Occasionally a liquid, nonionic compound classified primarily as an emulsifier may serve as both wetter and dispersant.
Most preferred wetting agents are alkylbenzene and alkylnaphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isethionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acidesters, petroleum sulfonates, sulfonated vegetable oils, and ditertiary acetylenic glycols. Preferred dispersants are methyl cellulose, polyvinyl alcohol, lignin sulfonates, polymeric alkylnaphthalene sulfonates, sodium naphthalenesulfonate,polymethylene bisnaphthalenesulfonate, and sodium-N-methyl-N-(long chain acid) taurates.
Wetting and dispersing agent in these preferred wettable powder compositions of this invention are usually present at concentrations of from about 0.5 weight percent to 5 weight percent. The inert extender then completes the formulation. Whereneeded, 0.1 weight percent to 1.0 weight percent of the extender may be replaced by a corrosion inhibitor or an antifoaming agent or both.
Thus, wettable powder formulations of the invention will contain from about 25 to 90 weight percent active material, from 0.5 to 2.0 weight percent wetting agent, from 0.25 to 5.0 weight percent dispersant, and from 9.25 to 74.25 weight percentinert extender, as these terms are described above.
When the wettable powder contains a corrosion inhibitor or an antifoaming agent or both, the corrosion inhibitor will not exceed about 1 percent of the composition, and the antifoaming agent will not exceed about 0.5 percent by weight of thecomposition, both replacing equivalent amounts of the inert extender.
B. HIGH STRENGTH COMPOSITIONS AND AQUEOUS SUSPENSION CONCENTRATES
High-strength compositions generally consist of 90 to 99.5% active ingredient and 0.5 to 10% of a liquid or solid surfactant such as those described by McCutcheon in "Detergents and Emulsifiers" 1970 Annual. Such high-strength compositions canoften be used in a manner similar to the wettable powders but they are also suitable for further formulation.
The aqueous suspension concentrates are prepared by mixing together and sandgrinding an aqueous slurry of water-insoluble active ingredient in the presence of dispersing agents. Thus there is obtained a concentrated slurry of very finely dividedparticles in which the active ingredient is substantially all below 5 microns in size. This concentrated aqueous suspension is characterized by its extremely small particle size so that upon diluting and spraying, a very uniform coverage is obtained.
These aqueous suspension concentrates will contain from 15 to 40% of active ingredient, from 45 to 70% water with the remainder made up of surfactants, corrosion inhibitors, and suspending agents.
Suspensions in organic liquids can be prepared in a similar manner such as by replacing the water with mineral oil.
C. DUSTS
Dusts are dense powder compositions which are intended for application in dry form, in accordance with the preferred compositions and methods of the invention. Dusts are characterized by their free-flowing and rapid settling properties so thatthey are not readily windborne to areas where their presence is not desired. They contain primarily an active material and a dense, free-flowing, solid extender.
Their performance is sometimes aided by the inclusion of a wetting agent, and convenience in manufacture frequently demands the inclusion of an inert, absorptive grinding aid. For the dust compositions of this invention, the inert extender maybe either of vegetable or mineral origin, the wetting agent is preferably anionic or nonionic, and suitable absorptive grinding aids are of mineral origin.
Suitable classes of inert solid extenders for use in the dust compositions are those organic or inorganic powders which possess high bulk density and are very free-flowing. They are also characterized by possessing relatively low surface areasand are poor in liquid absorption. Suitable classes of grinding aids are natural clays, diatomaceous earths, and synthetic mineral fillers derived from silica or silicate. Among ionic and nonionic wetting agents, the most suitable are the members ofthe group known to the art as wetting agents and emulsifiers. Although solid agents are preferred because of ease in incorporation some liquid nonionic agents are also suitable in the dust formulations.
Preferred inert solid extenders for the dusts of this invention are micaceous talcs, pyrophyllite, dense kaolin clays, tabacco dust and ground calcium phosphate rock such as that known as "Phosphodust," a trademark of the American AgriculturalChemical Company.
Preferred grinding aids are attapulgite clay, diatomaceous silica, synthetic fine silica and synthetic calcium and magnesium silicates. preferred wetting agents are those previously described under wettable power formulations.
The inert solid extenders in the dusts of this invention are usually present in concentrations of from about 30 to 90 weight percent of the total composition. The grinding aid will usually constitute 5 to 50 weight percent of the composition,and the wetting agent will constitute from about 0 to 1.0 weight percent of the composition. Dust compositions can also contain other surfactants such as dispersing agents in concentrations of up to about 0.5 weight percent.
The wettable powders described above can also be used in the preparation of dusts. While such wettable powders could be used directly in dust form, it is more advantageous to dilute them by blending with the dense dust diluent. In this manner,dispersing agents, corrosion inhibitors, and antifoam agents may also be found as components of a dust.
Thus, the dust compositions of this invention will comprise about 5 to 20 weight percent active material, 5 to 50 weight percent absorptive filler, 0 to 1.0 weight percent wetting agent, and about 30 to 90 weight percent dense, free-flowing dustdiluent, as these terms are used herein. Such dust formulations can contain, in addition, minor amounts of dispersants, corrosion inhibitors, and antifoam agents, derived from the wettable powders used to make the dusts.
D. EMULSIFIABLE OILS
Emulsifiable oils are usually solutions of active material in nonwater miscible solvents together with a surfactant.
For the compounds of this invention, emulsifiable oils can be made by mixing the active ingredient with a solvent and surfactant. Suitable solvents for the compounds of this invention are aromatic hydrocarbons including many weed oils,chlorinated solvents, and nonwater miscible ethers, esters, or ketones. Suitable surfactants are those anionic or nonionic agents known to the art as emulsifying agents. Such compounds can be found listed in "Detergents and Emulsifiers" 1970 Annual byJohn W. McCutcheon, Inc.
Emulsifying agents most suitable for the emulsifiable oil compositions of this invention are long-chain alkyl or mercaptan polyethoxy alcohols, alkylaryl polyethoxy alcohols, sorbitan fatty acid esters, polyoxyethylene ethers with sorbitan fattyacid esters, polyethylene glycol esters with fatty or rosin acids, fatty alkylol amide condensates, calcium and amine salts of fatty alcohol sulfates, oil soluble petroleum sulfonates or, preferably, mixtures of these emulsifying agents. Suchemulsifying agents will comprise from about 1 to 10 weight percent of the total composition. As described above, however, up to 5 parts of emulsifying agent for each part of thioallophanimidate can be used.
Thus, emulsifiable oil compositions of the present invention will consist of from about 15 to 50 weight percent active material, about 40 to 82 weight percent solvent, and about 1 to 10 weight percent emulsifier, as these terms are defined andused above.
In some instances the oil solution may be intended merely for extension with other oils, such as weed oils. In this instance the emulsifying agents may be omitted and may be replaced by additional solvent.
E. GRANULES AND PELLETS
Granules and pellets are physically stable, particulate compositions containing a compound of either Formula (I) or (II) which adheres to or is distributed through a basic matrix of a coherent, inert carrier with macroscopic dimensions. In orderto aid leaching of the active ingredient from the granule or pellet, a surfactant can be present.
For the compounds of this invention, the inert carrier is preferably of mineral origin, and the surfactant is a compound known in the art as a wetting agent. Such compounds are listed by J. W. McCutcheon in "Detergents and Emulsifiers" 1970Annual.
Suitable carriers are natural clays, some pyrophyllites and vermiculite. Suitable wetting agents are anionic or nonionic.
For the granule compositions of this invention, most suitable carriers are of two types. The first are porous, absorptive, preformed granules, such as preformed and screened granular attapulgite or heat expanded, granular, screened vermiculite. On either of these, a solution of the active agent can be sprayed and will be absorbed at concentrations up to 25 weight percent of the total weight. The second, which are also suitable for pellets, are initially powdered kaolin clays, hydratedattapulgite, or bentonite clays in the form of sodium, calcium or magnesium bentonites. Water-soluble salts, such as sodium salts, may also be present to aid in the disintegration of granules or pellets in the presence of moisture. These ingredientsare blended with the active components to give mixtures that are granulated or pelleted, followed by drying, to yield formulations with the active component distributed uniformly throughout the mass. Such granules and pellets can also be made with 25 to30 weight percent active component, but more frequently a concentration of about 10 weight percent is desired for optimum distribution. The granular compositions of this invention are most useful in a size range of 15 - 30 mesh.
The most suitable wetting agents for the granular compositions of this invention depend upon the type of granule used. When preformed granules are sprayed with active material in liquid form the most suitable wetting agents are nonionic, liquidwetters miscible with the solvent. These are compounds more generally known to the art as emulsifiers, and comprise alkylaryl polyether alcohols, alkyl polyether alcohols, polyoxyethylene sorbitan fatty acid esters, polyethylene glycol esters with fattyor rosin acids, fatty alkylol amide condensates, oil soluble petroleum or vegetable oil sulfonates, or mixtures of these. Such agents will usually comprise up to about 5 weight percent of the total composition.
When the active ingredient is first mixed with a powdered carrier and subsequently granulated, or pelleted, liquid nonionic wetters can still be used, but it is usually preferable to incorporate at the mixing stage one of the solid, powderedanionic wetting agents such as those previously listed for the wettable powders. Such agents will comprise from about 0 to 2 weight percent of the total composition.
Thus, the preferred granular or pelleted formulations of this invention comprise about 5 to 30 weight percent active material, about 0 to 5 weight percent wetting agent, and about 65 to 95 weight percent inert material carrier, as these terms areused herein.
F. ULTRA-LOW-VOLUME APPLICATIONS
While conventional applications of sprayable formulations have usually been made in a dilute form (for example at a rate of about 220 liters/ha or more), the compounds of this invention can also be applied at higher concentrations in the typical"ultra-low-volume" or "low-volume" applications from aircraft or ground sprayers. For this purpose wettable powders can be dispersed in small amounts of aqueous or nonaqueous carrier. The suspension or emulsifiable concentrates can be used directly orwith minor dilution. Special compositions particularly suitable for ULV applications are solutions or finely divided suspensions in one or more carriers such as dialkylformamides, N-alkyl pyrrolidones, dimethyl sulfoxide, water, esters, ketones,glycols, glycol ethers and the like. Other suitable carriers include aromatic hydrocarbons (halogenated and nonhalogenated), aliphatic hydrocarbons (halogenated and nonhalogenated) and the like.
The following examples provide further illustration of this invention. All percentages are give by weight unless otherwise indicated.
Percent Methyl 4-isopropyl-N-methoxycarbonyl-1- thioallophanimidate 40 Sodium alkylnaphthalenesulfonate 2 Oleic ester of sodium isethionate 3 Attapulgite 55
The above ingredients are blended and hammer milled to yield a water dispersible powder.
Forty kg of the above formulation can be suspended in 600 liters of water and applied to a bare, sandy soil around a tank farm in the spring before annual weeds emerge. The treatment will control weed growth.
Percent Methyl 4-isopropyl-N-ethoxycarbonyl-1- thioallophanimidate 50 Dialkyl ester of sodium sulfosuccinic acid 2 Partially desulfonated sodium ligninsulfonate 3 Kaolin 45
After blending, the above ingredients are micropulverized.
Ten kg of the above formulation and 2 kg of diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] can be suspended in 400 liters of water and applied to a hectare of dormant alfalfa to control weeds.
Percent Methyl 4-tert-butyl-N-methylthiolcarbonyl-1- thioallophanimidate 30 Calcium/magnesium ligninsulfonate 15 Hydrated attapulgite 2 Pentachlorophenol 0.5 Sodium carbonate 2.0 Water 50.5
The above ingredients are mixed and then sand ground until essentially all particles of active compound are 5 microns or less.
Twenty kg of this formulation can be suspended in 400 liters of water and applied to a ratoon sugarcane field just after harvest to control numerous weeds in the cane.
Forty kg of the above formulation and three kg of bromacil (Hyvar X) can be mixed with 400 liters of water and applied as a spot treatment to areas infested with weeds. Thorough coverage of the plant foliage is essential for good postemergencecontrol.
The following compounds may be substituted one at a time for methyl 4-tert-butyl-N-methylthiolcarbonyl-1-thioallophanimidate above in like amount by weight. When formulated and applied in like manner, like results will be obtained.
Percent Methyl 4-isopropyl-N-methoxycarbonyl-1- thioallophanimidate 22 Mixed polyoxyethylene ethers and oil soluble sulfonates 10 Spray oil (for example, Orchex 796) 68
A mixture of the above ingredients is sand ground until essentially all particles of thioallophanimidate are 5 microns or less.
Four kg of the above formulation and one half kg of 2-chloro-4-ethylamino-6-isopropylamino-S-triazine formulated in an 80% wettable powder can be suspended in 400 liters of water and applied preemergence to corn to control weeds.
Percent Methyl 4-isopropyl-N-isopropoxycarbonyl-1- thioallophanimidate 12 Mixed polyoxyethylene ethers and oil soluble sulfonates 10 Isophorone 78
Mixing the above ingredients yields a homogeneous solution which may be used directly in low volumne applications or which may be extended with water or additional solvent for conventional application.
Ten kg of the above formulation can be combined with 1 liter of paraquat and 350 liters of water and applied post-emergence to a hectare of cover crop growing where corn will be planted (silt loam soil, organic matter content 1-3%). Thetreatment will provide complete control of the cover crop and the corn can then be planted directly into the cover crop stubble without plowing, disking, etc. This treatment will also provide control of many serious weeds throughout the growing season ofthe corn.
All the active compounds of this invention may be formulated and applied in like manner.
Percent Solution of Example 14 20 Preformed clay granules, 15-30 mesh 80
The isophorone solution of active ingredient is sprayed on the preformed granules which are agitated in such a way as to obtain uniform coverage of the granules.
Fifty kg of the above granular formulation can be distributed with a spreader over a hectare of asparagus in the early spring before the spears have emerged to control weeds.
Percent Methyl 4-isopropyl-N-ethoxycarbonyl-1- thioallophanimidate 25 Anhydrous sodium sulfate 10 Calcium/magnesium ligninsulfonate 5 Sodium alkylnaphthalenesulfonate 1 Calcium/magnesium bentonite 59
The above ingredients are blended, hammer milled, and then moistened with about 12% water. This mixture is extruded as approximately 3 mm diameter cylinders and cut as extruded to produce 3 mm .times. 3 mm pellets. These may be used as suchafter drying, or the dried pellets may be crushed to pass a USS No. 15 sieve. The fraction held on a USS No. 30 sieve may be packaged for use and the fines recycled.
The above pellets can be uniformly distributed along fences and pipelines at a rate of 160 kg/ha. The pellets should be applied early in the spring before vegetative growth begins. Full season control of many serious weeds will be provided thusreducing potential fire hazard and improving appearance.
The following compounds may be substituted one at a time for methyl 4-isopropyl-N-ethoxycarbonyl-1-thioallophanimidate above in like amount by weight. When formulated and applied in like manner, like results will be obtained.
Methyl 4-tert-butyl-N-methylthiocarbonyl-1-thioallophanimidate
Percent Methyl 4-tert-butyl-N-methoxycarbonyl-1- thioallophanimidate 15 Polyoxyethylene ethers & esters 4 Dimethylformamide 81
The above ingredients are mixed together to yield a homogeneous solution particularly suitable for low volume applications. It may, of course, also be diluted for conventional application.
Ten kg of this formulation can be mixed with 200 liters of water and applied preemergence to a hectare of corn planted in a silt loam soil containing 3% organic matter to control weeds.
All of the active compounds of this invention may be formulated and applied in like manner.
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