Benzothiadiazine compounds

Abstract

New and valuable substituted 2,1,3-benzothiadiazine compounds having a herbicidal action, herbicides containing these compounds as active ingredients, proceses for controlling the growth of unwanted plants with these compounds, and methods of manufacturing them.

Description

The present invention relates to new and valuable substituted 2,1,3-benzothiadiazine compounds having a herbicidal action, herbicides containing these compounds as active ingredients, processes for controlling the growth of unwanted plants with these compounds, and methods of manufacturing them.

It is known that 3-isopropyl-2,1,3-benzothiadiazin-(4)-one-2,2-dioxide has a selective herbicidal action (German Pat. No. 1,542,836). Other herbicides from this class of compounds are also known which may be used for removing unwanted plants from a number of crop plants (German Laid-Open Applications DOS Nos. 2,444,383; 2,443,901; and 2,458,343).

We have now found that compounds of the formula ##STR1## where R.sup.1 and R.sup.2 are identical or different and each denotes alkyl, cycloalkyl, alkenyl, alkynyl, haloalkenyl, haloalkynyl, alkoxycarboalkyl, alkoxycarboalkenyl, dialkylketone, azidoalkyl, thiocyanatoalkyl, cyanoalkyl, benzyl, unsubstituted or substituted carbamidoalkyl, unsubstituted or halo- or methyl-substituted aryl, and the following radicals, the final alkyl in each case having more than 1 carbon atom; unsubstituted or substituted haloalkyl or alkylmercaptoalkyl, arylmercaptoalkyl and alkoxyalkyl; R.sup.1 further denotes hydroxyalkyl having more than 1 carbon atom or methyl substituted by O-alkyl-N-alkylaminophosphorothio, O,O-dialkylphosphoro, O,O,O-trialkylphosphinylimino, alkoxydithiocarbonyl, alkoxycarbamoyl, alkoxycarbamoyl-N-aryl, alkylsulfinyl, alkylsulfonyl, thiocarbamido, isothiuronium hydrochloride, ##STR2## or unsubstituted or substituted acylamido, diacylamido or isoxazole; each X independently denotes halogen, --NO.sub.2, lower alkyl, halogen lower alkyl, cycloalkyl, aryl, --SCN, --CN, --CO.sub.2 R.sup.3, ##STR3## --Y"R.sup.4, --SO.sub.2 R.sup.3, --SO.sub.2 OR.sup.3, ##STR4## --CCl.sub.3, --CF.sub.3, --CH.sub.2 --O--CH.sub.3, ##STR5## or --Y'--CF.sub.2 C(Z).sub.3, m denotes one of the integers 0, 1, 2, 3 and 4 an n denotes one of the integers 1 and 2, R.sup.3 denoting lower alkyl, R.sup.4 denoting lower alkyl or hydrogen, R.sup.5 denoting lower alkyl or aryl, each Y, Y' and Y" independently denoting oxygen or sulfur, and each Z independently denoting hydrogen, fluoro, bromo or chloro, enable unwanted broadleaved plants and Cyperaceae to be controlled beyond the known range for this class of compounds, in more crops and with much less risk than was hitherto the case.

The compounds according to the invention have better solubility in nonpolar hydrocarbons, e.g., vegetable or animal oils, and therefore offer technological advantages in the manufacture and application of the compounds as herbicidal agents. The compounds of the invention are thus a considerable enrichment of the art.

The new benzothiadiazine compounds are obtained by reacting 2,1,3-benzothiadiazine compounds of the formula ##STR6## where R.sup.2, Y, X, m and n have the above meanings, with

(a) a halogen compound of the formula

Hal--R.sup.1 II, where R.sup.1 has the above meanings and Hal denotes a halogen atom, or

(b) a sulfate of the formula

SO.sub.2 (OR.sup.1).sub.2 III, or

(c) a sulfone ester of the formula

ArSO.sub.2 OR.sup.1 IV, where R.sup.1 has the above meanings and Ar denotes aryl, in the presence or absence of an acid binder and of a solvent, or by reacting salts of compounds of the formula I with a halogen compound of the formula II or a sulfate of the formula III or a sulfone ester of the formula IV in the presence of a solvent, or by reacting benzothiadiazine compounds of the formula ##STR7## where R.sup.2, Y, X, m and n have the above meanings and Hal denotes a halogen atom, with a salt of hydrocyanic acid, thiocyanic acid, hydrazoic acid, unsubstituted or substituted carbamic or thiocarbamic acid, alkoxydithiocarbamic acid, O-alkyl-N-alkylaminothiophosphoric acid, an O,O,O-trialkylphosphite or thiourea, or by reacting compounds of the formula ##STR8## where R.sup.2, Y, X, m and n have the above meanings, with an isocyanate of the formula O.dbd.C.dbd.N--R.sup.5 VII, where R.sup.5 denotes lower alkyl or phenyl.

The reaction of starting compounds I and II is preferred.

Examples of meanings for R.sup.1 and R.sup.2 are methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tertbutyl, cyclobutyl, n-pentyl, 2-pentyl, 3-pentyl, tert-amyl, neopentyl, 2-methylbutyl, 3-methylbutyl, 3-methyl-2-butyl, cyclopentyl, n-hexyl, 4-methyl-2-pentyl, 2,3-dimethylbutyl, 2-methyl-1-pentyl, 2-hexyl, 3-methyl-2-pentyl, 3-methylpentyl, 4-methylpentyl, 3-methyl-3-pentyl, 4,4-dimethylbutyl, cyclohexyl, heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-octyl, 2-octyl, 3-octyl, 4-octyl, 5-octyl, 5-ethyl-2-heptyl, 2,6-dimethyl-4-heptyl, 7-ethyl-2-methyl-4-nonyl, 2,4-dimethyl-3-pentyl, 3-methyl-2-heptyl, 5-ethyl-2-nonyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, 6-ethyl-3-decyl, 6-ethyl-3-octyl, 2-methyl-2-pentyl, 2,3-dimethyl-2-butyl, 2-methyl-2-hexyl, 3-ethyl-3-pentyl, 3-methyl-3-hexyl, 2,3-dimethylpentyl-3, 2,4-dimethyl-2-pentyl, 2,2,3-trimethyl-3-butyl, 2-methyl-2-heptyl, 4-methyl-4-heptyl, 2,4-dimethyl-2-hexyl, 2-methyl-2-octyl, 1-methyl-1-cyclopentyl, 1-methyl-1-cyclohexyl, 1-ethyl-1-cyclohexyl, chlorotert-butyl, 1,1-dichloro-2-methyl-2-propyl, 1,3-dichloro-2-methyl-2-propyl, 1-cyclohexyl-1-ethyl, 1-chloroethyl, 2-chloroethyl, 1-chloropropyl, 2-chloropropyl, 3-chloropropyl, 1-chloro-2-propyl, 2-chlorobutyl, 2-chloro-2-methyl-3-propyl, 1-fluoroethyl, 2-fluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 1-fluoro-2-propyl, 2-fluorobutyl, 2-fluoro-2-methyl-3-propyl, 2-bromoethyl, 3-bromopropyl, 4-chlorobutyl, 2-chlorocyclohexyl, 1,1,1-trifluoroisopropyl, hexafluoro-2-methylisopropyl, hexafluoroisopropyl, hexachloroisopropyl, 1,2-dibromallyl, 2,2,2-trifluoroethyl, 1-chlorobutyn-2-yl-4, 3-chlorobutyn-1-yl-4, 1-chlorobuten-2-yl-4, 2,2,2-trichloroethyl, 1-chloropentyn-2-yl-4, 2,2,2-tribromoethyl, 3,4,4-trichlorobuten-3-yl-2, 1-bromo-2-propyl, 1,3-dibromo-2-propyl, 3-chlorobuten-1-yl-4, benzyl, o,m,p-toluene, o,m,p-fluorophenyl, vinyl, ethynyl, propen-1-yl, propyn-1-yl, allyl, propargyl, crotyl, butyn-2-yl-1, methallyl, buten-1-yl-3, butyn-1-yl-3, buten-1-yl-4, 2-methylbuten-1-yl-3, 2-methylbuten-2-yl-1, 2-methylbuten-2-yl-4, 3-methylbuten-1-yl-3, 3-methylbutyn-1-yl-3, 2-methylbuten-1-yl-4, 2-ethylhexen-2-yl-1, hexen-5-yl-1, undecen-10-yl-1, 1-ethynylcyclohexyl, methoxyethyl, ethoxyethyl, 3-methoxypropyl, methoxyisopropyl, 3-methoxybutyl, 1-methoxybutyl-2, ethoxy-tert-butyl, methoxy-tert-butyl, cyclohexoxy-tert-butyl, 2-methoxybutyl, 4-methoxybutyl, .beta.-methylmercaptoethyl, .beta.-ethylmercaptoethyl, 3-methylmercaptopropyl, 3-methylmercaptobutyl, 1-methylmercaptobutyl-2, methylmercapto-tert-butyl, 2-methylmercaptobutyl, 4-methylmercaptobutyl, 3-n-butoxyethyl, 2-ethoxypropyl, 3-ethoxy-2-propyl, 2-methylbutanon-2-yl-2, 2-methylpentanon-4-yl-2, 3-butanon-1-yl, 3-butanon-2-yl, 2-propanon-1-yl, 2-pentanon-1-yl, methyl acetate-2, ethyl acetate-2, methyl propionate-2, methyl propionate-3, methyl butyrate-2, methyl butyrate-3, methyl butyrate-4, methyl-(2-vinylpropionate-2), methyl-(2-vinylacetate-2), methylcarbamoylmethyl, dimethylcarbamoylmethyl, carbamoylmethyl, carbamoylethyl, .alpha.-cyanoethyl, .beta.-cyanoethyl, .gamma.-cyanoethyl, and .beta.-pheylmercaptoethyl.

R.sup.1 may also denote cyanomethyl, thiocyanomethyl, azidomethyl, dimethylcarbamoylthiomethyl, dimethyldithiocarbamoylmethyl, diethylcarbamoylthiomethyl, diethyldithiocarbamoylmethyl, diisopropyldithiocarbamoylmethyl, diisobutylcarbamoylthiomethyl, hexamethylenecarbamoylthiomethyl, N-ethyl-N-butylcarbamoylthiomethyl, N-ethyl-N-butyldithiocarbamoylmethyl, 2-methylhexahydroazepinecarbodithiomethyl, 2,4,4-trimethylazetidinecarbithiomethyl, 2,4,4-trimethylazetidinecarbodithiomethyl, chloroacetoamidomethyl, phthalyliminomethyl, phenylcarbamoyloxymethyl, O-ethyl-N-isopropylaminophosphorothiomethyl, methylsulfynylmethyl, ethylsulfynylmethyl, methylsulfonylmethyl, ethylsulfonylmethyl, 3-methylisoxazole-5-methyl, 3-methyl-4-chloroisoxazole-5-methyl, O,O-dimethylphosphoromethyl, O,O-diethylphosphoromethyl, thiocarbamidomethyl, methoxycarbamoyl-N-phenylmethyl, ethoxycarbamoylmethyl, p-fluorophenylcarbamoyloxymethyl, diisobutylcarbamoylthiomethyl, ethoxydithiocarbonylmethyl, isothiuronium hydrochloride methyl, O,O,O-triethylphosphynyliminomethyl, and the radicals .beta.-hydroxyethyl, .alpha.-acetamido-.beta.,.beta.,.beta.-trichloroethyl, .alpha.-formamido-.beta.,.beta.,.beta.-trichloroethyl, .alpha.-[.alpha.-methoxycarbomethylthio]-acetic acid methyl ester, .alpha.-ethoxycarbamidoacetic acid, .beta.,.beta.,.beta.-trichloroethyl-.alpha.-acetic acid.

The term "halogen" denotes fluorine, chlorine, bromine and iodine. The terms "lower alkyl" and "halogen lower alkyl" denote linear or branched, unsubstituted or halogen-substituted alkyl of from 1 to 6 carbon atoms.

The term "cycloalkyl" denotes for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl. The term "aryl" denotes phenyl and substituted phenyl such as halophenyl or tolyl.

If the starting materials are the sodium salt of 3-ethyl-2,1,3-benzothiadiazin-(4)-one-2,2-dioxide and butynyl chloride, the reaction may be represented by the following scheme: ##STR9##

If the starting materials are 3-ethyl-2,1,3-benzothiadiazin-(4)-one-2,2-dioxide and dimethyl sulfate (b) or methyl p-toluenesulfonate (c), the reaction is represented by the following schemes: ##STR10##

If the starting materials are 1-chloromethyl-3-ethyl-2,1,3-benzothiadiazin-(4)-one-2,2-dioxide and the dimethylammonium salt of dimethyldithiocarbamic acid, the reaction is represented by the following scheme: ##STR11##

If the starting materials are 1-methylol-3-ethyl-2,1,3-benzothiadiazin-(4)-one-2,2,-dioxide and phenyl isocyanate, the reaction may be represented by the following scheme: ##STR12##

In a preferred embodiment of methods a, b and c according to the invention, a 2,1,3-benzothiadiazin-(4)-one-2,2-dioxide or a salt thereof is reacted with a halogen compound, an alkyl sulfate or a sulfone ester in the presence or absence of an inert solvent and of an acid binder at a temperature of from -30.degree. to +150.degree. C., preferably from +10.degree. to +90.degree. C., for from 10 minutes to 6 hours, at atmospheric or superatmospheric pressure, and continuously or batchwise.

In method d according to the invention, for instance a compound of the formula V is reacted with a salt of O-alkyl-N-alkylaminothiophosphoric acid, hydrocyanic acid, thiocyanic acid, hydrazoic acid, ethoxydithiocarbamic acid or of an unsubstituted or substituted carbamic or thiocarbamic acid, or with an O,O,O-trialkylphosphite or thiourea, in the presence or absence of a solvent and of an acid binder at a temperature of from -30.degree. to +150.degree. C., preferably from +10.degree. to +90.degree. C., for from 10 minutes to 6 hours, at atmospheric or superatmospheric pressure, and continuously or batchwise.

In method e according to the invention, for instance a compound of the formula VI is reacted with an isocyanate of the formula VII in the presence or absence of a solvent at a temperature of from -30.degree. to +150.degree. C., preferably from +10.degree. to +90.degree. C., for from 30 minutes to 6 hours, at atmospheric or superatmospheric pressure, and continuously or batchwise.

Preferred inert solvents in the processes according to the invention include hydrocarbons such as ligroin, benzene fractions, e.g., those within a boiling range of from 70.degree. to 140.degree. C., cyclohexane, pentane, hexane, petroleum ether, and o-, m- and p-xylene; nitrohydrocarbons such as nitrobenzene and nitroethane; nitriles such as acetonitrile, butyronitrile and isobutyronitrile; ethers such as diethyl ether, di-n-propyl ether, tetrahydrofuran, dioxane and anisole; esters such as acetoacetic ester, ethyl acetate, isobutyl acetate, methyl benzoate and phenyl acetate; amides such as formamide, methylformamide and dimethylformamide; and ketones such as acetone, methyl ethyl ketone, cyclohexanone and acetophenone. If the compounds of the formula I or VI (and not their salts) are used, halohydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, 1,1- and 1,2-dichloroethane, 1,1,1- and 1,1,2-trichloroethane, chlorobenzene, o-, m- and p-dichlorobenzene and o-, m- and p-chlorotoluene are also preferred solvents. If the salts of compounds of the formula I are used, water is also a preferred solvent in methods a, b and c. As acid binder, any of the agents conventionally used for this purpose may be employed. Preferred examples are alkali metal hydroxides, alkali metal carbonates and tertiary organic bases. Particularly suitable compounds are sodium hydroxide, sodium carbonate, sodium bicarbonate, triethylamine, pyridine, trimethylamine, .alpha.-, .beta.- and .gamma.-picoline, lutidine, N,N-dimethylaniline, N,N-dimethylcyclohexylamine, quinoline, tri-n-propylamine, n-propyldiisopropylamine and tri-n-butylamine.

In addition to starting materials I, their alkali metal, alkaline earth metal or ammonium salts may also be advantageously used as starting materials. The compounds of the formulae I, V and VI used as starting materials are advantageously employed in an amount of from 0.3 to 1, preferably 0.8 to 1, mole per mole of starting material II, III, IV or VII.

The starting materials may be added in any order. The following procedure is particularly preferred. A solution of starting materials II, III or IV in one of the abovementioned inert solvents is run into a solution or suspension of starting material I, or salt thereof, in one of the abovementioned inert solvents; alternatively, a solution or a suspension of a salt of O-alkyl-N-alkylaminothiophosphoric, hydrocyanic, thiocyanic, hydrazoic, alkoxydithiocarbamic or a substituted or unsubstituted carbamic or thiocarbamic acid, or of an O,O,O-trialkylphosphite or of thiourea in one of the abovementioned inert solvents is run into a solution of starting material V; alternatively, a solution of starting material VII in one of the abovementioned solvents is run into a solution of starting material VI. The reaction is then carried out in the abovementioned temperature range.

To accelerate the reaction of starting materials I with fluorine or chlorine compounds of the formula II, an alkali metal or alkaline earth metal salt of a heavy halogen atom, e.g., sodium or calcium iodide, may be added as catalyst. If a two-phase solvent system is used, quaternary ammonium compounds are also suitable as catalyst. The amount of catalysts to be used in accordance with the invention is from 0.1 to 10 wt%, based on starting material II. To isolate the compounds of the formula VIII from the reaction mixture in methods a to e of the invention, the reaction mixture is stirred--when solvents miscible with water are used--into a dilute aqueous alkaline solution. The oil which separates out is if desired extracted, washed with water and dried. If the solvent is only slightly polar and immiscible with water, the reaction solution may also be extracted direct with a dilute aqueous alkaline solution and water. If desired, the reaction mixture may also be preconcentrated, taken up in a solvent immiscible with water, and purified as described above. The desired end products are obtained by drying and concentrating the organic phase. If desired, they may be further purified in conventional manner, e.g., by recrystallization or chromatography.

EXAMPLE 1

At 22.degree. C. and while stirring, 22.8 parts of methyl chloroacetate was introduced over a period of 10 minutes into a solution of 52.4 parts of 3-isopropyl-2,1,3-benzothiadiazin-(4)-one-2,2-dioxide-1-sodium salt in 200 parts of acetone. After stirring for 1 hour at 50.degree. C., the reaction mixture was concentrated in vacuo, taken up in 250 parts of methylene chloride and extracted 3 times with 100 ml of 0.5 N caustic soda solution and with water. After drying over magnesium sulfate and concentration in vacuo, 1-methylcarbomethoxy-3-isopropyl-2,1,3-benzothiadiazin-(4)-one-2,2-dioxide was obtained in the form of colorless crystals; m.p.: 93.degree.-96.degree. C.

EXAMPLE 2

While stirring and at 24.degree. C., 25.3 parts of 1-chlorobutyne-3 was dripped over a period of 10 minutes into a solution of 1 part of sodium iodide and 80 parts of 3-isopropyl-2,1,3-benzothiadiazin-(4)-one-2,2-dioxide-1-potassium salt in 630 parts of acetonitrile. After the reaction mixture had been stirred for 10 hours at 82.degree. C., it was concentrated in vacuo, taken up in 300 parts of methylene chloride, extracted four times with 0.5 N caustic soda solution, each time with 100 ml, and extracted with water. After drying over magnesium sulfate, chormatographing using neutral aluminum oxide and concentration in vacuo, 1-butyn-(3')-yl-3-isopropyl-2,1,3-benzothiadiazin-(4)-one-2,2-dioxide was isolated in the form of colorless crystals; m.p.: 66.degree.-70.degree. C.

EXAMPLE 3

At 10.degree. C. and while stirring, 16.5 parts of diethyl sulfate was introduced over a period of 15 minutes into a solution of 24 parts of 3-isopropyl-2,1,3-benzothiadiazin-(4)-one-2,2-dioxide and 4.5 parts of sodium hydroxide in 25 parts of water. The reaction mixture was then stirred for 10 hours at 20.degree. C., 150 parts of 1,2-dichloroethane was added, and the resultant mixture was extracted twice with 0.5 N caustic soda solution, each time in an amount of 70 ml, and with water. After drying, concentration in vacuo and trituration with cyclohexane, 1-ethyl-3-isopropyl-2,1,3-benzothiadiazin-(4)-one-2,2-dioxide was isolated in the form of colorless crystals; m.p.: 56.degree.-58.degree. C.

EXAMPLE 4

At 10.degree. C. and while stirring, a solution of 16 parts of the dimethylammonium salt of O-ethyl-N-isopropylaminothiophosphoric acid in 60 parts of acetonitrile was introduced over a period of 10 minutes into a solution of 20.2 parts of 1-chloromethyl-3-isopropyl-2,1,3-benzothiadiazin-(4)-one-2,2-dioxide in 160 parts of acetonitrile. The reaction mixture was then stirred for 2 hours at 25.degree. C., concentrated in vacuo, taken up in 200 parts of diethyl ether, and extracted 3 times with a 10% sodium bicarbonate solution, each time with 100 parts, and with water. After drying over magnesium sulfate, concentration in vacuo and trituration with cyclohexane, 1-methyl(O-ethyl-N-isopropylaminophosphorothio)-3-isopropyl-2,1,3-benzothiadiazin-(4)-one-2,2-dioxide was obtained in the form of colorless crystals; m.p.: 79.degree.-84.degree. C.

EXAMPLE 5

100 parts of 1-chloromethyl-3-isopropyl-2,1,3-benzothiadiazin-(4)-one-2,2-dioxide and 150 parts of sodium azide were stirred in 800 parts of dimethylformamide for 6 hours at 25.degree. C. The suspension was then diluted with 5 times its volume of water. After 1 hour, the precipitated crystals were suction filtered and dried. There was obtained 100 parts (98% of theory) of 1-azidomethyl-3-isopropyl-2,1,3-benzothiadiazin-(4)-one-2,2-dioxide; m.p.: 83.degree. C.

Further active ingredients corresponding to the general formula were prepared by analogous methods. They are listed in Table I, m denoting O.

TABLE 1__________________________________________________________________________R.sup.1 R.sup.2 Y n m.p. (.degree.C.)__________________________________________________________________________C.sub.2 H.sub.5 CH.sub.3 O 2n-C.sub.3 H.sub.7 CH.sub.3 O 2 39i-C.sub.3 H.sub.7 CH.sub.3 O 2 ##STR13## CH.sub.3 O 2n-C.sub.4 H.sub.9 CH.sub.3 O 2CH.sub.3 CH.sub.3 S 2CH.sub.3 CH.sub.3 O 1i-C.sub.3 H.sub.7 CH.sub.3 O 1i-C.sub.3 H.sub.7 CH.sub.3 S 1i-C.sub.4 H.sub.9 CH.sub.3 O 2sec-C.sub.4 H.sub.9 CH.sub.3 O 2tert-C.sub.4 H.sub.9 CH.sub.3 O 2CH.sub.3 C.sub.2 H.sub.5 O 2C.sub.2 H.sub.5 C.sub.2 H.sub.5 O 2C.sub.2 H.sub.5 C.sub.2 H.sub.5 O 1n-C.sub.3 H.sub.7 C.sub.2 H.sub.5 O 2n-C.sub.3 H.sub.7 C.sub.2 H.sub.5 S 2i-C.sub.3 H.sub.7 C.sub.2 H.sub.5 O 2 ##STR14## C.sub.2 H.sub.5 O 2n-C.sub.3 H.sub.7 C.sub.2 H.sub.5 O 2sec-C.sub.4 H.sub.9 C.sub.2 H.sub.5 O 2i-C.sub.4 H.sub.9 C.sub.2 H.sub.5 O 2tert-C.sub.4 H.sub.9 C.sub.2 H.sub.5 O 2i-C.sub.3 H.sub.7 C.sub.2 H.sub.5 S 2CH.sub.3 n-C.sub.3 H.sub.7 O 2C.sub.2 H.sub.5 n-C.sub.3 H.sub.7 O 2i-C.sub.3 H.sub.7 n-C.sub.3 H.sub.7 O 2n-C.sub.3 H.sub.7 n-C.sub.3 H.sub.7 O 2i-C.sub.3 H.sub.7 n-C.sub.3 H.sub.7 O 1n-C.sub.4 H.sub.9 n-C.sub.3 H.sub.7 O 2i-C.sub.4 H.sub.9 n-C.sub.3 H.sub.7 O 2sec-C.sub.4 H.sub.9 n-C.sub.3 H.sub.7 O 2tert-C.sub.4 H.sub.9 n-C.sub.3 H.sub.7 O 2C.sub.2 H.sub.5 n-C.sub.3 H.sub.7 S 2 ##STR15## n-C.sub.3 H.sub.7 O 2 ##STR16## n-C.sub.3 H.sub.7 O 2C.sub.10 H.sub.21 n-C.sub.3 H.sub.7 O 2C.sub.9 H.sub.19 n-C.sub.3 H.sub.7 O 2n-C.sub.5 H.sub.11 n-C.sub.3 H.sub.7 O 2sec-C.sub.4 H.sub.9 n-C.sub.3 H.sub.7 O 1CH.sub.3 i-C.sub.3 H.sub.7 O 2 54-55n-C.sub.3 H.sub.7 i-C.sub.3 H.sub.7 O 2 n.sub.D.sup. 25 = 1.5359i-C.sub.3 H.sub.7 i-C.sub.3 H.sub.7 O 2 44-45 ##STR17## i-C.sub.3 H.sub.7 O 2CH.sub.3 i-C.sub.3 H.sub.7 S 2CH.sub.3 i-C.sub.3 H.sub.7 O 1n-C.sub.4 H.sub.9 i-C.sub.3 H.sub.7 O 2i-C.sub.4 H.sub.9 i-C.sub.3 H.sub.7 O 2sec-C.sub.4 H.sub.9 i-C.sub.3 H.sub.7 O 2 n.sub.D.sup. 25 = 1.5316sec-C.sub.4 H.sub.9 i-C.sub.3 H.sub.7 O 1C.sub.2 H.sub.5 i-C.sub.3 H.sub.7 S 2tert-C.sub.4 H.sub.9 i-C.sub.3 H.sub.7 O 2n-C.sub.5 H.sub.11 i-C.sub.3 H.sub.7 O 2 ##STR18## i-C.sub.3 H.sub.7 O 2 ##STR19## i-C.sub.3 H.sub.7 O 2CH(C.sub.2 H.sub.5).sub.2 i-C.sub.3 H.sub.7 O 2CH(C.sub.2 H.sub.5).sub.2 i-C.sub.3 H.sub.7 O 1CH.sub.2 C(CH.sub.3).sub.3 i-C.sub.3 H.sub.7 O 2CH.sub.2CH.sub.2CH(CH.sub.3).sub.2 i-C.sub.3 H.sub.7 O 2 n.sub.D.sup. 25 = 1.5278C(CH.sub.3).sub.2 C.sub.2 H.sub.5 i-C.sub.3 H.sub.7 O 2 ##STR20## i-C.sub.3 H.sub.7 O 2 ##STR21## i-C.sub.3 H.sub.7 O 2n-C.sub.6 H.sub.13 i-C.sub.3 H.sub.7 O 2 ##STR22## i-C.sub.3 H.sub.7 O 2n-C.sub.3 H.sub.7 i-C.sub.3 H.sub.7 O 1n-C.sub.5 H.sub.11 i-C.sub.3 H.sub.7 O 2n-C.sub.7 H.sub.15 i-C.sub.3 H.sub.7 O 2n-C.sub.8 H.sub.17 i-C.sub.3 H.sub.7 O 2n-C.sub.9 H.sub.19 i-C.sub.3 H.sub.7 O 2n-C.sub.10 H.sub.21 i-C.sub.3 H.sub.7 O 2 ##STR23## i-C.sub.3 H.sub.7 O 2 n.sub.D.sup. 25 = 1.5561 ##STR24## i-C.sub.3 H.sub.7 O 2 n.sub.D.sup. 25 = 1.5610CH.sub.3 n-C.sub.4 H.sub.9 O 2C.sub.2 H.sub.5 n-C.sub.4 H.sub.9 O 2n-C.sub.3 H.sub.7 n-C.sub.4 H.sub.9 O 2n-C.sub.3 H.sub.7 n-C.sub.4 H.sub.9 S 2i-C.sub.3 H.sub.7 n-C.sub.4 H.sub.9 O 2n-C.sub.4 H.sub.9 n-C.sub.4 H.sub.9 O 2i-C.sub.4 H.sub.9 n-C.sub.4 H.sub.9 O 2tert-C.sub.4 H.sub.9 n-C.sub.4 H.sub.9 O 2 ##STR25## n-C.sub.4 H.sub.9 O 2CH.sub.3 sec-C.sub.4 H.sub.9 O 2C.sub.2 H.sub.5 sec-C.sub.4 H.sub.9 O 2 68-71n-C.sub.3 H.sub.7 sec-C.sub.4 H.sub.9 O 2i-C.sub.3 H.sub.7 sec-C.sub.4 H.sub.9 O 2tert-C.sub.4 H.sub.9 sec-C.sub.4 H.sub.9 O 2CH.sub.3 i-C.sub.4 H.sub.9 O 2C.sub.2 H.sub.5 i-C.sub.4 H.sub.9 O 2n-C.sub.3 H.sub.7 i-C.sub.4 H.sub.9 O 1i-C.sub.3 H.sub.7 i-C.sub.4 H.sub.9 O 2n-C.sub.4 H.sub. 9 i-C.sub.4 H.sub.9 S 2CH.sub.3 tert-C.sub.4 H.sub.9 O 2C.sub.2 H.sub.5 tert-C.sub.4 H.sub.9 O 2n-C.sub.3 H.sub.7 tert-C.sub.4 H.sub.9 O 2n-C.sub.4 H.sub.9 tert-C.sub.4 H.sub.9 O 1CH.sub.3 ##STR26## O 2C.sub.2 H.sub.5 ##STR27## O 2tert-C.sub.4 H.sub.9 ##STR28## O 2CH.sub.3 CH(C.sub.2 H.sub.5).sub.2 O 2C.sub.2 H.sub.5 CH(C.sub.2 H.sub.5).sub.2 O 2n-C.sub.3 H.sub.7 CH(C.sub.2 H.sub.5).sub.2 O 2i-C.sub.3 H.sub.7 CH(C.sub.2 H.sub.5).sub.2 O 2tert-C.sub.4 H.sub.9 CH(C.sub.2 H.sub.5).sub.2 O 2 ##STR29## i-C.sub.3 H.sub.7 O 2 111-115 ##STR30## i-C.sub.3 H.sub.7 O 2 98-100CH.sub.3 ##STR31## O 2C.sub.2 H.sub.5 ##STR32## O 2n-C.sub.3 H.sub.7 ##STR33## O 2tert-C.sub.4 H.sub.9 ##STR34## O 2CH.sub.3 ##STR35## O 2C.sub.2 H.sub.5 ##STR36## O 2n-C.sub.3 H.sub.7 ##STR37## O 2n-C.sub.3 H.sub.7 ##STR38## O 2 68-73n-C.sub.3 H.sub.7 ##STR39## O 2CH.sub.3 CH.sub.2CH.sub.2 Cl O 2n-C.sub.3 H.sub.7 CH.sub.2CH.sub.2 Cl O 2i-C.sub.3 H.sub.7 CH.sub.2CH.sub.2 Cl O 2i-C.sub.3 H.sub.7 CH.sub.2CH.sub.2 Cl O 1CH.sub.3 ##STR40## O 2C.sub.2 H.sub.5 ##STR41## O 2CH.sub. 3 ##STR42## O 2n-C.sub.3 H.sub.7 ##STR43## O 2C.sub.2 H.sub.5 ##STR44## S 2CHCH.sub.2 CH.sub.3 O 2CCH CH.sub.3 O 2CHCHCH.sub.3 CH.sub.3 O 2CCCH.sub.3 CH.sub.3 O 2CH.sub.2CHCH.sub.2 CH.sub.3 O 2CH.sub.2CCH CH.sub.3 O 2 122-126CH.sub.2CHCHCH.sub.3 CH.sub.3 O 2CH.sub.2CCCH.sub.3 CH.sub.3 O 2 ##STR45## CH.sub.3 O 2 ##STR46## CH.sub.3 O 2 ##STR47## CH.sub.3 O 2CH.sub.2CH.sub.2CHCH.sub.2 CH.sub.3 O 2CH.sub.2CH.sub.2CCH CH.sub.3 O 2 ##STR48## CH.sub.3 O 2 ##STR49## CH.sub.3 O 2 ##STR50## CH.sub.3 O 2 ##STR51## CH.sub.3 O 2 ##STR52## CH.sub.3 O 2 ##STR53## CH.sub.3 S 2 ##STR54## CH.sub.3 O 2CH.sub.2C CH CH.sub.3 O 1CH.sub.2CCH CH.sub.3 S 2CHCH.sub.2 C.sub.2 H.sub.5 O 2CCH C.sub.2 H.sub.5 O 2CHCHCH.sub.3 C.sub.2 H.sub.5 O 2CCH.sub.3 C.sub.2 H.sub.5 O 2CH.sub.2CHCH.sub.2 C.sub.2 H.sub.5 O 2CH.sub.2CCH C.sub.2 H.sub.5 O 2 71-75CH.sub.2CHCHCH.sub.3 C.sub.2 H.sub.5 O 2CH.sub.2CCCH.sub.3 C.sub.2 H.sub.5 O 2 ##STR55## C.sub.2 H.sub.5 O 2 ##STR56## C.sub.2 H.sub.5 O 2 ##STR57## C.sub.2 H.sub.5 O 2CH.sub.2CH.sub.2CHCH.sub.2 C.sub.2 H.sub.5 O 2CH.sub.2CH.sub.2CCH C.sub.2 H.sub.5 O 2 ##STR58## C.sub.2 H.sub.5 O 2 ##STR59## C.sub.2 H.sub.5 O 2 ##STR60## C.sub.2 H.sub.5 O 2 ##STR61## C.sub.2 H.sub.5 O 2 ##STR62## C.sub.2 H.sub.5 O 2CHCH.sub.2 n-C.sub.3 H.sub.7 O 2CCH n-C.sub.3 H.sub.7 O 2CHCHCH.sub.3 n-C.sub.3 H.sub.7 O 2CCHCH.sub.3 n-C.sub.3 H.sub.7 O 2CH.sub.2CHCH.sub.2 n-C.sub.3 H.sub.7 O 2CH.sub.2CCH n-C.sub.3 H.sub.7 O 2 53-57CH.sub.2CHCHCH.sub.3 n-C.sub.3 H.sub.7 O 2CH.sub.2CCCH.sub.3 n-C.sub.3 H.sub.7 O 2 ##STR63## n-C.sub.3 H.sub.7 O 2 ##STR64## n-C.sub.3 H.sub.7 O 2 ##STR65## n-C.sub.3 H.sub.7 O 2CH.sub.2CH.sub.2CHCH.sub.2 n-C.sub.3 H.sub.7 O 2CH.sub.2CH.sub.2CCH n-C.sub.3 H.sub.7 O 2 ##STR66## n-C.sub.3 H.sub.7 O 2 ##STR67## n-C.sub.3 H.sub.7 O 2 ##STR68## n-C.sub.3 H.sub.7 O 2 ##STR69## n-C.sub.3 H.sub.7 O 2 ##STR70## n-C.sub.3 H.sub.7 O 2CH.sub.2CCH n-C.sub.3 H.sub.7 O 1CH.sub.2CCH n-C.sub.3 H.sub.7 S 2CH CH.sub.2 i-C.sub.3 H.sub.7 O 2CCH i-C.sub.3 H.sub.7 O 2CHCHCH.sub.3 i-C.sub.3 H.sub.7 O 2CCCH.sub.3 i-C.sub.3 H.sub.7 O 2CH.sub.2CH CH.sub.2 i-C.sub.3 H.sub.7 O 2 41-43CH.sub.2CCH i-C.sub.3 H.sub.7 O 2 108-112CH.sub.2CHCHCH.sub.3 i-C.sub.3 H.sub.7 O 2 n.sub.D.sup.25 = 1.5436CH.sub.2CCCH.sub.3 i-C.sub.3 H.sub.7 O 2 ##STR71## i-C.sub.3 H.sub.7 O 2 ##STR72## i-C.sub.3 H.sub.7 O 2 ##STR73## i-C.sub.3 H.sub.7 O 2CH.sub.2CH.sub.2CHCH.sub.2 i-C.sub.3 H.sub.7 O 2CH.sub.2CH.sub.2CCH i-C.sub.3 H.sub.7 O 2 66-69 ##STR74## i-C.sub.3 H.sub.7 O 2 ##STR75## i-C.sub.3 H.sub.7 O 2 ##STR76## i-C.sub.3 H.sub.7 O 2 ##STR77## i-C.sub.3 H.sub.7 O 2 ##STR78## i-C.sub.3 H.sub.7 O 2 114-115 ##STR79## i-C.sub.3 H.sub.7 O 2 106-109 ##STR80## i-C.sub.3 H.sub.7 O 2CH.sub.2CHCH.sub.2 i-C.sub.3 H.sub.7 S 2CH.sub.2CCH i-C.sub.3 H.sub.7 O 1 ##STR81## i-C.sub.3 H.sub.7 O 2 71-73 ##STR82## i-C.sub.3 H.sub.7 O 2 75-77CH.sub.2CHCH.sub.2 ##STR83## O 2CH.sub.2CCH ##STR84## O 2CH.sub.2CCH ##STR85## O 2CH.sub.2CHCH.sub.2 n-C.sub.4 H.sub.9 O 2CH.sub.2CCH n-C.sub.4 H.sub.9 O 2CH.sub.2CHCHCH.sub.3 n-C.sub.4 H.sub.9 O 2CH.sub.2CCCH.sub.3 n-C.sub.4 H.sub.9 O 2 ##STR86## n-C.sub.4 H.sub.9 O 2 ##STR87## n-C.sub.4 H.sub.9 O 2CHCH.sub.2 sec-C.sub.4 H.sub.9 O 2CCH sec-C.sub.4 H.sub.9 O 2CHCHCH.sub.3 sec-C.sub.4 H.sub.9 O 2CCCH.sub.3 sec-C.sub.4 H.sub.9 O 2CH.sub.2CHCH.sub.2 sec-C.sub.4 H.sub.9 O 2CH.sub.2CCH sec-C.sub.4 H.sub.9 O 2 55-59CH.sub.2CCH sec-C.sub.4 H.sub.9 S 2CH.sub.2CHCHCH.sub.3 sec-C.sub.4 H.sub.9 O 1CH.sub.2CCCH.sub.3 sec-C.sub.4 H.sub.9 O 2 ##STR88## sec-C.sub.4 H.sub.9 O 2 ##STR89## sec-C.sub.4 H.sub.9 O 2 ##STR90## sec-C.sub.4 H.sub.9 O 2CH.sub.2C CH CH(C.sub.2 H.sub.5).sub.2 O 2CH.sub.2CCH ##STR91## O 2CH.sub.2CCH ##STR92## O 2CH.sub.2CCH ##STR93## O 2CH.sub.2CCH CH.sub.2CH.sub.2 Cl O 2CH.sub.2CCH ##STR94## O 2CH.sub.2CCH ##STR95## O 2CH.sub.2CCH ##STR96## O 2CH.sub.2CCH ##STR97## S 2CH.sub.2CCH ##STR98## O 2CH.sub.2CH.sub.2 Cl C.sub.2 H.sub.5 O 2CH.sub.2CH.sub.2 Br i-C.sub.3 H.sub.7 O 2 n.sub.D.sup.25 = 1.5648CH.sub.2CH.sub.2 Cl i-C.sub.3 H.sub.7 S 2CH.sub.2CCCH.sub.2 Cl i-C.sub.3 H.sub.7 O 2 68-72 ##STR99## i-C.sub.3 H.sub.7 O 2 221 ##STR100## i-C.sub.3 H.sub.7 O 2 170 ##STR101## i-C.sub.3 H.sub.7 O 2 209-211 ##STR102## i-C.sub.3 H.sub.7 O 2 89-90CH.sub.2C CCH.sub.2 Cl sec-C.sub.4 H.sub.9 O 2CH.sub.2CHCHCH.sub.2 Cl i-C.sub.3 H.sub.7 O 2CH.sub.2 CH.sub.2OCH.sub.3 CH.sub.3 O 2CH.sub.2CH.sub.2OCH.sub.3 C.sub.2 H.sub.5 O 2CH.sub.2CH.sub.2OCH.sub.3 n-C.sub.3 H.sub.7 O 2CH.sub.2CH.sub.2OCH.sub.3 i-C.sub.3 H.sub.7 O 2 62-63CH.sub.2CH.sub.2OCH.sub.3 i-C.sub.3 H.sub.7 O 1CH.sub.2CH.sub.2Oi-C.sub. 3 H.sub.7 i-C.sub.3 H.sub.7 O 2CH.sub.2CH.sub.2OCH.sub.3 n-C.sub.4 H.sub.9 O 2CH.sub.2CH.sub.2OCH.sub.3 sec-C.sub.4 H.sub.9 O 2CH.sub.2CH.sub.2SCH.sub.3 CH.sub.3 O 2CH.sub.2CH.sub.2SCH.sub.3 n-C.sub.3 H.sub.7 O 2CH.sub.2CH.sub.2SCH.sub.3 i-C.sub.3 H.sub.7 O 2CH.sub.2CH.sub.2SCH.sub.3 n-C.sub.4 H.sub.9 O 2CH.sub.2CH.sub.2SCH.sub.3 sec-C.sub.4 H.sub.9 O 2CH.sub. 2CO.sub.2 CH.sub.3 CH.sub.3 O 2CH.sub.2CO.sub.2 CH.sub.3 C.sub.2 H.sub.5 O 2CH.sub.2 CO.sub.2 CH.sub.3 n-C.sub.3 H.sub.7 O 2CH.sub.2 CO.sub.2 CH.sub.3 i-C.sub.3 H.sub.7 S 2CH.sub.2 CO.sub.2 H i-C.sub.3 H.sub.7 O 2 98CH.sub.2CO.sub.2 CH.sub.3 n-C.sub.4 H.sub.9 O 2CH.sub.2CO.sub.2 CH.sub.3 sec-C.sub.4 H.sub.9 O 2CH.sub.2CO.sub.2 CH.sub.3 tert-C.sub.4 H.sub.9 O 2CH.sub.2CH.sub.2 CO.sub.2 CH.sub.3 i-C.sub.3 H.sub.7 O 2 ##STR103## i-C.sub.3 H.sub.7 O 2CH.sub.2CHCHCO.sub.2 CH.sub.3 i-C.sub.3 H.sub.7 O 2CH.sub.2 CH.sub.2 OH i-C.sub.3 H.sub.7 O 2 n.sub. D.sup.25 = 1.5459 ##STR104## i-C.sub.3 H.sub.7 O 2 n.sub. D.sup.25 = 1.5929 ##STR105## C.sub.2 H.sub.5 O 2 ##STR106## n-C.sub.3 H.sub.7 O 2 ##STR107## i-C.sub.3 H.sub.7 O 2 n.sub.D.sup.25 = 1.5464 ##STR108## sec-C.sub.4 H.sub.9 O 2 ##STR109## n-C.sub.2 H.sub.5 O 2 ##STR110## i-C.sub.3 H.sub.7 O 2 82-86CH.sub.2CCH ##STR111## O 2 ##STR112## i-C.sub.3 H.sub.7 O 2 69-73 ##STR113## ##STR114## O 2CH.sub.2C CH CH.sub.2CCH O 2CH.sub.2CCH CH.sub.2CCH S 2 ##STR115## CH.sub.3 O 2 ##STR116## i-C.sub.3 H.sub.7 O 2 161-163 ##STR117## C.sub.2 H.sub.5 O 2 ##STR118## i-C.sub.3 H.sub.7 O 2 136-137 ##STR119## sec-C.sub.4 H.sub.9 O 2 ##STR120## i-C.sub.3 H.sub.7 O 2 132-133 ##STR121## i-C.sub.3 H.sub.7 O 2 106 ##STR122## n-C.sub.3 H.sub.7 O 2CH.sub.2SCN i-C.sub. 3 H.sub.7 O 2 124-126CH.sub.2SCN C.sub.2 H.sub.5 O 2CH.sub.2CN n-C.sub.3 H.sub.7 O 2CH.sub.2CN i-C.sub.3 H.sub.7 O 2 119-121CH.sub.2CN i-C.sub.3 H.sub.7 S 2CH.sub.2CN i-C.sub.3 H.sub.7 O 1CH.sub.2CH.sub.2 CN n-C.sub.3 H.sub.7 O 2CH.sub.2CH.sub.2 CN i-C.sub.3 H.sub.7 O 2 115-117 ##STR123## C.sub.2 H.sub.5 O 2 ##STR124## n-C.sub.3 H.sub.7 O 2 ##STR125## i-C.sub.3 H.sub.7 O 2 139-141 ##STR126## i-C.sub.3 H.sub.7 O 2 216-217 ##STR127## n-C.sub.3 H.sub.7 O 2 ##STR128## C.sub.2 H.sub.5 O 2 ##STR129## i-C.sub.3 H.sub.7 O 2 105-107 ##STR130## ##STR131## O 2 ##STR132## i-C.sub.3 H.sub.7 O 2 101-102CH.sub.2NHCO.sub.2 C.sub.2 H.sub.5 i-C.sub.3 H.sub.7 O 2 186 ##STR133## i-C.sub.3 H.sub.7 O 2 153-156 ##STR134## i-C.sub.3 H.sub.7 O 2 138-140 ##STR135## i-C.sub.3 H.sub.7 O 2 ##STR136## i-C.sub.3 H.sub.7 O 2 ##STR137## n-C.sub.3 H.sub.7 O 2 ##STR138## i-C.sub.3 H.sub.7 O 2 141-143 ##STR139## sec-C.sub.4 H.sub.9 O 2 ##STR140## i-C.sub.3 H.sub.7 O 2 139-141 ##STR141## sec-C.sub.4 H.sub.9 O 2 ##STR142## i-C.sub.3 H.sub.7 O 2 ##STR143## n-C.sub.3 H.sub.7 O 2 ##STR144## i-C.sub.3 H.sub.7 O 2 85-87 ##STR145## sec-C.sub.4 H.sub. 9 O 2 ##STR146## C.sub.2 H.sub.5 O 0 ##STR147## i-C.sub.3 H.sub.7 O 2 139-141 ##STR148## i-C.sub.3 H.sub.7 O 2 124-126 ##STR149## i-C.sub.3 H.sub.7 O 2 70 ##STR150## i-C.sub.3 H.sub.7 O 2 79-80 ##STR151## C.sub.2 H.sub.5 O 2 ##STR152## i-C.sub.3 H.sub.7 O 2 107 ##STR153## sec-C.sub.4 H.sub.9 O 2 ##STR154## i-C.sub.3 H.sub.7 O 2 110-113 ##STR155## i-C.sub.3 H.sub.7 O 2 73-76 ##STR156## sec-C.sub.4 H.sub.9 O 2 ##STR157## i-C.sub.3 H.sub.7 O 2 72-74 ##STR158## i-C.sub.3 H.sub.7 O 2 101-102 ##STR159## i-C.sub.3 H.sub.7 O 2 91-92 ##STR160## i-C.sub.3 H.sub.7 O 2 181CH.sub.2NP(OC.sub.2 H.sub.5).sub.3 i-C.sub.3 H.sub.7 O 2 n.sub.D.sup. 25 = 1.5072CH.sub.2CH.sub.2 OH sec-C.sub.4 H.sub.9 O 2CH.sub.2CH.sub.2 OH ##STR161## O 2CH.sub.2CH.sub.2 OH ##STR162## O 2CH.sub.2CH.sub.2 OH C.sub.6 H.sub.5 O 2CH.sub.2CH.sub.2 OH ##STR163## O 2CH.sub.2CH.sub.2 OH ##STR164## O 2CH.sub.2CH.sub.2 OH ##STR165## O 2CH.sub.2 SCN sec-C.sub.4 H.sub.9 O 1CH.sub.2 CN sec-C.sub.4 H.sub.9 O 2CH.sub.2 SCN ##STR166## O 2CH.sub.2 SCN ##STR167## O 2CH.sub.2 SCN ##STR168## O 2CH.sub.2 CO.sub.2 CH.sub.3 C.sub.6 H.sub.5 O 2CH.sub.2 CO.sub.2 CH.sub.3 ##STR169## O 2CH.sub.2 CO.sub.2 CH.sub.3 ##STR170## S 2(CH.sub.2).sub.4 OH i-C.sub.3 H.sub.7 O 2__________________________________________________________________________X Ring position m R.sup.1 R.sup.2 Y n m.p. (.degree.C.)__________________________________________________________________________CH.sub.3 5,6,7 1 CH.sub.3 i-C.sub.3 H.sub.7 O 2CH.sub.3 8 1 CH.sub.2CCH i-C.sub.3 H.sub.7 O 2 140-144CH.sub.3 8 1 CH.sub.2CCH i-C.sub.3 H.sub.7 S 2CH.sub.3 8 1 CH.sub.2 CN i-C.sub.3 H.sub.7 O 2CH.sub.3 7 1 CH.sub.2 CN i-C.sub.3 H.sub.7 O 2CH.sub.3 5,6 1 CH.sub.2 CN i-C.sub.3 H.sub.7 O 2CH.sub.3 5,6,7,8 1 CH.sub.2CCCH.sub.2 Cl i-C.sub.3 H.sub.7 O 2CH.sub.3 5,6,7,8 1 tert-C.sub.4 H.sub.9 i-C.sub.3 H.sub.7 O 2CH.sub.3 5,6,7,8 1 tert-C.sub.4 H.sub.9 i-C.sub.3 H.sub.7 S 2CH.sub.3 6,8 2 CH.sub.2CCH i-C.sub.3 H.sub.7 O 2 98-101CH.sub.3 6,8 2 CH.sub.2 CN i-C.sub.3 H.sub.7 O 2CH.sub.3 6,8 2 CH.sub.2SCN i-C.sub.3 H.sub.7 O 2CH.sub.3 5,6,7,8 1 ##STR171## i-C.sub.3 H.sub.7 O 2CH.sub.3 5,6,7,8 1 ##STR172## i-C.sub.3 H.sub.7 O 2CH.sub.3 5,6,7,8 1 CH.sub.2CO.sub.2 CH.sub.3 i-C.sub.3 H.sub.7 O 2CH.sub.3 5,6,7,8 1 ##STR173## i-C.sub.3 H.sub.7 O 2CH.sub.3 5,6,7,8 1 ##STR174## i-C.sub.3 H.sub.7 O 2CH.sub.3 5,6,7,8 1 ##STR175## i-C.sub.3 H.sub.7 O 2CH.sub.3 5,6,7,8 1 ##STR176## sec-C.sub.4 H.sub.9 O 2CH.sub.3 5,6,7,8 1 CH.sub.2 N.sub.3 i-C.sub.3 H.sub.7 O 2CH.sub.3 5,6,7,8 1 CH.sub.2CH.sub.2 CN i-C.sub.3 H.sub.7 O 1CH.sub.3 8 1 CH.sub.2CH.sub.2 OH i-C.sub.3 H.sub.7 O 2 83-86Cl 7 1 CH.sub.2CCH i-C.sub.3 H.sub.7 O 2 97-103Cl 7 1 CH.sub.2 N.sub.3 i-C.sub.3 H.sub.7 O 2Cl 5,6,7,8 1 CH.sub.2 CN i-C.sub.3 H.sub.7 O 2Cl 5,6,7,8 1 tert-C.sub.4 H.sub.9 sec-C.sub.4 H.sub.9 O 2CH.sub.3 5 1 CH.sub.2CCH i-C.sub.3 H.sub.7 O 2 87-91Cl 5,6,7,8 1 CH.sub.2CCCH.sub.2 Cl ##STR177## O 2I 6 1 CH.sub.2CCH i-C.sub.3 H.sub.7 O 2 105-109Cl 8 1 CH.sub.2 SCN i-C.sub.3 H.sub.7 O 2Cl 5,6,7 1 CH.sub.2 SCN i-C.sub.3 H.sub.7 O 2Cl 5,6,7,8 1 CH.sub.2 CO.sub.2 CH.sub.3 sec-C.sub.4 H.sub.9 O 2Cl 5,6,7,8 1 ##STR178## ##STR179## O 2Cl 7 1 CH.sub.2CH.sub.2 OH i-C.sub.3 H.sub.7 O 2 93-96Cl 5,6,8 1 CH.sub.2CH.sub.2 OH i-C.sub.3 H.sub.7 O 2Cl 7 1 ##STR180## i-C.sub.3 H.sub.7 O 2 94-97F 5,6,7,8 1 ##STR181## i-C.sub.3 H.sub.7 O 2F 5,6,7,8 1 ##STR182## sec-C.sub.4 H.sub.9 S 2F 5,6,7,8 1 ##STR183## i-C.sub.3 H.sub.7 O 2F 5,6,7,8 1 ##STR184## i-C.sub.3 H.sub.7 O 2C.sub.6 H.sub.5 8 1 CH.sub.2 CN i-C.sub.3 H.sub.7 O 2C.sub.6 H.sub.5 5,6,7,8 1 CH.sub.2 SCN sec-C.sub.4 H.sub.9 O 2C.sub.6 H.sub.5 5,6,7,8 1 CH.sub.2 CH.sub.2 OH ##STR185## O 2Br 6 1 CH.sub.3 i-C.sub.3 H.sub.7 O 1 135-137Br 6 1 CH.sub.2 C.sub.6 H.sub.5 i-C.sub.3 H.sub.7 O 1 110-111C.sub.6 H.sub.5 5,6,7,8 1 CH.sub.2 N.sub.3 ##STR186## O 2Cl 8 1 CH.sub.2CCH i-C.sub.3 H.sub.7 O 2 86-90SCN 5,6,7,8 1 CH.sub.2 N.sub.3 i-C.sub.3 H.sub.7 O 2SCN 5,6,7,8 1 CH.sub.2 CN i-C.sub.3 H.sub.7 O 2SCN 5,6,7,8 1 CH.sub.2 CN i-C.sub.3 H.sub.7 S 2SCN 5,6,7,8 1 CH.sub.2 CO.sub.2 CH.sub.3 i-C.sub.3 H.sub.7 S 2SCN 5,6,7,8 1 CH.sub.2 SCN sec-C.sub.4 H.sub.9 O 1SCN 5,6,7,8 1 ##STR187## i-C.sub.3 H.sub.7 O 2CO.sub.2 CH.sub.3 5,6,7,8 1 CH.sub.2 SCN i-C.sub.3 H.sub.7 O 2CO.sub.2 CH.sub.3 5,6,7,8 1 CH.sub.2 CN i-C.sub.3 H.sub.7 O 2CO.sub.2 CH.sub.3 5,6,7,8 1 CH.sub.2CCH i-C.sub.3 H.sub.7 O 2CO.sub.2 CH.sub.3 5,6,7,8 1 CH.sub.2CH.sub.2 OH i-C.sub.3 H.sub.7 O 2N(CH.sub.3).sub.2 5,6,7,8 1 CH.sub.2 N.sub.3 i-C.sub.3 H.sub.7 O 2N(CH.sub.3).sub.2 5,6,7,8 1 ##STR188## i-C.sub.3 H.sub.7 O 2N(CH.sub.3).sub.2 5,6,7,8 1 tert-C.sub.4 H.sub.9 sec-C.sub.4 H.sub.9 O 2OCH.sub.3 5,6,7,8 1 CH.sub.2C CH i-C.sub.3 H.sub.7 O 2OCH.sub.3 5,6,7,8 1 CH.sub.2 SCN i-C.sub.3 H.sub.7 O 2SCH.sub.3 5,6,7,8 1 CH.sub.2 CN i-C.sub.3 H.sub.7 O 2SCH.sub.3 5,6,7,8 1 CH.sub.2CCH ##STR189## O 1SCH.sub.3 5,6,7,8 1 CH.sub.2CCCH.sub.2 Cl i-C.sub.3 H.sub.7 O 2Cl 6 1 CH.sub.2CCH i-C.sub.3 H.sub.7 O 1 92-94Cl 6 1 CH.sub.2 C.sub.6 H.sub.5 C.sub.2 H.sub.5 O 1 105-109SO.sub.2 CH.sub.3 5,6,7,8 1 CH.sub.2 N.sub.3 i-C.sub.3 H.sub.7 O 2SO.sub.2 CH.sub.3 5,6,7,8 1 ##STR190## i-C.sub.3 H.sub.7 O 2SO.sub.2 N(CH.sub.3).sub.2 5,6,7,8 1 ##STR191## i-C.sub.3 H.sub.7 O 2SO.sub.2 N(CH.sub.3).sub.2 5,6,7,8 1 CH.sub.2CH.sub.2 OH i-C.sub.3 H.sub.7 O 2CCl.sub.3 5,6,7,8 1 CH.sub.2 CN i-C.sub.3 H.sub.7 O 2SO.sub.2 OCH.sub.3 5,6,7,8 1 CH.sub.2 CN sec-C.sub.4 H.sub.9 O 2CCl.sub.3 5,6,7,8 1 ##STR192## i-C.sub.3 H.sub.7 O 2CF.sub.3 5,6,7,8 1 CH.sub.2 N.sub.3 i-C.sub.3 H.sub.7 O 2CF.sub.3 5,6,7,8 1 CH.sub.2CCH i-C.sub.3 H.sub.7 O 2CF.sub.3 5,6,7,8 1 CH.sub.2 CO.sub.2 CH.sub.3 sec-C.sub.4 H.sub.9 S 2 ##STR193## 5,6,7,8 1 CH.sub.2 CN i-C.sub.3 H.sub.7 O 2 ##STR194## 5,6,7,8 1 CH.sub.2 SCN i-C.sub.3 H.sub.7 O 2 ##STR195## 5,6,7,8 1 CH.sub.2 CH.sub.2 CN i-C.sub.3 H.sub.7 O 2OH 5,6,7,8 1 CH.sub.2CCH i-C.sub.3 H.sub.7 O 2SH 5,6,7,8 1 CH.sub.2CCH i-C.sub.3 H.sub.7 O 2SO.sub.2 NHCH.sub.3 5,6,7,8 1 ##STR196## i-C.sub.3 H.sub.7 O 2OCF.sub.2 CH.sub.3 5,6,7,8 1 CH.sub.2CCCH.sub.2 Cl i-C.sub.3 H.sub.7 O 1OCF.sub.2 CF.sub.3 5,6,7,8 1 tert-C.sub.4 H.sub.9 i-C.sub.3 H.sub.7 O 2OCF.sub.2 CF.sub.3 5,6,7,8 1 ##STR197## i-C.sub.3 H.sub.7 O 2OCF.sub.2 CCl.sub.3 5,6,7,8 1 CH.sub.2 CN i-C.sub.3 H.sub.7 O 2Cl 6 1 CH.sub.3 C.sub.2 H.sub.5 O 1 96-98Br 6 1 CH.sub.3 C.sub.2 H.sub.5 O 1 104-105NO.sub.2 6 1 CH.sub.2 SCN ##STR198## O 2NO.sub.2 6 1 CH.sub.2 N.sub.3 CH.sub.2CHCH.sub.2 O 2NO.sub.2 8 1 CH.sub.2 CN ##STR199## O 2NO.sub.2 5,7 1 CH.sub.2 CO.sub.2 CH.sub.3 i-C.sub.3 H.sub.7 O 2NO.sub.2 6 2 CH.sub.2 N.sub.3 i-C.sub.3 H.sub.7 O 2CH.sub.3 8NO.sub.2 5,6,7,8 1 ##STR200## i-C.sub.3 H.sub.7 O 2NO.sub.2 5,6,7,8 1 CH.sub.2 SCN C.sub.6 H.sub.5 O 2NO.sub.2 6 1 CH.sub.2 SCN ##STR201## O 2CH.sub.2 F 5,6,7,8 1 CH.sub.2 N.sub.3 i-C.sub.3 H.sub.7 O 1CH.sub.2 OCH.sub.3 5,6,7,8 1 CH.sub.2 CN i-C.sub.3 H.sub.7 O 2 ##STR202## 8 1 CH.sub.2 CN i-C.sub.3 H.sub.7 O 2-- -- 0 CH.sub.2 N.sub.3 CH.sub.3 O 2 108-- -- 0 ##STR203## i-C.sub.3 H.sub.7 O 2 137-- -- 0 ##STR204## i-C.sub.3 H.sub.7 O 2 68-- -- 0 CH.sub.2NP(OCH.sub.3).sub.3 i-C.sub.3 H.sub.7 O 2 viscous oil-- -- 0 ##STR205## i-C.sub.3 H.sub.7 O 2 n.sub.D.sup.20 = 1.5497-- -- 0 ##STR206## i-C.sub.3 H.sub.7 O 2 129-132-- -- 0 ##STR207## i-C.sub.3 H.sub.7 O 2 146-148__________________________________________________________________________

EXAMPLE 6

Herbicidal action of the new 2,1,3-benzothiadiazine compounds

Greenhouse experiments and experiments in the open were carried out in order to study the herbicidal and selective properties of the new compounds.

I. Greenhouse experiments

Plastic flowerpots having a volume of 300 cm.sup.3 were filled with a sandy loam, and test plants were grown therein, separated by species.

The plants were either grown from seed, or from pregerminated tubers (e.g., Cyperus esculentus) or from transplanted vegetatively reproduced species. For the preemergence treatment, only seeds were suitable. The active ingredients were suspended or emulsified in water as distributing agent, and sprayed onto the surface of the soil by means of atomizing nozzles. After treatment, the vessels were lightly sprinkler-irrigated, and then covered with transparent plastic hoods until the plants emerged. In postemergence treatment (leaf treatment) the plants were first grown to a height of from 3 to 10 cm, depending on their habit, before being treated. The plants were of course not sprinkler-irrigated immediately, and no hoods were placed on the pots. The test plants were placed in either the cooler or warmer sections of the greenhouse, depending on their temperature requirements. The experimental period was from 2 to 4 weeks. During this period the plants were tended and their reactions to the various treatments were evaluated. The application rates of the compounds under investigation are given as kg of active ingredient per hectare. Assessment was on a 0 to 100 scale, 0 denoting no damage or normal emergence, and 100 denoting no emergence or destruction of the plants.

II. Experiments in the open

Here, postemergence treatments were carried out on small plots. The active ingredients were applied as an emulsion or suspension in water as carrier and distribution medium, with the aid of a motor-driven plot spray mounted on a hitch. All the experiments were observed for several weeks and also assessed on the 0 to 100 scale.

Results

The representatives of the new compounds listed in Tables 2 to 6 control unwanted plants better than the comparative agent 1-chloromethyl-3-isopropyl-2,1,3-benzothiadiazin-(4)-one-2,2-dioxide, and have an action similar to, and sometimes poorer than, that of comparative agent 3-isopropyl-2,1,3-benzothiadiazin-(4)-one-2,2-dioxide. Tolerance was in some crops the same as that of the comparative agents. However, in crops in which prior art agents from this class of compounds cannot be used, or only at considerable risk, such as potatoes, onions and sunflowers (these only being given by way of example), the compounds according to the invention proved to be far better tolerated; this is their value and the advance they represent.

TABLE 1______________________________________List of plant names AbbreviationBotanical name in tables English term______________________________________Abutilon theophrastii Abut. theo. velvet leafAllium cepa -- onionAmaranthus spp. Amar. spp. pigweedAmmania coccinea Amman. cocc. redstemChenopodium spp. Chenop. spp. lambsquartersChrysanthemum segetum Chrys. seget. corn marigoldCucumis sativus Cucumis sat. cucumberCyperus esculentus Cyper. escul. yellow nutsedgeDatura stramonium Datura stram. JimsonweedGalium aparine Gali. apar. catchweed bedstrawGalinsoga spp. Galins. app. gallant soldierGlycine max -- soybeanHelianthus annuus Helianth. annuus sunflowerHordium vulgare Hord. vulg. barleyLaminum spp. -- deadnettleMatricaria spp. Matric. spp. chamomileMedicago sativa Medic. sat. alfalfaMentha piperita Mentha pip. peppermintOryza sativa Oryza sat. ricePhaseolus vulgaris Phaseol. vulg. snapbeanRaphanus spp. -- wild radishSida spinosa Sida spin. prickly sidaSinapis spp. -- yellow charlockSolanum nigrum Solan. nigr. black nightshadeSolanum tuberosum Solan. tub. potatoStellaria media Stell. med. chickweedZea mays -- Indian corn______________________________________ TABLE 2__________________________________________________________________________Selective herbicidal action in vegetables; postemergence treatment in thegreenhouse ##STR208## Application Test plants and % damageCompound Substituent rate Allium Cucumis Phaseol. Abut. Datura Lamium Solan. Stell.no. R kg/ha cepa sat. vulg. theo. stram. spp. nigr. med.__________________________________________________________________________ 0.5 10 0 0 78 95 80 57 831 CH.sub.2CCH 1.0 20 0 0 82 -- 80 80 97 2.0 25 0 0 88 -- 100 93 97 0.5 0 0 0 98 100 80 82 702 CH.sub.2CN 1.0 10 0 0 98 -- 100 82 100 2.0 20 10 0 98 -- -- 98 100 0.5 30 0 0 48 95 60 20 583 CH.sub.2Cl 1.0 32 0 0 52 -- 60 20 80 (prior art) 2.0 40 0 0 52 -- 100 40 95 0.5 63 0 0 68 100 50 88 824 H 1.0 65 5 0 72 -- 50 92 88 (prior art) 2.0 65 10 0 78 -- 100 98 95__________________________________________________________________________ 0 = no damage 100 = plants destroyed TABLE 3__________________________________________________________________________Selective herbicidal action in sunflowers and other crops; postemergencetreatmentin the greenhouse ##STR209## Application Test plants and % damageCompound Substituent rate Helianth. Hord. Zea Datura Sida Stell.no. R kg/ha annuus vulg. mays stram. spin. med.__________________________________________________________________________ ##STR210## 2.0 4.0 0 5 0 0 5 10 95 -- 95 -- 65 --4 H 2.0 100 0 0 100 93 95 4.0 100 0 7 -- -- --6 CH.sub.2CHCH.sub.2 2.0 0 0 0 95 -- 50 4.0 10 0 0 -- -- --7 CH.sub.2CH.sub.2CH.sub.3 2.0 0 0 0 95 -- 80 4.0 0 0 12 -- -- --__________________________________________________________________________ 0 = no damage 100 = plants destroyed TABLE 4__________________________________________________________________________Action and selectivity; postemergence treatment in the greenhouse ##STR211## Appli- Test plants and % damageCom- cation Men- Ory-pound Substituent rate Hord. Medic. tha. za Zea Amar. Amman. Cyper. Chenop. Chrys. Galium Matri.no. R kg/ha vulg. sat. pip. sat. mays spp. cocc. escul. spp. seget. apar. spp.__________________________________________________________________________ 0.5 0 -- 0 0 0 100 10 33 100 100 33 1008 CH.sub.2N.sub.3 1.0 0 0 0 0 0 100 70 32 100 100 82 100 4.0 0 0 0 8 0 -- -- 42 -- -- 95 100 0.5 0 -- -- 0 0 15 95 50 -- 100 -- 1009 CH.sub.2SCN 1.0 0 -- -- 0 10 20 95 60 -- 100 -- 100 4.0 0 -- -- 20 10 -- -- 95 -- -- -- -- 0.5 -- -- 0 0 5 75 -- 10 -- 92 10 1003 CH.sub.2 Cl 1.0 -- 0 0 0 5 75 -- 15 -- 98 60 100 4.0 -- 20 0 0 10 -- -- 35 -- -- -- -- 0.5 0 -- 0 0 0 23 85 26 100 99 50 1004 H 1.0 0 0 0 0 0 43 88 34 100 99 60 100 4.0 0 20 0 0 7 -- -- 60 -- -- -- --__________________________________________________________________________ 2 100 = plants destroyed 0 = no action TABLE 5__________________________________________________________________________Selective herbicidal action; postemergence treatment in the openApplication Test plants and % damageCompound rate Glyc. Solan. Zea Chenop. Galins. Gali. Sinapis/no. kg/ha max. tub. mays spp. spp. apar. Raphanus__________________________________________________________________________8 2.0 5 4 0 94 95 88 1009 1.0 2 -- 0 86 92 -- 100 2.0 5 -- -- -- -- -- --2 1.0 10 -- 0 53 13 100 90 2.0 -- -- -- 75 20 100 904 2.0 6 14 0 90 95 88 100__________________________________________________________________________ 0 = no damage 100 = plants destroyed TABLE 6______________________________________Pre- and postemergence treatment withnew 2,1,3-benzothiadiazine derivativesin the greenhouse ##STR212##Com- Test plant andpound % damageno. Substituent kg/ha Method Sida spinosa______________________________________10 ##STR213## 1.0 2.0 1.0 2.0 pre pre post post 95 95 95 95 1.0 pre 60 2.0 pre 604 H 1.0 post 95 2.0 post 95 1.0 pre 80 2.0 pre 928 CH.sub.2N.sub.3 1.0 post 78 2.0 post 95______________________________________ 0 = no damage 100 = plants destroyed pre = preemergence treatment post = postemergence treatment TABLE 7__________________________________________________________________________Biological action of new 2,1,3-benzothiadiazine derivatives on Sinapisalba;postemergence treatment in the greenhouse ##STR214##Compound Substituents Ring Sinapis alba andno. R.sup.1 R.sup.2 X position kg/ha % damage__________________________________________________________________________ ##STR215## C.sub.3 H.sub.7 i H -- 2.0 100CH.sub.2CCH C.sub.4 H.sub.9 sec H -- 2.0 100CH.sub.2CH.sub.2 Br C.sub.3 H.sub.7 i H -- 2.0 75CH.sub.2CCCH.sub.2 Cl C.sub.3 H.sub.7 i H -- 2.0 90 ##STR216## C.sub.3 H.sub.7 i H -- 2.0 100CH.sub.2 COCH.sub.3 C.sub.3 H.sub.7 i H -- 2.0 90 ##STR217## C.sub.3 H.sub.7 i H -- 2.0 100CH.sub.2 CH.sub.2 CN C.sub.3 H.sub.7 i H -- 2.0 100 ##STR218## C.sub.3 H.sub.7 i H -- 2.0 100 ##STR219## C.sub.3 H.sub.7 i H -- 2.0 100 ##STR220## C.sub.3 H.sub.7 i H -- 2.0 100 ##STR221## C.sub.3 H.sub.7 i H -- 2.0 100 ##STR222## C.sub.3 H.sub.7 i H -- 2.0 80 ##STR223## C.sub. 3 H.sub.7 i H -- 2.0 100 ##STR224## C.sub.3 H.sub.7 i H -- 2.0 100 ##STR225## C.sub.3 H.sub.7 i H -- 2.0 100CH.sub.2 NP(OC.sub.2 H.sub.5).sub.3 C.sub.3 H.sub.7 i H -- 2.0 100CH.sub.2 CCH C.sub.3 H.sub.7 i Cl 7 2.0 100CH.sub.2 CCH C.sub.3 H.sub.7 i Cl 8 2.0 80CH.sub.2N.sub.3 CH.sub.3 H -- 2.0 100 ##STR226## C.sub.3 H.sub.7 i H -- 2.0 100CH.sub.2NP(OCH.sub.3).sub.3 C.sub.3 H.sub.7 i H -- 2.0 100 ##STR227## C.sub. 3 H.sub.7 i H -- 2.0 100__________________________________________________________________________ 0 = no damage 100 = plants destroyed

The new active ingredients may be used for controlling unwanted plant growth in the following crops:

______________________________________Botanical name English term______________________________________Ananas comosus pineappleArachis hypogaea peanuts (groundnuts)Asparagus officinalis asparagusAvena sativa oatsBeta vulgaris spp. altissima sugarbeetBeta vulgaris spp. rapa fodder beetBeta vulgaris spp. esculenta table beet, red beetBrassica napus var. napus rapeBrassica napus var. napobrassicaBrassica napus var. rapa turnipsBrassica rapus var. silvestrisCamellia sinensis tea plantsCarthamus tinctorius safflowerCitrus limon lemonCitrus maxima grapefruitCitrus reticulataCitrus sinensis orange treesCaffea arabica (Coffea canephora, coffee plantsCoffea liberica)Cucumis melo melonsCynodon dactylon Bermudagrass in turf and lawnsDaucus carota carrotsElaeis guineensis oil palmsFragaria vesca strawberriesGossypium hirsutum(Gossypium arboreumGossypium herbaceum cottonGossypium vitifolium)Helianthus tuberosusHevea brasiliensis rubber plantsHumulus lupulus hopsIopmoea batatas sweet potatoesLactuca sativa lettuceLens culinaris lentilsLinum usitatissimum flaxLycopersicon lycopersicum tomatoesMalus spp. apple treesManihot esculenta cassavaMusaspp. banana plantsNicotiana tabacum(N. rustica) tobaccoOlea europaea olive treesPanicum miliaceumPhaseolus lunatus limabeansPhaseolus mungo mungbeansPennisetum glaucumPetroselinum crispum parsleyspp. tuberosumPicea abies Norway spruceAbies alba fir treesPinus spp. pine treesPisum sativum English peasPrunus avium cherry treesPrunus domestica plum treesPrunus persica peach treesPyrus communis pear treesRibes sylvestre redcurrantsRibes uva-crispaRicinus communisSaccharum officinarum sugar caneSecale cereale ryeSesamum indicum SesameSorghum bicolor (s. vulgare) grain sorghumSorghum dochnaSpinacia oleracea spinachTheobroma cacao cacao plantsTrifolium pratense red cloverTriticum aestivum wheatVaccinium corymbosum blueberriesVaccinium vitis-idaea cranberriesVicia faba tick beansVigna sinensis (V. unguiculata) cow peasVitis vinifera grapes______________________________________

To further increase the spectrum of action of the new individual active ingredients, to achieve synergistic effects or to improve persistence in the soil, numerous other herbicidal compounds and growth regulators may be used as components for mixtures and combination. Depending on the area of use and the unwanted plants to be controlled, the following substances or similar derivatives are suitable as components: ##STR228## and salts

______________________________________ ##STR229##R R.sup.1 R.sup.2______________________________________ ##STR230## NH.sub.2 Cl ##STR231## NHCH.sub.3 Cl______________________________________ ______________________________________ ##STR232##R R.sup.1 R.sup.2 R.sup.3 R.sup.4______________________________________H SO.sub.2 NH.sub.2 H n . C.sub.3 H.sub.7 n . C.sub.3 H.sub.7H.sub.3 C H.sub.3 C H H ##STR233##______________________________________ ______________________________________ ##STR234##R R.sup.1 R.sup.2______________________________________ ##STR235## H ##STR236##______________________________________ ______________________________________ ##STR237## R.sup.1 R.sup.2______________________________________ ##STR238## H CH.sub.2CCCH.sub.2 Cl ##STR239## H i-C.sub. 3 H.sub.7 ##STR240## H CH.sub.3______________________________________ ______________________________________ ##STR241##R R.sup.1 R.sup.2______________________________________ ##STR242## H CH.sub.3 ##STR243## H C.sub.2 H.sub.5 ##STR244## CH.sub.3 CH.sub.3 ##STR245## H CH.sub.3 ##STR246## ##STR247##______________________________________ ______________________________________ ##STR248##R X Y R.sup.1______________________________________CH.sub.3 Cl Cl Na ##STR249## Cl H CH.sub.3 ##STR250## H H H salts ##STR251## H CH.sub.3 CH.sub.3 ##STR252## H CH.sub.3 C.sub.2 H.sub.5 ##STR253## H CH.sub.3 i . C.sub.3 H.sub.7 ##STR254## H CH.sub.3 CH.sub.3______________________________________ ______________________________________ ##STR255##R X Y R.sup.1______________________________________ ##STR256## H CH.sub.3 ##STR257## ##STR258## H CH.sub.3 Na ##STR259## H CH.sub.3 Na______________________________________ ______________________________________ ##STR260##R R.sup.1 X R.sup.2 R.sup.3______________________________________H tert . C.sub.4 H.sub.9 SCH.sub.3 H C.sub.2 H.sub.5H i . C.sub.3 H.sub.7 SCH.sub.3 H i . C.sub.3 H.sub.7H C.sub.2 H.sub.5 SCH.sub.3 H C.sub.2 H.sub.5H i . C.sub.3 H.sub.7 SCH.sub.3 H C.sub.2 H.sub.5H i . C.sub.3 H.sub.7 Cl H C.sub.2 H.sub.5H i . C.sub.3 H.sub.7 Cl H ##STR261##H C.sub.2 H.sub.5 Cl H C.sub.2 H.sub.5H C.sub.2 H.sub.5 Cl H ##STR262##H i . C.sub.3 H.sub.7 Cl H i . C.sub.3 H.sub.7H i . C.sub. 3 H.sub.7 OCH.sub.3 H i . C.sub.3 H.sub.7H C.sub.2 H.sub.5 Cl H ##STR263##H C.sub.2 H.sub.5 Cl H ##STR264## ##STR265## Cl H ##STR266##______________________________________ ______________________________________ ##STR267##R R.sup.1 R.sup.2______________________________________ ##STR268## H ##STR269## ##STR270## H C.sub.2 H.sub.5 ##STR271## H ##STR272## ##STR273## H ##STR274## ##STR275## H CH.sub.3______________________________________ ______________________________________ ##STR276##X Y R______________________________________Br Br H saltsI I H salts ##STR277## salts, esters ##STR278## salt, esters______________________________________ ______________________________________ ##STR279## R R.sup.1 R.sup.2 R.sup.3______________________________________ ##STR280## H CH.sub.3 CH.sub.3 ##STR281## H CH.sub.3 CH.sub.3 ##STR282## CH.sub.3 CH.sub.3 H______________________________________ ##STR283## R R.sup.1 R.sup.2 R.sup.3______________________________________ ##STR284## H CH.sub.3 CH.sub.3 ##STR285## H CH.sub.3 CH.sub.3 ##STR286## H CH.sub.3 ##STR287## ##STR288## H CH.sub.3 OCH.sub.3 ##STR289## H CH.sub.3 OCH.sub.3 ##STR290## H CH.sub.3 CH.sub.3 ##STR291## H CH.sub.3 OCH.sub.3 ##STR292## H CH.sub.3 OCH.sub.3 ##STR293## H CH.sub.3 CH.sub.3 ##STR294## CH.sub.3 CH.sub.3 H ##STR295## ##STR296## H CH.sub.3 OCH.sub.3 ##STR297## H CH.sub.3 CH.sub. 3______________________________________ ______________________________________ ##STR298##R R.sup.1 R.sup.2 R.sup.3______________________________________Cl Cl Cl HF Cl Cl HNO.sub.2 CF.sub.3 H HCl CF.sub.3 H COOH salts and estersCl Cl H HCl Cl H OCH.sub.3Cl Cl H ##STR299##H CF.sub.3 Cl OC.sub.2 H.sub.5______________________________________ ______________________________________ ##STR300##R R.sup.1 R.sup.2______________________________________tert.-C.sub. 4 H.sub.9 NH.sub.2 SCH.sub.3tert.-C.sub. 4 H.sub.9 ##STR301## SCH.sub.3 ##STR302##______________________________________ ______________________________________ ##STR303##R R.sup.1 R.sup.2 R.sup.3______________________________________ ##STR304## sec-C.sub. 4 H.sub.9 H HH CH.sub.3 H H salts, estersH sec-C.sub. 4 H.sub.9 H H salts, esters ##STR305## tert.-C.sub. 4 H.sub.9 H H ##STR306## ##STR307##______________________________________ ______________________________________ ##STR308##R R.sup.1 R.sup.2 X______________________________________CH.sub.3 CH.sub.3 H CH.sub.3OSO.sub.2 OCH.sub.3 CH.sub.3 Br CH.sub.3OSO.sub.2 OCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3OSO.sub.2 O ##STR309## ##STR310##______________________________________ __________________________________________________________________________ ##STR311##R R.sup.1 R.sup.2 R.sup.3__________________________________________________________________________H n . C.sub.3 H.sub.7 CH.sub.2CHCH.sub.2 CH.sub.3Na n . C.sub.3 H.sub.7 CH.sub.2CHCH.sub.2 CH.sub.3 ##STR312## ##STR313## ##STR314##__________________________________________________________________________ ______________________________________ ##STR315##R R.sup.1 R.sup.2 R.sup.3 R.sup.4______________________________________Cl H Cl OCH.sub.3 H salts, esters, amidesCl Cl H Cl H . (CH.sub.3).sub.2 NH______________________________________ ______________________________________ ##STR316##R R.sup.1 R.sup.2______________________________________ ##STR317## CH.sub.3 H salts, esters, amides ##STR318## H H salts, esters, amides ##STR319## H H salts, esters, amides______________________________________ ______________________________________ ##STR320##R R.sup.1 R.sup.2______________________________________ ##STR321## H H salts, esters, amides ##STR322## CH.sub.3 H salts, esters, amides ##STR323## CH.sub.3 H salts, esters, amides______________________________________ ______________________________________ ##STR324##R R.sup.1______________________________________ ##STR325## H salts, esters, amides ##STR326## H salts, esters, amides ##STR327## ##STR328## ##STR329## ##STR330## ##STR331## salts, esters ##STR332## ##STR333## ##STR334## salts ##STR335## ##STR336## salts, esters, amides______________________________________

It is also possible to apply the new compounds according to the invention, either alone or in combination with other herbicides, in admixture with further crop protection agents, e.g., agents for combatting pests, or phytopathogenic fungi or bacteria. Of further interest is the miscibility of the compounds with mineral salt solutions used to eliminate nutritional or trace element deficiencies.

Spreader-stickers are nonphytotoxic oils may be added to ensure the herbicidal action.

Application may be effected for instance in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used; in any case they should ensure as fine a distribution of the active ingredient as possible.

For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, etc. and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alcohol glycol ether, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenol polyglycol ethers, alkylaryl polyester alcohols, isotridecyl alcohols, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.

The formulations contain from 0.1 to 95, and preferably 0.5 to 90, % by weight of active ingredient. Application rates vary from 0.1 to 10, especially from 0.5 to 5, kg of active ingredient per hectare.

EXAMPLE 7

90 parts by weight of compound 1 is mixed with 10 parts by weight of N-methyl-.alpha.-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

EXAMPLE 8

20 parts by weight of compound 2 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 9

20 parts by weight of compound 5 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 10

20 parts by weight of compound 6 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210.degree. and 280.degree. C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 11

20 parts by weight of compound 1 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-.alpha.-sulfonic acid, 17 parts by weight of the sodium salt of a ligninsulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquid is obtained containing 0.1% by weight of the active ingredient.

EXAMPLE 12

3 parts by weight of compound 2 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.

EXAMPLE 13

30 parts by weight of compound 5 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

EXAMPLE 14

40 parts by weight of compound 6 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution in 100,000 parts by weight of water gives an aqueous dispersion containing 0.04 wt% of active ingredient.

EXAMPLE 15

20 parts of compound 1 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.

Claims

1. A compound of the formula ##STR337## where R.sup.1 is lower alkynyl; lower haloalkenyl; lower haloalkynyl; lower alkoxycarboalkyl; lower alkoxycarboalkenyl; lower alkanoylalkyl; lower azidoalkyl; lower thiocyanatoalkyl; lower cyanoalkyl; carbamyl-lower alkyl; carbamyl-lower alkyl substituted by halogen; halo- or methyl substituted phenyl; lower alkylmercaptoalkyl, lower phenylmercaptoalkyl, wherein in said alkylmercaptoalkyl and phenylmercaptoalkyl the final alkyl has more than 1 carbon atom; or methyl substituted by lower O-alkyl-N-alkylaminophosphorothio, lower O,O-dialkylphosphoro, lower O,O,O-trialkylphosphinylimino, lower alkoxy thiocarbonyl thio, lower alkylsulfinyl, thiocarbamido, isothiuronium hydrochloride, ##STR338## lower alkanoylamido, lower alkanoylamido substituted by halogen, phthalylimidoalkyl, isoxazole or isoxazole substituted by methyl or halogen;

R.sup.2 is isopropyl;

n is 2;

R and R.sup.3 are lower alkyl,

R.sup.4 is lower alkyl or hydrogen,

R.sup.5 is lower alkyl or phenyl; and

each Y and Y' independently is oxygen or sulfur.

2. 1-propargyl-3-isopropyl-2,1,3-benzothiadiazin-(4)-one-2,2-dioxide.

3. 1-azidomethyl-3-isopropyl-2,1,3-benzothiadiazin-(4)-one-2,2-dioxide.

4. 1-thiocyanatomethyl-3-isopropyl-2,1,3-benzothiadiazin-(4)-one-2,2-dioxide.

5. 1-cyanomethyl-3-isopropyl-2,1,3-benzothiadiazin-(4)-one-2,2-dioxide.

6. 1-thiocarbamidomethyl-3-isopropyl-2,1,3-benzothiadiazin-(4)-one-2,2-dioxide.

7. 1-methyl-(O-ethyl-N-isopropylaminophosphorothio)-3-isopropyl-2,1,3-benzothiadiazin-(4)-one-2,2-dioxide.

8. 1-propargyl-3-sec-butyl-2,1,3-benzothiadiazin-(4)-one-2,2-dioxide.