Intermediate isocyana to benzenesulfonamide compounds

FIELD OF THE INVENTION
This invention relates to a class of compounds, i.e., benzenesulfonamide derivatives, having substituted thereon a pyrimidinyl moiety, which compounds exhibit desirable pre- and post-emergent herbicidal activity. In other aspects, this invention relates to herbicidal compositions incorporating such compounds and to a method of controlling the growth of undesirable plants, such as weeds. In further aspects, this invention relates to novel intermediates useful for the production of the novel herbicides and to processes for producing such compounds.
BACKGROUND OF THE INVENTION
Weeds compete with crops for light, moisture, nutrients and space and consequently inhibit the production of foliage, fruit or seed of agricultural crops. The presence of weeds may also reduce the quality of the harvested crop and reduce harvesting efficiency. Weed control is essential for maximum production of many agronomic and horticultural crops including corn, (Zea mays L.), cotton (Gossypium SP), sunflower (Helianthus annus L.) and soybeans (Glycine max (L.) Merr.). Weeds on non-cropped areas may cause a fire hazard, undesirable drifting of sand or snow, or irritation to persons with allergies. Consequently, it is desirable to suppress growth of unwanted weeds.
While a large number of compounds exhibiting herbicidal activity are known, it is nonetheless advantageous to obtain additional compounds which effectively control the growth of unwanted vegetation.
DESCRIPTION OF RELATED ART
U.S. Pat. No. 4,859,229 to Wenger discloses certain substituted 3-aryluracils having an ether (thio)carbamyloxy or sulphamyloxy substituent on the aromatic moiety, and weed control compositions based thereon. Compounds according to the present invention have different structures and effect greater selectivity to certain crops.
Lutz and Trotto in J. Heterocyclic Chemistry, (1972), 9, (3), 513 discuss means of synthesizing 6-(trifluoromethyl) cytosines and 6-(trifluoromethyl) uracils. It will become apparent that the compounds and processes disclosed in the above references differ significantly from those herein disclosed.
SUMMARY OF THE INVENTION
In one aspect, this invention relates to compounds of formula I below: ##STR2## wherein: R is hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, formyl, C.sub.2 -C.sub.6 alkanoyl, C.sub.3 -C.sub.4 alkenyl or C.sub.3 -C.sub.4 alkynyl, or alkali metal;
X is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.8 alkoxy, cyano, or halogen;
Y is hydrogen, halogen, or C.sub.1 -C.sub.4 dialkylamino;
R.sup.1 is hydrogen, C.sub.1 -C.sub.8 straight chain or branched alkyl, C.sub.3 -C.sub.8 cycloalkyl, C.sub.3 -C.sub.8 alkenyl, C.sub.3 -C.sub.8 alkoxy or C.sub.3 -C.sub.8 hydroxyalkyl;
R.sup.2 is hydrogen, C.sub.1 -C.sub.8 straight chain or branched alkyl, C.sub.3 -C.sub.8 alkenyl, C.sub.3 -C.sub.8 cycloalkyl, halo substituted C.sub.3 -C.sub.8 alkenyl, C.sub.3 -C.sub.8 alkynyl, C.sub.1 -C.sub.4 alkoxy, hydroxy C.sub.1 -C.sub.4 alkyl, cyano C.sub.1 -C.sub.4 alkyl, 2,3-epoxypropyl, 2,2-dialkoxyethyl, alkoxyalkyl, phenyl, aralkyl, C.sub.1 -C.sub.4 acyl, C.sub.1 -C.sub.4 carbalkoxyalkyl, C.sub.1 -C.sub.4 carbalkoxyalkyl substituted by C.sub.1 -C.sub.4 alkyl, phenylmethyl or methylthioethyl, (1,3-dioxolan-2-yl) alkyl, dialkylaminoethyl, or tetrahydrofuranylmethyl;
R.sup.3 is hydrogen, halogen or C.sub.1 -C.sub.4 alkyl;
R.sup.4 is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 haloalkyl
R.sup.1 and R.sup.2 taken together form a C.sub.3 -C.sub.8 membered heterocyclic ring containing one or more heteroatoms; as well as salts of the compounds of formula I in which R is hydrogen or R.sup.1 is hydrogen.
In another aspect, this invention relates to an herbicidal composition comprising:
(a) a compound having the structure of formula (I) above; and
(b) a suitable carrier:
In yet another aspect of the present invention, a process (hereinafter referred to as "process A") for preparing the above-described class of compounds having the structural formula I is described. In the process of forming the above described class of compounds, with the proviso that R is an alkali metal, a compound having the structural formula ##STR3## where R.sup.3 is hydrogen or C.sub.1 -C.sub.4 alkyl; R.sup.4 is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 haloalkyl; and R.sup.5 is C.sub.1 -C.sub.6 alkyl, is reacted with sodium hydride. The product of this reaction is further reacted with a novel isocyanatobenzenesulfonamide having the structural formula: ##STR4## where X and Y have the meanings given above for the compound of this invention and with the proviso that R.sup.1 and R.sup.2 cannot be hydrogen. The product of formula I, where R is an alkali metal, may be isolated or further reacted to produce other compounds of formula I.
Additional compounds in accordance with this invention where R is C.sub.1 -C.sub.4 alkyl, C.sub.3 -C.sub.4 alkenyl, C.sub.1 -C.sub.4 haloalkyl, or C.sub.3 -C.sub.4 alkynyl, are made by reacting a precursor compound of the present invention where R. is an alkali metal, with an alkylating agent, R-Z, where R has the meanings defined above and Z represents a leaving group.
In further accordance with the process of making the compounds of this invention, a compound in which R is hydrogen is prepared by reacting a precursor compound of the present invention wherein R is an alkali metal, with a strong acid.
The novel isocyanatobenzenesulfonamide .. intermediate is prepared by phosgenation of the amino-substituted benzenesulfonamide.
Another process (hereinafter referred to as "process B") for preparing the above described class of compounds having the structural formula I first involves the chlorosulfonation of certain 3-aryl substituted 2,4-(1H,3H)-pyrimidinediones having the structural formula ##STR5## where R, R.sup.3, R.sup.4, X and Y have the meanings given above with the proviso that R is not alkali metal, formyl, alkanoyl, alkenyl or alkynyl, to produce novel pyrimidinyl substituted benzenesulfonyl chloride intermediates of the structural formula ##STR6## The pyrimidinyl substituted benzenesulfonyl chloride is then reacted with an appropriate amine to produce compounds of formula I.
In still further accordance with the instant invention another process (hereinafter referred to as "process C") for making the aforesaid compounds is carried out by reacting certain substituted pyrimidinylbenzenesulfonamides with an alkyl halide in the presence of sodium hydride in N, N-dimethylformamide or other suitable solvents.
In yet still further accordance with a process of making certain compounds of formula I (hereinafter referred to as process D), the products of process C may be hydrogenated over a palladium/carbon catalyst.
It has been found that certain of the aforedescribed [3,6-dihydro-2,6-dioxo-1(2H)-pyrimidinyl]benzenesulfonamides possess excellent herbicidal properties. These properties are surprisingly effective in both pre- and post-emergent applications. That is, the class of compounds of the present invention effectively controls undesired vegetation both prior to and after emergence from soil.
In still another aspect of the present invention, a method for controlling weeds and other undesirable vegetation is disclosed. In this method, an herbicidally effective amount of a compound having the structural formula I is applied to the locus to be protected along with a suitable carrier.
DETAILED DESCRIPTION OF THE INVENTION.
The compositions of this invention contain compounds having the structural formula (I) shown below: ##STR7## wherein: R is hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, formyl, C.sub.2 -C.sub.6 alkanoyl, C.sub.3 -C.sub.4 alkenyl or C.sub.3 -C.sub.4 alkynyl, or alkali metal;
X is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.8 alkoxy, cyano, or halogen;
Y is hydrogen, halogen, or C.sub.1 -C.sub.4 dialkylamino;
R.sup.1 is hydrogen, C.sub.1 -C.sub.8 straight chain or branched alkyl, C.sub.3 -C.sub.8 cycloalkyl, C.sub.3 -C.sub.8 alkenyl, C.sub.3 -C.sub.8 alkoxy or C.sub.3 -C.sub.8 hydroxyalkyl;
R.sup.2 is hydrogen, C.sub.1 -C.sub.8 straight chain or branched alkyl, C.sub.3 -C.sub.8 alkenyl, C.sub.3 -C.sub.8 cycloalkyl, halo substituted C.sub.3 -C.sub.8 alkenyl, C.sub.3 -C.sub.8 alkynyl, C.sub.1 -C.sub.4 alkoxy, hydroxy C.sub.1 -C.sub.4 alkyl, cyano C.sub.1 -C.sub.4 alkyl, 2,3-epoxypropyl, 2,2-dialkoxyethyl, alkoxyalkyl, phenyl, aralkyl, C.sub.1 -C.sub.4 acyl, C.sub.1 -C.sub.4 carbalkoxalkyl, C.sub.1 -C.sub.4 carbalkoxyalkyl substituted by C.sub.1 -C.sub.4 alkyl, phenylmethyl or methylthioethyl, (1,3-dioxolan-2-yl)alkyl, dialkylaminoethyl, or tetrahydrofuranylmethyl;
R.sup.3 is hydrogen, halogen or C.sub.1 -C.sub.4 alkyl;
R.sup.4 is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 haloalkyl
R.sup.1 and R.sup.2 taken together form a C.sub.1 -C.sub.4 membered heterocyclic ring containing one or more heteroatoms; as well as salts of the compounds of formula I in which R is hydrogen or R.sup.1 is hydrogen.
Preferably, compounds according to the present invention have the structural formula I wherein R is C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.4 alkynyl; X is halogen or C.sub.1 -C.sub.4 alkyl; Y is halogen or hydrogen; R.sup.1 is hydrogen or C.sub.1 -C.sub.3 alkyl or C.sub.3 -C.sub.8 hydroxyalkyl; R.sup.2 is C.sub.1 -C.sub.3 alkyl, C.sub.3 -C.sub.8 cycloalkyl, C.sub.3 -C.sub.4 alkenyl, alkoxylalkyl, aralkyl, hydroxy C.sub.1 -C.sub.4 alkyl or 2,3-epoxypropyl, R.sup.3 is hydrogen, and R.sup.4 is trifluoromethyl
Still more preferably, compounds according to the present invention have structural formula I wherein R is methyl; X is chlorine or fluorine; Y is fluorine or hydrogen; R.sup.1 is hydrogen, methyl, or C.sub.1 -C.sub.4 hydroxylalkyl; R.sup.2 is hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.3 -C.sub.6 cycloalkyl, C.sub.1 -C.sub.4 alkoxy, alkoxyalkyl, hydroxy C.sub.1 -C.sub.4 alkyl, cyanoalkyl, 2,2-dialkoxyethyl, carbalkoxyalkyl, R.sup.3 is hydrogen; and R.sup.4 is trifluoromethyl.
Most preferably, compounds according to the instant invention have the structural formula I wherein R is methyl X is chlorine Y is hydrogen or fluorine; R.sup.1 is methyl, ethyl, or hydrogen; R.sup.2 is methyl, ethyl, methoxy, hydroxyethyl, acetyl, methoxyethyl, 2,2-dimethoxyethyl, 1-carbethoxyethyl, or 1-carbethoxy-2-methylpropyl; R.sup.3 is hydrogen; and R.sup.4 is trifluoromethyl.
The present invention is also directed to a composition having utility as an herbicidal agent which comprises a compound having the structural formula I and a suitable carrier therefor.
Preferably, compositions of the present invention comprise a compound having the structural formula I in which R, X, Y, R.sup.1 and R.sup.2 incorporate the embodiments indicated in the above described preferable compounds and a suitable carrier therefor.
Still more preferably, compositions of the present invention comprise a compound having the structural formula I where R, X, Y, R.sup.1 and R.sup.2 incorporate the embodiments disclosed for the above described still more preferable compounds and a suitable carrier therefor.
Most preferably, compositions of the present invention comprise a compound having the structural formula I where R, X, Y, R.sup.1 and R.sup.2 incorporate the embodiments disclosed for the above described most preferable compounds and a suitable carrier therefor.
The principal utility of the compositions of the present application are as herbicides and are made of:
(a) an herbicidally effective amount of a novel pyrimidylbenzenesulfonamide compound according to the present invention and
(b) a suitable carrier.
Such compositions may comprise one or more of the novel pyrimidinylbenzenesulfonamides of this invention. To prepare such agriculturally useful compositions, the active ingredient(s) may be mixed with an adjuvant to provide compositions in the form of finely-divided particulate solids, granules, pellets, wettable powders, flowable liquids, soluble powders, solutions, and aqueous or organic solvent dispersions or emulsions. Such formulations may be of several different physical and chemical types which can be made by one with ordinary skill in the art. For instance, the agriculturally active compound may be impregnated on finely-divided or granular inorganic or organic carriers such as appapulgite clay, sand., vermiculite, corn cob, activated carbon or other granular carriers known to the art. The impregnated granules may then be spread on, or incorporated into the soil.
Alternatively, the active ingredient(s) may be formulated as a wettable powder by grinding into a fine powder and mixing with an inactive powdered carrier to which a surface active dispersing agent has been added. Typical powdered solid carriers are the various mineral silicates (such as mica, talc, pyrophyllite, clays and the like) or powdered organic materials (e.g., corn cob). The wettable powder may then be dispersed in water and sprayed on the soil surface, or on crop or weed plants.
Similarly, an emulsifiable concentrate may be prepared by dissolving the active ingredient(s) in a solvent such as naphtha, toluene, or other aromatic or aliphatic hydrocarbon to which a surface active dispersing agent generally has been added. The emulsifiable concentrate may then be dispersed in water and applied by spraying.
The concentration of active ingredient(s) in the composition may vary widely, typically ranging from about 1% to about 95% by weight. The concentration of active ingredient(s) in dispersions applied to the soil or foliage is typically between about 0.002% and about 80% by weight.
Formulations containing the active ingredient(s) may be dispersed in water or an organic liquid (such as oil) and applied to target plants. Surface active agents may be added to the solution to be applied to increase its qualitative or quantitative range of activity. Suitable surface active agents are well known to those skilled in the art. Reference may be made to McCutcheon's Detergents and Emulsifiers (1980, Allured Publ. Co., Ridgewood, N.J.) for examples of appropriate surface active agents. Similarly, such formulation may be applied to the soil either as a liquid or a granule.
In preemergence herbicidal applications, the compound of this invention is typically applied at a rate from about 0.01 to about 10 pounds per acre (about 0.01 to about 11 kg/ha) to soil which contains weed and crop seed. Such application is made either to the surface of the soil or into the upper one to three inches (2.5 to 7.5 cm.) of soil. When employed as a postemergence herbicide, the compound is typically applied at a rate of from about 0.01 to about 10 pounds per acre (about 0.01 to about 11 kg/ha) to the aerial portions of weeds.
The most suitable rate of application in any given case depends on such factors which include the plant species, the stage of plant development, the method of application, the specific biological effect desired, the air and soil temperature, soil type, soil pH, soil fertility, moisture, organic matter content, the condition and vigor of the target plants, the relative humidity and wind velocity of the air around the crop at the time of treatment, the extent and density of the foliar canopy of the target plant, the quantity and intensity of rainfall before and after treatment, light intensity and light duration per day. All of these factors can have an influence on the efficacy of the chemicals for a given weed control use. However, one skilled in the art can, by routine experimentation, readily determine optimum conditions for employment of any of the particular pyrimidinyl benzenesulfonamide compounds of this invention.
The herbicidal use may include control of vegetation at industrial sites or selective weed control in crop fields.

The following examples are intended to further illustrate the invention and are not intended to .limit the scope of the invention in any manner.
The first set of examples (A-1 through A-6) are illustrative of process A for producing [3,6-dihydro-2,6-dioxo-1(2H)-pyrimidinyl]benzenesulfonamides by reacting an amino substituted benzenesulfonamide with excess phosgene in ethyl acetate to form an isocyanatobenzenesulfonamide intermediate, which is in turn reacted with an ester compound, e.g., ethyl-3-amino-4,4,4-trifluoro-2-butenoate in the presence of sodium hydride and then subsequently reacted with an acid to yield compounds of formula I where R is hydrogen. Suitable acids include mineral acids such as hydrochloric acid and sulfuric acid Substituents R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, X, Y and Z all have the meanings indicated above with the proviso that R.sup.1 and R.sup.2 are not hydrogen. Examples A-1 through A-3 depict known compounds which are used to make the novel products of Examples A-4 through A-6.
Products of the above reaction may, in turn, be reacted with alkylating compounds designated R-Z in basic conditions to yield further compounds of formula I. R has the meanings designated above and Z is a leaving group which may include, e.g., halogens, alkylsulfonates or arylsulfonates.
The general reaction scheme for process A is depicted below: ##STR8##
The second set of examples (B-1 through B-7) are illustrative of process B for producing [3,6-dihydro-2,6-dioxo-1(2H)-pyrimidinyl]benzenesulfonamides by chlorosulfonation of certain aryl substituted pyrimidinediones to form pyrimidinylbenzenesulfonyl chloride intermediates which are then reacted with an amine. Chlorosulfonation may be accomplished with. chlorosulfonic acid. Substituent groups in this set of examples, namely, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, X, Y and Z, all have the meanings given above. If both X and Y are fluorine, the compounds of this reaction may be further reacted with an amine to form products wherein ##STR9##
The reaction scheme for process B is generally depicted below: ##STR10##
The third set of examples (C-1 and C-2) are illustrative of process C for producing [3,6-dihydro-2,6-dioxo-1(2H)-pyrimidinyl]benzenesulfonamides by reacting certain substituted pyrimidinylbenzenesulfonamides with an alkyl halide in the presence of sodium hydride in N,N-dimethylformamide. The reaction scheme for process C is generally depicted below: ##STR11##
The fourth example (D-1) is illustrative of process D for producing [3,6-dihydro-2,6-dioxo-1(2H)-pyrimidinyl]benzenesulfonamides. In this process, the products of process C or certain other compounds of formula I may be hydrogenated over palladium/carbon catalyst. The reaction scheme for process D is generally depicted below: ##STR12##
The fifth set of examples (Example V) illustrates the effectiveness of certain compounds of this invention as a preemergence herbicide.
The sixth set of examples (Example VI) illustrates the effectiveness of certain compounds of this invention as a postemergence herbicide.
I. Preparation of [3,6-dihydro-2,6-dioxo- (2H) pyrimidinyl]benzenesulfonamides by Process A
EXAMPLE 1
Preparation of 2-chloro-5-nitrobenzenesulfonylchloride.
To a mixture of 104 g of commercially available sodium 2-chloro-5-nitrobenzenesulfonate, 200 ml of acetonitrile and 200 ml of sulfolane stirred at 25.degree. C., was added 153 ml of phosphorus oxychloride over a period of 30 minutes. The temperature was not allowed to exceed 40.degree. C. After completion of the addition, the reaction mixture was heated to 70.degree. C. for 1.5 hours. On cooling to 0.degree. C., the reaction mixture was poured over ice. The resulting solid product was washed with cold water, filtered and air-dried to give 77.6 g of the title compound with a melting point of 87.degree.-89.degree. C.
EXAMPLE A-2
Preparation of N,N-dimethyl-2-chloro-5-nitrobenzenesulfonamide.
To a solution of 80 g of 2-chloro-5nitrobenzenesulfonyl chloride (Example A-1 above) in 200 ml of methylene chloride heated to reflux, was slowly added a solution of 30 g of dimethylamine hydrochloride in 30 ml of water followed by a dropwise addition of triethylamine. After completion of the addition, the reaction mixture was refluxed for 20 minutes, cooled to room temperature and concentrated by rotatory evaporation. The residue was treated with water and the resulting solid was filtered and recrystallized from ethanol, affording 61 g of the title compound, mp 138.degree.-140.degree. C.
EXAMPLE A-3
Preparation of N,N,-dimethyl-5-amino-2-chlorobenzenesulfonamide.
A mixture of 200 g of stannous chloride dihydrate and 250 ml of concentrated hydrochloric acid was cooled to 10.degree. C. To the stirred mixture was added 50 g of N,N-dimethyl-2-chloro-5-nitrobenzenesulfonamide (Example A-2 above) in portions maintaining the temperature of 10.degree. C. After removing the cooling bath, the reaction temperature rose to 55.degree. C. and was held for two hours. The reaction mixture was cooled and filtered to remove the complex of the product with stannic chloride. The product was treated with water to decompose the complex and extracted with methylene chloride. Removal of solvent from the dried extract on a rotary evaporator gave 22 g of the title compound as a solid with a melting point of 125.degree.-126.degree. C.
EXAMPLEA-4
Preparation of N,N-dimethyl-2-chloro-5-isocyanatobenzenesulfonamide.
50 g of N,N-dimethyl-2-chloro-5-aminobenzenesulfonamide (Example A-3 above) was treated with an excess of phosgene in ethyl acetate as is generally described in "Organic Functional Group Preparations" by S. R. Sandler and W. Karo on pages 364-365 (Academic Press, N.Y., 1983) (preparation of organic isocyanates), which disclosure is herein incorporated by reference. 48 g of the title compound was isolated as a tan solid with a melting point of 82.degree.-85.degree. C.
This compound is a novel intermediate in process A and is used in the preparation of several pyrimidinylbenzenesulfonamides of this invention. The structures of this and all previously synthesized intermediates were confirmed by NMR and IR spectroscopy.
EXAMPLE A-5
Preparation of N,N-dimethyl-2-chloro-5-[3,6- dihydro-4-trifluoromethyl-2,6-dioxo-1 (2H)-pyrimidinyl]benzenesulfonamide (Compound #5)
To 30 ml of dried tetrahydrofuran (THF) cooled to -5.degree. C. was added, under nitrogen, 3.6 g of sodium hydride as a 60% dispersion mineral oil. To the stirred slurry was added a solution of 10 g of ethyl 3-amino-4,4,4-trifluoro-2-butenoate in 30 ml of THF over a period of 30 minutes. After stirring at -5.degree. C. for 1 hour, the reaction mixture was cooled to -65.degree. C. and a solution of N, N-dimethyl-2-chloro-5-isocyanatobenzenesulfonamide (Example A-4 above) in 30 ml of THF was added dropwise maintaining the temperature below -60.degree. C. The mixture was stirred at -65.degree. C. for 2 hours and allowed to warm to room temperature. After stirring for 17 hours, solvent was removed using a rotary evaporator. About 50 ml of water was added to the residue. The resulting mixture was filtered to remove a small amount, of undissolved solid and the filtrate was acidified with hydrochloric acid. The resulting precipitate was filtered to give 13 g of the title compound as a beige solid, m.p. 281.degree.-283.degree. C.
Spectral data for this compound appears in Table I.
EXAMPLE A-6
Preparation of N,N-dimethyl-2-chloro-5-[3,6-dihydro-3-methyl-4-trifluoromethyl-2,6-dioxo-1 (2H) pyrimidinyl]benzenesulfonamide (Compound #6).
A mixture of 4.0 g of compound #5 (Example A-5 above), 1.7 g of sodium bicarbonate, 1.4 ml of dimethyl sulfate and 50 ml of acetone was heated to reflux for 3 hours. Filtration of the solids and evaporation of the solvent from the filtrate yielded a solid. The solid was washed with water and was recrystallized from ethanol to give 2.5 g of the title compound with a melting point of 194.degree.-196.degree. C.
II. Preparation of [3,6-dihydro-2,6-dioxo-1(2H)-pyrimidinyl]benzenesulfonamides by process B
EXAMPLE B-1
Preparation of 3-(4-chloro-2-fluorophenyl)-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione, sodium salt compound with tetrahydrofuran (1:1).
Under a blanket of nitrogen, 21.2 g of a 60% dispersion of sodium hydride in mineral oil was washed three times with 50 ml of hexane. To a stirred slurry of sodium hydride and 300 ml of dried tetrahydrofuran (THF) cooled to -10.degree. C. was added a solution of 100 g of ethyl 3-amino-4,4,4-trifluoro-2-butenoate in 400 ml of THF over a period of one hour. The temperature was held below -5.degree. C. during the addition. The resulting clear brown solution was stirred an additional 15 minutes at -5.degree. C. and then cooled to -70.degree. C. using a Dry Ice/acetone bath. A solution of 91.5 g of 4-chloro-2-fluorophenyl isocyanate and 200 ml of THF was added over one hour while maintaining the temperature between -55.degree. C. and -70.degree. C. The reaction mixture was allowed to slowly warm to room temperature and was stirred at this temperature for 24 hours. A white solid separated and was filtered and washed with hexane to give 95.5 g of the title compound as a white powder with a melting point >300.degree. C. An additional 57.2 g of the title compound was obtained by concentrating the filtrate to 200 ml and seeding with a small amount of crystals from the first crop. The NMR spectra of both crops were consistent with the structure of the title compound as a 1:1 molecular addition compound with THF.
The compound described in example B-1 is an intermediate of process B in the synthesis of [3,6-dihydro-2,6-dioxo-1(2H)-pyrimidinyl]benzenesulfonamides. Other examples may be found in Table B-1 following. NMR spectroscopy was used to confirm the structures of these compounds.
TABLE B-1______________________________________ ##STR13##IntermediateCompound# X Y m NMR(300Mhz, DMSOd.sub.6, .delta.)______________________________________A CH.sub.3 H 1 1.75(m, 4H, CH.sub.2), 2.32(s, 3H, CH.sub.3), 3.60(m, 4H, CH.sub.2), 5.58(s, 1H, H.sub.5), 6.39(m, 2H, ArH), 7.15(m, 2H, ArH)B Cl H 1 1.75(m, 4H, CH.sub.2), 3.60(m, 4H, CH.sub.2), 5.61(s, 1H, H.sub.5), 7.10(m, 2H, ArH), 7.42(m, 2H, ArH)C Br H 0.9 1.76(m, 3.5H, CH.sub.2), 3.60(m, 3.5H, CH.sub.2), 5.58(s, 1H, H.sub.5), 7.05(m, 2H, ArH), 7.60(m, 2H, ArH)D F H 1 1.75(m, 4H, CH.sub.2), 3.60(m, 4H, CH.sub.2), 5.61(s, 1H, H.sub.5), 7.15(m, 4H, ArH)E F F 0.1.sup.a 5.61(s, 1H, H.sub.5), 7.08(m, 1H, ArH) 7.25(m, 2H, ArH)______________________________________ .sup.a Sodium salt was soluble in THF. Methylene chloride was used to precipitate the product.
EXAMPLE B-2
Preparation of 3-(4-chloro-2-fluorophenyl)-1-methyl-6-trifluoromethyl-2,4-(1H,3H) -pyrimidinedione.
A mixture of 130 g of the product of Example B-1, 40 ml of iodomethane and 600ml of acetone was stirred 18 hours at room temperature and then heated to a mild reflux for 8.5 hours. Volatiles were removed using a rotary evaporator. The solid residue was then partitioned between methylene chloride and water. The organic layer was washed with water and dried with magnesium sulfate. Rotary evaporation of the solvent gave an oil which was triturated with hexane. Filtration of the resulting solid gave 96.1 g of the title compound with a melting point of 114.degree.-116.degree. C.
The compound described in example B-2 is an intermediate of process B in the synthesis of [3,6-dihydro-2,6-dioxo-1(2H)-pyrimidinyl]benzenesulfonamides. Other examples may be found in Table B-2 following. NMR spectroscopy was used to confirm the structures of these compounds.
TABLE B-2______________________________________ ##STR14##IntermediateCompound NMR(300Mhz,# X Y MP .degree.C. CDCl.sub.3, .delta.)______________________________________F CH.sub.3 H 122-124 2.39(s, 3H, CH.sub.3), 3.53(d, 3H, CH.sub.3), 6.35(s, 1H, H.sub.5), 7.08(m, 2H, ArH), 7.29(m, 2H, ArH)G Cl H 145-147 3.53(d, 3H, CH.sub.3), 6.35(s, 1H, H.sub.5), 7.14(m, 2H, ArH), 7.46(m, 2H, ArH)H F F 89-92 3.55(d, 3H, CH.sub.3), 6.36(s, 1H, H.sub.5), 7.00(m, 2H, ArH), 7.25(m, 1H, ArH)I F H 121-122.5 3.54(d, 3H, CH.sub.3), 6.36(s, 1H, H.sub.5), 7.18(d, 4H, ArH)J Br H 158.5-161 3.54(d, 3H, CH.sub.3), 6.36(s, 1H, H.sub.5), 7.10(m, 2H, ArH) 7.63(m, 2H, ArH)______________________________________
EXAMPLE B-3
Preparation of 2-chloro-4-fluoro-5-[(3,6-dihydro-3-methyl-4-trifluoromethyl-2,6-dioxo-1(2H)-pyrimidinyl]benzenesulfonyl chloride.
To 85 ml of chlorosulfonic acid at room temperature was added, in portions, 50 g of the product of Example B-2, with stirring. The reaction solution was heated to 130.degree. C. for four hours. Analysis of a hydrolyzed sample of the reaction mixture by thin layer chromatography (TLC) showed no starting material present. The mixture was cooled to 10.degree. C. and very cautiously poured over a mixture of ice and methylene chloride. The organic layer was separated, washed with water and dried with magnesium sulfate. The solution containing the product was concentrated on a rotary evaporator and diluted with hexane forming a granular slurry. The product was filtered to give 52.5 g of the title compound as a light tan solid, melting point 121.degree.-125.degree. C.
The compounds listed in Table. B-3 were prepared by the chlorosulfonation of the appropriately substituted 3-phenyl-2,4(1H,3H)-pyrimidinediones as described in the example above and are novel intermediates to prepare the desired [3,6-dihydro-2,6-dioxo-1(2H)-pyrimidinyl]benzenesulfonamides of this invention by process B. The structures of these compounds were confirmed by NMR spectroscopy.
TABLE B-3______________________________________ ##STR15##IntermediateCompound NMR(300Mhz,# R X Y MP .degree.C. CDCl.sub.3 .delta.)______________________________________K CH.sub.3 CH.sub.3 H 143-144 2.83(s, 3H, CH.sub.3), 3.55(d, 3H, CH.sub.3), 6.38(s, 1H, H.sub.5), 7.49(dd, 1H, ArH.sub.4), 7.54(d, 1H, ArH.sub.3) 7.95(d, 1H, ArH.sub.6)L H CH.sub.3 H 226-228 (+DMSOd.sub.6)2.82(s, dec 3H, CH.sub.3), 6.17(s, 1H, H.sub.5), 7.57(m, 2H, ArH.sub.3,4), 7.98(d, 1H, ArH.sub.6), 12.6(br, 1H, NH)M CH.sub.3 Cl H 180-185 3.55(d, 3H, CH.sub.3), 6.38(s, 1H, H.sub.5), 7.53(dd, 1H, ArH.sub.4), 7.76(d, 1H, ArH.sub.3), 8.03(d, 1H, ArH.sub.6)N CH.sub.3 Br H 176-179 3.52(s, 3H, CH.sub.3), 6.34(s, 1H, H.sub.5), 7.42(dd, 1H, ArH.sub.4) 7.95(d, 1H, ArH.sub.3), 8.04(d, 1H, ArH.sub.6)O CH.sub.3 F H 179-183 3.56(s, 3H, CH.sub.3), 6.39(s, 1H, H.sub.5), 7.46(m, 1H, ArH), 7.60(m, 1H, ArH), 7.88(m, 1H, ArH.sub.6)P CH.sub.3 F F 110-113 3.58(d, 3H, CH.sub.3), 6.39(s, 1H, H.sub.5) 7.26(t, 1H, ArH.sub.3), 7.97(m, 1H, ArH.sub.6)______________________________________
EXAMPLE B-4
Preparation of N,N-diethyl-2-chloro-4-fluoro-5-(3,6-dihydro-3-methyl-4-trifluoromethyl-2,6-dioxo-1(2H) pyrimidinyl)benzenesulfonamide (Compound #18).
To a solution of 1.5 ml of diethylamine and 20 ml of methylene chloride cooled to 5.degree. C. as added, with stirring, a solution of 2.0 g of the product of Example B-3 and 10 ml of methylene chloride over 15 minutes. After 30 minutes the reaction mixture was poured into cold dilute sulfuric acid. The organic layer was separated and dried over magnesium sulfate. Removal of the volatiles by rotary evaporation gave 1.9 g of tan solid. Recrystallization of the product from ethanol afforded 1.8 g of the title compound, m.p. 190.degree.-191.degree. C. Spectral data for this compound is found in Table I.
EXAMPLE B-5
Preparation of N-ethyl-2-chloro-4-fluoro-5-(3,6-dihydro-3-methyl-4-trifluoromethyl-2,6, -dioxo-1(2H)pyrimidinyl)benzenesulfonamide (Compound #67).
To a solution of 2.0 g of the product of Example B-3 in 30 ml of methylene chloride cooled to 5.degree. C. was added 0.8 ml of a 70% solution of ethylamine in water. After stirring 1 hour at 5.degree. C. the reaction mixture was stirred 16 hours at room temperature. The product was isolated as a solid weighing 2.4 g following the procedure set forth in Example B-4 above. Recrystallization from ethanol gave 1.7 g of the title compound as a white crystalline solid with a melting point of 195-296.degree. C. Spectral data for this compound is found in Table I.
EXAMPLE B-6
Preparation of N-cyanomethyl-N-methyl-2-chloro-4-fluoro-5-(3,6-dihydro-3-methyl-4-trifluoromethyl-2,6-dioxo-1(2H)-pyrimidinyl)benzenesulfonamide (Compound #72).
To a stirred mixture of 2.0 g of the compound of Example B-3, 0.54 g of methylaminoacetonitrile hydrochloride and 30 ml of methylene chloride cooled to 5.degree. C., was added a solution of 1.4 ml of triethylamine and 10 ml methylene chloride. The reaction mixture was stirred for 22 hours at room temperature and worked up as described in Example B-4. Evaporation of solvent produced 2.2 g of a foam which crystallized from isopropanol giving 1.8 g of the title compound as a beige solid, melting point 155.degree.-157.degree. C. Spectral data for this compound is found in Table I.
EXAMPLE B-7
Preparation of N, N-dimethyl-2-fluoro-4-dimethylamino-5-(3,6-dihydro-3-methyl-4-trifluoromethyl-2,6-dioxo-1(2H)-pyrimidinyl)benzenesulfonamide (Compound #50).
To a solution of 2.0 g of 2,4,-difluoro-5-(3,6-dihydro-3-methyl-4-trifluoromethyl-2,6-dioxo-1(2H)pyrimidinyl)benzenesulfonyl chloride and 30 ml of methylene chloride cooled to 5.degree. C. was added 1.9 ml of a 40% solution of dimethylamine in water over 15 minutes. Analysis of the reaction mixture by TLC after 2 hours of stirring showed a single component. Work up was carried out as described in Example B-4. Two grams of crude solid was obtained and recrystallized from ethanol giving 1.7 g of a white solid, melting point 185.degree.-194.degree. C. NMR analysis of the product showed a 2:1 mixture of N,N-dimethyl-2,4-difluoro-5-(3,6-dihydro-3-methyl-4-trifluoromethyl-2,6-dioxo-1(2H)-pyrimidinyl)benzenesulfonamide (Compound #49) and the title compound. A mixture of 1.6 g of the product, 30 ml of methylene chloride and 3.8 ml of a 40% solution of dimethylamine in water was stirred at room temperature for 21 hours. The organic layer was separated, washed with water and dried over magnesium sulfate. After removal of volatiles using a rotary evaporator there remained 1.6 g of a solid. Recrystallization of the product from ethanol gave 1.4 g of the title compound as fine white crystals, m.p. 223.5.degree.-225.degree. C. Spectral data for this compound is found in Table I.
III. Preparation of [3,6-dihydro-2,6-dioxo-1 (2H) -pyrimidinyl]benzenesulfonamides by Process C
EXAMPLE C-1
Preparation of N-(2-methoxyethyl)-N-methyl-2-chloro-5-(3,6-dihydro-3-methyl-4-trifluoromethyl-2,6-dioxo-1(2H)-pyrimidinyl)benzenesulfonamide (Compound #53).
To a stirred slurry of 0.2 g of a 60% dispersion of sodium hydride in mineral oil and 30 ml of N,N-dimethylformamide (DMF) cooled to 5.degree. C. was added 1.95 g of N-(2-methoxyethyl)-2-chloro-5-(3,6-dihydro-3-methyl-4-trifluoromethyl-2,6-dioxo-1(2H)-pyrimidinyl)benzenesulfonamide (Compound #52) prepared according to the procedure set forth above Process B using 2-chloro-5-(3,6-dihydro-3-methyl-4-trifluoromethyl-2,6-dioxo-1(2H)pyrimidinyl)benzenesulfonyl chloride and 2-methoxyethylamine After stirring for 1 hour at 5.degree. C. 0.6 ml of iodomethane was added to the reaction mixture. After stirring at room temperature for 16 hours, the mixture was concentrated using a rotary evaporator. The resulting gummy residue was treated several times with water until a solid had formed. The solid was recrystallized from ethanol to give 1.3 g of the title compound as a white crystalline solid, m.p. 108.degree.-110.degree. C. Spectral data for this compound is found in Table I.
EXAMPLE C-2
Preparation of N-acetyl-N-methyl-2-chloro-5-(3,6-dihydro-3-methyl-4-trifluoromethyl-2,6-dioxo-1(2H)pyrimidinyl)benzenesulfonamide (Compound #55).
To a stirred mixture of 0..noteq.g of a 60% dispersion of sodium hydride in mineral oil and 30 ml of DMF cooled to 5.degree. C. was added 1.5 g of N-methyl-2-chloro-5-(3,6-dihydro-3-methyl-4-trifluoromethyl-2,6-dioxo-1(2H) -pyrimidinyl)benzenesulfonamide. (Compound #40), prepared from 2-chloropyrimidinyl)benzenesulfonyl chloride and a 40% solution of methylamine in water following the procedure of Process B. After stirring for 1 hour at 5.degree. C., 0.75 ml of acetic anhydride was added to the reaction mixture. After stirring at room temperature for 18 hours, the mixture was concentrated using a rotary evaporator. On treating the residue with cold water, 1.6 g of a brown solid was obtained. Further treatment of the solid with boiling ethanol and filtration gave 1.25 g of the title compound as an off-white solid, m.p. 193.degree.-195.degree. C. Spectral data for this compound is found in Table I.
IV. Preparation of [3,6-dihydro-2,6-dioxo-1(2H)pyrimidinyl]benzenesulfonamides by Process D
EXAMPLE D-1
Preparation of N-methyl-N-propyl-2-chloro-5-(3,6-dihydro-3-methyl-4-trifluoromethyl-2,6-dioxo-1(2H)pyrimidinyl)benzenesulfonamide (Compound #38).
A mixture of 1.6 g of N-methyl-N-(2-propenyl)-2-chloro -5-(3,6-dihydro-3-methyl-4-trifluoromethyl-2,6-dioxo-1(2H)-pyrimidinyl)benzenesulfonamide (Compound #29), prepared by process C from Compound #28 and iodomethane, 100 ml of ethyl acetate and 200 mg of 5% palladium/carbon catalyst was hydrogenated in a Paar.RTM. apparatus at 28 psi of hydrogen. After 30 minutes, the catalyst was filtered and solvent removed from the filtrate by rotary evaporation. The glassy residue was treated with ethanol to give 1.4 g of the title compound as a light gray powder, m.p. 143.5.degree.-145.degree. C.
Spectral data for this compound is found in Table I. Certain compounds described in Table I exhibited non-crystalline characteristics which are noted (when applicable) in the column designated M.P..degree. C. (melting point). Such characteristics are designated "foam", "glass" and "resins". "Foam" may result when solvent is forced out of the product under vacuum. "Glass" is a non-crystalline solid lacking a distinct melting point. "Resin" is a substantially clear, semi-solid amorphous substance.
TABLE I ##STR16## COMPOUND PROCESS METHOD No. R R.sup.1 R.sup.2 X Y MP .degree.C. NMR(SOLVENT) ppm OF PREPARATION 1. H CH.sub.3 CH.sub.3 Cl Cl 288-290 (Acetoned.sub.6)2.87(s, 6H), A 6.3(s, 1H), 7.61(m, 1H), 7.78(d, 1H), 8.05(s, 1H) 2. CH.sub.3 CH.sub.3 CH.sub.3 Cl Cl 221-223 (CDCl.sub.3)2.9(s, 6H), 3.5(s,A 3H), 6.35(s, 1H), 7.7(s, 1H), 8.01(s, 1H) 3. CH.sub.2 CCH CH.sub.3 CH.sub.3 Cl Cl 223-225 (CDCl.sub. 3)2.3(d, 2H), 2.9(s, A 6H), 4.7(s, 2H), 6.4(s, 1H), 7.8(s, 1H), 8.0(s, 1H) 4. CH.sub.2 C CHH.sub.2 CH.sub.3 CH.sub.3 Cl Cl 171-173 (CDCl.sub.3)2.9(s, 6H), 4.5(q, A 2H), 5.3(t, 2H), 6.0(m, 1H), 6.3(s, 1H), 7.7(s, 1H), 7.9(s, 1H) 5. H CH.sub.3 CH.sub.3 Cl H 281-283 (Acetoned.sub.6)2.85( s, 6H), A 6.28(s, 1H), 7.65(d, 1H), 7.78(d, 1H), 8.05(s, 1H) 6. CH.sub.3 CH.sub.3 CH.sub.3 Cl H 194-196 (CDCl.sub.3)2.9(s, 6H), 3.5(s, A 3H), 6.35(s, 1H), 7.41(m, 1H), 7.6(m, 1H), 7.8(m, 1H) 7. CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 Cl H 148-149 (CDCl.sub.3)1.36(t, 3H), 2.9(s, A 6H), 4.02(q, 2H), 6.35(s, 1H), 7.38(m, 1H), 7.65(d, 1H), 7.95(d, 1H) 8. Na CH.sub.3 CH.sub.3 OCH.sub.3 H >250 (Dmsod.sub.6) 2.75(s, 6H), A 3.92(s, 3H), 5.62(s, 1H) 7.30(m, 3H) 9. H CH.sub.3 CH.sub.3 OCH.sub.3 H 247-249 (Dmsod.sub.6)2.77(s, 6H), 3.96(s, A 3H), 6.33(s, 1H), 7.37(d, 1H), 7.58(m, 1H), 7.73(d, 1H), 12.5(brs, 1H) 10. CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 H 168-170 (Dmsod.sub.6)2.77(s, 6H), 3.39(s, A 3H), 3.96(s, 3H), 6.48(s, 1H), 7.36(d, 1H), 7.55(m, 1H), 7.70(d, 1H) 11. CH.sub.3 H H CH.sub.3 H 231-232 (Dmsod.sub.6)2.64(s, 3H), 3.39(s, B 3H), 6.49(s, 1H), 7.40(dd, 1H), 7.48(m, 3H), 7.78(d, 1H) 12. CH.sub.3 CH.sub. 3 CH.sub.3 CH.sub.3 H 148-150 (CDCl.sub.3)2.67(s, 3H), 2.80(s, B 6H), 3.54(d, 3H), 6.35(s, 1H), 7.33(m, 1H), 7.45(d, 1H), 7.77(d, 1H) 13. CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.3 H 156-157 (CDCl.sub.3)1.13(t, 6H), 2.65(s, B 3H), 3.32(q, 4H), 3.54(d, 3H), 6.35(s, 1H), 7.30(m, 1H), 7.41(d, 1H), 7.78(d, 1H) 14. CH.sub.3 C.sub.3 H.sub.7 -i H CH.sub.3 H 168-169 (CDCl.sub.3)1.08(d, 6H), 2.68(s, B 3H), 3.50(m, 1H), 3.53(d, 3H), 4.62(d, 1H), 6.35(s, 1H), 7.31(m, 1H), 7.44(d, 1H), 7.88(d, 1H) 15. CH.sub.3 C.sub.4 H.sub.9 -t H CH.sub.3 H 178-180 (CDCl.sub.3)1.22(s, 9H), 2.70(s, B 3H), 3.54(s, 3H), 4.77(s, 1H), 6.35(s, 1H), 7.30(m, 1H), 7.41(d, 1H), 7.90(d, 1H) 16. CH.sub.3 CH.sub.3 CH.sub.3 Cl F 223-225 (CDCl.sub.3)2.95(s, 6H), 3.60(s, B 3H), 6.40(s, 1H), 7.46(d, 1H), 8.06(d, 1H) 17. CH.sub.3 (CH.sub.2).sub.4 CH.sub.3 H 1 80-181 (CDCl.sub.3)1.88(m, 4H), 2.69(s, B 3H), 3.31(m, 4H), 3.54(d, 3H), 6.35(s, 1H), 7.30(m, 1H), 7.44(d, 1H), 7.80(d, 1H) 18. CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 Cl F 190-191 (CDCl.sub.3)1.15(t, 6H), 3.39(q, B 4H), 3.55(d, 3H), 6.35(s, 1H), 7.42(d, 1H), 8.07(d, 1H) 19. CH.sub.3 C.sub.4 H.sub. 9 -n C.sub.4 H.sub.9 -n Cl F 135-136 (CDCl.sub.3)0.88(t, 6H), 1.27(m, B 4H), 1.48(m, 4H)3.29(m, 4H), 3.55(d, 3H), 6.35(s, 1H), 7.40(d, 1H), 8.05(d, 1H) 20. CH.sub.3 H H Cl F 257-258 (Dmsod.sub. 6)3.41(s, 3H), 6.58(s, B 1H), 7.80(s, 2H), 7.94(d, 1H), 8.20(d, 1H) 21. CH.sub.3 CH.sub.2 CHCH.sub.2 CH.sub.2 CHCH.sub.2 Cl F 162-164 (CDCl.sub.3)3.55(d, 3H), 3.92(d, B 4H), 5.20(m, 4H), 5.68(m, 2H), 6.35(s, 1H), 7.41(d, 1H), 8.08(d, 1H) 22. CH.sub.3 C.sub.3 H.sub.7 -n C.sub.3 H.sub.7 -n Cl F 157-158 (CDCl.sub.3)0.84(t, 6H), 1.54(m, B 4H), 3.25(m, 4H), 3.55(d, 3H), 6.35(s, 1H), 7.41(d, 1H), 8.05(d, 1H) 23. CH.sub.3 CH.sub.3 C.sub.4 H.sub.9 -n Cl F 142-143 (CDCl.sub.3)0.91(t, 3H), 1.32(m, B 2H), 1.54(m, 2H), 2.87(s, 3H), 3.22(t, 2H), 3.55(d, 3H), 6.35(s, 1H), 7.41(d, 1H), 8.04(d, 1H) 24. CH.sub.3 (CH.sub.2).sub.4 Cl F 254-255 (CDCl.sub.3)1.91(m, 4H), 3.41(m, B 4H), 3.56(d, 3H), 6.35(s, 1H), 7.43(d, 1H), 8.05(d, 1H) 25. CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 OH Cl F 163-164 (CDCl.sub.3)2.98(s, 3H), 3.38(t, B 2H), 3.55(d, 3H), 3.70(m, 2H), 4.17(t, 1H), 6.36(s, 1H), 7.48(d, 1H), 8.07(d, 1H) 26. CH.sub.3 CH.sub.3 CH.sub.2 C.sub.6 H.sub.5 Cl F 135-136 (CDCl.sub.3)2.75(s, 3H), 3.55(d, B 3H), 4.42(m, 2H), 6.35(s, 1H), 7.31(m, 5H), 7.44(d, 1H), 8.09(d, 1H) 27. CH.sub.3 CH.sub.3 C.sub.6 H.sub.11 -c Cl F 189-190 (CDCl.sub.3)0.95-1.82(m, 10H) B 2.83(s, 3H), 3.55(d, 3H), 3.68(m, 1H), 6.35(s, 1H), 7.41(d, 1H), 8.06(d, 1H) 28. CH.sub.3 H CH.sub.2 CHCH.sub.2 Cl H 168-170 (CDCl.sub.3)3.53(d, 3H), 3.60(m, B 2H), 5.12(m, 2H), 5.71(m, 1H), 6.35(s, 1H), 7.40(m, 2H), 7.64(d, 1H), 7.94(d, 1H) 29. CH.sub.3 CH.sub.3 CH.sub.2 CHCH.sub.2 Cl H 145-146 (CDCl.sub.3)2.83(s, 3H), 3.54(d, C 3H), 3.86(d, 2H), 5.25(m, 2H), 5.77(m, 1H), 6.35(s, 1H), 7.35(dd, 1H), 7.63(d, 1H), 7.97(d, 1H) 30. CH.sub.3 H C.sub.3 H.sub.7 -i Cl H 193-194 (CDCl.sub.3)1.10(d, 6H), 3.49(m, B 1H), 3.54(d, 3H), 4.94(d, 1H), 6.36(s, 1H), 7.37(dd, 1H), 7.64(d, 1H), 7.99(d, 1H) 31. CH.sub.3 CH.sub.3 C.sub.3 H.sub.7 -i Cl H 172-175 (CDCl.sub.3)1.12(d, 6H), 2.82(s, C 3H), 3.54(d, 3H), 4.15(m, 1H), 6.35(s, 1H), 7.33(dd, 1H), 7.61(d, 1H), 7.98(d, 1H) 32. CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 Cl H 181-182 (CDCl.sub.3)1.14(t, 6H), 3.39(q, B 4H), 3.54(d, 3H), 6.35(s, 1H), 7.33(dd, 1H), 7.61(d, 1H), 7.97(d, 1H) 33. CH.sub.3 CH.sub.3 CH.sub.2 C CH Cl H 131-133 (CDCl.sub.3)2.25(t, 1H), 2.96 B 3H), 3.54(d, 3H), 4.13(d, 2H), 6.35(s, 1H), 7.36(dd, 1H), 7.63(d, 1H), 7.97(d, 1H) 34. CH.sub.3 H C.sub.3 H.sub.5 -c Cl H 190-191 (CDCl.sub.3)0.63(m, 4H), 2.24(m, B 1H), 3.54(d, 3H), 5.43(s, 1H), 6.36(s, 1H), 7.41(dd, 1H), 7.65(d, 1H), 8.03(d, 1H) 35. CH.sub.3 CH.sub.3 C.sub.3 H.sub.5 -c Cl H 139-141 (CDCl.sub.3)0.67(m, 4H), 2.27(m, C 1H), 2.99(s, 3H), 3.54(d, 3H), 6.34(s, 1H), 7.38(dd, 1H), 7.64(d, 1H), 8.00(d, 1H) 36. CH.sub.3 CH.sub.3 C.sub.6 H.sub.5 Cl H 170-171 (CDCl.sub.3)3.38(s, 3H), 3.51(d,B 3H), 6.31(s, 1H), 7.18-7.37(m, 6H), 7.61(d, 1H), 7.77(d, 1H) 37. CH.sub.3 H C.sub.6 H.sub.5 Cl H 225-226 (CDCl.sub.3)3.51(s, 3H), 6.33(s, B 1H), 7.10(m, 5H), 7.38(dd, 1H), 7.56(d, 1H), 8.03(d, 1H), 10.21(s, 1H) 38. CH.sub.3 CH.sub.3 C.sub.3 H.sub.7 -n Cl H 143-145 (CDCl.sub.3)0.89(t, 3H), 1.59(m, D 2H), 2.88(s, 3H), 3.22(t, 2H), 3.54(d, 3H), 6.35(s, 1H), 7.35(dd, 1H), 7.62(d, 1H), 7.95(d, 1H) 39. CH.sub.3 CH.sub.3 CH.sub.2 CH(OCH.sub.3).sub.2 Cl H glass (CDCl.sub.3)2.99(s, 3H), 3.38(s+ B d, 8H), 3.54(d, 3H), 4.47(t, 1H), 6.36(s, 1H), 7.36(dd, 1H), 7.64(d, 1H), 7.96(d, 1H) 40. CH.sub.3 H CH.sub.3 Cl H 210-212 (CDCl.sub.3)2.64( d, 3H), 3.54(d, B 3H), 6.36(s, 1H), 6.44(q, 1H), 7.39(dd, 1H), 7.65(d, 1H), 7.95(d, 1H) 41. CH.sub.3 CH.sub.3 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5 Cl H 130-132 (CDCl.sub.3)1.24(t, 3H), 2.99(s, C 3H), 3.51(s, 3H), 4.16(s+ q, 4H), 6.35(s, 1H), 7.37(dd, 1H), 7.63(d, 1H), 7.98(d, 1H) 42. CH.sub.3 CH.sub.3 CH.sub.2 C(Cl)CH.sub.2 Cl H 138-140 (CDCl.sub.3)2.88(s, 3H), 3.55(d, C 3H), 4.10(s, 2H), 5.40(m, 1H), 5.47(m, 1H), 6.36(s, 1H), 7.38(dd, 1H), 7.65(d, 1H), 7.98(d, 1H) 43. CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 Cl H 156-158 (CDCl.sub.3)1.18(t, 3H), 2.91(s, B 3H), 3.32(q, 2H), 3.55(d, 3H), 6.36(s, 1H), 7.35(dd, 1H), 7.63(d, 1H), 7.96(d, 1H) 44. CH.sub.3 CH.sub.3 CH.sub.2 CN Cl H 170-171 (CDCl.sub.3)2.98(s, 3H), 3.55(d, B 3H), 4.32(s, 2H), 6.36(s, 1H), 7.43(dd, 1H), 7.68(d, 1H), 7.98(d, 1H) 45. CH.sub.3 CH.sub.3 OCH.sub.3 Cl H 223-234 (CDCl.sub.3)2.96(s, 3H), 3.55(d,B 3H), 3.74(s, 3H), 6.36(s, 1H), 7.44(dd, 1H), 7.69(d, 1H), 7.92(d, 1H) 46. CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 OH Cl H 134-137 (CDCl.sub.3)2.21(bs, 1H), 3.00(s, B 3H), 3.40(t, 2H), 3.54(d, 3H), 3.73(t, 2H), 6.36(s, 1H), 7.36(dd, 1H), 7.64(d, 1H), 7.97(d, 1H) 47. CH.sub.3 CH.sub.3 CH.sub.3 F H 170-172 (CDCl.sub.3)2.85(d, 6H), 3.55(d, B 3H), 6.36(s, 1H), 7.34(t, 1H), 7.43(m, 1H), 7.75(dd, 1H) 48. CH.sub.3 CH.sub.3 CH.sub.3 Br H 205-207 (CDCl.sub.3)2.91(s, 6H), 3.55(d, B 3H), 6.36(s, 1H), 7.27(dd, 1H), 7.86(d, 1H), 7.96(d, 1H) 49. CH.sub.3 CH.sub.3 CH.sub.3 F F 205-207 (CDCl.sub.3)2.85(d, 6H), 3.56(d, B 3H), 6.36(s, 1H), 7.14(t, 1H), 7.85(t, 1H) 50. CH.sub.3 CH.sub.3 CH.sub.3 F N(CH.sub.3).sub.2 223-225 (CDCl.sub.3)2.78(s , 6H), 2.82(s, B 6H), 3.54(d, 3H), 6.34(s, 1H), 7.10(d, 1H), 7.60(d, 1H), 51. CH.sub.3 CH.sub.3 C.sub.4 H.sub.9 -n Cl H 140-142 (CDCl.sub.3)0.90(t, 3H), 1.32(m, B 2H), 1.55(m, 2H), 2.88(s, 3H), 3.25(t, 2H), 3.55(d, 3H), 6.36(s, 1H), 7.34(dd, 1H), 7.63(d, 1H), 7.95(d, 1H) 52. CH.sub.3 H CH.sub.2 CH.sub.2 OCH.sub.3 Cl H 119-121 (CDCl.sub.3)3.18(m, 2H), 3.24(s,B 3H), 3.36(t, 2H), 3.55(s, 3H), 5.47(t, 1H), 6.36(s, 1H), 7.38(dd, 1H), 7.65(d, 1H), 7.97(d, 1H) 53. CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 Cl H 108-110 (CDCl.sub.3)2.99(s, 3H), 3.30(s,C 3H), 3.47(t, 2H), 3.55(s+ m, 5H), 6.38(s, 1H), 7.34(dd, 1H), 7.64(d, 1H), 7.95(d, 1H) 54. CH.sub.3 CH.sub.3 ##STR17## Cl H foam (CDCl.sub.3)2.56(m, 1H), 2.78(m,1H), 2.99(s, 3H), 3.10(m,2H), 3.55(d, 3H), 3.80(m,1H), 6.36(s, 1H), 7.38(dd,1H), 7.65(d, 1H), 7.97(d,1H) C 55. CH.sub.3 CH.sub.3 C(O)CH.sub.3 Cl H 193-195 (CDCl.sub.3)2.35(s, 3H), 3.32(s, C 3H), 3.55(s, 3H), 6.36(s, 1H), 7.45(dd, 1H), 7.66(d, 1H), 8.09(d, 1H) 56. CH.sub.3 H ##STR18## Cl F glass (CDCl.sub.3)1.20(td, 3H), 1.41(dd,3H), 3.55(s, 3H), 4.08(m,5. 81(m, 1H), 6.35+6.36(2s, 1H), 7.44(d, 1H),8.01(d, 1H) B 57. CH.sub.3 H ##STR19## Br H foam (CDCl.sub.3)3.08(m, 2H), 3.54(s,6H), 4.29(m, 1H), 5.72(d,1H), 6.35(s, 1H), 7.08-7.25(m, 6H), 7.76(d, 1H),7.91(d, 1H) B 58. CH.sub.3 H ##STR20## Cl F foam (CDCl.sub.3)0.92(m, 6H), 1.16(m,3H), 2.10(m, 1H), 3.55(s, 3H), 3.83(m,1H), 4.02(m, 2H), 5.67(d, 1H), 6.35(d,1H), 7.43(d, 1H), 7.97(d, 1H) B 59. CH.sub.3 H ##STR21## Br H foam (CDCl.sub.3)1.18(td, 3H), 2.07(s+m, 5H), 2.58(t, 2H), 3.56(s,3H), 4.10(q+m, 3H), 6.08(d,1H), 6.37(s, 1H), 7.32(dd,1H), 7.88(dd, 1H), 7.98(dd,1H) B 60. CH.sub.3 H CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5 Cl H glass (CDCl.sub.3)1.27(t, 3H), 2.53(t, B 2H), 3.25(q, 2H), 3.56(s, 3H), 4.16(q, 2H), 5.89(t, 1H), 6.37(s, 1H), 7.43(m, 1H), 7.66(d, 1H), 7.99(d, 1H) 61. H CH.sub.3 CH.sub.3 CH.sub.3 H 310 dec (Dmsod.sub.6)2.60(s, 3H), 2.73(s, B 6H), 6.33(s, 1H), 7.52(m, 2H), 7.75(s, 1H), 12.5(brs, 1H) 62. H H C.sub.2 H.sub.5 CH.sub.3 H 240-242 (Dmsod.sub.6)0.99(t, 3H), 2.62(S, B 3H), 2.85(m, 2H), 6.32(s, 1H), 7.47(m, 2H), 7.70(t, 1H), 7.78(s, 1H), 12.5(s, 1H) 63. H CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 H 247-250 (Dmsod.sub.6)1.09(t, 3H), 2.58(s, B 3H), 2.77(s, 3H), 3.19(q, 2H), 6.33(s, 1H), 7.50(m, 2H), 7.75(s, 1H), 12.5(s, 1H) 64. H H C.sub.3 H.sub.7 -i CH.sub.3 H 217-220 (Dmsod.sub.6)0.98(d, 6H), 2.62(s, B 3H), 3.27(m, 1H), 6.32(s, 1H), 7.46(m, 2H), 7.68(d, 1H), 7.81(s, 1H), 12.5(s, 1H) 65. H H CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.3 H 238-240 (Dmsod.sub.6 )2.61(s, 3H), 2.97(q, B 2H), 3.11(s, 3H), 3.28(t, 2H), 6.32(s, 1H), 7.47(m, 2H), 7.78(d, 1H), 7.85(t, 1H) 12.5(s, 1H) 66. CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 Cl F 190-191 (CDCl.sub.3)1.18(t, 3H), 2.90(s, B 3H), 3.31(q, 2H), 3.56(d, 3H), 6.36(s, 1H), 7.42(d, 1H), 8.04(d, 1H) 67. CH.sub.3 H C.sub.2 H.sub.5 Cl F 195-196 (CDCl.sub.3)1.11(t, 3H), 3.00(m, B 2H), 3.55(s, 3H), 6.37(s, 1H), 7.17(t, 1H), 7.46(d, 1H), 8.06(d, 1H) 68. CH.sub.3 H CH.sub.3 Cl F 187-189 (CDCl.sub.3)2.62( d, 3H), 3.55(s, B 3H), 6.37(s, 1H), 7.08(d, 1H), 7.47(d, 1H), 8.05(d, 1H) 69. CH.sub.3 CH.sub.3 CH.sub. 2 CCH Cl F 178-179 (CDCl.sub.3)2.26(t, 1H), 2.97(s, B 3H), 3.56(d, 3H), 4.12(d, 2H), 6.36(s, 1H), 7.43(d, 1H), 8.05(d, 1H) 70. CH.sub.3 H C.sub.3 H.sub.5 -c Cl F 187-190 (CDCl.sub.3)0.50(m, 4H), 2.27(m, B 1H), 3.52(s, 3H), 6.41(s, 1H), 7.62(d, 1H), 8.18(d+s, 2H) 71. CH.sub.3 CH.sub.3 CH.sub.2 CH(OCH.sub.3).sub.2 Cl F glass (CDCl.sub.3)2.99(s, 3H), 3.38(s+ B m, 8H), 3.56(d, 3H), 4.47(t, 1H), 6.36(s, 1H), 7.44(d, 1H), 8.02(d, 1H) 72. CH.sub.3 CH.sub.3 CH.sub.2 CN Cl F 155-157 (CDCl.sub.3)2.98(s, 3H), 3.56(d, B 3H), 4.32(s, 2H), 6.37(s, 1H), 7.48(d, 1H), 8.07(d, 1H) 73. CH.sub.3 CH.sub.3 OCH.sub.3 Cl F 167-169 (CDCl.sub.3)2.94(s, 3H), 3.56(d, B 3H), 3.74(s, 3H), 6.36(s, 1H), 7.48(d, 1H), 8.00(d, 1H) 74. CH.sub.3 H CH.sub.2 CH.sub.2 OCH.sub.3 Cl F 170-172 (CDCl.sub.3)3.17(m, 2H), 3.25(s, B 3H), 3.37(t, 2H), 3.56(s, 3H), 5.48(t, 1H), 6.36(s, 1H), 7.45(d, 1H), 8.05(d, 1H) 75. CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 Cl F oil (CDCl.sub.3)3.00(s, 3H), 3.31(s, C 3H), 3.48(m, 2H), 3.55(m, 5H), 6.37(s, 1H), 7.45(d, 1H), 8.06(d, 1H) 76. CH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 Cl F 203-204 (CDCl.sub.3)3.29(t, 4H), 3.56(s, B 3H), 3.73(t, 4H), 6.36(s, 1H), 7.45(d, 1H), 8.02(d, 1H) 77. CH.sub.3 CH.sub.2 CH.sub.2 OH CH.sub.2 CH.sub.2 OH Cl F 160-164 (CDCl.sub.3)3.48, 3.55, 3.62(t+ B s+brs, 9H), 3.78(t, 4H), 6.36(s, 1H), 7.44(d, 1H), 8.06(d, 1H) 78. CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 CN Cl F foam (CDCl.sub.3)2.69(t, 2H), 3.00(s, 3H), 3.56(d, 3H), 3.60(t, 2H), 6.36(s, 1H), 7.46(d, 1H), 8.05(d, 1H) 79. CH.sub.3 CH.sub.3 ##STR22## Cl F foam (CDCl.sub.3)3.00(s, 3H), 3.47(t, 2H),3.56(d, 3H), 3.88(m, 4H), 5.04(t,1H), 6.36(s, 1H), 7.42(d, 1H),8.05(d, 1H) 80. CH.sub.3 H CH.sub.2 CH(OCH.sub.3).sub.2 Cl F foam (CDCl.sub.3)3.13(t, 2H), 3.30(d, 6H), 3.56(d, 3H), 4.25(t, 1H), 5.33(t, 1H), 6.36(s, 1H), 7.45(d, 1H), 8.03(d, 1H) 81. CH.sub.3 CH.sub.3 CH.sub.2 CH(OCH.sub.3).sub.2 Br H foam (CDCl.sub.3)2.98(s, 3H), 3.39(s+m, 8H), 3.55(d, 3H), 4.47(t, 1H), 6.36(s, 1H), 7.28(dd, 1H), 7.86(d, 1H), 7.97(d, 1H) 82. CH.sub.3 CH.sub.3 CH.sub.2 CH(OCH.sub.3).sub.2 F H resin (CDCl.sub.3)2.99(d, 3H), 3.30(d, 2H), 3.39(s, 6H), 3.56(d, 3H), 4.49(t, 1H), 6.37(s, 1H), 7.30-7.48(m, 2H), 7.79(dd, 1H) 83. CH.sub.3 CH.sub.3 ##STR23## Br H foam (CDCl.sub.3)2.99(s, 3H), 3.50(d, 2H),3.54(d, 3H), 3.90(m, 4H), 5.06(t,1H), 6.35(s, 1H), 7.26(dd, 1H),7.99(d, 1H) 84. CH.sub.3 CH.sub.3 CH.sub.2 CHO Cl F foam (CDCl.sub.3)2.96(s, 3H), 3.56(d, 3H), 4.17(s, 2H), 6.37(s, 1H), 7.46(d, 1H), 8.06(d, 1H), 9.64(s, 1H) 85. CH.sub.3 CH.sub.3 CH.sub.2 CH(OCH.sub.3).sub.2 F Fresin (CDCl.sub.3)2.99(d, 3H), 3.29(dd, 2H), 3.39(d, 6H), 3.57(d, 3H), 4.49(t, 1H), 6.37(s, 1H), 7.15(t, 1H), 7.87(t, 1H)
V. Preemergence Control
To illustrate the effectiveness of the compounds of this invention as preemergence herbicides, 300 mg of each of the below listed compounds were dissolved in 10 ml acetone to which 30 mg of an emulsifying agent, ethoxylated sorbitan monolaurate, were added. The solution was diluted to 100 ml with distilled water. Ten milliliters of the 3000 ppm solution were diluted to 250 ppm with distilled water. The chemical was applied at the rate of 10 lb/A (11.2 kg/ha) by drenching 46 ml of the 250 ppm solution on the surface of soil in 41/2 inch (11.25 cm) plastic pots wherein seeds of the following weeds had been planted: Prickly sida (Sida spinosa L.) (PS), jimsonweed (Datura stramonium L. (JW), tall morningglory (Ipomea purpurea L. Roth) (TM), switchgrass (Panicum virgatum L.) (SG), barnyardgrass (Echinochloa crusgalli L. Beauv.) (BG), and green foxtail (Setaria viridis (L.), Beauv.) (GF). The percent control of the weeds compared to untreated checks was determined two weeks after treatment. The results of such testing are summarized in Table II. The data presented in such table indicated the good to excellent herbicidal efficacy of the compounds of this invention.
TABLE II______________________________________Preemergence Activity of 10 lb/A (11.2 kg/ha)Percent Weed Control at 11.2 kg/haCom-pound# VL JW PS TM SG BG GF______________________________________ 1 0 0 -- 0 35 50 20 2 100 100 -- 100 95 90 100 3 0 0 -- 0 0 0 0 4 0 0 -- 0 0 0 0 5 0 0 -- 50 75 0 65 6 100 100 -- 100 100 100 100 7 100 100 -- 100 100 95 100 8 0 0 -- 0 0 0 0 9 0 0 -- 0 0 0 010 100 0 -- 100 0 0 9011 100 50 -- 100 100 0 9512 100 100 -- 100 100 100 10013 100 100 -- 100 100 100 10014 100 40 -- 95 65 0 10015 100 95 -- 100 100 100 10016 100 -- -- 95 100 100 10017 100 -- 100 100 100 60 10018 100 -- 100 100 100 100 10019 100 -- 100 25 100 35 10020 100 -- 100 100 100 95 10021 100 -- 100 90 100 95 10022 100 -- 100 100 100 100 10023 95 -- 100 0 100 -- 9524 100 -- 100 90 100 -- 5025 100 -- 100 100 100 -- 10026 100 -- 100 100 100 -- 10027 95 -- 100 25 100 -- 10028 100 -- 100 100 100 20 10029 100 -- 100 100 100 100 10030 100 -- 100 100 100 45 10031 100 -- 100 100 100 90 10032 100 -- 100 100 90 95 10033 100 -- 100 100 90 100 10034 100 -- 100 100 100 100 10035 100 -- 100 100 100 100 10036 100 -- 100 0 0 20 037 0 -- 0 0 0 0 5038 100 -- 100 95 100 40 7539 100 -- 100 100 100 100 10040 100 -- 100 100 100 60 10041 100 -- 100 100 100 100 10042 100 -- 100 95 100 90 10043 100 -- 100 100 100 100 10044 100 -- 100 100 100 100 10045 100 -- 100 100 100 100 10046 100 -- 100 100 100 100 10047 100 -- 100 100 100 100 10048 100 -- 100 100 100 100 10049 100 -- 100 100 100 100 10050 100 -- 100 0 100 0 9551 0 -- 0 80 20 50 9552 100 -- 100 100 100 100 10053 100 -- 100 95 100 100 10054 100 -- 100 100 100 100 10055 100 -- 100 100 100 100 10056 100 -- 100 100 100 100 10057 100 -- 100 100 100 95 10058 100 -- 100 100 100 100 10059 85 -- 100 100 100 0 10060 100 -- 100 100 100 0 10061 0 -- 0 0 0 0 062 0 -- 100 0 0 60 10063 0 -- 0 0 100 0 5064 90 -- 100 100 95 90 10065 0 -- 0 0 0 0 5066 100 -- 100 100 100 100 10067 100 -- 100 100 100 100 10068 100 -- 100 100 100 100 10069 100 -- 100 80 100 80 10070 100 -- 100 100 100 100 10071 100 -- 100 100 100 100 10072 100 -- 100 100 100 100 10073 100 -- 100 90 100 100 10074 100 -- 100 100 100 100 10075 100 -- 100 100 100 100 10076 100 -- 100 100 100 100 10077 100 -- 100 100 100 100 10078 100 100 100 100 100 100 10079 100 100 100 100 100 100 10080 100 100 100 90 100 100 10081 100 100 100 100 100 100 10082 100 100 100 90 90 95 10083 100 100 100 100 100 100 10084 100 100 100 100 100 100 10085 100 100 100 100 100 100 100______________________________________
VI. Postemergence Control
To test the effectiveness of the compounds of this invention as postemergence herbicides, the 3000 ppm solution described in Example V (Preemergence Control) was atomized employing a DeVILBISS.TM. sprayer, wetting the foliage to the drip point. The remainder of the procedure was the same as described in Example 4. The weeds, which were the same species as described in Example V, were treated six days after emergence. The percent weed control was evaluated two weeks after treatment. The results of such testing are summarized in Table III.
TABLE III______________________________________Postemergence Herbicide Activity of 3000 ppmPercent Weed Control at 11.2 kg/haCom-pound# VL JW PS TM SG BG GF______________________________________ 75 15 -- 50 0 10 5 2 100 100 -- 95 75 90 80 3 100 100 -- 100 100 100 100 4 20 0 -- 30 20 75 65 5 15 10 -- 15 0 5 0 6 100 100 -- 100 45 80 95 7 100 100 -- 100 20 55 50 8 0 0 -- 0 0 0 0 9 0 0 -- 0 0 0 010 50 30 -- 55 0 5 511 95 95 -- 100 0 25 1012 100 100 -- 100 25 60 4513 100 95 -- 100 10 70 5514 80 50 -- 70 35 0 2515 95 50 -- 95 5 5 1016 100 100 -- 100 100 100 10017 100 -- -- 100 75 80 9518 100 -- -- 90 100 90 10019 95 -- -- 40 30 45 3520 100 -- 80 100 70 65 4521 100 -- 90 100 95 85 8522 100 -- 100 100 95 70 8523 100 -- 100 100 75 100 8524 100 -- 90 100 80 80 4525 100 -- 100 100 40 75 4526 100 -- 95 100 40 75 6527 100 -- 90 100 35 60 2028 100 -- 100 75 50 85 2029 100 -- 100 100 10 75 5530 100 -- 100 100 15 40 2531 100 -- 100 85 30 70 1532 100 -- 100 70 60 75 10033 100 -- 100 95 95 80 10034 100 -- 95 100 30 40 9535 100 -- 100 100 75 80 5036 100 -- 30 15 5 20 2537 65 -- 40 10 0 15 2038 100 -- 100 95 20 45 1539 100 -- 100 100 100 100 10040 100 -- 100 100 90 35 8041 100 -- 100 100 100 95 9042 100 -- 100 60 40 50 3043 100 -- 100 100 100 90 8544 100 -- 100 95 55 70 4545 100 -- 100 90 10 45 5546 100 -- 100 100 5 70 9547 95 -- 95 90 10 15 10048 100 -- 100 100 100 90 10049 100 -- 100 100 100 75 10050 95 -- 90 40 0 0 051 100 -- 100 95 10 30 2052 100 -- 100 100 100 50 10053 100 -- 100 100 100 95 10054 100 -- 100 100 100 100 10055 100 -- 100 95 20 90 6556 100 -- 100 100 100 100 10057 100 -- 100 100 100 60 7058 100 -- 100 100 100 100 9559 95 -- 95 65 0 0 060 100 -- 100 100 95 95 9061 15 -- 0 0 0 0 062 15 -- 10 20 0 0 063 10 -- 5 10 15 0 064 25 -- 50 10 10 0 7565 0 -- 0 0 0 0 066 100 -- 100 100 90 75 8567 100 -- 100 100 100 100 10068 100 -- 100 100 100 95 10069 100 -- 100 100 85 65 8070 100 -- 100 100 90 90 9571 100 -- 100 100 100 100 10072 100 -- 100 100 100 100 10073 100 -- 100 100 100 100 10074 100 -- 100 100 90 75 9575 100 -- 100 100 100 100 10076 100 -- 100 100 100 95 10077 100 -- 100 100 100 100 10078 100 100 100 100 100 100 9579 100 100 100 100 100 100 10080 100 100 100 100 80 70 8081 100 100 100 100 65 95 9082 100 100 100 60 20 35 1583 100 100 100 100 100 100 9084 100 100 100 100 100 100 10085 100 100 100 100 100 90 65______________________________________

Number	Date	Country
0071839	Feb 1983	EPX
1157889	Jul 1969	GBX

Intermediate isocyana to benzenesulfonamide compounds

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