5-amino-6-pyridazone derivatives, their preparation and herbicidal mixtures containing these derivatives

The present invention relates to 5-amino-6-pyridazones of the formula Ia and/or Ib ##STR2## where R.sup.1 is C.sub.1 -C.sub.4 -alkyl which may carry up to three halogen atoms,
R.sup.2 is C.sub.1 -C.sub.4 -alkyl or C.sub.3 -C.sub.6 -alkenyl, where these groups may carry up to two phenyl radicals, or C.sub.3 -C.sub.6 -alkynyl,
A is --CO-- or --SO.sub.2 --,
B is C.sub.1 -C.sub.6 -alkyl, C.sub.2 -C.sub.6 -alkenyl or C.sub.2 -C.sub.6 -alkynyl, where these groups may carry up to three of the following radicals: halogen, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkylthio and/or phenyl,
an isocyclic or heterocyclic C.sub.3 -C.sub.7 -cycloalkyl group or an isocyclic or heterocyclic C.sub.3 -C.sub.7 -cycloalkenyl group, where these groups may be fused with one or two cycloalkyl groups of this type or with one or two benzene nuclei, where the total number of ring members is from 3 to 16 and these cyclic radicals may carry up to three of the following groups: halogen, C.sub.1 -C.sub.4 -alkyl, C.sub.2 -C.sub.6 -alkenyl, C.sub.2 -C.sub.6 -alkynyl and/or phenyl,
a mononuclear to trinuclear aromatic or heteroaromatic radical which may carry up to three of the following groups: C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -haloalkoxy, C.sub.1 -C.sub.4 -alkylthio, C.sub.1 -C.sub.4 -alkylsulfinyl, C.sub.1 -C.sub.4 -alkylsulfonyl, cyano, nitro, carbo-C.sub.1 -C.sub.4 -alkoxy, N,N-di-C.sub.1 -C.sub.4 -alkylcarbamido and/or halogen.
The present invention furthermore relates to the preparation of these compounds and their use as herbicides.
DE-B 1 105 232 discloses that N-substituted 4-amino-6-pyridazones have a herbicidal action. Particularly for use in the proximity of crops, for example by the postemergence method, however, it is desirable to have compounds which exhibit higher selectivity at a lower application rate.
We have found that this object is achieved by the 5-amino-6-pyridazone derivatives Ia and Ib defined at the outset.
We have also found that the compounds Ia and Ib have an advantageous herbicidal action, particularly by the postemergence method, and are selective with respect to a number of crops and are accordingly useful as herbicides.
We have furthermore found a process for the preparation of the compounds Ia and Ib.
For the preparation of the novel compounds Ia, a pyridazone II is reacted with hydrazine to give a 5-amino-6-pyridazone III, which is then derivatized with a compound of the formula IV. ##STR3##
In formula II, R is C.sub.1 -C.sub.4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl and the four isomeric butyl radicals, but in particular methyl or ethyl, and Hal is halogen, such as fluorine, chlorine, bromine or iodine, but in particular chlorine or bromine.
The reduction with hydrazine is preferably carried out in an aqueous medium, with or without the addition of an inert solvent, such as diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, methanol, ethanol, isopropanol or dimethyl sulfoxide, at from 20.degree. to 120.degree. C., preferably from 60.degree. to 100.degree. C., continuously or batchwise, under atmospheric or superatmospheric pressure (from 1 to 10 bar).
The subsequent reaction with IV is carried out in a conventional manner (Houben-Weyl, Vol. 8, page 655 et seq. and Vol. E5, page 972 et seq.) preferably under from 0.5 to 10 bar, in particular under atmospheric pressure, continuously or batchwise, at from 0.degree. to 100.degree. C., preferably from 20.degree. to 40.degree. C., in a solvent and in the presence of a base.
In formula IV, X is halogen, e.g. chloride, bromide or iodide, or carboxylate, such as acetate or propionate, but preferably chloride or bromide. As a rule, these radicals can readily be eliminated.
Suitable bases are tertiary amines, such as triethylamine, the picolines, N,N-dimethylaniline or pyridine, or inorganic bases, such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium bicarbonate, barium hydroxide and sodium acetate. Triethylamine and pyridine are preferred.
Examples of suitable solvents are n-hexane, decalin, toluene, methylene chloride, diethyl ether, tetrahydrofuran, dioxane, dimethylformamide, methanol, ethanol and isopropanol and mixtures of these.
The required pyridazones II are obtained, for example, under the conditions described in German Laid-Open Application DOS 2,526,643, by reacting a dihalo-6-pyridazone of the general formula VI with roughly the stoichiometric amount of an alcoholate of the formula VII, where M is an alkali metal cation, in particular the sodium or potassium ion, and R is alkyl of 1 to 4 carbon atoms, in particular methyl or ethyl, in the presence of an organic solvent, preferably the corresponding alcohol, at from 0.degree. to 100.degree. C., preferably from 10.degree. to 40.degree. C. ##STR4##
The compounds of the formula Ib are obtained in a conventional manner (Houben-Weyl, Vol. E5, page 998 et seq.) by alkylation, alkenylation or alkynylation of the compounds Ia. For this purpose, the compound Ia is reacted with a reagent of the formula V, where Y is a group which can be readily eliminated, such as halogen, e.g. chloride, bromide or iodide, sulfonate, such as tosylate, mesylate or trifluoromethylsulfonate, or alkylsulfate, such as methylsulfate or ethylsulfate. ##STR5##
The reaction can be carried out in the presence or absence of a solvent, continuously or batchwise, under atmospheric or superatmospheric pressure (from 1 to 10 bar), at from 20.degree. to 180.degree. C., preferably from 100.degree. to 160.degree. C., in the presence of a strong base.
Suitable bases for this purpose are, for example, sodium hydride, potassium hydride, lithium methylate, sodium methylate, sodium ethylate, potassium tertbutylate, lithium amide, sodium amide, potassium hydroxide and potassium carbonate. Sodium hydride, sodium methylate and potassium tert-butylate are preferred.
Examples of suitable solvents are n-hexane, decalin, toluene, diethyl ether, ethylene glycol dimethyl ether, dioxane, dimethylformamide, dimethyl sulfoxide, acetone, methanol, ethanol and isopropanol. Dimethylformamide is preferred.
To enable the compounds Ia and/or Ib to be used as envisaged as herbicides, the following radicals are suitable:
Suitable alkyl groups R.sup.1 are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and tert-butyl, preferably methyl or ethyl, and suitable haloalkyl groups R.sup.1 are trifluoromethyl, difluoromethyl, fluoromethyl, trichloromethyl, dichloromethyl, chloromethyl, difluorochloromethyl, 1-fluoroethyl, 2-fluoroethyl and 2,2,2-trifluoroethyl, trifluoromethyl and difluoromethyl being preferred.
Suitable alkyl groups R.sup.2 are the radicals stated under R.sup.1, in particular n-propyl, n-butyl and isobutyl, suitable alkenyl groups R.sup.2 are, for example, vinyl, allyl, 2-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl, 1-methyl-2-pentenyl, 2,4-pentadienyl and 1-methyl-2,4-pentadienyl, preferably allyl, and suitable alkynyl groups R.sup.2 are, for example, 2-propynyl, 1-methyl-2-propynyl, 2-methyl-2-propynyl and the isomeric pentynyl and hexynyl radicals, 2-propynyl being preferred.
Suitable alkyl groups B are the radicals stated under R.sup.1 and n-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2,3-dimethylbutyl and 2-ethylbutyl, in particular n-pentyl, 3-methylbutyl, n-hexyl and 4-methylpentyl; suitable alkenyl groups B are vinyl and the radicals stated under R.sup.2, 2-methyl-2-propenyl, 2-pentenyl and 2,4-pentadienyl are preferred;
suitable alkynyl groups B are ethynyl and the radicals stated under R.sup.2, 3-butynyl, 3-pentynyl and 4-hexynyl are preferred;
suitable cycloalkyl groups B are, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and adamantyl as an example of a bridged system, cyclopentyl and cyclohexyl being preferred;
suitable cycloalkenyl groups B are, for example, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl and cycloheptenyl, and norbornenyl as an example of a bridged system, preferably cyclopentenyl, cyclohexenyl and norbornenyl;
suitable heterocyclic aliphatic groups B are, for example, epoxyethyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, thietanyl, tetrahydrothienyl and tetrahydrothiopyranyl, and xanthenyl as an example of a benzofused group, preferably tetrahydrofuranyl, tetrahydropyranyl, tetrahydrothienyl, tetrahydrothiopyranyl and xanthenyl;
suitable heterocyclic alkenyl rings B include dihydrofuranyl, dihydrothienyl and dihydropyranyl, in particular dihydropyranyl and dihydrothienyl;
suitable isoaromatic radicals B are, for example, phenyl, naphthyl, anthracenyl and phenanthrenyl, in particular the phenyl and the naphthyl ring, and
suitable heteroaromatic groups B are, for example, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, quinolyl or isoquinolyl, furanyl, thienyl, isoxazolyl, oxazolyl, oxathiazolyl, isothiazolyl, thioxalyl and thiodioxalyl, preferably pyrrolyl, pyrazolyl, imidazolyl, pyridyl, quinolyl, furanyl, thienyl, isoxazolyl, oxazolyl, isothiazoly and thioxazolyl.
Preferred substituents of B are
alkyl, such as the radicals stated under R.sup.1, in particular methyl, ethyl or isopropyl;
alkenyl, such as vinyl or the radicals stated under R.sup.2, preferably vinyl, 2-propenyl or 2-butenyl;
alkynyl, such as ethynyl and the radicals stated under R.sup.2, in particular ethynyl or 2-propynyl;
haloalkyl, such as the radicals stated under R.sup.1, preferably trifluoromethyl or difluoromethyl;
halogen, such as fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine;
alkoxy, such as methoxy, ethoxy, n-propoxy, isopropoxy or the isomeric butoxy radicals, in particular methoxy or ethoxy, and
alkylthio, such as methylthio, ethylthio, n-propylthio, isopropylthio or the isomeric butylthio radicals, in particular methylthio or ethylthio.
The 5-amino-6-pyridazones Ia and/or Ib, or the herbicidal agents containing them, may be applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other 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, but they must ensure as fine a distribution of the active ingredients according to the invention 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, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, 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, dispersions, wettable powders or water-dispersible granules 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 ethers, 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, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetate, 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, attapulgus clay, 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 generally contain from 0.1 to 95, and preferably from 0.5 to 90, % by weight of active ingredient. The active ingredients are used in a purity of from 90 to 100, and preferably from 95 to 100, % (according to the NMR spectrum).
The 5-amino-6-pyridazones according to the invention may be formulated for instance as follows:
I. 90 parts by weight of compound no. 1.019 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.
II. 20 parts by weight of compound no. 1.036 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 and 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 and 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 wt % of the active ingredient.
III. 20 parts by weight of compound no. 1.039 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 and 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.
IV. 20 parts by weight of compound no. 1.065 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 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 and 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.
V. 20 parts by weight of compound no. 1.094 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 lignin-sulfonic 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 liquor is obtained containing 0.1% by weight of the active ingredient.
VI. 3 parts by weight of compound no. 1.139 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.
VII. 30 parts by weight of compound no. 1.119 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.
VIII. 20 parts by weight of compound no. 2.443 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 phenolurea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.
The active ingredients may be applied pre- or postemergence. If certain crop plants tolerate the active ingredients less well, application techniques may be used in which the herbicidal agents are sprayed from suitable equipment in such a manner that the leaves of sensitive crop plants are if possible not touched, and the agents reach the soil or the unwanted plants growing beneath the crop plants (post-directed, lay-by treatment).
The application rates depend on the objective to be achieved, the time of the year, the plants to be combated and their growth stage, and are from 0.001 to 5.0, preferably 0.01 to 1.0, kg of active ingredient per hectare.
In view of the number of application methods possible, the compounds according to the invention, or agents containing them, may be used in a further large number of crops for removing unwanted plants. The following crops are given by way of example:
______________________________________Botanical name Common name______________________________________Allium cepa onionsAnanas comosus pineapplesArachis hypogaea peanuts (groundnuts)Asparagus officinalis asparagusAvena sativa oatsBeta vulgaris spp. altissima sugarbeetsBeta vulgaris spp. rapa fodder beetsBeta vulgaris spp. esculenta table beets, red beetsBrassica napus var. napus rapeseedBrassica napus var. napobrassica swedesBrassica napus var. rapa turnipsBrassica rapa var. silvestrisCamellia sinensis tea plantsCarthamus tinctorius safflowerCarya illinoinensis pecan treesCitrus limon lemonsCitrus maxima grapefruitsCitrus reticulata mandarinsCitrus sinensis orange treesCoffea arabica (Coffea canephora, coffee plantsCoffea liberica)Cucumis melo melonsCucumis sativus cucumbersCynodon dactylon BermudagrassDaucus carota carrotsElais guineensis oil palmsFragaria vesca strawberriesGlycine max soybeansGossypium hirsutum (Gossypium cottonarboreum,Gossypium herbaceum, Gossypiumvitifolium)Helianthus annuus sunflowersHelianthus tuberosus Jerusalem artichokeHevea brasiliensis rubber plantsHordeum vulgare barleyHumulus lupulus hopsIpomoea batatas sweet potatoesJuglans regia walnut treesLactuca sativa lettuceLens culinaris lentilsLinum usitatissimum flaxLycopersicon lycopersicum tomatoesMalus spp. apple treesManihot esculenta cassavaMedicago sativa alfalfa (lucerne)Mentha piperita peppermintMusa spp. banana plantsNicotiana tabacum (N. rustica) tobaccoOlea europaea olive treesOryza sativa ricePanicum miliaceum milletPhaseolus lunatus limabeansPhaseolus mungo mungbeansPhaseolus vulgaris snapbeans, green beans, dry beansPennisetum glaucum pearl milletPetroselinum crispum spp. tuberosum parsleyPicea abies Norway spruceAbies alba fir treesPinus spp. pine treesPisum sativum English peasPrunus avium cherry treesPrunus domestica plum treesPrunus dulcis almond treesPrunus persica peach treesPyrus communis pear treesRibes sylvestre redcurrantsRibes uva-crispa gooseberriesRicinus communis castor-oil plantsSaccharum officinarum sugar caneSecale cereale ryeSesamum indicum sesameSolanum tuberosum Irish potatoesSorghum bicolor (s. vulgare) sorghumSorghum dochna sorgoSpinacia oleracea spinachTheobroma cacao cacao plantsTrifolium pratense red cloverTriticum aestivum wheatTriticum durum durum wheatVaccinium corymbosum blueberriesVaccinium vitis-idaea cranberriesVicia faba tick beansVigna sinensis (v. unguiculata) cow peasVitis vinifera grapesZea mays Indian corn, sweet corn, maize______________________________________
To increase the spectrum of action and to achieve synergistic effects, the pyridazones of the formula Ia and/or Ib may be mixed and applied together with numerous representatives of other herbicidal or growth-regulating active ingredient groups. Examples of suitable components are diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran derivatives, cyclohexane-1,3-dione derivatives, quinolinecarboxylic acids, phenyloxy- and (hetero)aryloxyphenylpropionic acids and salts, esters and amides thereof, etc.
It may also be useful to apply the novel compounds of the formula Ia and/or Ib, either alone or in combination with other herbicides, in admixture with other crop protection agents, e.g., agents for combating pests or phytopathogenic fungi or bacteria. The compounds may also be mixed with solutions of mineral salts used to remedy nutritional or trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added.
The instructions given in the following synthesis examples were used, after appropriate modification of the starting materials, to obtain further compounds of the formula Ia and/or Ib. The compounds obtained are given with their physical data in the following tables; those compounds without these data may be prepared analogously from the appropriate materials. In view of their structural similarity with the compounds which have been manufactured and investigated, they are expected to have a similar action.

SYNTHESIS EXAMPLES
EXAMPLE 1
5-Acetylamino-1-methyl-6-pyridazone ##STR6##
a) At 80.degree. C., 240.8 g (1.38 mol) of 5-chloro-4-methoxy-1-methyl-6-pyridazone was added in portions to 1930 ml of hydrazine hydrate in such a manner that the temperature remained at 80.degree. C. without further heating. After cooling, the precipitate was filtered off, washed and dried. There was obtained 112.8 g (65.3%) of 5-amino-1-methyl-6-pyridazone of melting point 191.degree.-192.degree. C.
The 5-chloro-4-methoxy-1-methyl-6-pyridazone was prepared as follows in accordance with DE-OS 25 26 643:
295 g of 30% strength sodium methylate solution was added to 293 g (1.64 mol) of 4,5-dichloro-1-methyl-6-pyridazone in 690 ml of methanol in such a manner that a temperature of 30.degree. C. was not exceeded. After cooling and stirring for 12 hours at 25.degree. C., the precipitate which had formed was filtered off, washed and dried. There was obtained 241 g (84.3%) of 5-chloro-4-methoxy-1-methyl-6-pyridazone of melting point 189.degree.-191.degree. C.
b) A solution of 2.7 ml of acetyl chloride in 20 ml of dioxane was added dropwise to a solution of 4.0 g (0.032 mol) of 5-amino-1-methyl-6-pyridazone in 100 ml of pyridine. After stirring for 12 hours at 25.degree. C., the solvent was distilled off under reduced pressure, and the residue was taken up with methylene chloride, washed with sodium bicarbonate solution and dried. After the solvent had been stripped off under reduced pressure and the residue stirred with a small amount of diisopropyl ether, there was obtained 3.1 g (58.0%) of 5-acetylamino-1-methyl-6-pyridazone (active ingredient 1.001) of melting point 152.degree.-153.degree. C.
EXAMPLE 2
5-(2-Bromobenzamido)-1-methyl-6-pyridazone ##STR7##
Analogously to Example 1b) 8.0 g (81.2%) 5-(2-bromobenzamido)-1-methyl-6-pyridazone (active ingredient 1.082) of m.p. 190.degree. to 193.degree. C. was obtained from 4.0 g (0.032 mol) of 5-amino-1-methyl-6-pyridazone in 100 ml of pyridine and 7.7 g (0.035 mol) of 2-bromobenzoyl chloride in 20 ml of dioxane.
EXAMPLE 3
5-[N-(2-Bromobenzoyl)-N-methyl]-amino-1-methyl-6-pyridazone ##STR8##
2.9 g of 30% strength sodium methylate solution was added to 4.8 g (0.0156 mol) of 5-(2-bromobenzamido)-1-methyl-6-pyridazone in 50 ml of dimethylformamide. The methanol was then removed completely under reduced pressure and the reaction mixture was stirred for 2.5 hours at 80.degree. C. with 3 g of dimethyl sulfate. Water and 20 ml of concentrated ammonia solution were added and the product was extracted with ethyl acetate. After washing and drying, the organic phase was concentrated. Column chromatography using silica gel (eluant: cyclohexane/ethyl acetate) gave 3.8 g (75.5%) of 5-[N-(2-bromobenzoyl)-N-methyl]-amino-1-methyl-6-pyridazone (active ingredient 2.382) as a viscous oil.
.sup.1 H-NMR (DMSO-d.sub.6): 3.2 (s, 3H), 3.6 (s, 3H), 7.3 (m, 4H), 7.5 (m, 1H), 7.8 (d, I=5 Hz, 1H) ppm.
TABLE 1__________________________________________________________________________ ##STR9## Phys. dataNo. B A R.sup.1 mp (.degree.C.) .sup.1 H-NMR__________________________________________________________________________ (ppm)1.001 methyl CO CH.sub.3 152-1531.002 methyl SO.sub.2 CH.sub.31.003 ethyl CO CH.sub.3 115-1171.004 ethyl SO.sub.2 CH.sub.31.005 isopropyl CO CH.sub.31.006 tert.-butyl CO CH.sub.31.007 tert.-butylmethyl CO CH.sub.31.008 chloromethyl CO CH.sub.31.009 dichloromethyl CO CH.sub.31.010 2-chloroethyl CO CH.sub.31.011 methoxymethyl CO CH.sub.31.012 ethenyl CO CH.sub.31.013 1-methylethenyl CO CH.sub.31.014 ethynyl CO CH.sub.31.015 benzyl CO CH.sub.3 154-1561.016 cinnamyl CO CH.sub.3 155-1571.017 cyclopropyl CO CH.sub.3 165-1661.018 1-methylcyclopropyl CO CH.sub.31.019 2-methylcyclopropyl CO CH.sub.3 138-1401.020 1-phenylcyclopropyl CO CH.sub.31.021 2,2-dichloro-1-methylcyclopropyl CO CH.sub.31.022 cyclopentyl CO CH.sub.31.023 1-phenylcyclopentyl CO CH.sub.31.024 9-fluorenyl CO CH.sub.31.025 cyclohexyl CO CH.sub.3 138-1391.026 1-methylcyclohexyl CO CH.sub.3 95-971.027 2-methyl-norborn-2-en-5-yl CO CH.sub.3 104-1501.028 tetrahydropyran-3-yl CO CH.sub.31.029 tetrahydropyran-4-yl CO CH.sub.31.030 5,6-dihydro-2-methyl-4H-pyran-3-yl CO CH.sub.3 129-1301.031 5,6-dihydro-2,6,6-trimethyl-4H-pyran-3-yl CO CH.sub.31.032 xanthen-9-yl CO CH.sub.31.033 5,6-dihydro-3-methyl-4H-thiopyran-2-yl CO CH.sub.31.034 tetrahydrothiopyran-3-yl CO CH.sub.3 156-1571.035 tetrahydrothiopyran-4-yl CO CH.sub.31.036 phenyl CO CH.sub.3 111-1121.037 phenyl CO CH(CH.sub.3).sub.21.038 phenyl CO C(CH.sub.3).sub.31.039 phenyl SO.sub.2 CH.sub.3 161-1631.040 2-methylphenyl CO CH.sub.3 144-1461.041 2-methylphenyl SO.sub.2 CH.sub.31.042 2-methylphenyl SO.sub.2 CH.sub.31.043 4-methylphenyl CO CH.sub.3 151-1531.044 2,4-dimethylphenyl CO CH.sub.31.045 2,4-dimethylphenyl SO.sub.2 CH.sub.31.046 2,6-dimethylphenyl CO CH.sub.31.047 2,6-dimethylphenyl SO.sub.2 CH.sub.31.048 2-trifluoromethylphenyl CO CH.sub.3 185-1871.049 2-trifluoromethylphenyl SO.sub.2 CH.sub.31.050 2-methoxyphenyl CO CH.sub.3 160-1631.051 2-methoxyphenyl SO.sub.2 CH.sub.31.052 2,6-dimethoxyphenyl CO CH.sub.3 160-1641.053 2,6-dimethoxyphenyl SO.sub.2 CH.sub.31.054 2-trifluoromethoxyphenyl CO CH.sub.31.055 2-methylthiophenyl CO CH.sub.31.056 2-methylsulfinylphenyl CO CH.sub.31.057 2-methylsulfonylphenyl CO CH.sub. 31.058 2-fluorophenyl CO CH.sub.3 194-2001.059 2-fluorophenyl SO.sub.2 CH.sub.31.060 2-fluorophenyl CO CH.sub.2CF.sub.31.061 2,3-difluorophenyl CO CH.sub.31.062 2,4-difluorophenyl CO CH.sub.3 198-2001.063 2,5-difluorophenyl CO CH.sub.31.064 2,6-difluorophenyl CO CH.sub.3 198-2061.065 2-chlorophenyl CO CH.sub.3 176-1781.066 2-chlorophenyl SO.sub.2 CH.sub.3 129-1361.067 2-chlorophenyl CO CH(CH.sub.3).sub.2 95-971.068 2-chlorophenyl CO C(CH.sub.3).sub.3 84-861.069 2-chlorophenyl CO CH.sub.2 CF.sub.31.070 3-chlorophenyl CO CH.sub.3 151-1531.071 3-chlorophenyl SO.sub.2 CH.sub.31.072 4-chlorophenyl CO CH.sub.3 231-2321.073 4-chlorophenyl SO.sub.2 CH.sub.31.074 2,3-dichlorophenyl CO CH.sub.31.075 2,4-dichlorophenyl CO CH.sub.3 153-1541.076 2,5-dichlorophenyl CO CH.sub.3 164-1661.077 2,6-dichlorophenyl CO CH.sub.31.078 2,6-dichlorophenyl SO.sub.2 CH.sub.31.079 2,4,6-trichlorophenyl CO CH.sub.31.080 2-chloro-6-methylphenyl CO CH.sub.31.081 2-chloro-6-methylphenyl SO.sub.2 CH.sub.31.082 2-bromophenyl CO CH.sub.3 190-1931.083 2-bromophenyl SO.sub.2 CH.sub.31.084 2-cyanophenyl CO CH.sub.31.085 2-cyanophenyl SO.sub.2 CH.sub.31.086 2-nitrophenyl CO CH.sub.3 178-1861.087 2-nitrophenyl SO.sub.2 CH.sub.31.088 2-carbomethoxyphenyl CO CH.sub.31.089 2-carbomethoxyphenyl SO.sub.2 CH.sub.31.090 2-carbethoxyphenyl CO CH.sub.31.091 2-carbethoxyphenyl SO.sub.2 CH.sub.31.092 2-(N,N-dimethylcarbamido)phenyl CO CH.sub.31.093 2-pyridyl CO CH.sub.31.094 3-pyridyl CO CH.sub.3 136-1371.095 2-fluoro-3-pyridyl CO CH.sub.3 154-1551.096 2-chloro-3-pyridyl CO CH.sub.31.097 4-chloro-3-pyridyl CO CH.sub.31.098 4-pyridyl CO CH.sub.31.099 5-pyrimidyl CO CH.sub.31.100 1-naphthyl CO CH.sub.31.101 2-naphthyl CO CH.sub.31.102 2-quinolinyl CO CH.sub.31.103 3-quinolinyl CO CH.sub.31.104 2-methyl-4-quinolinyl CO CH.sub.31.105 3,7-dichloro-8-quinolinyl CO CH.sub.31.106 7-chloro-3-methyl-8-quinolinyl CO CH.sub.31.107 7-chloro-3-methyl-8-quinolinyl CO CH.sub.31.108 2-pyrrolyl CO CH.sub.31.109 3-pyrrolyl CO CH.sub.31.110 3-chloro-2-pyrolyl CO CH.sub.31.111 1-methyl-2-pyrrolyl CO CH.sub.3 137-1381.112 2-furanyl CO CH.sub.31.113 3-methyl-2-furanyl CO CH.sub.31.114 5-bromo-2-furanyl CO CH.sub.3 165-1661.115 5-methyl-2-furanyl CO CH.sub.31.116 3-furanyl CO CH.sub.31.117 2,5-dimethyl-3-furanyl CO CH.sub.3 123-1251.118 2,4,5-trimethyl-3-furanyl CO CH.sub.31.119 2-thienyl CO CH.sub.3 162-1641.120 3-chloro-2-thienyl CO CH.sub.3 224-2261.121 5-methyl-2-thienyl CO CH.sub.3 147-1491.122 3-thienyl CO CH.sub.31.123 4-chloro-3-thienyl CO CH.sub.3 165-1671.124 1-methyl-5-pyrazolyl CO CH.sub.31.125 4-pyrazolyl CO CH.sub.31.126 1-methyl-4-pyrazolyl CO CH.sub.31.127 3,5-dimethyl-4-pyrazolyl CO CH.sub.31.128 1-methyl-2-imidazolyl CO CH.sub.31.129 4-imidazolyl CO CH.sub.31.130 2-methyl-4-imidazolyl CO CH.sub.31.131 4-methyl-5-imidazolyl CO CH.sub.31.132 5-isoxazolyl CO CH.sub.31.133 4-isoxazolyl CO CH.sub.31.134 3-isopropyl-5-isoxazolyl CO CH.sub.3 104-1051.135 3-methyl-4-isoxazolyl CO CH.sub.31.136 4-isothiazolyl CO CH.sub.31.137 1-methyl-4-carbethoxy-3-pyrazolyl CO CH.sub.3 194-1961.138 5-chloro-2-thienyl CO CH.sub.3 158-1601.139 2-thienyl SO.sub.2 CH.sub.3 186-1881.140 2,5-dichloro-3-thienyl SO.sub.2 CH.sub.3 152-1541.141 2,5-dichloro-3-thienyl CO CH.sub.3 170-1711.142 3-chloro-2-thienyl SO.sub.2 CH.sub.3 185-1871.143 2-chloro-3-thienyl CO CH.sub.3 185-1861.144 1-adamantyl CO CH.sub.3 1731.145 cyclobuyl CO CH.sub.3 139-1411.146 4-methyl-5-oxazolyl CO CH.sub.31.147 2-methyl-4-oxazolyl CO CH.sub.31.148 3-isopropyl-4-isoxazolyl CO CH.sub.3__________________________________________________________________________
TABLE 2__________________________________________________________________________ ##STR10## Phys. dataNo. B A R.sup.1 R.sup.2 mp (.degree.C.) .sup.1 H-NMR__________________________________________________________________________ (ppm)2.001 methyl CO CH.sub.3 CH.sub.32.002 methyl CO CH.sub.3 CH.sub.2 CH.sub.22.003 methyl CO CH.sub.3 CH(CH.sub.3).sub.22.004 methyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.005 methyl CO CH.sub.3 CH.sub.2 CCH2.006 methyl CO CH.sub.3 CH.sub.2 Ph2.007 methyl SO.sub.2 CH.sub.3 CH.sub.32.008 methyl SO.sub.2 CH.sub.3 CH.sub.2 CH.sub.32.009 methyl SO.sub.2 CH.sub.3 CH(CH.sub.3).sub.22.010 methyl SO.sub.2 CH.sub.3 CH.sub.2 CHCH.sub.22.011 methyl SO.sub.2 CH.sub.3 CH.sub.2 CCH2.012 methyl SO.sub.2 CH.sub.3 CH.sub.2 Ph2.013 ethyl CO CH.sub.3 CH.sub.32.014 ethyl CO CH.sub.3 CH.sub.2 CH.sub.32.015 ethyl CO CH.sub.3 CH(CH.sub.3).sub.22.016 ethyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.017 ethyl CO CH.sub.3 CH.sub.2 CCH2.018 ethyl CO CH.sub.3 CH.sub.2 Ph2.019 ethyl SO.sub.2 CH.sub.3 CH.sub.32.020 ethyl SO.sub.2 CH.sub.3 CH.sub.2 CH.sub.32.021 ethyl SO.sub.2 CH.sub.3 CH(CH.sub.3).sub.22.022 ethyl SO.sub.2 CH.sub.3 CH.sub.2 CHCH.sub.22.023 ethyl SO.sub.2 CH.sub.3 CH.sub.2 CCH2.024 ethyl SO.sub.2 CH.sub.3 CH.sub.2 Ph2.025 isopropyl CO CH.sub.3 CH.sub.32.026 isopropyl CO CH.sub.3 CH.sub.2 CH.sub.32.027 isopropyl CO CH.sub.3 CH(CH.sub.3).sub.22.028 isopropyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.029 isopropyl CO CH.sub.3 CH.sub.2 CCH2.030 isopropyl CO CH.sub.3 CH.sub.2 Ph2.031 tert.-butyl CO CH.sub.3 CH.sub.32.032 tert.-butyl CO CH.sub.3 CH.sub.2 CH.sub.32.033 tert.-butyl CO CH.sub.3 CH(CH.sub.3).sub.22.034 tert.-butyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.035 tert.-butyl CO CH.sub.3 CH.sub.2 CCH2.036 tert.-butyl CO CH.sub.3 CH.sub.2 Ph2.037 tert.-butylmethyl CO CH.sub.3 CH.sub.32.038 tert.-butylmethyl CO CH.sub.3 CH.sub.2 CH.sub.32.039 tert.-butylmethyl CO CH.sub.3 CH(CH.sub.3).sub.22.040 tert.-butylmethyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.041 tert.-butylmethyl CO CH.sub.3 CH.sub.2 CCH2.042 tert.-butylmethyl CO CH.sub.3 CH.sub.2 Ph2.043 chloromethyl CO CH.sub.3 CH.sub.32.044 chloromethyl CO CH.sub.3 CH.sub.2 CH.sub.32.045 chloromethyl CO CH.sub.3 CH(CH.sub.3).sub.22.046 chloromethyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.047 chloromethyl CO CH.sub.3 CH.sub.2 CCH2.048 chloromethyl CO CH.sub.3 CH.sub.2 Ph2.049 dichloromethyl CO CH.sub.3 CH.sub.32.050 dichloromethyl CO CH.sub.3 CH.sub.2 CH.sub.32.051 dichloromethyl CO CH.sub.3 CH(CH.sub.3).sub.22.052 dichloromethyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.053 dichloromethyl CO CH.sub.3 CH.sub.2 CCH2.054 dichloromethyl CO CH.sub.3 CH.sub.2 Ph2.055 2-chloroethyl CO CH.sub.3 CH.sub.32.056 2-chloroethyl CO CH.sub.3 CH.sub.2 CH.sub.32.057 2-chloroethyl CO CH.sub.3 CH(CH.sub.3).sub.22.058 2-chloroethyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.059 2-chloroethyl CO CH.sub.3 CH.sub.2 CCH2.060 2-chloroethyl CO CH.sub.3 CH.sub.2 Ph2.061 methoxymethyl CO CH.sub.3 CH.sub.32.062 methoxymethyl CO CH.sub.3 CH.sub.2 CH.sub.32.063 methoxymethyl CO CH.sub.3 CH(CH.sub.3).sub.22.064 methoxymethyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.065 methoxymethyl CO CH.sub.3 CH.sub.2 CCH2.066 methoxymethyl CO CH.sub.3 CH.sub.2 Ph2.067 ethenyl CO CH.sub.3 CH.sub.32.068 1-methylethenyl CO CH.sub.3 CH.sub.32.069 ethynyl CO CH.sub.3 CH.sub.32.070 benzyl CO CH.sub.3 CH.sub.32.071 cinnamyl CO CH.sub.3 CH.sub.32.072 cyclopropyl CO CH.sub.3 CH.sub.32.073 cyclopropyl CO CH.sub.3 CH.sub.2 CH.sub.32.074 cyclopropyl CO CH.sub.3 CH(CH.sub.3).sub.22.075 cyclopropyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.076 cyclopropyl CO CH.sub.3 CH.sub.2 CCH2.077 cyclopropyl CO CH.sub.3 CH.sub.2 Ph2.078 1-methylcyclopropyl CO CH.sub.3 CH.sub.32.079 1-methylcyclopropyl CO CH.sub.3 CH.sub.2 CH.sub.32.080 1-methylcyclopropyl CO CH.sub.3 CH(CH.sub.3).sub.22.081 1-methylcyclopropyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.082 1-methylcyclopropyl CO CH.sub.3 CH.sub.2 CCH2.083 1-methylcyclopropyl CO CH.sub.3 CH.sub.2 Ph2.084 2-methylcyclopropyl CO CH.sub.3 CH.sub.32.085 2-methylcyclopropyl CO CH.sub.3 CH.sub.2 CH.sub.32.086 2-methylcyclopropyl CO CH.sub.3 CH(CH.sub.3).sub.22.087 2-methylcyclopropyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.088 2-methylcyclopropyl CO CH.sub.3 CH.sub.2 CCH2.089 2-methylcyclopropyl CO CH.sub.3 CH.sub.2 Ph2.090 1-phenylcyclopropyl CO CH.sub.3 CH.sub.32.091 1-phenylcyclopropyl CO CH.sub.3 CH.sub.2 CH.sub.32.092 1-phenylcyclopropyl CO CH.sub.3 CH(CH.sub.3).sub.22.093 1-phenylcyclopropyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.094 1-phenylcyclopropyl CO CH.sub.3 CH.sub.2 CCH2.095 1-phenylcyclopropyl CO CH.sub.3 CH.sub.2 Ph2.096 2,2-dichloro-1-methyl- CO CH.sub.3 CH.sub.3 cyclopropyl2.097 2,2-dichloro-1-methyl- CO CH.sub.3 CH.sub.2 CH.sub.3 cyclopropyl2.098 2,2-dichloro-1-methyl- CO CH.sub.3 CH(CH.sub.3).sub.2 cyclopropyl2.099 2,2-dichloro-1-methyl- CO CH.sub.3 CH.sub.2 CHCH.sub.2 cyclopropyl2.100 2,2-dichloro-1-methyl- CO CH.sub.3 CH.sub.2 CCH cyclopropyl2.101 2,2-dichloro-1-methyl- CO CH.sub.3 CH.sub.2 Ph cyclopropyl2.102 cyclopentyl CO CH.sub.3 CH.sub.32.103 cyclopentyl CO CH.sub.3 CH.sub.2 CH.sub.32.104 cyclopentyl CO CH.sub.3 CH(CH.sub.3).sub.22.105 cyclopentyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.106 cyclopentyl CO CH.sub.3 CH.sub.2 CCH2.107 cyclopentyl CO CH.sub.3 CH.sub.2 Ph2.108 1-phenylcyclopentyl CO CH.sub.3 CH.sub.32.109 1-phenylcyclopentyl CO CH.sub.3 CH.sub.2 CH.sub.32.110 1-phenylcyclopentyl CO CH.sub.3 CH(CH.sub.3).sub.22.111 1-phenylcyclopentyl CO CH.sub.3 CH.sub. 2 CHCH.sub.22.112 1-phenylcyclopentyl CO CH.sub.3 CH.sub.2 CCH2.113 1-phenylcyclopentyl CO CH.sub.3 CH.sub.2 Ph2.114 9-fluorenyl CO CH.sub.3 CH.sub.32.115 9-fluorenyl CO CH.sub.3 CH.sub.2 CH.sub.32.116 9-fluorenyl CO CH.sub.3 CH(CH.sub.3).sub.22.117 9-fluorenyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.118 9-fluorenyl CO CH.sub.3 CH.sub.2 CCH2.119 9-fluorenyl CO CH.sub.3 CH.sub.2 Ph2.120 cyclohexyl CO CH.sub.3 CH.sub.32.121 cyclohexyl CO CH.sub.3 CH.sub.2 CH.sub.32.122 cyclohexyl CO CH.sub.3 CH(CH.sub.3).sub.22.123 cyclohexyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.124 cyclohexyl CO CH.sub.3 CH.sub.2 CCH2.125 cyclohexyl CO CH.sub.3 CH.sub.2 Ph2.126 1-methylcyclohexyl CO CH.sub.3 CH.sub.32.127 1-methylcyclohexyl CO CH.sub.3 CH.sub.2 CH.sub.32.128 1-methylcyclohexyl CO CH.sub.3 CH(CH.sub.3).sub.22.129 1-methylcyclohexyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.130 1-methylcyclohexyl CO CH.sub.3 CH.sub.2 C CH2.131 1-methylcyclohexyl CO CH.sub.3 CH.sub.2 Ph2.132 5-norbornen-2-yl CO CH.sub.3 CH.sub.32.133 5-norbornen-2-yl CO CH.sub.3 CH.sub.2 CH.sub.32.134 5-norbornen-2-yl CO CH.sub.3 CH(CH.sub.3).sub.22.135 5-norbornen-2-yl CO CH.sub.3 CH.sub.2 CHCH.sub.22.136 5-norbornen-2-yl CO CH.sub.3 CH.sub.2 CCH2.137 5-norbornen-2-yl CO CH.sub.3 CH.sub.2 Ph2.138 tetrahydropyran-3-yl CO CH.sub.3 CH.sub.32.139 tetrahydropyran-3-yl CO CH.sub.3 CH.sub.2 CH.sub.32.140 tetrahydropyran-3-yl CO CH.sub.3 CH(CH.sub.3).sub.22.141 tetrahydropyran-3-yl CO CH.sub.3 CH.sub.2 CHCH.sub.22.142 tetrahydropyran-3-yl CO CH.sub.3 CH.sub.2 CCH2.143 tetrahydropyran-3-yl CO CH.sub.3 CH.sub.2 Ph2.144 tetrahydropyran-4-yl CO CH.sub.3 CH.sub.32.145 tetrahydropyran-4-yl CO CH.sub.3 CH.sub.2 CH.sub.32.146 tetrahydropyran-4-yl CO CH.sub.3 CH(CH.sub.3).sub.22.147 tetrahydropyran-4-yl CO CH.sub.3 CH.sub.2 CHCH.sub.22.148 tetrahydropyran-4-yl CO CH.sub.3 CH.sub.2 CCH2.149 tetrahydropyran-4-yl CO CH.sub.3 CH.sub.2 Ph2.150 5,6-dihydro-2-methyl- CO CH.sub. 3 CH.sub.3 4H-pyran-3-yl2.151 5,6-dihydro-2-methyl- CO CH.sub.3 CH.sub.2 CH.sub.3 4H-pyran-3-yl2.152 5,6-dihydro-2-methyl- CO CH.sub.3 CH(CH.sub.3).sub.2 4H-pyran-3-yl2.153 5,6-dihydro-2-methyl- CO CH.sub.3 CH.sub.2 CHCH.sub.2 4H-pyran-3-yl2.154 5,6-dihydro-2-methyl- CO CH.sub.3 CH.sub.2 CCH 4H-pyran-3-yl2.155 5,6-dihydro-2-methyl- CO CH.sub.3 CH.sub.2 Ph 4H-pyran-3-yl2.156 5,6-dihydro-2,6,6- CO CH.sub.3 CH.sub.3 trimethyl-4H-pyran-3-yl2.157 5,6-dihydro-2,6,6- CO CH.sub.3 CH.sub.2 CH.sub.3 trimethyl-4H-pyran-3-yl2.158 5,6-dihydro-2,6,6- CO CH.sub.3 CH(CH.sub.3).sub.2 trimethyl-4H-pyran-3-yl2.159 5,6-dihydro-2,6,6- CO CH.sub.3 CH.sub.2 CHCH.sub.2 trimethyl-4H-pyran-3-yl2.160 5,6-dihydro-2,6,6- CO CH.sub.3 CH.sub.2 CCH trimethyl-4H-pyran-3-yl2.161 5,6-dihydro-2,6,6- CO CH.sub.3 CH.sub.2 Ph trimethyl-4H-pyran-3-yl2.162 xanthen-9-yl CO CH.sub.3 CH.sub.32.163 xanthen-9-yl CO CH.sub.3 CH.sub.2 CH.sub.32.164 xanthen-9-yl CO CH.sub.3 CH(CH.sub.3).sub.22.165 xanthen-9-yl CO CH.sub.3 CH.sub.2 CHCH.sub.22.166 xanthen-9-yl CO CH.sub.3 CH.sub.2 CCH2.167 xanthen-9-yl CO CH.sub.3 CH.sub.2 Ph2.168 5,6-dihydro-3-methyl- CO CH.sub.3 CH.sub.3 4H-thiopyran-2-yl2.169 5,6-dihydro-3-methyl- CO CH.sub.3 CH.sub.2 CH.sub.3 4H-thiopyran-2-yl2.170 5,6-dihydro-3-methyl- CO CH.sub.3 CH(CH.sub.3).sub.2 4H-thiopyran-2-yl2.171 5,6-dihydro-3-methyl- CO CH.sub.3 CH.sub.2 CHCH.sub.2 4H-thiopyran-2-yl2.172 5,6-dihydro-3-methyl- CO CH.sub.3 CH.sub.2 CCH 4H-thiopyran-2-yl2.173 5,6-dihydro-3-methyl- CO CH.sub.3 CH.sub.2 Ph 4H-thiopyran-2-yl2.174 tetrahydrothiopyran- CO CH.sub.3 CH.sub.3 3-yl2.175 tetrahydrothiopyran- CO CH.sub.3 CH.sub.2 CH.sub.3 3-yl2.176 tetrahydrothiopyran- CO CH.sub.3 CH(CH.sub.3).sub.2 3-yl2.177 tetrahydrothiopyran- CO CH.sub.3 CH.sub.2 CHCH.sub.2 3-yl2.178 tetrahydrothiopyran- CO CH.sub.3 CH.sub.2 CCH 3-yl2.179 tetrahydrothiopyran- CO CH.sub.3 CH.sub.2 Ph 3-yl2.180 tetrahydrothiopyran- CO CH.sub.3 CH.sub.3 4-yl2.181 tetrahydrothiopyran- CO CH.sub.3 CH.sub.2 CH.sub.3 4-yl2.182 tetrahydrothiopyran- CO CH.sub.3 CH(CH.sub.3).sub.2 4-yl2.183 tetrahydrothiopyran- CO CH.sub.3 CH.sub.2 CHCH.sub.2 4-yl2.184 tetrahydrothiopyran- CO CH.sub.3 CH.sub.2 C CH 4-yl2.185 tetrahydrothiopyran- CO CH.sub.3 CH.sub.2 Ph 4-yl2.186 phenyl CO CH.sub.3 CH.sub.32.187 phenyl CO CH.sub.3 CH.sub.2 CH.sub.32.188 phenyl CO CH.sub.3 CH(CH.sub.3).sub.22.189 phenyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.190 phenyl CO CH.sub.3 CH.sub.2 CCH2.191 phenyl CO CH.sub.3 CH.sub.2 Ph2.192 phenyl CO CH(CH.sub.3).sub.2 CH.sub.32.193 phenyl CO C(CH.sub.3).sub.3 CH.sub.32.194 phenyl SO.sub.2 CH.sub.3 CH.sub.32.195 phenyl SO.sub.2 CH.sub.3 CH.sub.2 CH.sub.32.196 phenyl SO.sub.2 CH.sub.3 CH(CH.sub.3).sub.22.197 phenyl SO.sub.2 CH.sub.3 CH.sub.2 CHCH.sub.22.198 phenyl SO.sub.2 CH.sub.3 CH.sub.2 CCH2.199 phenyl SO.sub.2 CH.sub.3 CH.sub.2 Ph2.200 2-methylphenyl CO CH.sub.3 CH.sub.32.201 2-methylphenyl CO CH.sub.3 CH.sub.2 CH.sub.32.202 2-methylphenyl CO CH.sub.3 CH(CH.sub.3).sub.22.203 2-methylphenyl CO CH.sub.3 CH.sub.2 CH CH.sub.22.204 2-methylphenyl CO CH.sub.3 CH.sub.2 CCH2.205 2-methylphenyl CO CH.sub.3 CH.sub.2 Ph2.206 2-methylphenyl SO.sub.2 CH.sub.3 CH.sub.32.207 2-methylphenyl SO.sub.2 CH.sub.3 CH.sub.2 CH.sub.32.208 2-methylphenyl SO.sub.2 CH.sub.3 CH(CH.sub.3).sub.22.209 2-methylphenyl SO.sub.2 CH.sub.3 CH.sub.2 CHCH.sub.22.210 2-methylphenyl SO.sub.2 CH.sub.3 CH.sub.2 CCH2.211 2-methylphenyl SO.sub.2 CH.sub.3 CH.sub.2 Ph2.212 3-methylphenyl CO CH.sub.3 CH.sub.32.213 4-methylphenyl CO CH.sub.3 CH.sub.32.214 2,4-dimethylphenyl CO CH.sub.3 CH.sub.32.215 2,4-dimethylphenyl CO CH.sub.3 CH.sub.2 CH.sub.32.216 2,4-dimethylphenyl CO CH.sub.3 CH(CH.sub.3).sub.22.217 2,4-dimethylphenyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.218 2,4-dimethylphenyl CO CH.sub.3 CH.sub.2 CCH2.219 2,4-dimethylphenyl CO CH.sub.3 CH.sub.2 Ph2.220 2,4-dimethylphenyl SO.sub.2 CH.sub.3 CH.sub.32.221 2,4-dimethylphenyl SO.sub.2 CH.sub.3 CH.sub.2 CH.sub.32.222 2,4-dimethylphenyl SO.sub.2 CH.sub.3 CH(CH.sub.3).sub.22.223 2,4-dimethylphenyl SO.sub.2 CH.sub.3 CH.sub.2 CHCH.sub.22.224 2,4-dimethylphenyl SO.sub.2 CH.sub.3 CH.sub.2 CCH2.225 2,4-dimethylphenyl SO.sub.2 CH.sub.3 CH.sub.2 Ph2.226 2,6-dimethylphenyl CO CH.sub.3 CH.sub.32.227 2,6-dimethylphenyl CO CH.sub.3 CH.sub.2 CH.sub.32.228 2,6-dimethylphenyl CO CH.sub.3 CH(CH.sub.3).sub.22.229 2,6-dimethylphenyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.230 2,6-dimethylphenyl CO CH.sub.3 CH.sub.2 CCH2.231 2,6-dimethylphenyl CO CH.sub.3 CH.sub.2 Ph2.232 2,6-dimethylphenyl SO.sub.2 CH.sub.3 CH.sub.32.233 2,6-dimethylphenyl SO.sub.2 CH.sub.3 CH.sub.2 CH.sub.32.234 2,6-dimethylphenyl SO.sub.2 CH.sub.3 CH(CH.sub.3).sub.22.235 2,6-dimethylphenyl SO.sub.2 CH.sub.3 CH.sub.2 CHCH.sub.22.236 2,6-dimethylphenyl SO.sub.2 CH.sub.3 CH.sub.2 CCH2.237 2,6-dimethylphenyl SO.sub.2 CH.sub.3 CH.sub.2 Ph2.238 2-trifluoromethylphenyl CO CH.sub.3 CH.sub.32.239 2-trifluoromethylphenyl CO CH.sub.3 CH.sub.2 CH.sub.32.240 2-trifluoromethylphenyl CO CH.sub.3 CH(CH.sub.3).sub.22.241 2-trifluoromethylphenyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.242 2-trifluoromethylphenyl CO CH.sub.3 CH.sub.2 CCH2.243 2-trifluoromethylphenyl CO CH.sub.3 CH.sub.2 Ph2.244 2-trifluoromethylphenyl SO.sub.2 CH.sub.3 CH.sub.32.245 2-methoxyphenyl CO CH.sub.3 CH.sub.32.246 2-methoxyphenyl CO CH.sub.3 CH.sub.2 CH.sub.32.247 2-methoxyphenyl CO CH.sub.3 CH(CH.sub.3).sub.22.248 2-methoxyphenyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.249 2-methoxyphenyl CO CH.sub.3 CH.sub.2 CCH2.250 2-methoxyphenyl CO CH.sub.3 CH.sub.2 Ph2.251 2-methoxyphenyl SO.sub.2 CH.sub.3 CH.sub.32.252 2,6-dimethoxyphenyl CO CH.sub.3 CH.sub.32.253 2,6-dimethoxyphenyl CO CH.sub.3 CH.sub.2 CH.sub.32.254 2,6-dimethoxyphenyl CO CH.sub.3 CH(CH.sub.3).sub.22.255 2,6-dimethoxyphenyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.256 2,6-dimethoxyphenyl CO CH.sub.3 CH.sub.2 CCH2.257 2,6-dimethoxyphenyl CO CH.sub.3 CH.sub.2 Ph2.258 2,6-dimethoxyphenyl SO.sub.2 CH.sub.3 CH.sub.32.259 2-trifluoromethoxyphenyl CO CH.sub.3 CH.sub.32.260 2-trifluoromethoxyphenyl CO CH.sub.3 CH.sub.2 CH.sub.32.261 2-trifluoromethoxyphenyl CO CH.sub.3 CH(CH.sub.3).sub.22.262 2-trifluoromethoxyphenyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.263 2-trifluoromethoxyphenyl CO CH.sub.3 CH.sub.2 CCH2.264 2-trifluoromethoxyphenyl CO CH.sub.3 CH.sub.2 Ph2.265 2-methylthiophenyl CO CH.sub.3 CH.sub.32.266 2-methylsulfinylphenyl CO CH.sub.3 CH.sub.32.267 2-methylsulfonylphenyl CO CH.sub.3 CH.sub.32.268 2-fluorophenyl CO CH.sub.3 CH.sub.32.269 2-fluorophenyl CO CH.sub.3 CH.sub.2 CH.sub.32.270 2-fluorophenyl CO CH.sub.3 CH(CH.sub.3).sub.22.271 2-fluorophenyl CO CH.sub.3 CH.sub.2 CHCH.sub.2 75-772.272 2-fluorophenyl CO CH.sub.3 CH.sub.2 CCH2.273 2-fluorophenyl CO CH.sub.3 CH.sub.2 Ph 98-1002.274 2-fluorophenyl SO.sub.2 CH.sub.3 CH.sub.32.275 2-fluorophenyl SO.sub.2 CH.sub.3 CH.sub.2 CH.sub.32.276 2-fluorophenyl SO.sub.2 CH.sub.3 CH(CH.sub.3).sub.22.277 2-fluorophenyl SO.sub.2 CH.sub.3 CH.sub.2 CHCH.sub.22.278 2-fluorophenyl SO.sub.2 CH.sub.3 CH.sub.2 CCH2.279 2-fluorophenyl SO.sub.2 CH.sub.3 CH.sub.2 Ph2.280 2-fluorophenyl CO CH.sub.2 CF.sub.3 CH.sub.32.281 2-fluorophenyl CO CH.sub.2 CF.sub.3 CH.sub.2 CH.sub.32.282 2-fluorophenyl CO CH.sub.2 CF.sub.3 CH(CH.sub.3).sub.22.283 2-fluorophenyl CO CH.sub.2 CF.sub.3 CH.sub.2 CHCH.sub.22.284 2-fluorophenyl CO CH.sub.2 CF.sub.3 CH.sub.2 CCH2.285 2-fluorophenyl CO CH.sub.2 CF.sub.3 CH.sub.2 Ph2.286 2,3-difluorophenyl CO CH.sub.3 CH.sub.32.287 2,3-difluorophenyl CO CH.sub.3 CH.sub.2 CH.sub.32.288 2,3-difluorophenyl CO CH.sub.3 CH(CH.sub.3).sub.22.289 2,3-difluorophenyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.290 2,3-difluorophenyl CO CH.sub.3 CH.sub.2 CCH2.291 2,3-difluorophenyl CO CH.sub.3 CH.sub.2 Ph2.292 2,4-difluorophenyl CO CH.sub.3 CH.sub.32.293 2,4-difluorophenyl CO CH.sub.3 CH.sub.2 CH.sub.32.294 2,4-difluorophenyl CO CH.sub.3 CH(CH.sub.3).sub.22.295 2,4-difluorophenyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.296 2,4-difluorophenyl CO CH.sub.3 CH.sub.2 CCH2.297 2,4-difluorophenyl CO CH.sub.3 CH.sub.2 Ph2.298 2,5-difluorophenyl CO CH.sub.3 CH.sub.32.299 2,5-difluorophenyl CO CH.sub.3 CH.sub.2 CH.sub.32.300 2,5-difluorophenyl CO CH.sub.3 CH(CH.sub.3).sub.22.301 2,5-difluorophenyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.302 2,5-difluorophenyl CO CH.sub.3 CH.sub.2 CCH2.303 2,5-difluorophenyl CO CH.sub.3 CH.sub.2 Ph2.304 2,6-difluorophenyl CO CH.sub.3 CH.sub.32.305 2,6-difluorophenyl CO CH.sub.3 CH.sub.2 CH.sub.32.306 2,6-difluorophenyl CO CH.sub.3 CH(CH.sub.3).sub.22.307 2,6-difluorophenyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.308 2,6-difluorophenyl CO CH.sub.3 CH.sub.2 CCH2.309 2,6-difluorophenyl CO CH.sub.3 CH.sub.2 Ph2.310 2-chlorophenyl CO CH.sub.3 CH.sub.32.311 2-chlorophenyl CO CH.sub.3 CH.sub.2 CH.sub.32.312 2-chlorophenyl CO CH.sub.3 CH(CH.sub.3).sub.22.313 2-chlorophenyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.314 2-chlorophenyl CO CH.sub.3 CH.sub.2 CCH2.315 2-chlorophenyl CO CH.sub.3 CH.sub.2 Ph2.316 2-chlorophenyl SO.sub.2 CH.sub.3 CH.sub.32.317 2-chlorophenyl SO.sub.2 CH.sub.3 CH.sub.2 CH.sub.32.318 2-chlorophenyl SO.sub.2 CH.sub.3 CH(CH.sub.3).sub.22.319 2-chlorophenyl SO.sub.2 CH.sub.3 CH.sub.2 CHCH.sub.22.320 2-chlorophenyl SO.sub.2 CH.sub.3 CH.sub.2 CCH2.321 2-chlorophenyl SO.sub.2 CH.sub.3 CH.sub.2 Ph2.322 2-chlorophenyl CO CH(CH.sub.3).sub.2 CH.sub.32.323 2-chlorophenyl CO C(CH.sub.3).sub.3 CH.sub.32.324 2-chlorophenyl CO CH.sub.2 CF.sub.3 CH.sub.32.325 2-chlorophenyl CO CH.sub.2 CF.sub.3 CH.sub.2 CH.sub.32.326 2-chlorophenyl CO CH.sub.2 CF.sub.3 CH(CH.sub.3).sub.22.327 2-chlorophenyl CO CH.sub.2 CF.sub.3 CH.sub.2 CHCH.sub.22.328 2-chlorophenyl CO CH.sub.2 CF.sub.3 CH.sub.2 CCH2.329 2-chlorophenyl CO CH.sub.2 CF.sub.3 CH.sub.2 Ph2.330 3-chlorophenyl CO CH.sub.3 CH.sub.32.331 3-chlorophenyl SO.sub.2 CH.sub.3 CH.sub.32.332 4-chlorophenyl CO CH.sub.3 CH.sub.32.333 4-chlorophenyl SO.sub.2 CH.sub.3 CH.sub.32.334 2,3-dichlorophenyl CO CH.sub.3 CH.sub.32.335 2,3-dichlorophenyl CO CH.sub.3 CH.sub.2 CH.sub.32.336 2,3-dichlorophenyl CO CH.sub.3 CH(CH.sub.3).sub.22.337 2,3-dichlorophenyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.338 2,3-dichlorophenyl CO CH.sub.3 CH.sub.2 C CH2.339 2,3-dichlorophenyl CO CH.sub.3 CH.sub.2 Ph2.340 2,4-dichlorophenyl CO CH.sub.3 CH.sub.32.341 2,4-dichlorophenyl CO CH.sub.3 CH.sub.2 CH.sub.32.342 2,4-dichlorophenyl CO CH.sub.3 CH(CH.sub.3).sub.22.343 2,4-dichlorophenyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.344 2,4-dichlorophenyl CO CH.sub.3 CH.sub.2 CCH2.345 2,4-dichlorophenyl CO CH.sub.3 CH.sub.2 Ph2.346 2,5-dichlorophenyl CO CH.sub.3 CH.sub.32.347 2,5-dichlorophenyl CO CH.sub.3 CH.sub.2 CH.sub.32.348 2,5-dichlorophenyl CO CH.sub.3 CH(CH.sub.3).sub.22.349 2,5-dichlorophenyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.350 2,5-dichlorophenyl CO CH.sub.3 CH.sub.2 CCH2.351 2,5-dichlorophenyl CO CH.sub.3 CH.sub.2 Ph2.352 2,6-dichlorophenyl CO CH.sub.3 CH.sub.32.353 2,6-dichlorophenyl CO CH.sub.3 CH.sub.2 CH.sub.32.354 2,6-dichlorophenyl CO CH.sub.3 CH(CH.sub.3).sub.22.355 2,6-dichlorophenyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.356 2,6-dichlorophenyl CO CH.sub.3 CH.sub.2 CCH2.357 2,6-dichlorophenyl CO CH.sub.3 CH.sub.2 Ph2.358 2,6-dichlorophenyl SO.sub.2 CH.sub.3 CH.sub.32.359 2,6-dichlorophenyl SO.sub.2 CH.sub.3 CH.sub.2 CH.sub.32.360 2,6-dichlorophenyl SO.sub.2 CH.sub.3 CH(CH.sub.3).sub.22.361 2,6-dichlorophenyl SO.sub.2 CH.sub.3 CH.sub.2 CHCH.sub.22.362 2,6-dichlorophenyl SO.sub.2 CH.sub.3 CH.sub.2 CCH2.363 2,6-dichlorophenyl SO.sub.2 CH.sub.3 CH.sub.2 Ph2.364 2,4,6-trichlorophenyl CO CH.sub.3 CH.sub.32.365 2,4,6-trichlorophenyl CO CH.sub.3 CH.sub.2 CH.sub.32.366 2,4,6-trichlorophenyl CO CH.sub.3 CH(CH.sub.3).sub.22.367 2,4,6-trichlorophenyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.368 2,4,6-trichlorophenyl CO CH.sub.3 CH.sub.2 CCH2.369 2,4,6-trichlorophenyl CO CH.sub.3 CH.sub.2 Ph2.370 2-chloro-6-methylphenyl CO CH.sub.3 CH.sub.32.371 2-chloro-6-methylphenyl CO CH.sub.3 CH.sub.2 CH.sub.32.372 2-chloro-6-methylphenyl CO CH.sub.3 CH(CH.sub.3).sub.22.373 2-chloro-6-methylphenyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.374 2-chloro-6-methylphenyl CO CH.sub.3 CH.sub.2 CCH2.375 2-chloro-6-methylphenyl CO CH.sub.3 CH.sub.2 Ph2.376 2-chloro-6-methylphenyl SO.sub.2 CH.sub.3 CH.sub.32.377 2-chloro-6-methylphenyl SO.sub.2 CH.sub. 3 CH.sub.2 CH.sub.32.378 2-chloro-6-methylphenyl SO.sub.2 CH.sub.3 CH(CH.sub.3).sub.22.379 2-chloro-6-methylphenyl SO.sub.2 CH.sub.3 CH.sub.2 CHCH.sub.22.380 2-chloro-6-methylphenyl SO.sub.2 CH.sub.3 CH.sub.2 CCH2.381 2-chloro-6-methylphenyl SO.sub.2 CH.sub.3 CH.sub.2 Ph2.382 2-bromophenyl CO CH.sub.3 CH.sub.3 3.23(s)3H;3.63(s)3H; 7.32(m)4H;7.58(m)1H; 7,82(d)1H;J=5Hz2.383 2-bromophenyl CO CH.sub.3 CH.sub.2 CH.sub.32.384 2-bromophenyl CO CH.sub.3 CH(CH.sub.3).sub.22.385 2-bromophenyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.386 2-bromophenyl CO CH.sub.3 CH.sub.2 CCH2.387 2-bromophenyl CO CH.sub.3 CH.sub.2 Ph2.388 2-cyanophenyl CO CH.sub.3 CH.sub.32.389 2-cyanophenyl CO CH.sub.3 CH.sub.2 CH.sub.32.390 2-cyanophenyl CO CH.sub.3 CH(CH.sub.3).sub.22.391 2-cyanophenyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.392 2-cyanophenyl CO CH.sub.3 CH.sub.2 CCH2.393 2-cyanophenyl CO CH.sub.3 CH.sub.2 Ph2.394 2-cyanophenyl SO.sub.2 CH.sub.3 CH.sub.32.395 2-nitrophenyl CO CH.sub.3 CH.sub.32.396 2-nitrophenyl CO CH.sub.3 CH.sub.2 CH.sub.32.397 2-nitrophenyl SO.sub.2 CH.sub.3 CH.sub.2 CH.sub.32.398 2-nitrophenyl CO CH.sub.3 CH(CH.sub.3).sub.22.399 2-nitrophenyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.400 2-nitrophenyl CO CH.sub.3 CH.sub.2 CCH2.401 2-nitrophenyl CO CH.sub.3 CH.sub.2 Ph2.402 2-nitrophenyl SO.sub.2 CH.sub.3 CH.sub.32.403 2-carbomethoxyphenyl CO CH.sub.3 CH.sub.32.404 2-carbomethoxyphenyl CO CH.sub.3 CH.sub.2 CH.sub.32.405 2-carbomethoxyphenyl CO CH.sub.3 CH(CH.sub.3).sub.22.406 2-carbomethoxyphenyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.407 2-carbomethoxyphenyl CO CH.sub.3 CH.sub.2 CCH2.408 2-carbomethoxyphenyl CO CH.sub.3 CH.sub.2 Ph2.409 2-carbomethoxyphenyl SO.sub.2 CH.sub.3 CH.sub.32.410 2-carbethoxyphenyl CO CH.sub.3 CH.sub.32.411 2-carbethoxyphenyl SO.sub.2 CH.sub.3 CH.sub.32.412 2-(N,N-dimethylcarb- CO CH.sub.3 CH.sub.3 amido)phenyl2.413 2-pyridyl CO CH.sub.3 CH.sub.32.414 3-pyridyl CO CH.sub.3 CH.sub.32.415 2-fluoro-3-pyridyl CO CH.sub.3 CH.sub.32.416 2-chloro-3-pyridyl CO CH.sub.3 CH.sub.32.417 4-chloro-3-pyridyl CO CH.sub.3 CH.sub.32.418 4-pyridyl CO CH.sub.3 CH.sub.32.419 5-pyrimidyl CO CH.sub.3 CH.sub.32.420 1-naphthyl CO CH.sub.3 CH.sub.32.421 2-naphthyl CO CH.sub.3 CH.sub.32.422 2-quinolinyl CO CH.sub.3 CH.sub.32.423 3-quinolinyl CO CH.sub.3 CH.sub.32.424 2-methyl-4-quinolinyl- CO CH.sub.3 CH.sub.32.425 3,7-dichloro-8-quino- CO CH.sub.3 CH.sub.3 linyl2.426 1-methyl-2-pyrrolyl CO CH.sub.3 CH.sub.32.427 2-furanyl CO CH.sub.3 CH.sub.32.428 3-methyl-2-furanyl CO CH.sub.3 CH.sub.32.429 5-bromo-2-furanyl CO CH.sub.3 CH.sub.32.430 5-methyl-2-furanyl CO CH.sub.3 CH.sub.32.431 3-furanyl CO CH.sub.3 CH.sub.32.432 2,5-dimethyl-3-furanyl CO CH.sub.3 CH.sub.32.433 2,4,5-trimethyl-3- CO CH.sub.3 CH.sub.3 furanyl2.434 2-thienyl CO CH.sub.3 CH.sub.32.435 2-thienyl CO CH.sub.3 CH.sub.2 CH.sub.32.436 2-thienyl CO CH.sub.3 CH(CH.sub.3).sub.22.437 2-thienyl CO CH.sub.3 CH.sub.2 CHCH.sub.22.438 2-thienyl CO CH.sub.3 CH.sub.2 CCH2.439 2-thienyl CO CH.sub.3 CH.sub.2 Ph2.440 3-chloro-2-thienyl CO CH.sub.3 CH.sub.3 3.24(s)3H;3.60(s) 3H;7.32;7.56;7.64; 7.87;each(d) 1H; I=4Hz2.441 5-methyl-2-thienyl CO CH.sub.3 CH.sub.32.442 3-thienyl CO CH.sub.3 CH.sub.32.443 4-chloro-3-thienyl CO CH.sub.3 CH.sub.3 168-1712.444 1-methyl-5-pyrazolyl CO CH.sub.3 CH.sub.32.445 1-methyl-4-pyrazolyl CO CH.sub.3 CH.sub.32.446 1-methyl-2-imidazolyl CO CH.sub.3 CH.sub.32.447 5-isoxazolyl CO CH.sub.3 CH.sub.32.448 4-isoxazolyl CO CH.sub.3 CH.sub.32.449 3-isopropyl-5-isoxa- CO CH.sub.3 CH.sub.3 zolyl2.450 3-methyl-4-isoxazolyl CO CH.sub.3 CH.sub.32.451 4-isothiazolyl CO CH.sub.3 CH.sub.3__________________________________________________________________________
USE EXAMPLES
The action of the 5-amino-6-pyridazone derivatives I on the growth of test plants is illustrated in the following greenhouse experiments.
The vessels employed were plastic flowerpots having a volume of 300 cm.sup.3 and filled with a sandy loam containing about 3.0% humus. The seeds of the test plants were sown separately, according to species.
For postemergence treatment, either plants which had been sown in the pots and grown there were selected, or they were cultivated separately as seedlings and transplanted to the pots a few days before being treated. The plants were grown, depending on growth form, to a height of 3 to 15 cm before being treated with the active ingredients, which were suspended or emulsified in water as vehicle, and sprayed through finely distributing nozzles. The application rate for postemergence treatment was 0.25 kg/ha.
The pots were set up in the greenhouse, species from warmer climates in warmer areas (20.degree. to 35.degree. C.) and species from moderate climates at 10.degree. to 20.degree. C. The experiments were run for from 2 to 4 weeks. During this time the plants were tended and their reactions to the various treatments assessed. The assessment scale was 0 to 100, 100 denoting nonemergence or complete destruction of at least the visible plant parts, and 0 denoting no damage or normal growth.
The plants used in the greenhouse experiments were Chenopodium album, Stellaria media and Triticum aestivum.
The compounds 1.036, 1.039 and 1.065, applied postemergence at a rate of 0.250 kg/ha, combated unwanted plants extremely well and were well tolerated by wheat.
The compound 1.123, applied postemergence at a rate of 0.125 kg/ha, combated unwanted plants very well and was well tolerated by wheat.

Number	Name	Date
3210353	Reicheneder et al.	Oct 1965
3222159	Reicheneder et al.	Dec 1965
3420819	Nakagome et al.	Jan 1969
3652562	Reichender	Mar 1972
3671525	Reicheneder	Jun 1972
4077797	Fischer et al.	Mar 1978

Number	Date	Country
600532	Nov 1945	GBX
871674	Jun 1961	GBX

5-amino-6-pyridazone derivatives, their preparation and herbicidal mixtures containing these derivatives

Information

Patent Number

Date Filed

Date Issued

Inventors

Examiners

CPC

US Classifications

Field of Search

US

International Classifications

Abstract

Description

Claims

Priority Claims (1)

US Referenced Citations (6)

Foreign Referenced Citations (2)