Thia (oxa) diazole derivatives

The present invention relates to thia (oxa) diazole derivatives, herbicidal compositions in the form of mixture of such compound(s) with inert carrier(s), and processes for the production of such compounds.
In many cases of agricultural or horticultural cultivation, many kinds and amount of herbicides have come to be used for weed control in order to save the labor of removing weeds in the fields, however, in some occasion, phytotoxicity of herbicides may injure crops, or herbicides remaining in the field may cause environmental pollution.
Consequently, chemicals possessing greater efficacy and higher safty to mammal have been awaited to be developed.
3H-thiazolo-(2,3-c)-1,2,4-thiadiazole having the following formula: ##STR2## which are similar to but different from the compounds of the present invention at the point that it has double bond on thiazole ring have been reported on J. Org. Chem. 1975 40 (18) 2600-2604.
Also, compounds having the following formula and a process for the preparation thereof: ##STR3## wherein r.sub.1 is H, CH.sub.3 S-- or CH.sub.3 SO--, and r.sub.2 is H, or Cl, are described together with their medical fungicidal activity in J. Pharm. Sci. 1979, 68 (2) 182-185.
The Inventors of this invention, studied many thia-diazole derivatives in order to find a compound having herbicidal activity. As a result, they found that a group of compounds having the following partial structure formula: ##STR4## had herbicidal activity and exhibited selectivity on some crops, though said known compounds having doble bond(s) on the thiazole ring contained in the thiazolo (2,3-C) 1,2,4-thiadiazole ring do not have herbicidal activity.
The inventors, further, carried out investigation about the relation between the structure of the condensed ring of the compounds having the following partial structure formula: ##STR5## and the herbicidal activity thereof.
As the results, they found that almost all of the compounds having the condensed ring in the formula (II) wherein X represents ##STR6## and Y represents S, or O exhibited the excellent herbicidal activity.
On said condensed ring, substituent(s) of hydroxy, C.sub.1-8 hydrocarbon which may be substituted by halogen, C.sub.1-8 hydrocarbon-oxy or C.sub.1-8 hydrocarbon-thio, C.sub.1-8 hydrocarbon-carbonyloxy, C.sub.1-8 hydrocarbon-oxycarbonyl or C.sub.1-8 alkylidene, wherein hydrocarbon means and includes linear, branched or cyclic alkyl, alkenyl or alkynyl; or aryl aralkyl or alkylaryl, are preferred. For the substituents, it looks like the too bulky ones tend to decrease the herbicidal activity.
The inventors conducted further extensive investigation on the relation between the substituent(s) on the phenyl radical (right part of the formula (II) and herbicidal activity and selectivity thereof.
In order to easily explain in detail of said substituents, said substituted phenyl radical is shown as ##STR7##
As the results of the investigation, they found that a substituted phenyl radical of the formula ##STR8## which is explained in detail in the followings, exhibited herbicidal activity and selectivity by joining with the residue of the condensed ring of formula (III) as below: ##STR9## wherein
R represents same or different substituent(s) selected from the group consisting of halogen, nitro, cyano, --G--R.sup.1, ##STR10## di-C.sub.1-8 hydrocarbon-sulfamoyl and --L; and
n represents an integer of 1 to 5; and
wherein G represents ##STR11## in which r.sup.10 represents hydrogen or C.sub.1-8 hydrocarbon radical; and
R.sup.1 represents hydrogen, ##STR12## heterocyclic radical containing oxygen or nitrogen or --T; and
K represents oxygen or sulfur; and
R.sup.2 represents hydrogen, metal corresponding to one valency, C.sub.1-8 alkylidene amino or --U; and
each of R.sup.3 and R.sup.4 represents hydrogen, C.sub.1-8 hydrocarbon radical, or C.sub.1-8 hydrocarbon-oxy; and
R.sup.5 represents C.sub.1-8 hydrocarbon radical which may be substituted by hydrocabon-oxy; and
R.sup.6 represents hydrogen, or C.sub.1-8 hydrocarbon radical, which may be substituted by C.sub.1-8 hydrocarbon-oxycarbonyl; and
R.sup.7 represents hydrogen or C.sub.1-8 hydrocarbon radical; and
--L represents C.sub.1-8 hydrocarbon radical which may be substituted by halogen, hydroxy, cyano, ##STR13## C.sub.1-8 hydrocarbon-oxy, C.sub.1-8 hydrocarbon-carbonyloxy or ##STR14## and wherein each of r.sup.11, r.sup.12 and r.sup.13 represents C.sub.1-8 hydrocarbon radical; and
r.sup.14 represents C.sub.1-12 hydrocarbon radical; and
r.sup.15 represents C.sub.1-12 hydrocarbon radical which may be substituted by halogen or C.sub.1-8 hydrocarbon-oxycarbonyl; and
each of r.sup.16 and r.sup.17 represents hydrogen or C.sub.1-8 hydrocarbon radical; and
--T represents C.sub.1-16 hydrocarbon radical which may be substituted by halogen, nitro, cyano, --Q--r.sup.21, C.sub.1-8 hydrocarbon-carbonyloxy, tri-C.sub.1-8 alkylsilyl, ##STR15## or heterocyclic radical containing nitrogen; and
--U represents C.sub.1-12 hydrocarbon which may be substituted by cyano, C.sub.1-8 hydrocarbon-oxycarbonyl, C.sub.1-8 hydrocarbon-oxy, C.sub.1-8 hydrocarbon-thio, tri-C.sub.1-8 alkylsilyl or --O(CH.sub.2).sub.g --.sub.h Or.sup.28 ; and
r.sup.18 represents hydrogen, metal corresponding to one valency or C.sub.1-10 hydrocarbon radical; and
each of r.sup.19 and r.sup.20 represents C.sub.1-8 hydrocarbon radical:
wherein
Q represents --O-- or --S(O).sub.k -- (k=0, 1 or 2); and
r.sup.21 represents hydrogen or C.sub.1-12 hydrocarbon radical, which may be substituted by C.sub.1-8 hydrocarbon-oxy, C.sub.1-8 hydrocarbon-oxycarbonyl, halogen, nitro or methylendioxy, or C.sub.1-8 hydrocarbon-carbamoyl; and
W represents oxygen or sulfur; and
r.sup.22 represents hydrogen, metal corresponding to one valency, C.sub.1-8 alkylidene amino, or C.sub.1-16 hydrocarbon radical which may be substituted by halogen, C.sub.1-12 hydrocarbon-oxy, C.sub.1-12 hydrocarbon-thio, C.sub.1-8 hydrocarbon-carbonyl, C.sub.1-8 hydrocarbon-oxy-carbonyl-C.sub.1-8 hydrocarbon-thio, heterocyclic radical containing oxygen (which may be substituted by C.sub.1-8 hydrocarbon radical) tri-C.sub.1-8 alkylsilyl or cyano; and
Z represents oxygen or sulfur; and
each of r.sup.23 and r.sup.24 represents hydrogen, C.sub.1-8 hydrocarbon-oxy, C.sub.1-8 hydrocarbon-carbamoyl, C.sub.1-12 hydrocarbon radical, which may be substituted by C.sub.1-8 hydrocarbon-oxy or C.sub.1-8 hydrocarbon-oxycarbonyl; and
r.sup.25 represents C.sub.1-8 hydrocarbon radical; or heterocyclic radical containing nitrogen; and
r.sup.26 represents hydrogen, C.sub.1-8 hydrocarbon radical or C.sub.1-8 hydrocarbon-carbonyl which may be substituted by halogen; and
r.sup.27 represents amino, or C.sub.1-8 hydrocarbon radical; and
g represents an integer of 1 to 5; and
h represents an integer of 2 to 10, and
r.sup.28 represents C.sub.1-8 hydrocarbon radical:
In the course of said investigation, the inventors found that the phenyl radical substituted by halogen at 4-position gave high herbicidal activity to the compound and said phenyl radical substituted by halogen having --O(or S)--T or --COK--U (T, K and U have the same meaning as above-mentioned) at 3 or 5-position gave higher herbicidal activity, and further 2--F--4--Cl--5--O(or S)--T or 2--F--4--Cl--5--COK--U phenyl radical created the highest grade herbicidal activity within this invention, by joining with said condensed ring (III).
According to the first aspect of the present invention, there is provided a compound having the formula: ##STR16## wherein X represents --D--E--; and ##STR17##
each of r.sup.1 to r.sup.9 : hydroxy, C.sub.1-8 hydrocarbon radical which may be substituted by halogen, C.sub.1-8 hydrocarbon-oxy or C.sub.1-8 hydrocarbon-thio, C.sub.1-8 hydrocarbon-carbonyloxy or C.sub.1-8 hydrocarbon-oxycarbonyl, and r.sup.1, r.sup.2, r.sup.3, r.sup.4, r.sup.5, r.sup.6, r.sup.7, r.sup.8 and r.sup.9 may form ring(s) or C.sub.1-8 alkylidene(s) by joining each other.
Y represents ##STR18## and each of R and n represents as same as above-mentioned.
In this invention and in the claims of this invention, the word "hydorcarbon" or "hydrocarbon radical" means and includes linear, branched or cyclic alkyl, alkenyl or alkynyl; or aryl, aralkyl or alkylaryl. And "heterocyclic radical containing nitrogen means heterocyclic radical containing nitrogen in which oxygen and/or sulfur atom(s) may be contained, and "heterocyclic radical containing oxygen" means hetrocyclic radical containing oxygen in which nitrogen atom(s) may be contained.
According to the second aspect of the present invention there is provided a herbicidal composition comprising an inert carrier and an effective amount of the compound having the formula (IV).
The compounds of the present invention have little phytotoxicities to the crops such as corn, wheat, soybeans, peanuts, alfalfa, etc., while they possesses superior herbicidal activity against wide varieties of weeds such as common lambsquater, redroot pigweed, flatsedge, etc., irrespective of their growth stage. Particularly, the compounds show higher herbicidal activity in post emergence treatment.
The group of compounds having the formula (IV), in which X represents --CH.sub.2 -- and Y represents S and (R)n represents 2--F--4--Cl 5-substituted by alkoxycarbonylalkoxy, alkoxycarbonylalkoxylcarbonyl or alkoxycarbonylalkylthio, exhibited the highest herbicidal activity and selectivity for soybeans in post emergence treatment.
The compounds also exhibit high selectivity on rice plant and high herbicidal activity against barnyardgrass, monochoria, smallflower unbrella sedge, etc., regardless of their growth stage. Particularly, compounds having 2--F--4--Cl--5--C.sub.1-8 alkynyloxyphenyl radical exhibit higher selectivity and activity.
Further, they can be applied for the control of the weeds in orchards, lawn, roadway sides, vacant lots, etc.
According to a third aspect of the present invention, there is provided a process for the preparation of the compound of the formula (IV), comprising the step of reaction is illustrated by the following equation.
1. in case Y being sulfur and X being E (5 membered ring): ##STR19##
A compound having the formula (V) is reacted with a compound having the formula (VI) in an inert solvent, for example, ether, methylene dichloride, chloroform, ethyl acetate, for 0.5-10 hours at a temperature from -50.degree. C. to 50.degree. C. The obtained compound having the formula (VII) rearranges comparatively easily into the thio urea derivative having the formula ##STR20## when heated in the solvent.
Because of such unstability, it is desirable to be subjected to the following reaction without isolation.
Ring formation is carried out by using oxidizing agent in an organic solvent. As the organic solvent, a general inert solvent such as methylene dichloride, chloroform, N,N-dimethylformamide, ethyl acetate can be used.
At the condensation reaction of ring formation, acid binder(s) may be effectively used according to the kind of oxidizing agent. As the acid binder, an organic base such as triethylamine, pyridine, dimethyl aniline, or an inorganic base such as caustic soda, sodium carbonate, can be use. As the oxidizing agent, bromine, chlorine, sodium hypochlorite or the like are used. In case at least one of R being hydroxy, iodine is preberable as the oxidizing agent.
The compound having the formula (IV)' thus produced may be obtained by a usual procedure of separation and then purified by a conventional purifying procedure such as recrystallization, column chromatography etc.
2. in case Y being oxygen: ##STR21##
The reaction is carried out in the presence of organic or inorganic base in an inert solvent for one (1) to several tens of hours at a temperature from -20.degree. C. to 50.degree. C. As the base, triethylamine, pyridine, sodium carbonate etc. can be used, and as the solvent, methylene dichoride, chloroform etc. can be used.
The compound having the formula (IV)" thus produced may be obtained by a usual procedure of separation and then purified by a conventional purifying procedure such as recrystallization, column chromatography etc.
3. in case Y being sulfur: ##STR22## The reaction is carried out in the presence of organic or inorganic base in an inert solvent for one (1) to 10 hours at a temperature from -20.degree. C. to 50.degree. C. As the base, triethylamine, sodium carbonate, etc. can be used, and as the solvent methylene dichloride, chloroform, etc. can be used. The compound obtained having the formula (IV)'" thus produced may be obtained by a usual procedure of separation and then purified by a conventional purifying procedure such as recrystallization, column chromatography, etc.
The starting material having the formula (XII) can be prepared by chlorination of the corresponding isothiocyanate, and normally, the obtained compound is used to the following reaction without being isolated.
4. in case Y or E being SO, the compound is obtained by oxidation of the corresponding sulfur compound.
And the present compound is also obtainable by the following equation: ##STR23##
Further, owing to the difference of substituent(s) shown by --(R)n, a proper reaction is selected from following equations to prepare the compounds of this invention:
a. in case --GR.sup.1 type (R.sup.1 is not hydrogen): ##STR24##
b. in case ##STR25## type (R.sup.2 is not hydrogen): ##STR26##
c. in case --NH.sub.2 type (G: nitrogen, and r.sup.10 and R.sup.1 : hydrogen): ##STR27##
d. in case --SR.sup.1 type (--G: S): ##STR28##
e. in case ##STR29## type: ##STR30##
e'. in case ##STR31## type (R is not hydrogen): ##STR32##
f. in case ##STR33## the compound is obtainable by similar reaction to the above.
The chemical structure of the compound obtained was determined by means of NMR spectrum, Mass spectrum and IR spectrum.

The following Examples illustrate the invention.
EXAMPLE 1
3-(5-acetonyloxy-4-chloro-2-fluorophenylimino)-5,6-dihydro-6,6-dimethyl-3H-thiazolo(2,3-C)(1,2,4)thiadiazole
(Compound No. 232) ##STR34##
1.5 g of 2-amino-5,5-dimethyl-2-thiazoline was dissolved in 15 ml of methylene dichloride. To this was then added dropwise, under stirring at 0.degree. C., a solution of 3.0 g of 2-fluoro-4-chloro-5-acetonyloxyphenylisothiocyanate in 15 ml of methylene dichloride. After it was then stirred for one hour, the reaction solution was fed with 0.72 g pyridine, and while being ice-cooled, to the solution was added dropwise a solution of 1.7 g of bromine in 10 ml of methylene dichloride. The reaction solution was further stirred for 30 minutes, at the end of which the solution was washed with 30 ml of water, with 30 ml of 5% NaOH solution, and with 30 ml of water, in the order given. The methylene dichloride layer was dried over anhydrous magnesium sulfate. The same layer was filtered and then concentrated. The residue was purified by silica gel column chromatography to give 2.5 g of the objective product. (m.p. 107.degree.-108.degree. C.)
EXAMPLE 2
3-((4-chloro-2-fluoro-5-(1-ethoxycarbonylethoxy)phenylimino))-5,6-dihydro-6-methyl-3H-oxazolo(2,3-C)(1,2,4)thiadiazole
(Compound No. 359) ##STR35##
9.60 g of 4-chloro-2-fluoro-5-(1-ethoxycarbonylethoxy)phenyl isothiocyanate was dissolved in 100 ml of chloroform. The solution was then cooled to -10.degree. C. and was fed with 3.80 g of 5-methyl-2-amino-2-oxazoline. The reaction solution was stirred for five hours at 0.degree. C., and then a solution of 5.06 g of bromine in 30 ml of chloroform was added dropwise at -10.degree.-0.degree. C. After the dropwise addition ended, the reaction solution was washed with a 50 ml aqueous solution of 1N-NaOH, then with 50 ml water, and was dried over anhydrous magnesium sulfate. After magnesium sulfate was filtered off, chloroform was removed in vacuo. The residue obtained was purified by column chromatography to give 10.04 g of objective product. (n.sub.D.sup.26 1.5870)
EXAMPLE 3
3-(4-chloro-5-(1-cyanoethoxy)-2-fluorophenylimino)-6,7-dihydro-6-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole
(Compound No. 587 ) ##STR36##
3.25 g of 2-amino-4-methyl-1-pyrroline hydrochloride was suspended to 20 ml of chloroform. While it was ice-cooled, to the suspension was add dropwise a solution of 1 g of caustic soda in 60 ml of water. After 10 minutes of stirring, the reaction mixture, while it was ice-cooled, was further fed dropwise with a solution of 5.6 g of 2-fluoro-4-chloro-5-(1-cyanoethoxy)phenylisothiocyanate in 20 ml of chloroform. After stirring it for three hours at room temperature, the reaction solution was fed dropwise with a solution of 3.15 g of bromine in 10 ml of chloroform under ice-cooling. After stirring at room temperature for one hour, the reaction solution was washed with 30 ml of water. The chloroform layer was dried over anhydrous magnesium sulfate and was then filtered. The filtrate was concentrated and the residue was purified by silica gel column chromatography to give 5.0 g of the objective product. (m.p. 93.degree.-95.degree. C.)
EXAMPLE 4
3-(4-chloro-5-(1-ethoxycarbonylethoxy)-2-fluorophenylimino)-5,6-dihydro-7-methyl-3H-imidazo(2,1-C)(1,2,4)thiadiazole
(Compound No. 675) ##STR37##
1.56 g of 2-amino-3-methyl-1-imidazoline hydrobromide was suspended in 10 ml of chloroform. To this suspension was then added dropwise, under ice-cooled conditions, a solution of 0.37 g of caustic soda in 2 ml of water. After cooling it down to -15.degree. C., the reaction solution was fed dropwise with a solution of 2.31 g of 2-fluoro-4-chloro-5-(1-ethoxycarbonylethoxy)phenylisothiocyanate in 10 ml of chloroform. After stirring it for one hour at -15.degree. C., the reaction solution was again fed dropwise with a solution of 1.2 g of bromine in 10 ml of chloroform. After another hour of stirring the reaction solution was washed with 30 ml of water and the chloroform layer was dried over anhydrous magnesium sulfate before it was concentrated. The residue obtained was purified by silica gel column chromatography to give 1.48 g of the objective product. (m.p. 75.degree.-78.degree. C.)
EXAMPLE 5
3-(4-chloro-2 -fluoro-5-isopropoxyphenylimino)-5,6-dihydro-6,6-dimethyl-3H-thiazolo(2,3-C)(1,2,4)oxadiazole
(Compound No. 129) ##STR38##
To a solution of 5,5-dimethyl-2-hydroxyiminothiazolidine (1.5 g) and triethylamine (3 g) in chloroform (30 ml) was added dropwise a solution of 4-chloro-2-fluoro-5-isopropoxyphenylisocyanide dichloride (2.8 g) in chloroform (10 ml) at 5.degree.-10.degree. C., and the mixture was stirred at room temperature overnight. The reaction mixture was washed with water, dried over anhydrous magnesium sulfate. Chloroform was removed in vacuo, and the residue was purified by silica gel column chromatography to give 0.8 g of the objective product.
(n.sub.D.sup.20 1.5760)
EXAMPLE 6
3-(4-chloro-5-(1-ethoxycarbonyl ethoxy)-2-fluorophenylimino)-5,6,7,8-tetrahydro-(1,2,4)thiadiazole-(4,3-a)pyridine
(Compound No. 679) ##STR39##
The solution of 4-chloro-5-(1-ethoxycarbonylethoxy)-2-fluoro phenyl isothiocyanate (2.0 g) in carbon tetrachloride (10 ml) was added dropwise at 0.degree. C. with stirring to chlorine (0.9 g) in carbon tetrachloride (25 ml).
After stirring at room temperature for 16 hours, the reaction mixture was concentrated under a reduced pressure.
The residue was dissolved in chloroform, and 2-amino-3,4,5,6-tetrahydropyridine (0.51 g) and triethylamine (1.10 g) was added and stirred at 0.degree. C. for 2 hours.
Water was added, and the mixture was extracted with chloroform, dried over anhydrous magnesium sulfate, and concentrated.
The residue was purified by silica gel column chromatography (hexane-ethyl acetate 2:1) to give 0.18 g of the objective product. (m.p. 79.degree.-80.5.degree. C.)
EXAMPLE 7
3-(4-chloro-2-fluoro-5-(0,0-dimethylthio phosphoryloxy)phenylimino)-5,6-dihydro-6-methyl-3H-oxazolo(2,3-C)(1,2,4)thiadiazole
(compound No. 518) ##STR40##
0.6 g of 3-(4-chloro-2-fluoro-5-hydroxyphenylimino)-5,6-dihydro-6-methyl-3H-oxazolo(2,3-C)(1,2,4)thiadiazole and 0.27 g of anhydrous potassium carbonate were added to 40 ml of acetone. At room temperature, the reaction solution was fed dropwise with 0.32 g of 0,0-dimethylthiophosphoryl chloride. The solution was heated under reflux for four hours, and was then cooled, thereupon solid matter was filtered off and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography to give 0.3 g of the objective product. (m.p. 77.degree.-80.degree. C.)
EXAMPLE 8
3-(4-chloro-2-fluoro-5-(1-ethylthiocarbonylethoxy)phenylimino)-5,6-dihydro-6-methyl-3H-oxazolo(2,3-C)(1,2,4)thiadiazole
(Compound No. 410) ##STR41##
1.00 g of 3-(4-chloro-2-fluoro-5-(1-carboxyethoxy)phenylimino)-5,6-dihydro-6-methyl-3H-oxazolo(2,3-C)(1,2,4)thiadiazole was dissolved in 30 ml of chloroform. Under stirring at -10.degree. C., the solution was fed with 0.30 g of triethylamine and 0.3 g of methyl chlorocarbonate. After five minutes elapsed, the solution was further fed with 0.20 g of ethyl mercaptan and was stirred for three hours at 0.degree. C. The reaction solution was poured into 50 ml dilute hydrochloric acid to separate the chloroform layer out. The chloroform layer was washed with 30 ml of 1N-NaOH, then with 30 ml of water, and was dried over anhydrous magnesium sulfate. When this was accomplished, magnesium sulfate was filtered off, and the filtrate was concentrated. The residue was purified by column chromatography and the objective product was obtained as an oil in an amount of 0.5 g.
(n.sub.D.sup.26 1.6080)
EXAMPLE 9
3-(4-chloro-2-fluoro-5-(2-hydroxyimino-propoxy)phenylimino)-5,6-dihydro-6,6-dimethyl-3H-thiazolo(2,3-C)(1,2,4)thiadiazole
(Compound No. 191) ##STR42##
0.9 g of 3-(5-acetonyloxy-4-chloro-2-fluorophenylimino)-5,6-dihydro-6,6-dimethyl-3H-thiazolo(2,3-C)(1,2,4)thiadiazole and 0.25 g of hydroxyamine hydrochloride were dissolved in 10 ml of ethanol. The solution obtained was fed dropwise under stirring at room temperature with a solution of 0.14 g of caustic soda in 10 ml of water. After one hour of stirring at room temperature, the reaction solution was poured into 60 ml of water and the crystals that precipitated were filtered and washed with water to give 0.8 g of the objective product. (m.p. 152.degree.-156.degree. C.)
EXAMPLE 10
3-(4-chloro-5-fluoro-5-(1-(1-phenyl-2-propynyloxycarbonyl)ethoxy phenylimino)-6,7-dihydro-6-methyl-3H,5-pyrrolo(2,1-C)(1,2,4)thiadiazole
(Compound No. 610) ##STR43##
1.00 g of 3-(4-chloro-2-fluoro-5-(1-carboxyethoxy)phenylimino)-6,7-dihydro-6-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole was added to 10 ml of benzene, to which were then added under stirring at room temperature 0.83 g of thionyl chloride and a drop of pyridine. 20 hours of heating under reflux produced a corresponding acid chloride. The low-boiling component was distilled off under reduced pressure. The residue was again fed with 10 ml of benzene, and further at room temperature with 0.73 g of 1-phenyl-2-propyne-1-ol and with 0.44 g of pyridine, and was stirred for four hours. The reaction solution was poured into water to separate the benzene layer. The water layer was extracted with 30 ml of ethyl acetate. The organic layer, was combined, washed with 20 ml of 5% hydrochloric acid water, with 20 ml of 5% sodium hydrogen carbonate, and with 20 ml of saline solution in this order. After it was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure and the residue was purified by column chromatography to give 0.4 g of the objective product.
(n.sub.D.sup.21 1.5957)
EXAMPLE 11
3-(4-chloro-5-(1-thiocarbamoylethoxy)-2-fluorophenylimino)-6-6,7-dihydro-6-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole
(Compound No. 614) ##STR44##
1 g of 3-(4-chloro-5-(1-cyanoethoxy)-2-fluorophenylimino)-6,7-dihydro-6-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole and 0.3 g of triethylamine were dissolved in 2 ml of pyridine. To the solution, while it was ice-cooled, was gradually introduced hydrogen sulfide. The reaction mixture was TLC-analyzed with the progress of time and the reaction stopped as soon as raw material spot disappeared. The reaction liquid was fed with 10 ml of ethyl acetate and was washed with dilute hydrochloric acid. The ethylacetate layer was rinsed, dried over anhydrous magnesium sulfate filtered, and, concentrated under reduced pressure. The residue was purified by silicagel column chromatography to give 0.5 g of the objective product. (m.p. 134.5.degree.-135.degree. C.)
EXAMPLE 12
3-(4-chloro-5-(1-(N-chloroacetoxyamidino)ethoxy)-2-fluorophenylimino)-6,7-dihydro-6-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole
(Compound No. 577) ##STR45##
1 g of 3-(4-chloro-5-(1-cyanoethoxy)-2-fluorophenylimino)-6,7-dihydro-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole was dissolved in ethanol, to which was then added dropwise under stirring at room temperature a solution of 0.23 g hydroxylamine hydrochloride and 0.23 g anhydrous potassium carbonate in 3 ml of water. This reaction mixture was heated under reflux for two hours, at the end of which it was poured into ice-cooled water. The crystals that precipitated out were filtered, rinsed, and then dried, and 0.9 g of crude amidoxime was obtained. 0.9 g of crude amidoxime and 0.25 g of triethylamine were dissolved in 10 ml of THF, to which was then added dropwise, under ice-cooled conditions, a solution of 0.27 g of chloroacetyl chloride in 5 ml of THF. After it was stirred for one hour at 50.degree. C., the reaction solution was charged with 40 ml of water and 40 ml of chloroform. The chloroform layer was dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue obtained was then recrystallized from benzene to give 0.4 g of the objective product. (d.p. 128.degree.-129.degree. C.)
EXAMPLE 13
3-(5-carboxy-4-chloro-2-fluorophenylimino)-6,7-dihydro-6-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole
(Compound No. 561) ##STR46##
To a solution of 3-(4-chloro-2-fluoro-5-ethoxycarboxylphenylimino)-6,7-dihydro-6-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole (8.5 g) in tetrahydrofuran (60 ml) and methanol (30 ml) was added a aqueous solution (50 ml) of sodium hydroxide (2.9 g) at room temperature, and the mixture was stirred at 50.degree. C. for 0.5 hour. The reaction mixture was acidified with 1N hydrochloric acid, and concentrated to half volume. The residue was extracted with ethylacetate, washed with water, dried over anhydrous magnesium sulfate, and concentrated. The residue was crystallized from ether-n-hexane to give 7.5 g of the objective compound. (m.p. 210.degree.-213.degree. C.)
EXAMPLE 14
3-(4-chloro-5-(1-ethoxycarbonylethoxycarbonyl)-2-fluorophenylimino)-6,7-dihydro-6-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole
(Compound No. 683) ##STR47##
To a solution of 3-(5-carboxy-4-chloro-2-fluorophenylimino)-6,7-dihydro-6-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole (0.7 g) in acetonitrile (10 ml), there were added anhydrous potassium carbonate (0.3 g) and 2-bromopropionic acid ethyl ester (0.4 g) and the mixture was heated at reflux for 4 hours. After being allowed to cool to room temperature, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. The residue was recrystallized from ether-hexane to give 0.8 g of the objective product. (m.p. 83.degree.-84.degree. C.)
EXAMPLE 15
3-(4-chloro-2-fluoro-5-tert-butoxycarbonyl phenylimino)-6,7-dihydro-6-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole
(Compound No. 537) ##STR48##
To a solution of 3-(5-carboxy-4-chloro-2-fluorophenylimino)-6,7-dihydro-6-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole (3 g) in benzene (20 ml), there was added thionyl chloride 3.3 g), and the mixture was heated at reflux for 0.5 hour. The reaction mixture was concentrated under reduced pressure, the residue, which was dissolved in benzene (20 ml), was dropwise added to the suspension of potassium test-butoxide (2.1 g) in benzene (20 ml) at 5.degree.-10.degree. C. After stirring at room temperature for 2 hours, cold water was added to this reaction mixture. The benzene layer was washed with water, and dried over anhydrous magnesium sulfate. Benzene was removed in vacuo, and the residue was recrystallized from ether-n-hexane to give 1.5 g of the objective product. (m.p. 89.degree.-90.degree. C.)
EXAMPLE 16
3-(4-chloro-2-fluoro-5-(2-propynylamino)phenylimino)-5,6-dihydro-6,6-dimethyl-3H-thiazolo(2,3-C)(1,2,4)thiadiazole
(Compound No. 108) ##STR49##
To 3-(5-amino-4-chloro-2-fluorophenylimino)-5,6-dihydro-6,6-dimethyl-3H-thiazolo-(2,3-C)(1,2,4)thiadiazole (1.69 g) in ethanol (20 ml) was added anhydrous sodium carbonate (0.82 g) and 2-propynyl bromide (0.77 g).
The resultant mixture was refluxed for 19 hours. After being allowed to cool, water was added, and the mixture was extracted with chloroform, dried over anhydrous magnesium sulfate, and concentrated.
The residue was purified by silicagel column chromatography (benzenechloroform 2:1) to give 1.17 g of the objective product. (m.p. 117.degree.-117.5.degree. C.)
EXAMPLE 17
3-(5-amino-4-chloro-2-fluorophenylimino)-5,6-dihydro-6,6-dimethyl-3H-thiazolo-(2,3-C)(1,2,4)thiadiazole
(Compound No. 105) ##STR50##
3-(4-chloro-2-fluoro-5-nitrophenylimino)-5,6-dihydro-6,6-dimethyl-3H-thiazolo-(2,3-C)(1,2,4)thiadiazole (5.28 g) was dissolved in methyl ethyl ketone (40 ml), and acetic acid (1.96 g), iron powder (3.86 g), water (20 ml) was added.
The resultant mixture was stirred at room temperature for 30 minutes, and 70.degree. C. for 1.5 hours. After being allowed to cool 20% aqueous sodium hydroxide (20 ml) and ethyl acetate (40 ml) was added to the resultant mixture, followed by filtration on celite.
The organic layer was separated and the aqueous layer was extracted with chloroform, and the extracts were combined, dried over anhydrous magnesium sulfate and concentrated.
The residue was purified by silicagel solumn chromatography (benzene-CHCl.sub.3 1:6) to give 2.02 g of the objective product. (m.p. 141.degree.-142.degree. C.)
EXAMPLE 18
3-(4-chloro-2-fluoro-5-carboxymethylthiophenylimino)-6,7-dihydro-6-methyl-3H,5H-pyrrolo (2,1-C)(1,2,4)thiadiazole
(Compound No. 740) ##STR51##
To the solution of 2.0 g of 3-(4-chloro-2-fluoro-5-aminophenylimino-6,7-dihydro-6-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole in 5 ml of concentrated sulfuric acid and 50 ml of water was added 0.56 g of sodium nitrate in 5 ml of water at -5.degree.-0.degree. C. The reaction mixture was stirred for 30 minutes, then 0.1 g of urea was added to destroy excess sodium nitrite. 0.8 g of thiogycolic acid and 0.5 g of cupric carbonate in 10 ml of water was added to the reaction mixture at room temperature and stirred for one hour. The reaction mixture was extracted with ethyl acetate, organic layer was washed with water, dried over anhydrous magnesium sulfate and concentrated.
The residue was purified by silicagel column chromatography to obtain 0.5 g of the objective compound.
EXAMPLE 19
3-(4-chloro-2-fluoro-5-isopropoxycarbonylmethylthiophenylimino)-6-methyl-5,6,7,7a-tetrahydro-3H-pyrrolo(2,1-C)(1,2,4)thiadiazole
(Compound No. 707) ##STR52##
0.4 g of 3-(4-chloro-2-fluoro-5-carboxymethylthiophenylimino)-6-methyl-5,6,7,7a-tetrahydro-3H-pyrrolo(2,1-C)(1,2,4)thiadiazole, 0.22 g of isopropyl iodide, 0.15 g of anhydrous potassium carbonate and 10 ml of acetonitrile were mixed together and heated to reflux for 3 hours. After being allowed to cool the precipitate was filtered off. The filtrate was concentrated under reduced pressure. The residue was purified by silicagel column chromatography to obtain 0.2 g of the objective product. (m.p. 79.degree.-82.degree. C.)
EXAMPLE 20
Oxidation of 3-(4-chlorophenylimino)-6,6-dimethyl-5,6-dihydro-3H-thiazolo(2,3-C)(1,2,4)thiadiazole
(Compound No. 36 and 81) ##STR53##
To a solution of 3-(4-chlorophenylimino)-6,6-dimethyl-5,6-dihydro-3H-thiazolo(2,3-C)(1,2,4)thiadiazole (2.2 g) in dichloromethane (20 ml) was added a solution of m-chloroperbenzoic acid (3.0 g) in dichloromethane (20 ml) at room temperature. After stirring for 2 hours at room temperature, the reaction mixture was filtered. The filtrate was washed with 10% aqueous sodium hydroxide solution, dried over anhydrous magnesium sulfate and concentrated.
The residue was purified by silicagel column chromatography to obtain 0.6 g of 3-(4-chlorophenylimino)-6,6-dimethyl-5,6-dihydro-3H-thiazolo(2,3-C)(1,2,4)thiadiazole-2-oxide (m.p. 121.degree.-124.degree. C.) and 0.6 g of 3-(4-chlorophenylimino)-6,6-dimethyl-5,6-dihydro-3H-thiazolo(2,3-C)(1,2,4)thiadiazole-7-oxide. (m.p. 115.degree.-120.degree. C.)
Inclusive the above, each compound within the scope of this invention which can be prepared in analogous method(s) is tabulated in Table 1.
TABLE 1__________________________________________________________________________ poundCom- ##STR54## PropertiesPhysica lNo. X Y r.sup.1, r.sup.2, r.sup.3, r.sup.4 (R)n m.p.__________________________________________________________________________ .degree.C.1 S S 6,6-(CH.sub.3).sub.2 5-CF.sub.3 71-722 " " " 4-Cl, 5-CF.sub.3 103-1043 " " " 2-F, 4-Cl, 5-CH.sub.2 Cl 89-904 " " " 2-F, 4-Cl, 5-CH.sub.2 OCH.sub.3 80-835 " " " 2-F, 4-Cl, 5-CH.sub.2 OCOCH.sub.3 96-976 " " " 2-F, 4-Cl, 5-CH.sub.2 OH 169-1707 " " " 2-F, 4-Cl, 5-CHCHCOOC.sub.2 H.sub.5 89-918 " " " 2-F, 4-Cl, 5-CHNOC.sub.2 H.sub.5 n.sub.D.sup.22.5 1.63349 " " " 2-F, 4-Cl, 5-CHNOCH.sub.2 COOC.sub.2 H.sub.5 113-11410 " " " 2-F, 4-Cl, 5-COOC.sub.2 H.sub.4 OCH.sub.3 105-10711 " " " 2-F, 4-Cl, 5-COOC.sub.2 H.sub.5 108-10912 " " " 4-Cl, 5-COOC.sub.2 H.sub.5 74-7713 " " " 2-F, 4-Cl, 5-COO.sup.i C.sub.3 H.sub.7 76-7814 " " " 2-F, 4-Cl, 5-COOCH.sub.2 CCH 102-10315 " " " 2-F, 4-Cl, 5-COOCH.sub.2 COOC.sub.2 H.sub.5 n.sub.D.sup.27 1.593816 " " " 2-F, 4-Cl, 5-COOCH.sub.3 106-10717 " " " 2-F, 4-Cl, 5-COOH 239-24218 " " " 4-Cl, 5-COOH 221-22319 " " -- 4,5-Cl.sub.2 115- 11720 " " -- 3,5-Cl.sub.2 89-9121 " " 6,6-(CH.sub.3).sub.2 3,5-Cl.sub.2 145-14722 " " " 5-Cl 68-7023 " " " 4,5-Cl.sub.2 109-11024 " " " 3,5-Cl.sub.2, 4-OC.sub.2 H.sub.5 n.sub.D.sup.17.5 1.630125 " " " 2,4-F.sub.2, 5-Cl 103-103.526 " " " 2,3,4,5,6-F.sub.5 113.5-11527 " " " 2,5-F.sub.2, 4-Br 127-12828 " " " 2,4,5-F.sub.3 111-11229 " " " 2,5-F.sub.2, 4-Cl 133-13430 " " -- 4-Cl 114-11531 " " -- 4-CH.sub.3 102-10432 " " -- 2,4-Cl.sub.2 137-13933 " " -- 4-NO.sub.2 178-17934 " " -- 4-Br 138-14035 " " -- 2-Cl, 4-F 103-104.536 ##STR55## " 6,6-(CH.sub.3).sub.2 4-Cl 115-12037 S " 6-CH.sub.3 4-Cl 118-12238 " " " 4-Cl (HBr salt) 167-17039 " " " 2-F, 4-Cl 78-8040 " " 6,6-(CH.sub.3).sub.2 4-Cl 92-9441 " " " 4-Br 118-12042 " " " 4-CF.sub.3 112-11343 " " " 4-C.sub.3 H.sub.7 56-5744 " " " 2,4-Cl.sub.2 80-8245 " " " 2-Cl 74-7546 " " " ##STR56## 116-11847 " " " 4-F 88-9048 " " " 2-CF.sub.3, 4-Cl 106-10849 " " 6-CH.sub.3, 6-C.sub.2 H.sub.5 4-Cl 70-7150 " " 6-CH.sub.3, 6-C.sub.3 H.sub.7 4-Cl 162 dec.51 " " 6,6-(CH.sub.3).sub.2 4-OCF.sub.3 70-7152 " " " 2-CH.sub.3, 4-Cl 82-8353 " " " 2-F, 4-Cl 100-10254 " " " 2,4-F.sub.2 110-11155 " " " 2-OCH.sub.3, 4-Cl 137-13856 " " " 4-COOC.sub.2 H.sub.5 124-12557 " " " 4-Cl (HBr salt) 220-221 dec.58 " " " 4-NO.sub.2 153.5-154.559 " " " 2,4,6-Cl.sub.3 138-13960 " " " 2-F, 4-Br 98-9961 " " " ##STR57## 178-17962 " " " 4-Cl (CH.sub.3 SO.sub.3 H salt) 136-13863 " " " 4-Cl ((COOH).sub.2 salt) 121-12264 " " " 2-Cl, 4-F 102-10365 " " " 2,6-F.sub.2 91-9266 " " " 2,4,6-F.sub.3 86-8767 " " " 2,6-F.sub.2, 4-Br 103-10468 " " " 4-CH.sub.3 87-8869 " " " 2-Br, 4-CH.sub.3 130-13170 " " " 2-Br, 4-F 90-9171 " " " 4-OCH.sub.3 77-7972 " " " 2-Br, 4-NO.sub.2 151-15373 " " " 2-CH.sub.3, 4-Cl 77-7974 " " " 2,3-F.sub.2, 4-Br 156-15775 " " " 2-F, 4-OCH.sub.3 105-10776 " " " 2-OCH.sub.3, 4-F n.sub.D.sup.26.5 1.606977 " " " 2-F, 4-OCH.sub.2 CCH n.sub.D.sup.25 1.626978 " " " ##STR58## 134-13579 " " " ##STR59## n.sub.D.sup.25 1.577480 " " " 3-Cl, 4-F 72-7681 " ##STR60## " 4-Cl 121-12482 " S ##STR61## 4-Cl 105-10883 " " 6-CH.sub.2 SCH.sub.3 4-Cl 109.5-110.584 " " 6-iC.sub.3 H.sub.7 4-Cl 76.5-7985 " " " 2,4-Cl.sub.2 112-11386 " " 6-C.sub.2 H.sub.5 4-Cl 104-10787 " " " 2,4-Cl.sub.2 127-12988 " " " 2,4-F.sub.2 98-9989 " " " 4-I 103-10690 " " " 4-Br 104-10591 " " " 2-F, 4-Cl 91-9292 " " " 2-F, 4-Br 66-6793 " " 6-C.sub.3 H.sub.7 4-Cl 84-8594 " " 6-C.sub.4 H.sub.9 4-Cl n.sub.D.sup.31 1.642595 " " ##STR62## 4-Cl 124-12596 " " ##STR63## 2-Cl, 4-F 126-12997 " " " 4-Cl 111-11298 " " ##STR64## 4-Cl 107-10999 " " ##STR65## 4-Cl 107-110100 " " 5-CH.sub.3, (trans) 2-Cl, 4-F 78-82101 " " 6-iC.sub.3 H.sub.7 4-Cl 114-116102 " " 6,6-(CH.sub.3).sub.2 2-F, 4-Cl, 5-N(CH.sub.2 CCH).sub.2 141-141.5103 " " " ##STR66## 146.5-147.5104 " " " ##STR67## 94-97105 " " " 2-F, 4-Cl, 5-NH.sub.2 141-142106 " " " ##STR68## n.sub.D.sup.28.5 1.5981107 " " " 2-F, 4-Cl, 5-NHCH.sub.2 COOCH.sub.2 CHClCH.sub .2 Cl n.sub.D.sup.25 1.6031108 " " " 2-F, 4-Cl, 5-NHCH.sub.2 CCH 117-117.5109 " " " 2-F, 4-Cl, 5-NHCOC.sub.2 H.sub.5 170.5-174110 " " " 2-F, 4-Cl, 5-NHCOOCH.sub.3 111-114111 " " " 2-F, 4-Cl, 5-NO.sub.2 161.5-162112 " " " ##STR69## 134-135113 " " " ##STR70## 50-51114 " " " ##STR71## 250.degree. C. up115 " " " 2-F, 4-Cl, 5-OC.sub.2 H.sub.5 104-107116 " " " 2,4-Cl.sub.2, 5-OiCH.sub.3 H.sub.7 125-129117 " " " 2-F, 4-Br, 5-OiC.sub.3 H.sub.7 105-107118 " " " 2-F, 4-Cl, 5-OiC.sub.3 H.sub.7 n.sub.D.sup.21 1.6084119 " " " 2-F, 4-Cl, 5-OC.sub.3 H.sub.7 85-87120 " " " 2-F, 4-Cl, 5-OC.sub.4 H.sub.9 58-60121 " " " 2,4-Cl.sub.2, 5-OCF.sub.2 HCF.sub.2 H 104-106122 " " " ##STR72## 82-84123 " " " ##STR73## n.sub.D.sup.27 1.5975124 " " " ##STR74## n.sub.D.sup.24 1.5881125 " " " ##STR75## 80-82126 " " " ##STR76## n.sub.D.sup.28 1.5932127 " " " ##STR77## 95-96128 " " " ##STR78## n.sub.D.sup.28 1.5790129 " O " 2-F, 4-Cl, 5-O.sup.i C.sub.3 H.sub.7 n.sub.D.sup.20 1.5760130 " S " ##STR79## n.sub.D.sup.26.5 1.6093131 " " " ##STR80## 151-153132 " " " ##STR81## 55-57133 " " " ##STR82## n.sub.D.sup.28.5 1.6093134 " " " ##STR83## n.sub.D.sup.22 1.6020135 " " " ##STR84## n.sub.D.sup.24 1.6091136 " " " ##STR85## n.sub.D.sup.28 1.5798137 " " " ##STR86## n.sub.D.sup.28 1.6092138 " " " ##STR87## 96-99139 " " " ##STR88## 93-94140 " " " ##STR89## 152-154141 " " " ##STR90## 102-104142 " " " ##STR91## 110-112143 " " " ##STR92## 84-87144 " " " ##STR93## n.sub.D.sup.27 1.5739145 " " " ##STR94## 117-120146 " " 6-CH.sub.3 ##STR95## 158-160147 " " 6,6-(CH.sub.3).sub.2 ##STR96## 145-146148 " " " ##STR97## 52-54149 " " " ##STR98## 90-93150 " " " ##STR99## n.sub.D.sup.23 1.5912151 " " " ##STR100## n.sub.D.sup.22.5 1.5870152 " " " ##STR101## 84-85153 " " " ##STR102## 103-104154 " " " ##STR103## n.sub.D.sup.24.5 1.5545155 " " -- ##STR104## 84-86156 " " 6-CH.sub.3 ##STR105## 80-83157 " " 6.6-(CH.sub.3).sub.2 ##STR106## n.sub.D.sup. 20.5 1.5998158 " " " ##STR107## n.sub.D.sup.20 1.5870159 " " " ##STR108## n.sub.D.sup.26.5 1.5988160 " " " ##STR109## n.sub.D.sup.23 1.5903161 " " " ##STR110## n.sub.D.sup.17.5 1.5843162 " " " ##STR111## n.sub.D.sup.21 1.5838163 " " " ##STR112## 43-44164 " " " ##STR113## n.sub.D.sup.20.5 1.5777165 " " " ##STR114## 124-128166 " " " 2-F, (optical isomer) n.sub.D.sup.27 1.5670167 " " -- ##STR115## 111-113168 " " 6-CH.sub.3 ##STR116## 81-83169 " " 6,6-(CH.sub.3).sub.2 ##STR117## n.sub.D.sup.24 1.5971170 " " " ##STR118## n.sub.D.sup.27.5 1.5713171 " " " ##STR119## n.sub.D.sup.24 1.5784172 " " " ##STR120## 50-53173 " " " ##STR121## n.sub.D.sup.26 1.5941174 " " " ##STR122## n.sub.D.sup.29 1.5939175 " " " ##STR123## n.sub.D.sup.26 1.6002176 " " 6-CH.sub.3 ##STR124## 90-92177 " " 6,6-(CH.sub.3).sub.2 ##STR125## n.sub.D.sup.26 1.5885178 " " -- ##STR126## 163-165179 " " 6-CH.sub.3 ##STR127## 121-123180 " " 6,6-(CH.sub.3).sub.2 ##STR128## 203-205181 " " " ##STR129## 164-170182 " " " ##STR130## 44-46183 " " " ##STR131## n.sub.D.sup.26.5 1.6065184 " " " ##STR132## 73-75185 " " " ##STR133## 95-97186 " " 6-CH.sub.3 2-F, 4-Cl, 5-OCH(COOC.sub.2 H.sub.5).sub.2 n.sub.D.sup.29 1.5830187 " " 6,6-(CH.sub.3).sub.2 2-F, 4-Cl, OCH(COOC.sub.2 H.sub.5).sub.2 n.sub.D.sup.27.5 1.5820188 " " " ##STR134## n.sub.D.sup.22 1.6248189 " " " ##STR135## 124-126190 " " 6,6-(CH.sub.3).sub.2 ##STR136## n.sub.D.sup.26.5 1.5950191 " " " ##STR137## 152-156192 " " " 2-F, 4-Cl, 5-OCH.sub.2 CCCH.sub.3 98-99193 " " " 2-F, 4-Cl, 5-OCH.sub.2 CC.Cl 96-97194 " " -- 2-F, 4-Cl, 5-OCH.sub.2 CCH 116-117195 " " 6-CH.sub.3 2-F, 4-Cl, 5-OCH.sub.2 CCH 117-118196 " " 6,6-(CH.sub.3).sub.2 2-F, 4-Br, 5-OCH.sub.2 CCH 114-115197 " " " 2-F, 4-Cl, 5-OCH.sub.2 CCH 103-106198 " " " 2-F, 4,5-(OCH.sub.2 CCH).sub.2 104-105199 " " " 2,4-F.sub.2, 5-OCH.sub.2 CCH 99-100200 " " " 2,4-F, 5-OCH.sub.2 CCH, 6-Cl 106-108201 " " " 2,6-F, 4-Cl, 5-OCH.sub.2 CCH n.sub.D.sup.28 1.6040202 " " " 2-f, 4-OCH.sub.3, 5-OCH.sub.2 CCH 124-126203 " " " ##STR138## n.sub.D.sup.30 1.6310204 " " " 4-Cl, 5-OCH.sub.2 CCH n.sub.D.sup.23 1.6388205 " " 6-C.sub.2 H.sub.5 2-F, 4-Cl, 5-OCH.sub.2 CCH 126-128206 " O 6,6-(CH.sub.3).sub.2 2-F, 4-Cl, 5-OCH.sub.2 CCl.sub.2 CHCl.sub.2 155-157207 " S " 2-F, 4-Cl, 5-OCH.sub.2 CClCH.sub.2 126-128208 " " " 2-F, 4-Cl, 5-OCH.sub.2 CF.sub.3 91-92209 " " " 2-F, 4-Cl, 5-OCH.sub.2 CH.sub.2 OCHCH.sub.2 96-98210 " " " 2-F, 4-Cl, 5-OC.sub.3 H.sub.6 CN 91-93211 " " " 2-F, 4-Cl, 5-OC.sub.3 H.sub.6 COCH.sub.3 n.sub.D.sup.27 1.5841212 " " " 2-F, 4-Cl, 5-OC.sub.3 H.sub.6 COOC.sub.2 H.sub.5 n.sub.D.sup.24 1.5929213 " " " 2-F, 4-Cl, 5-OC.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.3 n.sub.D.sup.23 1.5880214 " " " 2-F, 4-Cl, 5-OC.sub.2 H.sub.4 OCH.sub.3 n.sub.D.sup.21.5 1.6109215 " " " 2-F, 4-Cl, 5-OC.sub.2 H.sub.4 OCOCH.sub.3 81-82216 " " " ##STR139## 125-127217 " " " ##STR140## 132-133218 " " " ##STR141## 137-139219 " " " ##STR142## 137-138220 " " " 2-F, 4-Cl, 5-OC.sub.2 H.sub.4 SCH.sub.3 119-121221 " " " 2-F, 4-Cl, 5-OC.sub.2 H.sub.4 SO.sub.2 CH.sub.3 151-154222 " " " 2-F, 4-Cl, 5-OC.sub.2 H.sub.4 SOCH.sub.3 n.sub.D.sup.26 1.6141223 " " " 2-F, 4-Cl, 5-OCH.sub.2 CHCCl.sub.2 99-102224 " " " 2-F, 4-Cl, 5-OCH.sub.2 CHCH.sub.2 72-73225 " " " 2-F, 4-Br, 5-OCH.sub.2 CHCH.sub.2 n.sub.D.sup.22.5 1.6391226 " " " 2,4-F.sub.2, 5-OCH.sub.2 CHCH.sub.2 50-53227 " " " 2-F, 4-Cl, 5-OCH.sub.2 CHCHCH.sub.3 65-67228 " " " 2-F, 4-Cl, 5-OCH.sub.2 CHCHCOOC.sub.2 n.sub.D.sup.24 1.5991229 " " " 2-F, 4-Cl, 5-OCH.sub.2 CHCHCl 108-109230 " " " 2-F, 4-Br, 5-OCH.sub.2 CN n.sub.D.sup.33 1.6257231 " " " 2-F, 4-Cl, 5-OCH.sub.2 CN 89-90232 " " " 2-F, 4-Cl, 5-OCH.sub.2 COCH.sub.3 107-108233 " " " ##STR143## 133-116234 " " " 2-F, 4-Br, 5-OCH.sub.2 COOC.sub.2 H.sub.5 105-106235 " " " 2-F, 4-Cl, 5-OCH.sub.2 COOCH.sub.2 CHClCH.sub. 2 Cl n.sub.D.sup.26 1.5979236 " " " ##STR144## 86-89237 " " " 2-F, 4-Cl, 5-OCH.sub.2 OC.sub.2 H.sub.5 54-55238 " " " 2-F, 4-Cl, 5-OCH.sub.2 OCH.sub.3 143.5-144239 " " " ##STR145## 107-109240 " " " ##STR146## 130-131.5241 " " " 2-F, 4-Cl, 5-OCH.sub.2 SCH.sub.3 110-114242 " " " 2-F, 4-Cl, 5-OCH.sub.2 SO.sub.2 CH.sub.3 48-51243 " " " 2-F, 4-Cl, 5-OCH.sub.2 SOCH.sub.3 122-124244 " " " ##STR147## n.sub.D.sup.28 1.6514245 " " " 2-F, 4-Cl, 5-OCH.sub.2 Si(CH.sub.3).sub.3 n.sub.D.sup.22 1.5871246 " " " 2,4-Cl.sub.2, 5-OCH.sub.3 129-130247 " " " 2-F, 4-Cl, 5-OCH.sub.3 131-132248 " " " 2-F, 4-Br, 5-OCH.sub.3 119-121249 " " " 2-F, 4,5-(OCH.sub.3).sub.2 178-179.5250 " " " 2,4-Cl.sub.2, 5-OCH.sub.2 C CH 124.5-125251 " " " ##STR148## n.sub.D.sup.24 1.5835252 " " " 2-F, 4-Cl, 5-OCOCH.sub.3 130-131253 " " " 2-F, 4-Cl, 5-OCON(CH.sub.3).sub.2 140-142254 " " " 2-F, 4-Cl, 5-OCONHC.sub.2 H.sub.5 136-138255 " " " 2-F, 4-Cl, 5-OH 207-208256 " " " ##STR149## n.sub.D.sup.28 1.5878257 " " " ##STR150## 105-108258 " " " ##STR151## 158-161259 " " " 2-F, 4-Cl, 5-OSO.sub.2 CH.sub.3 130-131260 O " 6-CH.sub.3 ##STR152## 130-132261 " " " 2-F, 4-Cl, 5-CH.sub.2 OCOCH.sub.3 72-73262 " " " 2-F, 4-Cl, 5-CHCHCOOC.sub.2 H.sub.5 115-116.5263 " " " 2-F, 4-CL, 5-CHNOC.sub.2 H.sub.5 99-102264 " " " 2-F, 4-Cl, 5-CHNOCH.sub.2 COOC.sub.2 H.sub.5 n.sub.D.sup.21.5 1.5720265 " " " 2-F, 4-Cl, 5-CON(CH.sub.3).sub.2 170-171266 " " " 2-F, 4-Cl, 5-CONHC.sub.2 H.sub.5 161-162267 " " " 2-F, 4-Cl, 5-CONH.sup.i C.sub.3 H.sub.7268 " " " 2-F, 4-Cl, 5-CONHCH.sub.2 CCH 163-165269 " " " 2-F, 4-Cl, 5-CONHOC.sub.2 H.sub.5 142-143.5270 " " " 2-F, 4-Cl, 5-COOC.sub.2 H.sub.5 123-124271 " " " 4-Cl, 5-COOC.sub.2 H.sub.5 n.sub.D.sup.23 1.6006272 " " " 2-F, 4-Cl, 5-COO.sup.i C.sub.3 H.sub.7 68-71273 " " " ##STR153## 127.5-129274 " " " ##STR154## 89-91275 " " " ##STR155## 112-114276 " " " 2-F, 4-Cl, 5-COOCH.sub.2 CCH 132-133.5277 " " " ##STR156## n.sub.D.sup.24 1.5653278 " " " 2-F, 4-Cl, 5-COOC.sub.2 H.sub.4 OCH.sub.3 93.5-94.5279 " " " ##STR157## 99-102280 " " " 2-F, 4-Cl, 5-COOCH.sub.2 COOC.sub.2 H.sub.5 n.sub.D.sup.26.5 1.5739281 " " " ##STR158## 109-111.5282 " " " 2-F, 4-Cl, 5-COOCH.sub.3 117-119283 " " " 2-F, 4-Cl, 5-COOH 227-230284 " " " 4-Cl, 5-COOH 206 dec.285 " " " 4-Cl 93-96286 " " " 2-F, 4-Cl 65-67287 " " " 2-F, 4-OCH.sub.3 72-73.5288 " " " 2-OCH.sub.3, 4-F 94-96289 " " " 2-F, 4-OCH.sub.2 CCH n.sub.D.sup.24 1.6070290 " " " ##STR159## 129-130291 " " " ##STR160## n.sub.D.sup.25 1.5642292 " " " ##STR161## 124-125293 " " " ##STR162## 94-96294 " " " ##STR163## 47-50295 " " 5,6-(CH.sub.3).sub.2 4-Cl 130-132 (cis)296 " " 5,6-(CH.sub.3).sub.2 4-Cl 89-90 (trans)297 " " 6-C.sub.2 H.sub.5 4-Cl 105-115298 " " " 2-F, 4-Cl n.sub.D.sup.23 1.5819299 " " " 2-F, 4-Br 49-50300 " " " 2,4,6-F.sub.3 93-94301 " " 6-C.sub.3 H.sub.7 4-Cl 107-111302 " " 6-CH.sub.3 ##STR164## 143-144303 " " " 2-F, 4-Cl, 5-NH.sub.2 n.sub.D.sup. 26 1.6347304 " " " 2-F, 4-Cl, 5-NHCH.sub.2 CCH 46-49305 " " " 2-F, 4-Cl, 5-NHCOCF.sub.3 153-156306 " " " 2-F, 4-Cl, 5-NO.sub.2 108-110307 " " " ##STR165## n.sub.D.sup.27.5 1.5870308 " " " ##STR166## 146-147309 " " " ##STR167## 147-148310 " " 6,6-(CH.sub.3).sub.2 ##STR168## 62-65311 " " 6-CH.sub.3 ##STR169## 68-71312 " " " 2-F, 4-Cl, 5-OC.sub.12 H.sub.25 n.sub.D.sup.26.5 1.5442313 " " " 2-F, 4-Cl, 5-O.sup.i C.sub.3 H.sub.7 n.sub.D.sup.28 1.5872314 " " " 2-F, 4-Cl, 5-OC.sub.3 H.sub.7 n.sub.D.sup.22.5 1.5891315 " " " 2-F, 4-Cl, 5-OC.sub.4 H.sub.9 n.sub.D.sup.23 1.5942316 " " " ##STR170## n.sub.D.sup.22 1.6010317 " " " ##STR171## n.sub.D.sup.27 1.5740318 " " " ##STR172## n.sub.D.sup.27 1.5680319 " " " ##STR173## n.sub.D.sup.24.5 1.5610320 " " " ##STR174## 71-73321 " " 6-C.sub.2 H.sub.5 ##STR175## 68-70322 " " 6-CH.sub.3 ##STR176## n.sub.D.sup.28 1.5770323 " " 6-C.sub.2 H.sub.5 ##STR177## n.sub.D.sup.28 1.5792324 " " 6-CH.sub.3 ##STR178## n.sub.D.sup.20 1.5605325 " " 6-C.sub.2 H.sub.5 ##STR179## n.sub.D.sup.21 1.5560326 " " 6-CH.sub.3 ##STR180## n.sub.D.sup.28 1.5580327 " " 6-C.sub.2 H.sub.5 ##STR181## n.sub.D.sup.28 1.5591328 " " 6-CH.sub.3 ##STR182## 110-112329 " " " ##STR183## n.sub.D.sup.20 1.5583330 " " " ##STR184## n.sub.D.sup.15 1.5764331 " " " ##STR185## n.sub.D.sup.26.5 1.5601332 " " " ##STR186## 71-73333 " " " ##STR187## n.sub.D.sup.22.5 1.5860334 " " " ##STR188## n.sub.D.sup.28.5 1.5921335 " " " ##STR189## n.sub.D.sup.22 1.5878336 " " " ##STR190## n.sub.D.sup.23 1.5783337 " " " ##STR191## n.sub.D.sup.28 1.5688338 " " " ##STR192## n.sub.D.sup.28 1.5619339 " " " ##STR193## n.sub.D.sup.27 1.5886340 " " " ##STR194## n.sub.D.sup.28 1.5971341 " " " ##STR195## 158-160342 " " " ##STR196## n.sub.D.sup.24.5 1.5663343 " " " ##STR197## 56-60344 " " " ##STR198## 149-153345 " " 6-C.sub.2 H.sub.5 ##STR199## n.sub.D.sup.17.5 1.5698346 " " 6-CH.sub.3 ##STR200## n.sub.D.sup.27 1.5608347 " " " ##STR201## 134-137348 " " " ##STR202## 109-113349 " " " ##STR203## 118-121350 " " " ##STR204## 50-53351 " " " ##STR205## 135-138352 " " " ##STR206## 155-158353 " " " ##STR207## 58-59354 " " " ##STR208## n.sub.D.sup.22 1.5669355 " " " ##STR209## 116-117356 " " " ##STR210## 108-108.5357 " " 6-C.sub.2 H.sub.5 ##STR211## 92-93358 " " 6-CH.sub.3 ##STR212## n.sub.D.sup.20.5 1.5456359 " " " ##STR213## n.sub.D.sup.26 1.5870360 " " " ##STR214## n.sub.D.sup.27 1.5696361 " " " ##STR215## 147-149362 " " " ##STR216## n.sub.D.sup.23 1.5901363 " " 6,6-(CH.sub.3).sub.2 ##STR217## n.sub.D.sup.26 1.5675364 " " 6-C.sub.2 H.sub.5 ##STR218## n.sub.D.sup.20.5 1.5682365 " " " ##STR219## n.sub.D.sup.21.5 1.5492366 " " 6-C.sub.3 H.sub.7 ##STR220## n.sub.D.sup.24 1.5572367 " " 6-CH.sub.3 ##STR221## n.sub.D.sup.28 1.5569368 " " 6-C.sub.2 H.sub.5 ##STR222## n.sub.D.sup.21.5 1.5399369 " " 6-CH.sub.3 ##STR223## 77-78370 " " " ##STR224## n.sub.D.sup.20.5 1.5680371 " " 6-C.sub.2 H.sub.5 ##STR225## n.sub.D.sup.25 1.5620372 " " 6-CH.sub.3 ##STR226## n.sub.D.sup.20.5 1.5635373 " " " ##STR227## n.sub.D.sup.24 1.5579374 " " " ##STR228## n.sub.D.sup.26 1.5554375 " " " ##STR229## 98-100376 " " " ##STR230## n.sub.D.sup.19 1.5960377 " " " ##STR231## 75-77378 " " " ##STR232## n.sub.D.sup.21.5 1.5751379 " " " ##STR233## 101-102380 " " " ##STR234## n.sub.D.sup.27.5 1.5540381 " " 6,6-(CH.sub.3).sub.2 ##STR235## n.sub.D.sup.26 1.5850382 " " 6-CH.sub.2 OCH.sub.3 ##STR236## n.sub.D.sup.27 1.5809383 " " 6-C.sub.2 H.sub.5 ##STR237## n.sub.D.sup.26 1.5785384 " " 6-C.sub.3 H.sub.7 ##STR238## n.sub.D.sup.24 1.5652385 " " 5-C.sub.2 H.sub.5 ##STR239## n.sub.D.sup.27 1.5775386 " " 6-CH.sub.3 ##STR240## n.sub.D.sup.21 1.5648387 " " " ##STR241## n.sub.D.sup.26.5 1.5778388 " " " ##STR242## n.sub.D.sup.24 1.5634389 " " " ##STR243## n.sub.D.sup.24 1.5613390 " " " ##STR244## n.sub.D.sup.19 1.5701391 " " " ##STR245## n.sub.D.sup.24 1.5613392 " " " ##STR246## n.sub.D.sup.30.5 1.5841393 " " 6-C.sub.2 H.sub.5 ##STR247## n.sub.D.sup.28 1.5820394 " " 6-CH.sub.3 ##STR248## 113-115395 " " " ##STR249## 104-106396 " " " ##STR250## n.sub.D.sup.26 1.5683397 " " 6-C.sub.2 H.sub.5 ##STR251## n.sub.D.sup.26 1.5883398 " " 6-CH.sub.3 ##STR252## n.sub.D.sup.22 1.5884399 " " " ##STR253## n.sub.D.sup.24 1.5773400 " " " ##STR254## n.sub.D.sup.22 1.5864401 " " " ##STR255## n.sub.D.sup.22 1.6042402 " " " ##STR256## n.sub.D.sup.26 1.5778403 " " 6-C.sub.2 H.sub.5 ##STR257## n.sub.D.sup.27 1.5836404 " " 6-CH.sub.3 ##STR258## 136-138405 " " 6,6-(CH.sub.3).sub.2 ##STR259## 210-212406 " " 6-C.sub.2 H.sub.5 ##STR260## 142-144407 " " 6-CH.sub.3 ##STR261## 215-220 dec.408 " " 6-C.sub.2 H.sub.5 ##STR262## 78-85409 " " 6-CH.sub.3 ##STR263## 49-51410 " " " ##STR264## n.sub.D.sup.26 1.6080411 " " " ##STR265## n.sub.D.sup.26 1.5985412 " " " ##STR266## n.sub.D.sup.26.5 1.5512413 " " " ##STR267## 111- 112414 " " 6-C.sub.2 H.sub.5 ##STR268## n.sub.D.sup.22 1.6091415 " " 6-CH.sub.3 ##STR269## n.sub.D.sup.23 1.6011416 " " " 2-F, 4-Cl, 5-OCH(COOC.sub.2 H.sub.5).sub.2 n.sub.D.sup.29.5 1.5512417 " " 6-C.sub.2 H.sub.5 2-F, 4-Cl, 5-OCH(COOC.sub.2 H.sub.5).sub.2 n.sub.D.sup.29 1.5540418 " " 6-CH.sub.3 ##STR270## n.sub.D.sup.26 1.5910419 " " " ##STR271## 99-101420 " " " ##STR272## 138-140421 " " " ##STR273## n.sub.D.sup.24 1.5825422 " " " ##STR274## 90-93423 " " " ##STR275## 31-34424 " " " ##STR276## n.sub.D.sup.27 1.5881425 " " " ##STR277## n.sub.D.sup.27 1.5861426 " " " ##STR278## 175-181427 " " " 2-F, 4-Cl, 5-OCH.sub.2 CCCH.sub.3 150-151428 " " " 2-F, 4-Cl, 5-OCH.sub.2 CCCl n.sub.D.sup.26.5 1.6135429 " " -- 2-F, 4-Cl, 5-OCH.sub.2 CCH 139-140430 " " 6-CH.sub.3 " 109-113431 " " " 2-F, 4,5-(OCH.sub.2 CCH).sub.2 122.5-123.5432 " " " 2,4-F.sub.2, 5-OCH.sub.2 CCH n.sub.D.sup.28.5 1.5855433 " " " 2,4-F.sub.2, 6-Cl, 5-OCH.sub.2 CCH n.sub.D.sup.28 1.5742434 " " " 2-F, 4-OCH.sub.3, 5-OCH.sub.2 CCH 158-160435 " " " 2-F, 4-Br, 5-OCH.sub.2 CCH 108-110436 " " " 4-Cl, 5-OCH.sub.2 CCH 110-111437 " " " 2-Br, 4-Cl, 5-OCH.sub.2 CCH 123-125438 " " 6,6-(CH.sub.3).sub.2 2-F, 4-Cl, 5-OCH.sub.2 CCH 105-108439 " " 5,6-(CH.sub.3).sub.2 (cis) 2-F, 4-Cl, 5-OCH.sub.2 CCH 122-123440 " " 5,6-(CH.sub.3).sub.2 (trans) 2-F, 4-Cl, 5-OCH.sub.2 CCH 118-119441 " " 6-CH.sub.2 OCH.sub.3 2-F, 4-Cl, 5-OCH.sub.2 CCH n.sub.D.sup.28 1.6015442 " " 6-CH.sub.2 O.sup.i C.sub.3 H.sub.7 2-F, 4-Cl, 5-OCH.sub.2 CCH n.sub.D.sup.28 1.5950443 " " 6-C.sub.2 H.sub.5 2-F, 4-Br, 5-OCH.sub.2 CCH 111-113444 " " " 2-F, 4-Cl, 5-OCH.sub.2 C CH 121-122445 " " 6-C.sub.3 H.sub.7 2-F, 4-Cl, 5-OCH.sub.2 CCH 113-115446 " " 5-C.sub.2 H.sub.5 2-F, 4-Cl, 5-OCH.sub.2 CCH n.sub.D.sup.27 1.6022447 " " 6-CH.sub.3 2-F, 4-Cl, 5-OCH.sub.2 CBrCBrCH.sub.3 n.sub.D.sup.26.5 1.6160448 " " " 2-F, 4-Cl, 5-OCH.sub.2 CF.sub.3 83.5-85449 " " " 2-F, 4-Cl, 5-OCH.sub.2 CH.sub.2 Br 94-96450 " " " 2-F, 4-Cl, 5-OC.sub.3 H.sub.6 CN 103-104451 " " " 2-F, 4-Cl, 5-OC.sub.3 H.sub.6 COOC.sub.2 H.sub.5 n.sub.D.sup.25.5 1.5735452 " " " ##STR279## n.sub.D.sup.20.5 1.6238453 " " " ##STR280## n.sub.D.sup.20 1.6275454 " " " 2-F, 4-Cl, 5-OC.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.3 52-53455 " " " ##STR281## n.sub.D.sup.18 1.6157456 " " " 2-F, 4-Cl, 5-OC.sub.2 H.sub.4 OCH.sub.3 90-90.5457 " " " 2-F, 4-Cl, 5-OC.sub.2 H.sub.4 OCOCH.sub.3 n.sub.D.sup.22 1.5810458 " " " ##STR282## 128-130459 " " " ##STR283## 157-158460 " " " ##STR284## 112-114461 " " " ##STR285## 120-121462 " " " ##STR286## 154-155463 " " " ##STR287## 110-112464 " " 2-F, 4-Cl, 5-OC.sub.2 H.sub.4 SCH.sub.2 COOCH.sub.3 105-107465 " " " ##STR288## n.sub.D.sup.21.6 1.6262466 " " " 2-F, 4-Cl, 5-OC.sub.2 H.sub.4 SCH.sub.3 n.sub.D.sup.26 1.6086467 " " " ##STR289## n.sub.D.sup.22 1.6320468 " " " 2-F, 4-Cl, 5-OCH.sub.2 CHCCl.sub.2 85-87469 " " " 2-F, 4-Cl, 5-OCH.sub.2 CHCH.sub.2 n.sub.D.sup.27 1.6035470 " " " 2,4-F.sub.2, 5-OCH.sub.2 CHCH.sub.2 n.sub.D.sup.28.5 1.5965471 " " 6-C.sub.2 H.sub.5 2-F, 4-Br, 5-OCH.sub.2 CHCH.sub.2 n.sub.D.sup.22.5 1.6172472 " " 6-CH.sub.3 2-F, 4-Cl, 5-OCH.sub.2 CHCHCOOC.sub.2 n.sub.D.sup. 25.5 1.5905473 " " " 2-F, 4-Cl, 5-OCH.sub.2 CHCHCl 94-95474 " " 6-C.sub.2 H.sub.5 2-F, 4-Cl, 5-OCH.sub.2 CHCHCl 78-81475 " " 6-CH.sub.3 2-F, 4-Cl, 5-OCH.sub.2 CN n.sub.D.sup.24 1.5675476 " " 6-C.sub.2 H.sub.5 2-F, 4-Br, 5-OCH.sub.2 CN n.sub.D.sup.23 1.6153477 " " 6-CH.sub.3 2-F, 4-Cl, 5-OCH.sub.2 COCH.sub.3 106-108478 " " " ##STR290## n.sup.28 1.5838479 " " " 2-F, 4-Cl, 5-OCH.sub.2 COOCH.sub.2 CHClCH.sub. 2 Cl 172-177 dec.480 " " " 2-F, 4-Cl, 5-OCH.sub.2 COOCH.sub.3 125-128481 " " " ##STR291## 91-93482 " " " 2-F, 4-Cl, 5-OCH.sub.2 OC.sub.2 H.sub.5 n.sub.D.sup.20.5 1.5929483 " " " 2-F, 4-Cl, 5-OCH.sub.2 OCH.sub.3 70-72484 " " " ##STR292## 50-52485 " " 6-C.sub.2 H.sub.5 ##STR293## n.sub.D.sup.21 1.5790486 " " 6-CH.sub.3 ##STR294## n.sub.D.sup.26 1.6005487 " " " ##STR295## 209-210 dec.488 " " " ##STR296## n.sub.D.sup.28 1.6308489 " " " ##STR297## 176-177490 " " " ##STR298## 101-102491 " " " ##STR299## 156-157492 " " " 2-F, 4-Cl, 5-OCH.sub.2 SCH.sub.2 CHCH.sub.2 n.sub.D.sup.21 1.5999493 " " " 2-F, 4-Cl, 5-OCH.sub.2 SCH.sub.2 COOCH.sub.3 n.sub.D.sup.19.5 1.5973494 " " " ##STR300## n.sub.D.sup.20.5 1.6181495 " " " 2-F, 4-Cl, 5-OCH.sub.2 SCH.sub.3 69-71496 " " " 2-F, 4-Cl, 5-OCH.sub.2 SO.sub.2 CH.sub.3 56-59497 " " " ##STR301## 65-67498 " " " 2-F, 4-Cl, 5-OCH.sub.2 SOCH.sub.3 43-46499 " " " ##STR302## 166-168 dec.500 " " " ##STR303## n.sub.D.sup.29 1.6420501 " " " ##STR304## n.sub.D.sup.26 1.6220502 " " " ##STR305## n.sub.D.sup.25.5 1.6270503 " " " ##STR306## n.sub.D.sup.26 1.6371504 " " " ##STR307## n.sub.D.sup.20.5 1.6290505 " " " 2-F, 4-Cl, 5-OCH.sub.2 Si(CH.sub.3).sub.3 39-42506 " " " 2-F, 4,5-(OCH.sub.3).sub.2 127-128507 " " 6-C.sub.2 H.sub.5 2-F, 4-Cl, 5-OCH.sub.3 87-89508 " " 6-CH.sub.3 2,4-Cl.sub.2, 5-OCH.sub.2 CCH 123-124509 " " " ##STR308## 47-49510 " " " ##STR309## 92-94511 " " 6,6-(CH.sub.3).sub.2 ##STR310## n.sub.D.sup.24 1.5600512 " " 6-CH.sub.3 2-F, 4-Cl, 5-OCOCH.sub.3 155-158513 " " 6-C.sub.2 H.sub.5 2-F, 4-Cl, 5-OCOCH.sub.3 136-137514 " " " ##STR311## 54-56515 " " 6-CH.sub.3 2-F, 4-Cl, 5-OH 164-166516 " " 6-C.sub.2 H.sub.5 2-F, 4-Cl, 5-OH 137-139517 " " 6-CH.sub.3 ##STR312## n.sub.D.sup.27.5 1.5869518 " " " ##STR313## 77-80519 " " " ##STR314## n.sub.D.sup.20.5 1.5985520 " " 6-C.sub.2 H.sub.5 ##STR315## 112-114521 CH.sub.2 " " 2-F, 4-Cl, 5-CH.sub.2 CN 113-114522 " " " 2-F, 4-Cl, 5-CH.sub.2 COOC.sub.2 H.sub.5 n.sub.D.sup.20 1.5855523 " " " 2-F, 4-Cl, 5-CH.sub.2 COOCH.sub.2 CCH n.sub.D.sup.20.5 1.5992524 " " " ##STR316## 75-77525 " " " 2-F, 4-Cl, 5-CHCHCOOC.sub.2 H.sub.5 147-148.5526 " " " ##STR317## 147-149527 " " " 2-F, 4-Cl, 5-CHCHCOOCH.sub.2 C CH 116.5-117.5528 " " 6-CH.sub.3 2-F, 4-Cl, 5-CHCHCOOCH.sub.3 161-164529 " " " 2-F, 4-Cl, 5-CHCHCOOH 205-207530 " " " 2-F, 4-Cl, 5-CHCHCOONa 257-260531 " " " 2-F, 4-Cl, 161-163 ##STR318##532 " " " ##STR319## 97-98533 " " " ##STR320## 134-135534 " " " ##STR321## n.sub.D.sup.21.5 1.5820535 " " " ##STR322## 133.5-135536 " " " ##STR323## 71-72537 " " " 2-F, 4-Cl, 5-COO.sup.t C.sub.4 H.sub.9 89-90538 " " " 4-Cl, 5-COOC.sub.2 H.sub.5 n.sub.D.sup.23 1.6150539 " " " 2-F, 4-Cl, 5-COOC.sub.2 H.sub.5 88-90540 " " " 2-OCH.sub.3, 4-Cl, 5-COOC.sub.2 H.sub.5 77-79541 " " " 2-F, 4-Cl, 5-COOC.sub.3 H.sub.7 101-102542 " " " ##STR324## 66-67.5543 " " " ##STR325## 85-86.5544 " " " ##STR326## 78- 80545 " " " ##STR327## 58-60546 " " " ##STR328## n.sub.D.sup.19.5 1.6066547 " " " 2-F, 4-Cl, 5-COO.sup.i C.sub.3 H.sub.7 90-91548 " " " 2-F, 5-COO.sup.i C.sub.3 H.sub.7 107.5-108.5549 " " " ##STR329## 78-80550 " " " ##STR330## 89.5-91551 " " " ##STR331## 87-88552 " " " ##STR332## 91-93553 " " " ##STR333## 110-111.5554 " " " 2-F, 4-Cl, n.sub.D.sup.22.5 1.5671 5-COOC.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.3555 " " " 2-F, 4-Cl, 5-COOC.sub.2 H.sub.4 (OC.sub.2 H.sub.4).sub.3 OCH.sub.3 n.sub.D.sup.22.5 1.5596556 " " " 2-F, 4-Cl, 5-COOC.sub.3 H.sub.6(OC.sub.3 H.sub.6 ) .sub.7OCH.sub.3 n.sub.D.sup.21.5 1.5115557 " " " 2-F, 4-Cl, 5-COOCH.sub.2 Si(CH.sub.3).sub.3 98-101558 " " " 4-Cl, 5-COOCH.sub.3 101-102559 " " " 2-F, 4-Cl, 5-COOCH.sub.3 99-100.5560 " " " 4-Cl, 5-COOH 229 dec.561 " " " 2-F, 4-Cl, 5-COOH 210-213562 " " " ##STR334## 118-119.5563 " " " 2-F, 4-Cl, 5-COONa 285-286564 " " " ##STR335## n.sub.D.sup.26 1.6210565 " " " ##STR336## n.sub.D.sup.22 1.6036566 " " -- ##STR337## 91-92567 " " 6-OCH.sub.3 ##STR338## n.sub.D.sup.28 1.6001568 " " " ##STR339## 59-60569 " " " ##STR340## 70-70.5570 " " " ##STR341## 91.5-92571 " " " ##STR342## 76-78572 " " " ##STR343## 118-120573 " " " ##STR344## 77-80574 " " " ##STR345## 75-78575 " " " ##STR346## 64-67576 " " " 2-F, 4-Cl, 5-O.sup.i C.sub.3 H.sub.7 n.sub.D.sup.28 1.6012577 " " " ##STR347## 128-129578 " " " ##STR348## n.sub.D.sup.21.5 1.5912579 " " -- ##STR349## 124-126580 " " 6-CH.sub.3 ##STR350## 85-86581 " " " ##STR351## n.sub.D.sup.20.5 1.5879582 " " " ##STR352## n.sub.D.sup.20.5 1.6100583 " " " ##STR353## n.sub.D.sup.20 1.5989584 " " " ##STR354## n.sub.D.sup.20.5 1.6003585 " " " ##STR355## n.sub.D.sup.20.5 1.6205586 " " " ##STR356## n.sub.D.sup.22 1.5837587 " " " ##STR357## 93-95588 " " " ##STR358## 108-110589 " " " ##STR359## 98.5-99.5590 " " " ##STR360## n.sub.D.sup.22.5 1.5751591 " " " ##STR361## 115-116592 " " " ##STR362## 143.5-144593 " " " ##STR363## n.sub.D.sup.23.5 1.5450594 " " " ##STR364## 61.5-62.5595 " " 6-C.sub.2 H.sub.5 ##STR365## 81-82596 " " 6-CH.sub.3 ##STR366## n.sub.D.sup.19.5 1.5687597 " " " ##STR367## 103-104598 " " " ##STR368## 71-72599 " " " ##STR369## n.sub.D.sup.20.5 1.5640600 " " -- ##STR370## 107-109601 " " 6-CH.sub.3 ##STR371## 116-116.5602 " " 6,6-(CH.sub.3).sub.2 ##STR372## n.sub.D.sup.23 1.5814603 " " 6-C.sub.2 H.sub.5 ##STR373## 92-94604 " " 6-CH.sub.3 ##STR374## 58.5-60.5605 " " " ##STR375## n.sub.D.sup.22.5 1.5711606 " " " ##STR376## n.sub.D.sup.18.5 1.5946607 " " " ##STR377## n.sub.D.sup.22.5 1.5929608 " " " ##STR378## n.sub.D.sup.20 1.5615609 " " " ##STR379## 73-75610 " " " ##STR380## n.sub.D.sup.21 1.5957611 " " " ##STR381## 103-105612 " " " ##STR382## n.sub.D.sup.19.5 1.5804613 " " " ##STR383## 142-143614 " " " ##STR384## 134.5-135615 " " " ##STR385## 81-83616 " " " ##STR386## 110-112617 " " -- 2-F, 4-Cl, 5-OCH.sub.2 CCH 104-106.5618 " " 6-CH.sub.3 2-F, 4-Cl, 5-OCH.sub.2 CCH 129-130619 " " 6-C.sub.2 H.sub.5 2-F, 4-Cl, 5-OCH.sub.2 C CH 149-150620 " " 6-CH.sub.3 2-F, 4-Cl, 5-(OC.sub.2 H.sub.4) .sub.3OCH.sub. 3 n.sub.D.sup.17.5 1.5740621 " " " 2-F, 4-Cl, 5-(OC.sub.2 H.sub.4 ) .sub.4OCH.sub .3 n.sub.D.sup.19.5 1.5572622 " " " ##STR387## n.sub.D.sup.26 1.6132623 " " " ##STR388## 82-83624 " " " ##STR389## 130-131625 " " " ##STR390## 127-128626 " " " ##STR391## 102-103627 " " " ##STR392## 79-80628 " " " 2-F, 4-Cl, 5-OC.sub.2 H.sub.4 OCH.sub.3 69-70629 " " " 2-F, 4-Cl, 5-OC.sub.2 H.sub.4 OCHCH.sub.2 61-62630 " " " 2-F, 4-Cl, 5-OC.sub.2 H.sub.4 OCONHCH.sub.3 102-103631 " " " 2-F, 4-Cl, 5-OC.sub.2 H.sub.4 OH 65-65.5632 " " " ##STR393## 96-97633 " " " ##STR394## 121-123634 " " " ##STR395## 98-100635 " " " ##STR396## 87-88636 " " " ##STR397## 71-72637 " " " ##STR398## 87-88638 " " " ##STR399## 96-97639 " " " ##STR400## 96-97640 " " " ##STR401## 85-86641 " " " ##STR402## 117-118642 " " " ##STR403## 105-107643 " " " ##STR404## 136-137.5644 " " " ##STR405## 74-75645 " " " ##STR406## 46-47646 " " " ##STR407## 124-125647 " " " 2-F, 4-Cl, 5-OCH.sub.2 CHCCl.sub.2 112-113648 " " " 2-F, 4-Cl, 5-OCH.sub.2 CHCHCOOC.sub.2 n.sub.D.sup.19.5 1.5865649 " " " ##STR408## 113-115650 " " " 2-F, 4-Cl, 5-OCH.sub.2 COOC.sub.2 H.sub.5 141-143651 " " " ##STR409## 142-144652 " " " 2-F, 4-Cl, (HCl salt) 150-151653 " " " 2-F, 4-Cl, 5-OCH.sub.2 COO.sup.i C.sub.3 H.sub.7 115-117654 " " " ##STR410## 71-74655 " " " 2-F, 4-Cl, 5-OCH.sub.2 COOCH.sub.2 CCH 140-142656 " " " 2-F, 4-Cl, 5-OCH.sub.2 COOCH.sub.2 CHCH.sub.2 97-99657 " " " 2-F, 4-Cl, 5-OCH.sub.2 COOCH.sub.2 CHClCH.sub. 2 Cl 107-110658 ##STR411## " -- 2-F, 4-Cl, 5-OCH.sub.2 COOCH.sub.3 104.5-105659 CH.sub.2 " 6-CH.sub.3 2-F, 4-Cl, 5-OCH.sub.2 COOCH.sub.3 124-126660 " " " 2-F, 4-Cl, 5-OCH.sub.2 COOH 162-163661 " " " 2-F, 4-Cl, 5-OCH.sub.2 OC.sub.2 H.sub.5 44-45662 " " " 2-F, 4-Cl, 5-OCH.sub.2 OCH.sub.3 68-69663 " " " ##STR412## 82-83664 " " " ##STR413## 101-102665 " " 6-C.sub.2 H.sub.5 ##STR414## 106-108666 " " 6-CH.sub.3 2-F, 4-Cl, 5-OCHCHCH.sub.2 COOC.sub.2 n.sub.D.sup.19.5 1.5975667 " " " ##STR415## 137-139668 " " " ##STR416## 159-160669 " " " 2-F, 4-Cl, 5-OH 161-163670 " " " 2-F, 4-Cl, 5-OH, 6-I 58-60671 " " " ##STR417## 107-109672 ##STR418## " -- 4-Cl 250 up673 ##STR419## " -- 4-Cl 94-97674 ##STR420## " -- 2-F, 4-Cl, 5-OCH.sub.2 CCH 130-132675 " " -- ##STR421## 75-78676 " " -- ##STR422## 138-138.5677 CH.sub.2 S " -- 4-Cl 120-122678 ##STR423## " -- 2-F, 4-Cl 97-100679 CH.sub.2 CH.sub.2 " -- ##STR424## 79-80.5680 " " -- 2-F, 4-Cl, 5-OCH.sub.2 COOCH.sub.3 101-103681 CH.sub.2 " 6-CH.sub.3 2-F, 4-Cl, 5-COOC(CH.sub.3).sub.2 COOCH.sub.3 117-119682 O " " ##STR425## 173-176683 CH.sub.2 " " ##STR426## 83-84684 " " " ##STR427## 158-160685 " " " ##STR428## 142.5 -143.5686 " " " ##STR429## 115.5-117687 " " " 2-F, 4-Cl, 5-COOCH(COOC.sub.2 118-119.5b.2688 " " " ##STR430##689 " " " 2-F, 4-Cl, 5-COOC.sub.2 H.sub.4 (OC.sub.2 H.sub.4).sub.6 OCH.sub.3 n.sub.D.sup.20.5 1.5429690 O " " ##STR431## 173-175691 " " " ##STR432## n.sub.D.sup.21.5 1.5767692 " " " 2-F, 4-Cl, 5-COO.sup.t C.sub.4 H.sub.9 124-126693 CH.sub.2 " " ##STR433## 145-146.5694 " " " 2-F, 4-Cl, 5-COOCH.sub.2 CHCHCOOC.sub.2 H.sub.5 115-116695 " " " 2-F, 4-Cl, 5-COOC.sub.3 H.sub.6 COOC.sub.2 H.sub.5 52-53696 CH.sub.2 " " ##STR434## 199.5-201697 CH.sub.2 CH.sub.2 " -- ##STR435## 111-112698 ##STR436## " 6.6-(CH.sub.3).sub.2 2-F, 4-Cl, 5-OCH.sub.2 COOCH.sub.3 108.5-109699 CH.sub.2 " " ##STR437## 124-125700 O " " ##STR438## n.sub.D.sup.18.5 1.6119701 CH.sub.2 " " ##STR439## 96-99702 " " " ##STR440## 121.5-122.5703 O " " ##STR441## 118-120704 " " " 2-F, 4-Cl, 5-OCH.sub.2 OCH.sub.2 CCH 72-73705 CH.sub.2 " " 2-F, 4-Cl, 5-OCHCHCOOC.sub.2 H.sub.5 72-73706 " " " 2-F, 4-Cl, 5-OCH.sub.2 SCH.sub.3 n.sub.D.sup.24.5 1.6135707 " " " 2-F, 4-Cl, 5-SCH.sub.2 COO.sup.i C.sub.3 H.sub.7 79-82708 " " " 2,4-F.sub.2, 3-OCH.sub.2 CCH n.sub.D.sup.24.5 1.5936709 " " " 2-F, 4-Cl, 5-OCH.sub.2 OCH.sub.2 OCH.sub.3 n.sub.D.sup.26 1.5840710 " " " 2,4-F.sub.2, 3-COOC.sub.2 H.sub.5711 " " " ##STR442## 135-137712 " " " 2-F, 4-Cl, 5-OCH.sub.2 OCH.sub.2 CHCH.sub.2 42-43713 " " " 2-F, 4-Cl, 5-CF.sub.3 80-81714 " " " ##STR443## 45-50715 " " " ##STR444##716 " " " 2-F, 4-Cl, 5-COCH.sub.3 93-94717 " " " ##STR445## n.sub.D.sup.24.5 1.5605718 " " " ##STR446## 89-93719 " " " ##STR447## 92-96720 " " " ##STR448## n.sub.D.sup.23.5 1.5608721 " " " ##STR449## 114-115722 " " " ##STR450## 158-170723 " " " ##STR451## n.sub.D.sup.24.5 1.5685724 " " " 2-F, 5-COOH 213-214725 " " " 2-F, 5-COO.sup.t C.sub.4 H.sub.9 113-114.5726 O " " 2-F, 4-Cl, 5-CN 136-138727 CH.sub.2 " " 2-F, 4-Cl, 5-CN 167.5-169728 " " " 2-F, 4-Cl, 5-COS.sup.i C.sub.3 H.sub.7 n.sub.D.sup.25.5 1.6195729 " " " 2-F, 4-Cl, 5-COCH(OCH.sub.3).sub.2 89-90.5730 O " " ##STR452## n.sub.D.sup.24.5 1.5647731 CH.sub.2 " " ##STR453## n.sub.D.sup.24.5 1.5900732 " " " ##STR454## 74-76733 " " " ##STR455## n.sub.D.sup.24 1.6080734 O " " ##STR456## n.sub.D.sup.24 1.5850735 CH.sub.2 " " ##STR457## n.sub.D.sup.24 1.6530736 O " " ##STR458## 153-154737 CH.sub.2 " " ##STR459## 105-106738 " " " 2-F, 4-Cl, 5-OCH.sub.2 S.sup.i C.sub.3 H.sub.7 66.5-67739 O " " 2-F, 4-Cl, 5-OCH.sub.2 S.sup.i C.sub.3 H.sub.7 64-65740 CH.sub.2 " " 2-F, 4-Cl, 5-SCH.sub.2 COOH *.sup.1741 CH.sub.2 S " 6CH.sub.2 2-F, 4-Cl, 5-OCH.sub.2 CCH *.sup.2742 CH.sub.2 " 6-CH.sub.3 2-F, 4-Cl, 5-SO.sub.2 N(CH.sub.3).sub.2 111-113743 " " " ##STR460## n.sub.D.sup.28 1.6000__________________________________________________________________________ *.sup.1 HNMR (90 MHz) (in CDCl.sub.3) .delta. 1.3 (3H, d), 2.1-2.6 (1H, m), 2.7-3.2 (2H, m), 3.2-3.6 (1H, m), 3.9-4.2 (1H, m), 3.65 (2H, s ), 6.8 (1H, d), 7.1 (1H, d) *.sup.2 HNMR (270 MHz) (in CDCl.sub.3) .delta. 2.60 (1H, t), 3.72 (2H, s) 4.58 (2H, s), 4.75 (2H, d), 5.20 (2H, d), 6.86 (1H, d), 7.22 (1H, d)
As mentioned previously, the compounds possess superior herbicidal activity. The compounds may be applied directly to the soil as pre-emergence treatment or to plant foliage as post-emergence treatment, or they can be mixed intimately with soil. The compounds may be applied to soil or to plant foliage in amount of 1 g or more per 10 are.
A herbicidal composition having a compound of this invention as its active ingredient may be formulated by mixing suitable carriers in a form generally used in agricultural chemicals such as wettable powder, water soluble powder, glanule, emulsifiable concentrate and flowable. As solid carriers, talc, white carbon, bentonite, clay, diatomaceous earth or the like may be used. As liquid carriers, water, alcohol, benzene, xylene, kerosene, mineral oil, cyclohexane, cyclohexanone, dimethylformamide or the like may be used. A surface active agent may, if necessary, be added in order to give a homogeneous and stable formulation.
Compounds can also be applied admixed with other chemicals, which are used in agronomic and horticultural management and which are compatible with such compounds. Such chemicals can be, but are not restricted to, the classes of chemical commonly known as fungicides, insecticides, acaricides, herbicides and plant growth regulators. In particular, by mixing it with the other herbicides, its applied dosage and manpower can be decreased and furthermore, the higher effect by synergetic function of both chemicals can be expected.
For admixture of the compound with known herbicides, the use is recommended of benthiocarb, molinate, MY-93 (S-2,2-dimethylbenzil) 1-piperidinecarbothioate) or other carbamate-type herbicides; thiocarbamate-type herbicides; butachlor, pretilachlor or other acid amide-type herbicides; chlormethoxynil, bifenox or other diphenylether-type herbicides; pyrazolate, pyrazoxyfen or other pyrazole-type herbicides; chlorsulfuron, sulfometuron or other sulfonylurea-type herbicides; MCP, MCPB or other phenoxy alkane carboxylic acid-type herbicides; diclofop-methyl or other phenoxy propionic acid-type herbicides; fluazifopbutyl or other pyridyloxyphenoxypropionic acid-type herbicides; piperophos, dymron, bentazon, oxadiazon, NTN-801 (2-benzothiazole-2-yloxy-N-methyl acetoanilide), naproanilid, HW-52 (4-ethoxymethoxybenzo-2',3'-dichloroanilide), KNW-242 (1-(3-methylphenyl)-5-phenyl-1H-1,2,4-triazole-3-carboxamide), S47 (N-(.alpha.,.alpha.-dimethylbenzil)-d-bromotertiary butyl acetoamide, sethoxydim, alloxydim-sodium and other cyclohexanedione-type herbicides. These herbicides in various combinations may also be mixed with a vegetable oil or an oil concentrate.
The concentration of the active ingredient in a herbicidal composition may vary according to type of formulation, and the concentration is, for example, in the range of 5-80 weight percent, preferably 30-60 weight percent, in wettable powder; 70-95 weight percent, preferably 80-90 weight percent, in water soluble powder; 5-70 weight percent, preferably 10-40 weight percent, in emulsifiable concentrate; 10-70 weight percent, preferably 20-50 weight percent, in flowable; 0.5-10 weight percent, preferably 1-5 weight percent, in glanule.
A wettable powder, a water soluble powder or an emulsifiable concentrate thus produced may be diluted with water to a specified concentration and used as a liquid suspension or a liquid emulsion for treating soils or plant foliage. Further, a flowable and a glanule may be directly used for soil or foliage treatment, otherwise, it may be diluted with water to a specified concentration and used as a liquid suspension for treating soils or plant foliage.
Non-limiting examples of herbicidal composition are illustrated by the following tests:
______________________________________Example 21 Wettable powder parts by weight______________________________________Compound No. 683 50White carbon 12Diatomaceoua earth 30Sodium alkylsulfate 8______________________________________
These are mixed homogeneously and reduced to fine particles to provide a wettable powder containing 50% of active ingredient. In use, it is diluted to a desired concentration with water, and is sprayed as suspension.
______________________________________Example 22 Emulsifiable concentrace parts by weight______________________________________Compound No. 430 40Xylene 35Dimethylformamide 15Polyoxyethylene phenyl ether 10______________________________________
These are mixed and dissolved to provide an emulsifiable concentrate containing 40% of active ingredient. In use, it is diluted to a desired concentration with water, and sprayed as an emulsion.
______________________________________Example 23 Flowable parts by weight______________________________________Compound No. 609 30Sun spray-7N (commcrcial product of 60Sun Oil Co., Ltd.)Polyoxyethylene alkylether 5Sorbitan alkylate 5______________________________________
These are mixed homogeneously to provide a flowable containing 30% of active ingredient.
______________________________________Example 24 Glanule parts by weight______________________________________Compound No. 197 3Talc 40Clay 40Bentonite 10Sodium alkyl sulfate 7______________________________________
These are mixed homogeneously to provide a glanule containing 3% of active ingredient.
The herbicidal effects of compounds are illustrated by the following tests:
Test 1
Paddy field test
Seeds of barnyardgrass (Echinochloa crus-galli), duck-tongue weed (Monochoria vaginalis), bulrush (Scirpus Hotarui) and small-flower umbrella plant (Cyperus difformis) were planted 0.2-0.5 cm in depth in plastic pots (15 cm depth and 14 cm diameter) containing paddy field soil, and two rice plants (variety: Nihonbare) at 2-3 leaf stage were transplanted. Next day pots were watered 2-3 cm in depth. Immediately granules of each compounds of this invention were applied at the dosage described in the table. The pots were kept in a greenhouse.
Three weeks after treatment, the degree of damage of the each plants was observed and evaluated on the scale of value of 0-10, which has the following meanings.
______________________________________Index Degree of damage______________________________________0 0%2 20-29%4 40-49%6 60-69%8 80-89%10 100______________________________________
Index 1, 3, 5, 7 and 9 mean the intermediate degree between 0 and 2, 2 and 4, 4 and 6, 6 and 8, 8 and 10 respectively. ##EQU1## The results are shown in Table 2.
TABLE 2______________________________________ApplicationRate ofActive Degree of DamageIngredient Rice(g/10 a) plant B.G.*.sup.1 D.T.W.*.sup.2 B.R.*.sup.3 S.U.P.*.sup.4______________________________________Com-poundNo. 10 50 1 4 10 10 10 13 50 1 10 10 10 10 15 50 1 0 10 10 10 28 50 0 5 10 10 10 54 50 0 3 10 9 8 73 50 0 0 10 10 9106 50 0 10 10 10 10115 50 0 9 10 10 10117 50 0 9 10 10 10119 25 0 10 10 10 10123 50 0 10 10 10 10127 25 0 10 10 10 10133 50 0 10 10 10 10134 50 0 9 10 10 10138 50 1 8 10 8 10142 50 0 3 10 10 10151 50 3 9 10 9 10182 50 0 4 10 10 10188 50 0 6 10 9 10194 25 1 10 10 10 10196 50 0 10 10 10 10197 50 0 10 10 10 10199 50 0 9 10 10 10202 50 0 4 10 10 10205 50 0 10 10 10 10207 25 0 9 10 10 10209 50 1 9 10 10 10212 25 0 0 10 10 10213 50 1 10 10 10 10214 50 1 10 10 10 10216 50 1 9 10 10 10219 50 0 10 10 9 10220 50 0 3 10 10 10223 50 0 8 10 7 9224 50 0 10 10 10 10227 25 0 4 10 10 10231 50 1 9 10 10 10234 50 0 0 10 10 10239 25 0 7 10 10 9241 50 0 10 10 10 10251 50 0 3 10 10 9256 50 0 9 10 10 10258 25 0 3 10 10 8263 50 0 10 10 7 10270 50 1 8 10 10 10292 50 0 2 10 5 8304 50 2 3 10 9 7309 50 0 1 10 10 10316 50 1 10 10 10 10318 50 0 10 10 10 10328 50 0 10 10 10 10331 50 0 0 10 10 10335 50 0 10 10 10 10341 50 0 3 10 10 10345 25 0 2 10 10 10350 50 0 10 10 10 10361 50 0 6 10 10 10368 25 0 0 10 10 10378 50 1 7 10 10 10381 50 0 0 10 9 10386 50 2 9 10 3 10396 50 1 8 10 10 10398 50 1 4 10 10 10409 50 0 2 10 9 9415 50 0 7 10 10 10418 50 0 2 10 10 10421 50 2 7 10 10 10430 25 1 10 10 10 10438 25 1 10 10 10 10439 25 0 5 10 10 10444 25 0 10 10 10 10458 50 0 10 10 7 10461 50 0 10 10 10 10465 50 1 10 10 10 10483 50 2 10 10 10 10487 25 0 0 9 3 9494 50 0 10 10 8 10505 50 0 10 10 5 10511 50 0 3 10 10 10514 50 0 2 10 10 10527 50 0 4 10 8 9565 50 2 10 10 10 10574 50 1 10 10 10 10580 50 0 10 10 10 10584 50 0 10 10 4 10589 50 1 3 10 10 10616 50 1 10 10 10 10618 50 0 10 10 10 10623 50 1 10 10 10 10629 50 0 3 10 10 10636 50 1 10 10 8 10663 50 0 4 10 7 10668 50 0 8 10 5 10674 50 0 5 10 10 10693 50 0 10 10 8 10697 50 0 10 10 3 10711 50 0 10 10 6 10716 50 0 7 10 9 10730 50 0 4 10 3 10Com-para-tiveCom-pound*(1) 100 0 4 8 4 1(2) 100 0 1 2 1 2______________________________________ *.sup.1 : B.G.-- barnyardgrass *.sup.2 : D.T.W.--ducktongue weed *.sup.3 : B.R.--bulrush *.sup.4 : S.U.P.--smallflower umbrella plant *(1) ##STR461## (2) ##STR462##
Test 2
Postemergence treatment test
Seeds of lambsquarter (Chenopodium album), pigweed (Amaranthus retroflexus), sedge (Cyperus microiria) and soybean were planted in clay pots (12 cm depth and 16 cm diameter) containing clay loam soil and were allowed to grow in greenhouse. When the plants were grown to a 3-10 cm height, aqueous suspensions, prepared by diluting an emulsifiable concentrate with water to specified concentration (500 ppm) were sprayed on the foliage of the plants at a rate of 100 1/10 a by using a micro-sprayer. Three weeks after treatment the degree of damage of the each plants was observed and evaluated on the same scale as in Test 1. The results are shown in Table 3.
TABLE 3______________________________________ Application Rate of Ac- tive Ingre-Compound dient Degree of DamageNo. (g/10 a) Soybean L.Q.*.sup.5 P.W.*.sup.6 S.D.*.sup.7______________________________________ 11 50 5 10 10 10 14 25 3 10 10 10124 25 2 10 9 10125 50 3 10 10 10139 50 1 10 10 10140 25 1 10 7 10150 25 2 9 10 10152 25 4 10 8 8153 25 1 7 8 7157 50 2 10 9 7161 25 2 9 9 8171 25 1 10 10 9173 50 5 10 10 10175 50 3 10 9 10176 50 2 10 10 10183 25 1 8 9 8190 25 2 9 7 7243 50 5 9 10 10245 25 1 5 9 8266 25 3 10 10 10269 25 6 10 10 10272 25 4 10 10 10274 50 4 10 10 10277 25 1 7 10 9279 25 2 10 10 10281 25 3 10 9 10282 50 5 10 10 10320 50 2 9 10 10325 25 3 10 10 10330 25 3 10 10 10353 25 4 10 10 10356 25 5 8 10 9358 25 1 8 10 8360 50 2 10 10 10365 50 3 10 10 10366 25 3 10 10 10369 25 4 10 10 10374 25 3 10 10 10376 25 4 10 9 9379 50 5 10 10 10387 25 4 10 10 10390 25 2 9 9 9391 25 2 9 10 9393 50 4 10 10 10394 25 1 9 8 8399 25 6 10 7 8404 25 5 10 10 10410 50 4 10 7 9411 25 2 9 9 8419 25 5 10 10 7420 25 7 10 10 10449 50 6 10 10 10456 25 9 9 10 9477 25 3 8 8 5480 50 6 10 10 10492 25 4 10 10 10510 25 3 10 10 10522 50 3 10 10 10532 50 4 l0 10 10533 50 2 10 10 10535 50 7 10 10 10536 25 2 10 10 10537 50 4 10 10 10544 50 4 10 10 10545 50 4 10 10 10546 50 2 10 10 10550 50 7 10 10 10555 50 3 10 10 10561 50 4 10 10 10562 50 2 10 10 10568 50 4 10 10 10569 50 3 10 10 10571 50 4 10 10 10572 50 2 10 10 10591 50 1 10 10 10592 50 2 7 6 5593 25 2 9 9 8595 25 5 10 10 10597 25 3 10 10 10598 25 4 10 10 10604 25 4 10 10 10605 25 4 10 10 10606 25 2 10 10 10607 50 6 10 10 10608 25 5 10 9 9609 25 1 10 10 10610 25 5 10 9 9611 25 5 10 10 10612 50 3 10 10 10613 50 2 10 10 10626 50 6 10 10 10632 25 7 10 10 10635 50 8 10 10 10638 25 4 10 10 10641 50 7 10 10 10646 50 7 10 10 10650 50 2 10 10 10653 50 1 10 10 10659 50 1 10 10 10660 50 5 10 10 10665 25 6 9 8 9683 25 2 10 10 10686 50 10 10 10 10689 50 8 10 10 10690 50 8 10 10 10691 50 10 10 10 10694 50 3 10 10 10707 25 1 10 10 10718 50 6 10 10 10719 25 2 10 10 10720 25 2 10 10 10721 50 3 10 10 10725 50 1 6 9 7728 50 6 10 10 10730 50 9 10 10 10733 50 8 10 10 10Compara-tiveCompound*(1) 400 4 3 3 4(2) 400 3 0 1 2______________________________________*.sup.5 L.Q. . . . lambsquater*.sup.6 P.W. . . . pigweed*.sup.7 S.D. . . . sedge *(1) The same compound as shown in Table 2(2)

Number	Date	Country	Kind
59-164855	Aug 1984	JPX
60-1446	Jan 1985	JPX

Thia (oxa) diazole derivatives

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