GB1590870A - N-(5-t-butyl-3-isoxazolyl) alkanamide derivatives having herbicidal activity - Google Patents

N-(5-t-butyl-3-isoxazolyl) alkanamide derivatives having herbicidal activity Download PDF

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GB1590870A
GB1590870A GB2474578A GB2474578A GB1590870A GB 1590870 A GB1590870 A GB 1590870A GB 2474578 A GB2474578 A GB 2474578A GB 2474578 A GB2474578 A GB 2474578A GB 1590870 A GB1590870 A GB 1590870A
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Shionogi and Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D261/00Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/10Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D261/14Nitrogen atoms
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES, AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES, AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof

Description

ERRATUM SPECIFICATION NO 1590870 Page 1, line 1 (71) after We, insert SHIONOGI SEIYAKU KABUSHIKI KAISHA known as THE PATENT OFFICE 9May 1983 Bas 251103/1 Our British Patent No. 1,471,743 describes and claims a compound represented by the formula: <img class="EMIRef" id="026384822-00010001" />

wherein R represents hydrogen, alkyl or aryl ; R'represents hydrogen or alkyl ; R2 represents a group of the formula <img class="EMIRef" id="026384822-00010002" />

wherein RZ and R4 each independendy represent hydrogen, alkyl, alkenyl, alkynyl, aralkyl, aryl, alkoxy, or alkylthio, or R'and R'and the adjacent nitrogen atom form a ring optionally including another hetero atom (nitrogen, oxygen, or sulfur), or R2 is a group of the formulaCOYRJ wherein RJ represents alkyl, alkenyl, alkynyl, aralkyl, or aryl, and Y represents oxygen or sulfur; and X represents hydrogen, alkyl, or halogen; provided that R and X may optionally be taken together to represent alkylene, and alkyl, aralkyl, and/or aryl groups may each be optionally substituted with one or more substituents selected from halogen, alkyl, alkoxy, nitro or hydroxy. This invention can be regarded as a modification of the invention of said earlier patent in that the meanings for groups X and R are more restricted and in place of the group R2 as defined in Patent No. 1,471,743 is to be found a group-CO-R2 as defined below.

The isoxazole derivatives of the present invention show excellent herbicidal activity and exhibit very low toxicity towards humans, fish and other animals. It has also been discovered that the present isoxazole derivatives are smoothly decomposed or degraded in soil after their application thereto as herbicides.

According to the present invention there is provided a compound of the formula: <img class="EMIRef" id="026384822-00010003" />

wherein R is t-butyl; R1 is hydrogen; R2 is alkyl (preferably C to C6), alkenyl (preferably C3 or C,) or cyclopropyl ; and X is hydrogen or halogen.

(54) N- (5-t-BUTYL-3-ISOXAZOLYL) ALKANAMIDE DERIVATIVES HAVING HERBICIDAL ACTIVITY (71) We, SHIONOGI & CO. LTD., a Japanese Body Corporate, of 12 3-chome, Dosho-machi, Higashi-ku, Osaka, Japan, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement :- The present invention relates to N- (5-t-butyl-3-isoxazolyl) alkanamide derivatives and to herbicidal formulations containing the same.

Our British Patent No. 1,471,743 describes and claims a compound represented by the formula : <img class="EMIRef" id="026384822-00020001" />

wherein R represents hydrogen, alkyl or aryl ; RI represents hydrogen or alkyl ; R2 represents a group of the formula <img class="EMIRef" id="026384822-00020002" />

wherein R3 and RZ each independently represent hydrogen, alkyl, alkenyl, alkynyl, aralkyl, aryl, alkoxy, or alkylthio, or R3 and RS and the adjacent nitrogen atom form a ring optionally including another hetero atom (nitrogen, oxygen, or sulfur), or R is a group of the formulaCOYR wherein R5 represents alkyl, alkenyl, alkynyl, aralkyl, or aryl, and Y represents oxygen or sulfur ; and X represents hydrogen, alkyl, or halogen ; provided that R and X may optionally be taken together to represent alkylene, and alkyl, aralkyl, and/or aryl groups may each be optionally substituted with one or more substituents selected from halogen, alkyl, alkoxy, nitro or hydroxy. This invention can be regarded as a modification of the invention of said earlier patent in that the meanings for groups X and R are more restricted and in place of the group R as defined in Patent No. 1,471,743 is to be found a groupCOR2 as defined below.

The isoxazole derivatives of the present invention show excellent herbicidal activity and exhibit very low toxicity towards humans, fish and other animals. It has also been discovered that the present isoxazole derivatives are smoothly decomposed or degraded in soil after their application thereto as herbicides.

According to the present invention there is provided a compound of the formula: <img class="EMIRef" id="026384822-00020003" />

wherein R is t-butyl ; R'is hydrogen ; R2 is alkyl (preferably C2 to Ce), alkenyl (preferably C3 or C,) or cyclopropyl ; and X is hydrogen or halogen.

Among suitable alkyl groups R2 are ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, pentyl and hexyl. Suitablc alkenyl groups R2 include allyl, isopropenyl, butenyl and butadienyl. Halogen may be, for example, chlorine or bromine.

The isoxazole derivatives (I) of the present invention can be prepared according to the following synthetic routes: Fttrst routo <img class="EMIRef" id="026384822-00030001" />

<tb> <SEP> X <SEP> NH-R1 <tb> <SEP> (ii) <SEP> RI <tb> <SEP> 1 <SEP> 2 <tb> <SEP> R1 <tb> <SEP> 1 <tb> <SEP> X <SEP> I <SEP> 1, <SEP> N-CO-R <tb> <SEP> R <SEP> J~ <SEP> oSN <tb> <SEP> y <tb> Second <SEP> roi <SEP> t./ <tb> <SEP> It <SEP> 1. <tb>

<SEP> I <tb> <SEP> 'N-CO-lt' <tb> <SEP> R <SEP> N <tb> <SEP> haloGenation <SEP> (X=halo6en) <tb> <SEP> (la) <tb> wherein A is a residue of a reactive group such as halogen (e. g. chlorine or bromine) or an ester (e. g. tosyloxy, mesyloxy or-O-CO-Rz).

First route : A compound (I) can be prepared by reacting an amine (II) with an acylating reagent (III) with or without the presence of a base (e. g. pyridine, triethylamine or sodium hydroxide) and in the presence or absence of an inert solvent (e. g. water, methanol, benzene, dimethylformamide or dimethylsulfoxide) at room temperature or with heating.

Second route : Halogenation of an isoxazole (Ia) can be carried out in a conventional manner.

Thus, an isoxazole (Ia) may be treated with a halogenating agent (e. g. chlorine, bromine or sulfuryl chloride) in an inert solvent (e. g. active acid, methylene chloride or chloroform) at room temperature or with heating.

The present invention includes a process for the preparation of a compound in accordance with the invention, which process is in accordance with the above routes.

Practical examples of the preparation of the present isoxazole derivatives (I) in accordance with each of the above routes are now given in the following Synthetic Examples.

Synthetic Example 1.

Propionic anhydride (5 ml) is added to 3-amino-5-t-butylisoxazole (2. SZ g), and the resultant mixture is stirred at room temperature for 3 hours and then allowed to stand at room temperature overnight. The reaction mixture is poured onto icy water (50 ml). The precipitated crystals are filtered and shaken with benzene. The benzene layer is washed with saturated aqueous sodium bicarbonate and water each twice, dried over anhydrous sodium sulfate and evaporated to remove the solvent. The residue is recrystallized from cyclohexane to give N- (5-t-butyl-3-isoxazolyl) propion amide (2.91 g) is colourless crystals melting at 95. 06 to 96.0 C.

Synthetic Examples 2 to 5.

The following products (Ia) are obtained from the corresponding amines (II) by reaction with the corresponding anhydride. (RCO) 20, by procedures similar to that described in Example 1. <img class="EMIRef" id="026384822-00040001" />

TABLE 1 <img class="EMIRef" id="026384822-00040002" />

<tb> <SEP> Product(Ia) <tb> Syn. <tb>

Ex. <SEP> R <SEP> ~ <SEP> R'R'm. <SEP> p. <SEP> or <SEP> b. <SEP> p. <tb>

<SEP> 2t-BuH- <SEP> (CH,), <SEP> CH, <SEP> 67.068.-5'C <tb> <SEP> 3 <SEP> t-Bu <SEP> H- <SEP> (CH), <SEP> CH, <SEP> 96.5-97.5''C <tb> <SEP> 4 <SEP> t-Bu <SEP> H- <SEP> (CHs), <SEP> CH, <SEP> 72.0-73. <SEP> 5 C <tb> <SEP> CH3 <tb> <SEP> 5 <SEP> t-Bu <SEP> H <SEP> CH <SEP> 123 <SEP> 0l24. <SEP> 0 C <tb> <SEP> cH3 <tb> Note) The abbreviations in Table 1 have the following significance: Bu (butyl), Pr (propyl), i- (iso-), t- (tertiary-), m. p. (melting point), b. p. (boiling point).

Synthetic Example 6.

To a solution of 3-amino-5-t-butylisoxazole (2.80 g) in pyridine (10 ml) is added dropwise isobutyryl chloride (2.34 g) keeping the mixture below 10 C. The reaction mixture is stirred with cooling for 30 minutes and at room temperature for 1 hour and evaporated to remove the pyridine. The residue is mixed with 5% hydrochloric acid solution (40 ml) and shaken with methylene chloride. The methylene chloride layer is separated, washed with saturated aqueous sodium bicarbonate and water, dried over anhydrous sodium sulfate and evaporated to remove the methylene chloride.

The result is chromatographed on a column of silica gel and recrystallized from nhexane to give N- (5-t-butyl-3-isoxazolyl)-isobutyramide (3.85 g) as colorless needles melting at 123.0 to 124.0 C.

Synthetic Examples 7 to 10.

Reactions are effected as in Example 6 to give the following products (Ia) : <img class="EMIRef" id="026384822-00050001" />

TABLE 2 <img class="EMIRef" id="026384822-00050002" />

<tb> <SEP> Product(la) <tb> Syn. <tb>

Ex. <SEP> R <SEP> Rl <SEP> R2 <SEP> m. <SEP> p. <SEP> or <SEP> b. <SEP> p. <tb>

<SEP> CH, <tb> <SEP> 7 <SEP> ~ <SEP> t-Bu <SEP> H-CH <SEP> 133. <SEP> 5-135. <SEP> 0 C <tb> <SEP> ""cl, <tb> <SEP> CH, <tb> <SEP> 8 <SEP> t-Bu <SEP> H-CH"96. <SEP> 5-97. <SEP> 5 C <tb> <SEP> (CH,), <SEP> CH, <tb> <SEP> cti <tb> <SEP> 9 <SEP> t-Bu <SEP> H-C11 <SEP> J <SEP> z <SEP> 146. <SEP> 0-147. <SEP> 0 C <tb> <SEP> cil2 <tb> <SEP> CH, <tb> 10 <SEP> t-Bu <SEP> H-C <SEP> 3 <SEP> 70. <SEP> 571. <SEP> 5 C <tb> <SEP> 4141-CH2 <tb> Note) The abbreviations in Table 2 have the meanings given above for Table 1.

Synthetic Example 11.

Methylene chloride (20 ml) and sulfuryl chloride (5. 40 g) are added to N- (5-t- butyl-3-isoxazolyl) cyclopropanecarboxamide (4.17 g) and refluxed with hearing for 1.5 hours. The methylene chloride and the unreacted sulfuryl chloride are evaporated under reduced pressure. The residue is chromatographed on a column of silica gel and recrystallized from benzene to give N- (5-t-butyl-4-chloro-3-isoxazolyl) cyclopropanecarboxamide (4.10 g) as colorless needles melting at 129.5 to 131.0 C.

Synthetic Examples 12 to 17. ~-' Reactions are effected as in Ex mple llP to give the following products (Ib) : <img class="EMIRef" id="026384822-00060001" />

<tb> <SEP> R1 <SEP> R1 <tb> <SEP> X <SEP> N <SEP> ^ <tb> t-Bu| <SEP> XCOR <SEP> halogelwati <SEP> ou <SEP> t <SEP> Bu3 <SEP> XCOR <tb> <SEP> 0- <SEP> ! <SEP> 0 <tb> <SEP> (Ia) <SEP> (Ib) <tb> TABLE 3 <img class="EMIRef" id="026384822-00060002" />

<tb> <SEP> Product(Ib) <tb> Syn. <tb>

Ex. <SEP> X <SEP> R'R2 <SEP> m. <SEP> p. <tb>

12 <SEP> Cl <SEP> H-CHzCH <SEP> 88. <SEP> 0-89. <SEP> 0'C <tb> <SEP> CH, <tb> 13 <SEP> Cl <SEP> H <SEP> CHX <SEP> CH <SEP> 96.5-97.5 C <tb> <SEP> CH, <tb> <SEP> CH, <tb> 14 <SEP> ci <SEP> H-Cf < <SEP> 99. <SEP> 0-100''C <tb> <SEP> CH, <SEP> CH, <tb> 15 <SEP> Cl <SEP> H- <SEP> (CH), <SEP> CH, <SEP> 80.0-81.5 C <tb> <SEP> /CH, <tb> 16 <SEP> Cl <SEP> H--CH <SEP> 92. <SEP> 0-93. <SEP> 0 C <tb> <SEP> (CH,), <SEP> CH, <tb> <SEP> -P"2 <tb> 17-Br <SEP> H <SEP> = <SEP> 2 <SEP> 111. <SEP> 0112. <SEP> 0 C <tb> <SEP> 2 <tb> Note) * : Bromine and 1,2-dichloroethane are used.

Experiment 1. a) Compound tested: Compound No. Compound 1 N- (5-t-butyl-3-isoxazolyl) propionamide 2 N- (5-t-butyl-3-isoxazolyl) isobutyramide 3 N- (5-t-butyl-3-isoxazolyl)-sec-valeramide 4 N- (5-t-butyl-3-isoxazolyl) valeramide S N- (5-t-buryl-3-isoxazolyl)-2-methylvaleramide 6 N- (5-t-butyl-3-isoxazolyl) hexanamide 7 N- (5-t-butyl-3-isoxazolyl)-2-methylexamaide 8 N- (5-t-butyl-3-isoxazolyl) cyclopropanecarboxamide 9 PCP-Na (Sodium pentachlorophenoxide) b) Test method: (1) Pre-emergence test: 25 seeds of a test plant were sown in sandy soil in a polyethylene cup (diameter: 9 cm). After sowing, the seeds were covered with sandy soil to about 5 mm depth and an aqueous suspension of a test compound at a concentration of 100 ppm using Tween 20 (trademark of Atlas Powder Co.) as a spreader was applied over the surface of the sandy soil. The application rate of the test compound was 10 g/are and 30 g/are in aqueous suspension (water dilution: 10 L/are) applied by a sprayer. Administration was effected at 25 C in a greenhouse in natural sunlight. The degree of germination was evaluated 3 weeks after the application.

(2) Post-emergence test: test compound was applied to young plants 10 days after seeding. Administration and evaluation were effected as described above (1). c) Method of evaluation : The number of surviving plants was determined by the naked eye and the survival percentage for the sown seeds was then calculated. The survival percentage was marked in six degrees as follows: Survival percentage of the plant tested Mark Not more than 10% 5 11-25% 4 26*S0% 3 5175% 2 76-90% 1 Not less than 91% 0 d) Result: TABLE 4. <img class="EMIRef" id="026384822-00070001" />

<tb>

<SEP> Herbicidal <SEP> Activity <tb> <SEP> Application <SEP> Pre-emergence <SEP> test <SEP> Post-emergence <SEP> test <SEP> <tb> Compound <SEP> rate <tb> <SEP> No. <SEP> (g/are) <SEP> A <SEP> B <SEP> C <SEP> D <SEP> E <SEP> F <SEP> A <SEP> B <SEP> C <SEP> D <SEP> E <SEP> F <SEP> <tb> <SEP> 1 <SEP> 10 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 4 <SEP> 4 <SEP> 1 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 5 <SEP> 4 <SEP> 5 <tb> <SEP> 30 <SEP> 0 <SEP> 2 <SEP> 3 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 0 <SEP> 1 <SEP> 2 <SEP> 5 <SEP> 5 <SEP> 5 <tb> <SEP> 2 <SEP> 10 <SEP> 0 <SEP> 3 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 0 <SEP> 1 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <tb> <SEP> 30 <SEP> 0 <SEP> 4 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 0 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <tb> <SEP> 3 <SEP> 10 <SEP> 0 <SEP> 0 <SEP> 1 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 4 <SEP> 0 <SEP> 0 <tb> <SEP> 30 <SEP> 0 <SEP> 3 <SEP> 4 <SEP> 4 <SEP> 4 <SEP> 1 <SEP> 0 <SEP> 0 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 3 <tb> <SEP> 4 <SEP> 10 <SEP> 0 <SEP> 0 <SEP> 2 <SEP> 2 <SEP> 2 <SEP> 2 <SEP> 0 <SEP> 1 <SEP> 4 <SEP> 3 <SEP> 4 <SEP> 5 <tb> <SEP> 30 <SEP> 0 <SEP> 4 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 50 <SEP> 2 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <tb> <SEP> 5 <SEP> 10 <SEP> 0 <SEP> 3 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 0 <SEP> 0 <SEP> 5 <SEP> 2 <SEP> 5 <SEP> 5 <tb> <SEP> 30 <SEP> 0 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 0 <SEP> 3 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <tb> <SEP> 6 <SEP> 10 <SEP> 0 <SEP> 0 <SEP> 2 <SEP> 3 <SEP> 1 <SEP> 1 <SEP> 0 <SEP> 1 <SEP> 5 <SEP> 5 <SEP> 3 <SEP> 3 <tb> <SEP> 30 <SEP> 0 <SEP> 0 <SEP> 2 <SEP> 5 <SEP> 2 <SEP> 0 <SEP> 0 <SEP> 1 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 3 <tb> <SEP> 7 <SEP> 10 <SEP> 0 <SEP> 0 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 0 <SEP> 0 <SEP> 2 <SEP> 5 <SEP> 5 <SEP> 5 <tb> <SEP> 30 <SEP> 0 <SEP> 4 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 0 <SEP> 0 <SEP> 2 <SEP> 5 <SEP> 5 <SEP> 5 <tb> <SEP> 8 <SEP> 10 <SEP> 0 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 0 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <tb> <SEP> 30 <SEP> 0 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 3 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <tb> <SEP> 9 <SEP> 10 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 2 <SEP> 3 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 2 <SEP> 5 <tb> <SEP> 30 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 2 <SEP> 3 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 4 <SEP> 5 <tb> <SEP> 50 <SEP> 0 <SEP> 2 <SEP> 2 <SEP> 0 <SEP> 5 <SEP> 5 <SEP> 0 <SEP> 0 <SEP> 4 <SEP> 2 <SEP> 5 <SEP> 5 <SEP> <tb> Note) The abbreviations each have the following significance: A (Triticum aertivum, B (Echinochloa crusgalli), C (Digitaria adscendens), D (Brassica campestris), E (Polygonum logisetum), F (Amaranthus retroflexus), Thus, it can be seen that the tested amides (I) (Compound Nos. 1 to 8) each exhibited hardly any herbicidal activity against Triticum aestivum but showed excellent and selective herbicidal activity against Echinochloa c ; usgalli, Digituria adscendens, Brassica campestris, Polygonum longisetum and Amaranthus retroflexus, and their herbicidal activities were far more potent than that of a commercially available herbicide, PCP-Na (Compound No. 9).

Experiment 2.

The toxicity of N- (5-t-butyl-3-isoxazolyl) isoburyramide was examined on Oryzias latipes and found to be very low in comparison with that of commercially available PCP-Na.

Experiment 3.

Herbicidal activity against Echinosfiloa crusgalli and Monochoria vaginalis in water-pooled paddy fields. a) Compound tested: Compound 1 N- (5-t-butyl-3-isoxazolyl)-2-methylpentanamide 2 N- (S-t-butyl-3-isoxazolyl) cyclopropanecarboxamide 3 Propanil (Control b) Test method : Into 2 X 1F'are of a Wagner pot was placed paddy field soil and water was poured in to a depth of 3 cm. 25 seeds of a test plant were sown. Test compound was applied to Echinochloa crusgalli at the time of pre-emergence, one leaf term, two leaves term and three leaves term and to Monochoria vaginalis at the time of pre-emergence, small leaf term, one leaf term and two leaves term. The application rate of the test compounds included 6.25 g, 12.5 g, 25 g, 50 g, 75 g and 100 g each per are. The number of surviving plants was examined in comparison with that in a non-applied section. The evaluation was marked in six degrees of survival percentage as in Experiment 1. d) Result : TABLE 5 <img class="EMIRef" id="026384822-00090001" />

<tb> <SEP> Application <SEP> Echinochloa <SEP> cnusgalli <SEP> Monochoria <SEP> vaginalis <SEP> <tb> Compound <SEP> rate <tb> <SEP> No. <SEP> (g/are) <SEP> PRE <SEP> 1L <SEP> 2L <SEP> 3L <SEP> PRE <SEP> SL <SEP> 1L <SEP> 2L <tb> <SEP> 6. <SEP> 25 <SEP> 2 <SEP> 1 <SEP> 1 <SEP> 0 <SEP> 0 <SEP> 4 <SEP> 3 <SEP> 3 <SEP> <tb> <SEP> 12.5 <SEP> 2 <SEP> 3 <SEP> 3 <SEP> 0 <SEP> 0 <SEP> 5 <SEP> 4 <SEP> 3 <tb> <SEP> 1 <SEP> 25 <SEP> 2 <SEP> 5 <SEP> 5 <SEP> 0 <SEP> 0 <SEP> 5 <SEP> 5 <SEP> 4 <SEP> <tb> <SEP> 50 <SEP> 3 <SEP> 5 <SEP> 5 <SEP> 2 <SEP> 2 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> <tb> <SEP> 75 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 2 <SEP> 3 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> <tb> <SEP> 100 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 4 <SEP> 3 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> <tb> <SEP> 6.25 <SEP> 3 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 4 <SEP> 5 <SEP> 5 <SEP> 5 <tb> <SEP> 12.5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <tb> <SEP> 2 <SEP> 25 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <tb> <SEP> -50 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> <tb> <SEP> . <SEP> 75 <SEP> 55555555 <SEP> <tb> <SEP> 100 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <tb> <SEP> 6.25 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 2 <SEP> 1 <SEP> 1 <tb> <SEP> 12.5 <SEP> 1 <SEP> 1 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 2 <SEP> 1 <tb> <SEP> 3 <SEP> 25 <SEP> 3 <SEP> 2 <SEP> 1 <SEP> 0 <SEP> 0 <SEP> 2 <SEP> 2 <SEP> 2 <SEP> <tb> <SEP> 50 <SEP> 4 <SEP> 2 <SEP> 1 <SEP> 0 <SEP> 0 <SEP> 3 <SEP> 3 <SEP> 3 <tb> <SEP> 75 <SEP> 4 <SEP> 3 <SEP> 2 <SEP> 0 <SEP> 2 <SEP> 4 <SEP> 3 <SEP> 3 <SEP> <tb> <SEP> 100 <SEP> 5 <SEP> 3 <SEP> 2 <SEP> 0 <SEP> 2 <SEP> 4 <SEP> 3 <SEP> 3 <tb> Note) The abbreviations each have the following significance: PRE (pre-emergence), IL (one leaf term), 2L (two leaves term), 3L (three leaves term), SL (small leaf term). d) Conclusion: Thus, the tested compounds of this invention (Ccmpounds Nos. 1 and 2) showed excellent herbicidal activity against Echinochloa crusgalli and Monochoria vaginalis in water-pooled paddy fields in comparison with a commercially available herbicide, propanil. Additionally, chemical poisoning of rice plants by any of the compounds (Compound Nos. 1-3) was almost never observed.

The present isoxazole derivatives (I) show excellent herbicidal activity against various grasses with a small rate of application. These compounds can also be used as non-selective or selective herbicides by changing the rate of application thereof. The herbicides of this invention are generally applicable to various crops including wheat, barley, corn, carrots, peanuts, peas and rice plants in order to protect them from un desired weeds and grasses. They can also be applied to sugar cane, potatoes, sweet potatoes, mentha, egg-plant or Spanish paprica after planting thereof. Virtually no harmful chemical effect at all is observed as a result of the action of the present herbi cides on these crops, such effects as are observed being so slight that the crops easily recover. Furthermore, the present herbicides are quite harmless to humans and domestic animals, and they also exhibit very low toxicity towards fish and shell fish. Thus, the herbicides of the present invention have a very high degree of safety'and also result in a suitable amount of residual active compound remaining in the soil after use thereof.

Thus, the present invention includes a herbicidal formulation which comprises a compound in accordance with the invention formulated for herbicidal use and, optionally, together with a diluent, carrier or excipient.

The present herbicidal formulations may, for example, be prepared by mixing the effective isoxazole derivative (I) with an inert solid or liquid carrier, optionally in combination with a further adjuvant (e. g. selected from emulsifiers, stabilizers, dispersants, suspending agents, spreaders, penetrants and wetting agents) and converting the resultant mixture into the desired preparation form (e. g. an emulsion, a wettable powder, granules, a dust, tablets or pills). Examples of suitable carriers are solid carriers (e. g. clay, talc, diatomaceous earth or bentonite) and liquid carriers (e. g. water, alcohols, acetone, benzene, toluene, xylene, solvent naphtha or cyclohexane).

The herbicidal formulations of this invention may also include, and the present compounds may be used with, agricultural chemicals (e. g. insecticides, fungicides or other herbicides), manuring ingredients (e. g. ammonium sulfate or urea) or soil treating agents.

The invention thus includes a method of producing a herbicidal effect in an environment, which method comprises administering to the environment an effective amount of a compound or formulation of the invention. Such a method may be used in treating crop areas to remove or inhibit the growth of weeds or grasses.

The invention also includes a method of killing a plant, which method comprises applying thereto an effective amount of a compound or formulation in accordance with the invention.

The herbicidal formulations of the present invention will now be illustrated by the following Examples.

Example A.

N- (5-t-butyl-3-isoxazolyl) isobutylamide (50 parts by weight), calcium ligninsulfonate (3 parts by weight), Sorpol (made by Toho Chemical Industry, Co., Ltd.) (3 parts by weight) and diatomaceous earth (44 parts by weight) are mixed and pul- verised to produce a wettable powder.

Example B.

N- (5-t-butyl-3-isoxazolyl)-2-methylvaleramide (5 parts by weight) and clay (95 parts by weight) are mixed and pulverized to produce a dust.

Example C.

N- (5-t-butyl-3-isoxazolyl) cycloprapanecarboxamide (5 parts by weight), calcium ligninsulfonate (. parts by weight), bentonite (30 parts by weight) and clay (60 parts by weight) are mixed, pulverized, mixed with water, kneaded, granulated and dried to produce granules.

Claims (34)

WHAT WE CLAIM IS :-
1. A compound of the formula: <img class="EMIRef" id="026384823-00100001" />
wherein R is t-butyl ; Rl is hydrogen; R ! is alkyl, alkenyl or cyclopropyl ; and X is hydrogen or halogen.
2. A compound as claimed in claim 1, wherein R2 is (C2 to C, ;) alkyl or (C3 or C,) alkenyl.
3. A compound as claimed in claim 2, wherein R2 is ethyl, propyl, i-propyl, buryl, r-butyl, pentyl, hexyl, allyl, isopropyl, butenyl or butadienyl.
4. A compound as claimed in any one of claims 1 to 3 wherein X is chlorine or bromine.
5. N-(5-t-butyl-3-isoxazolyl) propionamide.
6. N- (5-t-butyl-3-isoxazolyl) isobutyramide.
7. N- (5-t-butyl-3-isoxazolyl)-sec-valeramide.
8. N- (5-t-butyl-3-isoxazolyl) valeramide.
9. N-5-t-butyl-3-isoxazolyl)-2-methylvaleramide.
10. N- (5-t-butyl-3-isoxazolyl) hexanamide.
11. N- (5-t-butyl-3-isoxazolyl)-2-methylhexanamide.
12. N- (5-t-butyl-3-isoxazolyl) cyclopropanecarboxamide.
13. A compound as claimed in claim 1 and substantially as referred to hereinbefore, other than a compound as claimed in any one of claims 5 to 12.
14. A process for preparing a compound as claimed in claim 1, which process com- prises either a) reacting an amine of the formula: <img class="EMIRef" id="026384823-00110001" />
with an acylating reagent of the formula : ACOR2 (III) wherein A is a residue of reactive group; or b) halogenatmg an isoxazole of the formula : <img class="EMIRef" id="026384823-00110002" />
15. A process as claimed in claim 14, wherein A is halogen or an ester group.
16. A process as claimed in claim 14 or claim 15, wherein, in (a), the reaction is effected in the presence of a base.
17. A process as claimed in claim 16, wherein the base is pyridine, triethylamine or sodium hydroxide.
18. A process as claimed in any one of claims 14 to 17, wherein in (a), the reaction is effected in an inert solvent.
19. A process as claimed in claim 14, wherein the halogenation is achieved by the use of chlorinc, bromine or sulfuryl chloride as a halogenating agent.
20. A process as claimed in claim 14 or claim 19, wherein the halogenation is effected in an inert solvent.
21. A process as claimed in claim 14 and substantially as hereinbefore described in any one of the foregoing Synthetic Examples.
22. A compound as claimed in claim 1 which has been prepared by a process as claimed in any one of claims 14 to 21.
23. A herbicidal formulation which comprises a compound as claimed in any one of claims 1 to 13 and 22 formulated for herbicidal use.
24. A formulation as claimed in claim 23 also comprising a diluent, carrier or excipient.
25. A formulation as claimed in claim 24, wherein the diluent, carrier or excipient is clay, talc, diatomaceous earth, bentonite, water, an alcohol, acetone, benzene, toluene, xylene, solvent, naphtha or cyclohexane.
26. A formulation as claimed in any one of claims 23 to 25 also comprising an emulsifier, at stabiliser, a dispersant, a suspending agent, a spreader, a penetrant, a wetting agent, an insecticide, a fungicide, a herbicide other than a compound as claimed in any one of claims 1 to 13 and 22, a manuring ingredient or a soil treating agent.
27. A formulation as claimed in any one of claims 23 to 26 in the form of an emulsion, a wettable powder, granules, a dust, a pill or a tablet.
28. A formulation as claimed in claim 23 and substantially as hereinbefore des cribed in any one of Examples A to C.
29. A method of producing a herbicidal effect in an environment, which method comprises administering to the environment an effective amount of a compound as claimed in any one of claims 1 to 13 and 22 or a formulation as claimed in any one f claims 23 to 28.
30. A method as claimed in claim 29 when used in treating a crop area to remove or inhibit the growth of weeds or grasses.
31. A method as claimed in claim 30, wherein the crop is wheat, barley, corn, carrots, peanuts, peas, rice, sugar cane, potatoes, sweet potatoes, mentha, egg-plant or Spanish paprica.
32. A method as claimed in claim 29 and substantially as hereinbefore described in Experiment 1 or Experiment 3.
33. A crop which has been grown in an area to which a method as claimed in claim 30 or claim 31 has been applied.
34. A method of killing a plant, which method comprises applying thereto an effective amount of a compound as claimed in any one of claims 1 to 13 and 22 or of a formulation as claimed in any one of claims 23 to 28.
GB2474578A 1978-05-31 1978-05-31 N-(5-t-butyl-3-isoxazolyl) alkanamide derivatives having herbicidal activity Expired GB1590870A (en)

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0105548A1 (en) * 1982-10-05 1984-04-18 SHIONOGI &amp; CO., LTD. Propynylaminoisoxazole derivatives
US4500343A (en) * 1982-09-30 1985-02-19 Eli Lilly And Company Oxazolyl and thiazolyl amides as herbicides
US4593024A (en) * 1985-08-15 1986-06-03 International Minerals & Chemical Corp. Dihydroisoxazole compounds and anthelmintic use
US4694016A (en) * 1985-10-18 1987-09-15 International Minerals & Chemical Corp. Phthalamide derivatives with anthelmintic activity
US6344476B1 (en) 1997-05-23 2002-02-05 Bayer Corporation Inhibition of p38 kinase activity by aryl ureas
US7678811B2 (en) 2002-02-11 2010-03-16 Bayer Healthcare Llc Pyridine, quinoline, and isoquinoline N-oxides as kinase inhibitors
US7838541B2 (en) 2002-02-11 2010-11-23 Bayer Healthcare, Llc Aryl ureas with angiogenesis inhibiting activity
US7897623B2 (en) 1999-01-13 2011-03-01 Bayer Healthcare Llc ω-carboxyl aryl substituted diphenyl ureas as p38 kinase inhibitors
US7928239B2 (en) 1999-01-13 2011-04-19 Bayer Healthcare Llc Inhibition of RAF kinase using quinolyl, isoquinolyl or pyridyl ureas
US8076488B2 (en) 2003-02-28 2011-12-13 Bayer Healthcare Llc Bicyclic urea derivatives useful in the treatment of cancer and other disorders
US8110587B2 (en) 2002-02-11 2012-02-07 Bayer Healthcare Llc Aryl ureas as kinase inhibitors
US8124630B2 (en) 1999-01-13 2012-02-28 Bayer Healthcare Llc ω-carboxyaryl substituted diphenyl ureas as raf kinase inhibitors
US8207166B2 (en) 2004-04-30 2012-06-26 Bayer Healthcare Llc Substituted pyrazolyl urea derivatives useful in the treatment of cancer
US8637553B2 (en) 2003-07-23 2014-01-28 Bayer Healthcare Llc Fluoro substituted omega-carboxyaryl diphenyl urea for the treatment and prevention of diseases and conditions
US8796250B2 (en) 2003-05-20 2014-08-05 Bayer Healthcare Llc Diaryl ureas for diseases mediated by PDGFR

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4500343A (en) * 1982-09-30 1985-02-19 Eli Lilly And Company Oxazolyl and thiazolyl amides as herbicides
EP0105548A1 (en) * 1982-10-05 1984-04-18 SHIONOGI &amp; CO., LTD. Propynylaminoisoxazole derivatives
US4593024A (en) * 1985-08-15 1986-06-03 International Minerals & Chemical Corp. Dihydroisoxazole compounds and anthelmintic use
US4694016A (en) * 1985-10-18 1987-09-15 International Minerals & Chemical Corp. Phthalamide derivatives with anthelmintic activity
US6344476B1 (en) 1997-05-23 2002-02-05 Bayer Corporation Inhibition of p38 kinase activity by aryl ureas
US8841330B2 (en) 1999-01-13 2014-09-23 Bayer Healthcare Llc Omega-carboxyaryl substituted diphenyl ureas as raf kinase inhibitors
US8124630B2 (en) 1999-01-13 2012-02-28 Bayer Healthcare Llc ω-carboxyaryl substituted diphenyl ureas as raf kinase inhibitors
US7897623B2 (en) 1999-01-13 2011-03-01 Bayer Healthcare Llc ω-carboxyl aryl substituted diphenyl ureas as p38 kinase inhibitors
US7928239B2 (en) 1999-01-13 2011-04-19 Bayer Healthcare Llc Inhibition of RAF kinase using quinolyl, isoquinolyl or pyridyl ureas
US9181188B2 (en) 2002-02-11 2015-11-10 Bayer Healthcare Llc Aryl ureas as kinase inhibitors
US8071616B2 (en) 2002-02-11 2011-12-06 Bayer Healthcare Llc Pyridine, quinoline, and isoquinoline N-oxides as kinase inhibitors
US8110587B2 (en) 2002-02-11 2012-02-07 Bayer Healthcare Llc Aryl ureas as kinase inhibitors
US7838541B2 (en) 2002-02-11 2010-11-23 Bayer Healthcare, Llc Aryl ureas with angiogenesis inhibiting activity
US7678811B2 (en) 2002-02-11 2010-03-16 Bayer Healthcare Llc Pyridine, quinoline, and isoquinoline N-oxides as kinase inhibitors
US8242147B2 (en) 2002-02-11 2012-08-14 Bayer Healthcare Llc Aryl ureas with angiogenisis inhibiting activity
US8618141B2 (en) 2002-02-11 2013-12-31 Bayer Healthcare Llc Aryl ureas with angiogenesis inhibiting activity
US8076488B2 (en) 2003-02-28 2011-12-13 Bayer Healthcare Llc Bicyclic urea derivatives useful in the treatment of cancer and other disorders
US8796250B2 (en) 2003-05-20 2014-08-05 Bayer Healthcare Llc Diaryl ureas for diseases mediated by PDGFR
US8637553B2 (en) 2003-07-23 2014-01-28 Bayer Healthcare Llc Fluoro substituted omega-carboxyaryl diphenyl urea for the treatment and prevention of diseases and conditions
US8207166B2 (en) 2004-04-30 2012-06-26 Bayer Healthcare Llc Substituted pyrazolyl urea derivatives useful in the treatment of cancer

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