# Patent

## Title
Pyrazolone derivatives and their use as herbicides

## Abstract

This is a division, of application Ser. No. 290,002, filed Sept. 18, 1972, now U.S. Pat. No. 4,001,004.

## Background
1. Field of the Invention

This invention relates to a novel herbicidal composition for use in paddy fields.

2. Description of the Prior Art

Among existing herbicides used in transplanted paddy fields, pentachlorophenol, diphenyl ethers, etc. are well known for their excellent herbicidal effects when applied at the initial stage of growth of weeds. On the other hand, DCPA and SWEP.M (a mixture containing 20% of methyl-N-(3,4-dichlorophenyl) carbamate and 0.7% of ethyl 2-methyl-4-chlorophenoxy acetate) are also used as a herbicide but they are applied after the weeds have grown to some extent. DCPA, however, requires drainage of water completely from the paddy fields before its application. If the draining is insufficient, DCPA fails to give satisfactory weeding effects. In this connection, it is practically extremely difficult to drain water completely from paddy fields, so that DCPA is rarely employed in practical application. SWEP.M may be used in fields filled with water, but its herbicidal effects and phytotoxicity on rice plants vary considerably depending on particular temperatures and soil conditions, i.e., the herbicidal activities of the agent are reduced under low temperature conditions while the adverse effects of the agent become pronounced under high temperature conditions. Furthermore, in the paddy fields with continued leaching of water, the agent penetrates into the soil and is absorbed by roots of the rice plants, causing damage to the rice plants.

In addition, when SWEP.M is used in combination with carbamate or organic phosphorous base insecticides, a great problem occurs in practical applications in that rice plants are seriously damaged. Accordingly, it is strongly desired to develop a novel herbicide which has stable effects in removing weeds which have grown to a certain degree, without resulting in phytotoxicity to the rice plants.

It is therefore an object of the invention to provide a novel herbicidal composition of the nature described which will overcome the above-described disadvantages.

It is another object of the invention to provide a herbicidal composition which is effective for controlling annual weeds or perennial weeds which have already grown to a certain degree.

It is still another object of the invention to provide a herbicidal composition which retains its herbicidal effects for a long period of time.

It is yet another object of the invention to provide a herbicidal composition which may be used without draining of water in the paddy fields.

An important feature of the invention resides in a herbicidal composition for use in paddy fields comprising .alpha.-(.beta.-naphthoxy)-propionanilide and a thiocarbamate compound expressed by the formula ##STR1## Wherein A represents C.sub.2 H.sub.5, CH(CH.sub.3).sub.2, ##STR2## or  wherein X represents Cl, F, CH.sub.3, C.sub.2 H.sub.5, n-C.sub.3 H.sub.7, iso-C.sub.3 H.sub.7, tert-C.sub.4 H.sub.9, OCH.sub.3 or SCH.sub.3, and Y represents H or CH.sub.3); R.sub.1 and R.sub.2 represent alkyl containing 1 to 3 carbon atoms or R.sub.1 and R.sub.2, together with N form a 6-membered heterocyclic ring (1-hexamethyleneimine).

The .alpha.-(.beta.-naphthoxy)-propionanilide (hereinafter referred to as NOPA for abbreviation) has a melting point from 125.degree. to 127.degree. C.

The present inventors discovered as a result of an extensive study on various kinds of herbicides that the above-described herbicidal composition has remarkably high effects for controlling particularly annual weeds and perennial weeds at a relatively advanced stage of growth and retains herbicidal activities for a long period of time, so that it is made possible to control weeds completely which would germinate after the treatment.

The composition of the present invention includes NOPA which is effective for controlling annual and perennial broad-leaved weeds and the thiocarbamate compound (I) which is effective for controlling narrow-leaved weeds, with the result that excellent synergistic effects of these two compounds are obtained. Moreover, the composition does not necessarily require drainage of the paddy fields and gives excellent effects even when used in a water-filled field. The mixing ratio of NOPA to the compound (I) is preferably 1 : 1-4 but it may be varied over a relatively wide range according to particular requirements.

The compound (I) of the herbicidal composition of the present invention includes the following: ##STR3##

The herbicidal composition of the present invention may be used in combination with solid carriers such as diluent, filler and the like. If necessary, the herbicidal composition may be used in the form of a wettable powder or granules by addition of adjuvants such as a stabilizing agent, a dispersing agent, a suspending agent, a spreader, a penetrating agent, a wetting agent and the like. Moreover, the herbicide of the present invention may be provided in a form mixed with agricultural chemicals such as fungicides, insecticides or other herbicides, or fertilizers such as urea, ammonium sulfate, ammonium phosphate, potassium salts or soil conditioners and the like. When the herbicide of the present invention is formed into granules, it is desired that such granules contain therein 1 - 20% by weight of the composition of the present invention, and when formed into a wettable powder, 10 - 50%.

The herbicidal activities of the composition of the present invention will be understood from the following Experimental Examples.

3.3 Kg of soil having a variety of weeds naturally grown in paddy fields were put into a/5000 wagner pots. 0.8g. of each of N,P.sub.2 O.sub.5 and K.sub.2 O provided in the form of fertilizer was placed in the soil to which was then added a suitable amount of water. The mixture was fully agitated and the wagner pots were brought to irrigated conditions. On the other hand, rice plant seedlings (3 leaf stage) were grown in a greenhouse, and two stubbles of rice plants, each having two seedlings, were planted in each pot at a depth of 3cm. Then, 200mg. of barnyard grass seeds were sown over and mixed with the surface soil of each of the pots which were placed in a greenhouse to grow the seeds. 15 days after the planting, there grew in the pots weeds such as barnyard grass of leaf age 2.5 (5-10cm), Cyperus difformis (3-5cm), Monochoria vaginalis (2-5cm), Rotala indica (2-5cm) and Dopatrium junceum (2-5cm). A predetermined amount of NOPA, or a granulate of the compound (1) or a mixture of both compounds was added, as shown in Table I, to the water of each pot. One month after the treatment, the remaining amount of the weeds was examined with the results as shown in Table 1. During the test, the water depth of the pot was maintained at 3cm. __________________________________________________________________________ Rice Plant (% to hand- Weeds weeding weight) (% to no weeding weight) __________________________________________________________________________ Dose of                  Cyper- Mono-   Cal- Ele- Composition Number   Barn- us  choria  litri- ocharis Applied     of       yard dif- vagi- Rotala che- aci- (A.I g/a)   tiller Weight grass formis nalis indica verna cularis __________________________________________________________________________ 2 100.0 103.2 100.0 100.0 16.3 11.4 31.4 38.2 5 100.0 101.6 100.0 92.1 4.1 3.2 18.6 12.3 N O P A   10 100.0 100.1 99.8 84.6 0.0 0.0 0.0 0.0 20 100.0 99.4 94.3 71.4 0.0 0.0 0.0 0.0 5 100.0 101.3 28.3 18.3 94.2 88.1 98.2 26.8 Compound B 10 100.0 99.1 14.2 0.0 87.1 71.9 78.3 16.1 20 100.0 97.4 0.0 0.0 53.4 37.4 54.9 10.0 5 100.0 99.8 25.3 14.9 89.3 80.5 96.3 21.6 Compound D 10 100.0 98.3 5.4 0.0 72.8 68.4 69.2 13.5 20 90.0 91.2 0.0 0.0 42.3 31.1 54.6 0.0 5 100.0 93.5 37.9 31.2 100.0 96.8 100.0 63.2 Compound E 10 90.0 89.2 19.6 11.3 91.3 83.8 84.6 39.8 20 80.0 86.4 8.7 0.0 83.4 71.2 68.1 16.5 5 100.0 100.0 47.8 38.1 88.1 90.0 92.4 88.4 Compound F 10 100.0 98.2 18.4 14.2 80.0 82.1 78.9 70.0 20 90.0 95.6 0.0 0.0 68.4 72.0 66.4 43.9 5 100.0 99.1 49.3 48.1 90.0 89.9 93.4 70.4 Compound G 10 100.0 98.6 13.4 24.1 82.1 88.7 91.2 68.2 20 90.0 94.5 0.0 0.0 64.1 69.3 80.4 54.1 5 100.0 101.4 20.4 10.3 82.1 30.1 40.0 38.9 Compound H 10 110.0 99.8 0.0 0.0 20.0 0.8 30.0 24.1 20 110.0 92.4 0.0 0.0 0.0 0.0 10.0 0.0 5 104.2 101.6 18.4 12.4 79.4 31.4 41.0 36.5 Compound J 10 100.1 100.7 0.0 0.0 21.0 0.9 28.6 21.4 20 102.4 99.8 0.0 0.0 0.0 0.0 10.1 0.0 5 107.6 102.7 16.2 10.4 62.7 32.1 32.6 30.6 Compound K 10 109.2 101.6 0.0 0.0 19.1 0.9 21.4 19.8 20 101.4 100.2 0.0 0.0 0.0 0.0 9.7 0.0 5 105.6 100.7 21.9 10.9 81.2 45.0 25.0 30.2 Compound N 10 104.3 100.2 0.0 0.0 21.9 29.6 20.1 18.1 20 100.7 100.6 0.0 0.0 1.8 10.8 10.7 1.9 NOPA+Compound B 5     10  110.0 104.2 6.0 4.8 7.9 0.8 7.1 8.8 5     20  100.0 101.2 0.0 0.0 0.0 0.0 6.0 7.0 10     10  100.0 99.8 1.0 0.8 0.0 0.8 5.8 5.0 10     20  100.0 97.4 0.0 0.0 0.0 0.0 0.0 0.0 NOPA+Compound D 5     10  110.0 98.2 4.4 2.3 8.9 2.4 10.0 4.2 5     20  110.0 98.8 0.0 0.0 0.0 0.0 5.2 0.0 10     10  100.0 99.7 0.8 1.2 0.0 0.0 4.3 0.0 10     20  90.0 99.4 0.0 0.0 0.0 0.0 0.0 0.0 NOPA+Compound E 10     10  90.0 103.1 0.9 12.2 10.0 10.0 14.8 30.0 20      20 100.0 99.8 0.0 0.0 0.0 0.0 0.0 0.0 NOPA+Compound G 10     20  100.0 107.4 0.0 12.2 10.0 10.0 12.4 5.0 20     20  110.0 99.8 0.0 0.0 0.0 0.0 0.0 0.0 NOPA+Compound H 5     10  100.0 107.4 6.0 0.8 5.4 10.0 10.4 5.0 5     20  100.0 103.1 0.0 0.0 0.0 0.0 0.4 0.0 10     10  100.0 99.8 0.0 0.0 0.0 0.0 8.4 0.0 10     20  100.0 97.9 0.0 0.0 0.0 0.0 0.0 0.0 20     20  100.0 98.8 0.0 0.0 0.0 0.0 10.0 0.0 NOPA+Compound J 5      5  100.1 108.4 2.7 0.2 2.1 4.8 6.7 1.7 5     10  100.0 100.6 0.0 0.0 0.0 0.0 0.0 0.0 10     10  100.7 100.3 0.0 0.0 0.0 0.0 0.0 0.0 20     20  100.4 100.1 0.0 0.0 0.0 0.0 0.0 0.0 NOPA+Compound K 5      10 100.4 100.6 4.7 0.6 2.9 6.8 6.5 3.9 10      5  100.7 100.5 0.0 0.0 0.0 0.0 0.0 0.0 10     10  100.6 100.1 0.0 0.0 0.0 0.0 0.0 0.0 10     20  100.4 100.0 0.0 0.0 0.0 0.0 0.0 0.0 NOPA+Compound N 5      5  100.7 100.2 3.1 0.9 2.8 7.2 8.7 4.2 10     10  100.6 100.1 0.0 0.0 0.0 0.0 0.0 0.0 10     20  100.6 100.1 0.0 0.0 0.0 0.0 0.0 0.0 2 70.0 80.9 40.8 24.4 5.0 10.0 10.0 15.0 M C P A*  4 60.0 71.2 12.8 12.2 0.0 0.0 0.0 0.0 6 40.0 67.1 2.3 10.0 0.0 0.0 0.0 0.0 N I P**   20 100.0 98.8 60.0 40.0 80.0 60.0 74.0 79.9 90.0 92.1 100 100 100 100 100 100 no weeding           (2.64g (0.22 (0.24 (0.10 (0.07 (0.09 /pot) /pot) /pot) /pot) /pot) /pot) 100  100 hand weeding (10  3.45g tillers) /pot) __________________________________________________________________________ Note) *Sodium 2-methyl-4-chlorophenoxy acetate **2,4-dichloro-4'-nitrodiphenyl ether

In a concrete pot having a dimension of 50 .times. 50 .times. 50 cm was put soil of paddy fields having a variety of weeds naturally grown in the paddy fields. Rice plants were grown in the pot to use them as test specimens. The rice plants were transplanted in stubbles each containing two seedlings and spaced at a distance of 20 cm from each other. 15 days after transplanting a predetermined amount of the compounds to be tested was sprayed over the pot. One month after the treatment with the compounds, the remaining amount of weeds was examined with the test results as shown in Table 2. During the test the water depth of the concrete pot was maintained at 3 cm. __________________________________________________________________________ Rice Plant (% to hand Weeds weeding weight) (% to no weeding weight) __________________________________________________________________________ Dose of                  Eleo- Others __________________________________________________________________________ Composition Number   Barn- charis Broad- Narrow- Applied     of       yard acicu- leaved leaved (A.I g/a)   tiller Weight grass laris weeds weeds __________________________________________________________________________ 5           104.0 101.8 99.8 10.0 21.8 80.0 N O P A10   100.0 100.9 80.7 0.0 0.0 10.0 20          100.0 102.1 80.4 0.0 0.0 0.0 NOPA+Compound A 20     20  104.0 106.4 10.0 2.8 0.0 0.0 NOPA+Compound B 10     10  96.0 103.4 0.0 0.0 0.0 0.0 20     20  100.0 107.7 0.0 0.0 0.0 0.0 NOPA+Compound C 20     20  96.0 104.3 0.9 5.4 0.0 0.0 NOPA+Compound D 10     20  104.0 101.4 0.0 0.0 0.0 0.0 20     20  104.0 102.8 0.0 0.0 0.0 0.0 NOPA+Compound E 20     20 100.0 101.4 9.8 2.3 0.0 0.0 NOPA+Compound F 20     20  104.0 99.0 0.0 0.0 0.0 0.0 NOPA+Compound G 20     20  108.0 98.8 0.0 0.0 0.0 0.0 NOPA+Compound H 5     10  104.0 109.4 8.0 0.2 0.7 0.4 5     20  104.0 100.8 0.0 0.0 0.0 0.0 10     10  108.0 100.4 4.0 0.1 0.0 0.0 10     20  100.0 102.1 0.0 0.0 0.0 0.0 20     20  104.0 97.7 0.0 0.0 0.0 0.0 NOPA+Compound I 20     20  101.0 108.4 0.2 0.1 0.0 0.0 NOPA+Compound J 10     10  104.2 100.8 0.0 0.0 0.0 0.0 NOPA+Compound L 99. 10     10  99.4 98.7 0.0 0.0 0.0 0.0 NOPA+Compound M 10     10  107.3 100.9 0.0 0.0 0.0 0.0 NOPA+Compound N 10     10  104.0 102.4 0.0 0.0 0.0 0.0 M C P A 3   96.0 92.4 76.1 10.2 0.0 42.1 6           88.0 89.0 40.1 0.0 0.0 38.8 Simetryne*4.5 96.0 97.7 14.2 0.0 0.0 0.0 6           88.0 82.1 0.0 0.0 0.0 0.0 N T P20     104.0 107.0 78.1 98.8 60.5 70.2 96.0 90.9 100 100 100 100 no weeding           (38.4g (4.02g (28.4g (18.7g /pot) /pot) /pot) /pot) 100  100 --  --  --  -- hand weeding (25  (20.4g tillers /pot) /pot) __________________________________________________________________________ Note) *Simetryne...2-methylthio-4,6-bis(ethylamino)-S-triazine

Paddy fields having a variety of naturally occuring weed seeds were plowed and fertilized (with 1 kg of each of N,P.sub.2 O.sub.5 and K.sub.2 O per a). The paddy fields were then divided into sections each having an area of 10 m.sup.2 (2.5 .times. 4 m). Stubbles each having two rice seedlings of leaf age 5.0 were replanted in each section with a ridge width of 30 cm and with a stubble width of 15 cm. After the planting, the water depth of the field was maintained at 3 - 5 cm. At leaf ages of 2 - 3 cm of the weeds (15 days after the planting), 300 g/a of NOPA and compounds B, D or H and mixed granules of both compounds were dispersed over the watered paddy field.

The examination of the weed growth was carried out one month after the planting, while the examination of rice yields was carried out after 4 months to give the test results of Table 3. __________________________________________________________________________ Weeds (% to no weeding (air-dried weight)) Phytotoxicity Rice Plant __________________________________________________________________________ Dose of         Cyper-  Eleo-          Yield Composition Barn- us  Broad charis Herbici- Degree (% to Applied yard dif- leaf acicu- dal of phyto- hand- (A.I g/a)   grass formis weeds laris effect toxicity weeding) __________________________________________________________________________ 10 87.5 30.0 0.5 16.1 Low   No   89 N O P A   15 85.6 18.7 0.4 12.1 Low   No   90 20 84.7 12.7 0.1 9.8 Low   No   91 Compound B 10 0.6 0.4 37.5 11.2 Moderate No   92 20 0.4 0.1 29.7 2.0 Moderate No   93 Compound D 10 0.2 0.7 29.6 5.7 Moderate No   94 20 0.1 0.2 21.4 4.1 Moderate No   95 10 0.1 0.2 26.1 4.1 Moderate No   91 Compound H 15 0   0   24.5 2.5 High  No   92 20 0   0   16.7 1.7 High  No   95 10 0.7 0.8 28.7 7.8 Moderate No   94 Compound J 15 0.2 0.4 29.6 6.2 Moderate No   96 20 0   0   18.2 2.9 MOderate No   97 10 0.6 0.7 27.4 11.4 Moderate No   92 Compound M 15 0.1 0.4 25.6 7.1 Moderate No   95 20 0   0   18.9 2.1 High  No   96 10 0.9 0.8 48.6 5.7 Moderate No   89 Compound O 15 0.7 0.3 37.2 4.5 Moderate No   92 20 0   0   29.6 1.8 Moderate No   94 NOPA+Compound B 10     20  0.2 0.1 0.1 0.4 Very High No   98 20     20  0   0.1 0   0   Very High No   101 NOPA+Compound D 10     20  0.1 0.2 0   0.1 Very HIgh No   96 20     20  0   0   0   0   Very High No   99 NOPA+Compound H 10     10  0.3 0   0   0.1 Very High No 98 10     15  0.1 0.1 0   0.1 Very High No 97 10     20  0   0   0   0   Very High No   101 15     15  0   0   0   0   Very High No   104 15     20  0   0   0   0   Very High No   102 15     20  0   0   0   0   Very High No   101 NOPA+Compound J 10     10  0.1 0.1 0.2 0.1 Very High No   100 10     15  0   0.2 0   0   Very High No   104 10     20  0   0   0   0   Very High No   102 15     20  0   0   0   0   Very High No   107 20     20  0   0   0   0   Very High No   102 NOPA+Compound K 10     10  0.2 0.3 0.1 0.1 Very High No   100 10     15  0   0.1 0.2 0   Very High No   101 15     20  0   0   0   0   Very High No   100 20     20  0   0   0   0   Very High No   100 NOPA+Compound N 10     10  0.1 0.2 0.3 0.1 Very High No   102 10     15  0   0.1 0.1 0.1 Very High No   104 15     20  0   0   0   0   Very High No   102 20     20  0   0   0   0   Very High No   101 SWEP.M300   12.5 10.1 0.6 1.6 High  Moderate 91 100 100 100 100            84 no weeding  (19.7   89.5 (38.4 (6.4 g/m.sup.2) g/m.sup.2) g/m.sup.2) g/m.sup.2) 100 hand weeding --  --  --  --  --    --   (84.4 kg/a) __________________________________________________________________________

It is apparent from the above results that the herbicidal composition of the present invention have great weed-controlling effects. The herbicidal composition can easily be obtained as illustrated in detail in the following Examples. All parts appearing in the Examples are parts by weight.

25 parts of NOPA, 25 parts of Compound A, 45 parts of bentonite and 5 parts of sodium dodecylbenzenesulfonate were mixed to obtain 100 parts of a wettable powder.

7 parts of NOPA, 7 parts of Compound B, 83 parts of talc, 2 parts of polyoxyethylene glycol monolaurylate and 1 part of naphthalene sulfonate condensate were mixed together and then the resultant mixture was granulated by a conventional method using a granulating machine to obtain 100 parts of a granulate.

5 parts of NOPA, 7 parts of Compound D, 86 parts of talc and 2 parts of a polyethylene alkylphenyl ether were mixed together and the mixture was granulated by a conventional method using a granulating machine to obtain 100 parts of a granulate.

20 parts of NOPA, 30 parts of Compound E, 45 parts of talc and 5 parts of naphthalene sulfonate condensate were mixed to obtain 100 parts of a wettable powder.

30 parts of NOPA, 30 parts of Compound F, 2 parts of sodium ligninsulfonate and 38 parts of talc were mixed to obtain 100 parts of a wettable powder.

6 parts of NOPA, 7 parts of Compound G, 40 parts of bentonite, 44 parts of talc, 2 parts of sodium ligninsulfonate and 1 part of polyoxyethylenesorbitanalkyl ester were mixed together and the mixture was granulated by a conventional method using a granulating machine to obtain 100 parts of a granulate.

6 parts of NOPA, 7 parts of Compound H, 84 parts of talc, 2 parts of sodium ligninsulfonate and 1 part of sodium dodecylbenzenesulfonate were mixed together and then the mixture was granulated by a conventional method using a granulating machine to obtain 100 parts of a granulate.

20 parts of NOPA, 20 parts of Compound J, 4 parts of a sodium alkylbenzenesulfonte and 56 parts of talc were mixed to obtain 100 parts of a wettable powder.

7 parts of NOPA, 7 parts of Compound K, 40 parts of bentonite, 43 parts of talc, 2 parts of sodium ligninsulfonate and 1 part of polyoxyethylene sorbitanalkyl ester were mixed together and the mixture was granulated by a conventional method using a granulating machine to obtain 100 parts of a granulate.

7 parts of NOPA, 7 parts of Compound L, 60 parts of bentonite, 2 parts of talc and 4 parts of sodium dodecylbenzenesulfonate were mixed together and the mixture was granulated by a conventional method using a granulating machine to obtain 100 parts of granulate.

6 parts of NOPA, 7 parts of Compound N, 60 parts of bentonite, 23 parts of talc and 4 parts of sodium N-methyl-N-oleoyl-taurate were mixed together and the mixture was granulated by a conventional method using a granulating machine to obtain 100 parts of granulate.

Although the invention has been described above in preferred Examples, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the scope of the invention.

## Claims

1. A herbicidal composition for use in paddy fields consisting essentially of a herbicidally effective amount of a mixture of .alpha.-(.beta.-naphthoxy)-propionanilide and a synergistic proportion of a compound having the general formula ##STR4## and an inert carrier, the ratio of said .alpha.-(.beta.-naphthoxy)-propionanilide to said compound being 1:1-4.

2. A herbicidal composition according to claim 1 wherein said mixture is in the form of granules or a wettable powder.

3. A herbicidal composition according to claim 2 wherein said granules contain therein 1-20% of said mixture.

4. A herbicidal composition according to claim 2, wherein said wettable powder contains therein 10 - 50% of said mixture.

5. A herbicidal composition according to claim 1 further containing an inert diluent, an inert filler or an inert adjuvant.

6. A herbicidal composition according to claim 5, wherein said inert adjuvant is a stabilizing agent, dispersing agent, a suspending agent, a spreader, a penetrating agent or a wet spreader.