Description Substituted Bicycloheptandione Derivatives

Technical Field:

This invention relates to new substituted bicycloheptandione derivatives, their preparation methods and herbicides containing the said derivatives as effective components.

Background Art:

In many cases of agricultural or horticultural cultivation, a lot of kinds and amount of herbicides have come to be used for the weed control in order to save the labors consuming for removing weeds in the fields, however, in some occasion, phytotoxici ty of herbicides may injure crops, or herbicides remaining in the field may cause environmental pollution.

Consequently, chemicals possessing the excellent efficacy and the higher safety to mammal have been awaited to be developed.

Known patents disclosing compounds analogous to the compounds of this invention include EP-137963. EP-135191, EP-186118, EP-186119, EP-186120, Japanese open patent No. Sho 62-123145, EP-278907, EP-268795 and EP-264737.

The compounds of this invention are included in the claims of DE 3902818 (Corresponding to GB 2215333 and Japanese open patent No. Hei 2-1422). There are no descriptions on the compounds of this invention in the Description.

An object of this invention is to provide herbicides which are synthesized advantageously in an industrial scale, have certain efficacy at a lower dosage, are very safe and have well selectivity to crops.

Disclosure of Invention:

This invention is substituted bicycloheptandione derivatives having the

formula ( I)

(where R ¹ is a lower alkyl group, a phenyl group which may be substituted, an aralkyl group which may be substituted, or a heterocyclic group which may be substituted;

R ² is, same or different, a halogen, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an alkyl group, an alkoxyalkyl group, or an alkoxycarbonyl group, and n is 0 to 4;

R ³ and R ⁴ are, same or different, hydrogen or a lower alkyl group), or their salts.

The said substituents of the phenyl, aralkyl and heterocyclic groups of R ¹ are, same or different, halogen, hydroxy, nitro, cyano, alkyl, alkenyl, haloalkyl, haloalkenyl, alkoxy, haloalkoxy, haloalkeπy loxy, alkylthio, alkenylthio, alkynylthio, haloalkyl thio, haloalkenyl thio, monoalkyiamino, di a 1 ky 1 mino, a 1 koxya I ky 1 t h i o, a 1 ky 11 h i oa 1 ky 1 th i o, alkoxycarbonyl, alkylcarbonylalkoxy, alkylcarbonyl, alkoxyamino, alkylsulfonyl, alkeπylsulfonyl, a 1 kyny 1 su 1 f ony 1 , a 1 koxy 1 ky 1 su 1 f ony 1 , a 1 ky 1 t h i oa 1 ky 1 s u 1 f ony I , a lkylsulfonylalkylsulfonyl, haloalkylsulfonyl, alkoxycarbonylalkylthio, alkoxycarbonylalkylsulf iny 1 alkoxycarbony lalky lsulf ony 1, alkylamido, and aralkyloxy a phenyl group which may be substituted, an aralkyl group which may be substituted, a heterocyclic group which may be substituted, and an alkyl group substituted by a heterocyclic group which may be substituted.

The said heterocyclic group includes groups of pyrldyl, pyrimidyl, thienyl, furyl, pyrazolyl, pyrrolyl, imidazolyl, pyridaziπyl, pyrazinyl, indolyl and others.

The coapounds of this invention exhibit high herbicidal activity under

upland conditions by either method of soil treatment or plat foliage treatment. It is very efficacious against various kinds of upland weeds such as crabgrass, rice flatsedge velvetheaf and redroot pigweed, in a treatment of spraying it directly on the foliage of plant in particular. Same of these compounds have selectivity to crops such as wheat and soy beans.

Some of these compounds show plant growth retardent activity on crops, ornamental pot plants and fruit trees.

Some compounds also exhibit high selectivity on rice plant and high herbicidal activity against barnyard grass, smallflower unbre 1 lap Iant, arrowhead and Japanese bulrush, etc.

In addition to the above, the compounds of this invention can be applied for weed control to such places as orchards, lawn, railroad sides and vacant lots, etc.

Best Mode for Carrying Out the Invention:

The compounds of this invention are prepared' by the following methods. Preparation Method (a)

(ID (I)

(where R ¹ , R ² , R ³ , R\ and n are as defined above, and Q is a leaving group).

In the process, Compound ( I ) is obtained in a way that Compound ( II) is reacted in a solvent in the presence of 2 moles or an excessive amount of base at a temperature from -20°C to the boiling point of the solvent used, preferably 0 °C to 50 ^C C, for 30 minutes to several 10 hours.

The leaving group of Q includes halogen, alkylsulfonate and phenylsulfonate.

Bases used include alkali metal hydroxides such as KOH and NaOH, hydroxides

of alkaline earth metals, tri (Cι-C _G alkyl) amine, pyridine, DBU, t-BuOK, Triton B, sodium carbonate, sodium phosphate or the like. Solvents used include water, alcohol, methylene chloride, benzene, toluene, ethyl acetate, dimethylformamide, THF, dimethoxyethane, acetonitrile or the like.

Preparation Method (b)

Mono-substituted compounds, among the compounds of this invention, except those of which an alkoxycarbonyl group is at the 5 position of the bicyclo ring, may be prepared according to the following reaction.

(I)' (ID" (where r is an alkyl group).

If these compounds have different substituents at the 5 positons such as ( I ) ' or one substituent at the 5 position such as ( I ) '', stereoisomers exist with respect to the cyclopropane ring.

When CI ] '' is directly produced according to the above-described Preparation Method (a), the trans form is usually produced. In the preparation method, it is possible to separate cis and trans forms at the stage of [I 3 '. An appropriate selection of the methods allows to prepare the trans or cis form of CI ] ".

The material compound and the compound [I J of this invention have optical isomers, and a large number of tautomers can exist in the form of

(where R\ R ² , R ³ , R< and n are as defined above). The compounds of such forms are all included in this invention.

If Compound CI _) contains a free hydroxyl group when prepared by the above-described method, salts of the said compound, salts allowed particularly agriculturally and hort icul tural ly, enamines and their analogues, acrylate, sulfonale, carbamate or ether can be derived from the said compound.

Appropriate salts allowed agriculturally and horticul tural ly include salts of sodium, potassium, calcium, ammonium or the like.

Examples of ammonium salts are salts with ion represented by formula N ⁺ R'R R ^c R ^d (where R ¹ , R ^b , R ^c and R" are respectively selected from hydrogen and C _. -i ₀ alkyl groups substituted by, for instance, hydroxy group for some cases). If any of R" , R" , R ^c and R" are substituted alkyl groups in some cases, it is desirable that the group has 1 to 4 carbon atoms.

Appropriate enamines and their analogues are compounds of which their OH groups are respectively converted to a group represented by formula -NR'R' (where ' is for instance an alkyl or aryl group having 1 to 6 carbon atoms and which may be substituted in some cases, or for instance a phenyl group, and

R ^r is hydrogen, or for instance an alkyl or aryl group having 1 to 6 carbon atoms and which may be substituted in some cases, or for instance a phenyl group), halogen or SR' . (Where R ' is the same group as the above-described group R' )

Appropriate acrylate or ether derivatives are compounds of which their OH groups are respectively converted to a group represented by formula -OCOR ^h or - 0R ^h (where R ^h is the same group as the above-described group R ^e ).

Appropriate carbamate derivatives are compounds of which their OH groups are converted to a group represented by formula -0C(0)NR'R ^J (where R ¹ and R ¹ are respectively hydrogen or the same as the above-described R ^e ).

These derivatives can be prepared by usual methods.

The structure of the compounds of this invention are determined by such means as IR, NMR and MS.

This invention is further described in detail by reference to the following examples.

Example 1

3-(2-nltro-4-chlorobenzoyl) bicyclo C4,l,0 3 heptane-2, 4-dione (Compound I-

97)

0.5g (1.44 mmol) of 5-mesy 1 oxymethy 1-2- (2-n i tro-4-ch 1 orobenzoy1 ) cyclohexane-1, 3-dione was dissolved in 15ml of ethanol, to which 2ml of aqueous solution of sodium .hydroxide (sodium hydroxide: 0.17g, 4.31 mmol) was added with stirring at room temperature and resulting mixtures stirred at room temperature for another 2 hours. After the reactin was completed, the solvent was distilled. To the obtained residue were added 50ml of ethyl acetate and 10ml of water to dissolve it. Dilute hydrochloric acid was added until the aqueous layer became acidic. The organic layer was washed with saturated salt water and dried with magnesium sulfate. The solvent was distilled. The obtained residue was purified with silica gel column chromatography (eluate: chloroform) to give 0.38g (yield: 86X) of the intended product of light yellow crystal, m. . 132 - 134°C Example 2

3-(2-chloro-4-methy1su1fonyl-3-methoxybenzoyi)-cis-5-meth yl-cis-bicyclo C 4,1,0 3 heptane-2, 4-dione (Compound 1-195)

1.19g (2.6 mmol) of 3-(2-chloro-4-methanesulfony1-3-methoxybenzoyl)-trans- 5-e thoxycarbony l-cis-5-me thy 1-ci s-b i cyclo C4, l,0 3 heptane-2, 4-di one was dissolved in 7.8ml (7.8 mmol) of lN-NaOH while cooling with ice water, then reacted at room temperature for 4 hours. After the reaction was completed, 20ml of ice water and 20ml of ethyl acetate were added, neutralized with 1N-HC1 while cooling with ice water, and decarboxylated. The organic layer was washed with water and then with saturated salt water, and dried with MgSO _< . The solvent was distilled. The residue was purified with column chromatography (benzene : ethyl acetate = 5:1) to give 0.29g of the intended product of white crystal, m. p. 132 - 135 °C The obtained cis form and the trans form synthesized in the same manner as that used in Example 1 were characterized with NMR.

Representative examples of the compounds of this invention, including those obtained in the above examples, are shown in Tables 1 to 3.

Rx, Ry and Rz are the following substituents respectively in the tables. The trans and cis in the column of physical property are steric configurations of the substituent at the 5 position of the bicyclo ring and the cyclopropane ring.

Table 1

Structural Formula

Nα C R 2 ) n R 3 R4 Xm Physic l Properties

1 -(n=0)

2

3

4

5

6

7

8

9

10 5-CH3 mp 128- 130 ( trans)

11 1-CH3

12 5, 5-(CH3)2

13 1, 5,5-(CH3)3

14 -(n=0)

15

16

17

18

19

20 powder

21 5-CH3 p 178-180(trans)

22 1-CH3

23 5, 5-(CH3)2

24 1, 5.5-(CH3)3

25 -(n=0)

26

27

28

29

30

Nα ( R2)n R3 R4 X m Phys ical Proper t i es

31 -(π=0) 32 33 34 35 mp 151-3 36 5-CH3 mp 177-8(trans) 37 1-CH3 38 5, 5-(CH3)2 39 1, 5, 5-(CH3)3 40 -(n=0) 41 42 43 i ) 44 45 46 47 48 mp 177-180(dec). 49 5-CH3 mpl 25-7 (trans) 50 1-CH3 powder 51 5, 5-(CH3)2 52 1, 5, 5-(CH3)3 53 -(n=0) 54 mp 157-8 55 5-CH3 mpl54-6( trans) 56 1-CH3 oil 57 5, 5-(CH3)2 powder 58 1, 5,5-(CH3)3 59 -(n=0) 60

mp 146-8

mp 120-1

powder mp 131-4 ( trans)

Nα ( R2)n R 3 R 4 Xm Physical Properties

- 91 -(n=0) H H 2-N02-4-CH20CH3

- 92 5-CH3 H H 2-N02-4-CH20CH3

- 93 1-CH3 H H 2-N02-4-CH20CH3

- 94 -<n=0) H H 2-N02-4-CH3 mp 122-4

- 95 5-CH3 H H 2-N02-4-CH3

- 96 1-CH3 H H 2-N02-4-CH3

- 97 -<n=0) H H 2-N02-4-C1 mp 132-4

- 98 5-CH3 H H 2-N02-4-C1 mp 139-141 (trans)

- 99 1-CH3 H H 2-N02-4-C1 mp 77-9 -100 5,5-(CH3)2 H H 2-N0.2-4-C1 mp 134-5.5 -101 1, 5,5-(CH3)3 H H 2-N02-4-C1 powder -102 -(n=0) CH3 CH3 2-N02-4-C1 -103 H H 2-N02-4-CN -104 H H 2-N02-4-NHC0CH3 -105 H H 2-N02-4-N02 -106 H H 2-N02-4-0C5H11 -107 H H 2-N02-4-0CH20CH3 -108 H H 2-N02-4-0CH2SCH3 -109 H H 2-N02-4-0CH3- mp 76- 81(dec) -110 5-CH3 H H 2-N02-4-0CH3 -111 1-CH3 H H 2-N02-4-0CH3 -112 5, 5-(CH3)2 H H 2-N02-4-0CH3 -113 1,5.5-(CH3)3 H H 2-N02-4-0CH3 -114 ~(n=0) CH3 CH3 2-N02-4-0CH3 -115 H H 2-N02-4-0RX -116 H H 2-N02-4-0Ry -117 H H 2-N02-4-0RZ -118 H H 2-N02-4-SCH(CH3)C00C2H5 -119 H H 2-N02-4-SCH2CH20CH2CH20CH3 -120 H H 2-N02-4-SCH2CH20CH3

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Nα ( R 2)n R 3 R 4 Xm Physical Proper t i es

-181 1.5-(CH3)2 H H 2-N02-4-C1 mp 122-3

-182 5-CH3 H H 2-C1-4-S02CH3-5-0CH3 powder ( trans)

-183 5-CH3 H H 2-Cl-3-0CH2CH=CH2-4-S02CH3 powder ( trans)

-184 5-CH3 H H 2-C1-3-C02CH3-4-S02CH3

-185 5-CH3 H H 2-C1-4-CF3 nD 25.5 1.5369(trans)

-186 5-CH3 H H 2-Cl-3-0CH2(Br)C=CH2-4-S02CH3 powder ( trans)

-187 5-CH3 H H 2-C1 -3-0CH2C ≡ CH-4-S02CH3 mp 184-7(trans)

-188 5-CH3 H H 2-C1-3-0CH2CH2C1-4-S02CH3 p 103-5(trans)

-189 5-CH3-5-C02C2H5 H H 2-CH3-3-CH3-4-S02CH3 o i 1 ( trans)

-190 5-CH3 H H 2-C1-3-0C2H5-4-S02CH3 powder ( trans)

-191 5-CH(CH3)2 H H 2-N02-4-C1 mp 161-2(trans)

-192 5-CH3 H H 2-CH3-3-CH3-4-S02CH3 mp 164-7 (c i s)

-193 5-CH3 H H 2-C1-4-0CF3 nD 25.5 1.5248(trans)

-194 5-CH3 H H 2-CH(CH3)2-4-Cl nD 25.0 1.5710( trans)

-195 5-CH3 H H 2-C1-3-0CH3-4-S02CH3 mp 132-5 (c i s)

-196 5-CH3 H H 2-CH20CH3-4-S02CH3 nD 24.5 1.5662(trans)

-197 5-C2H5 H H 2-N02-4-C1 mp 109-11K trans)

-198 5-CH(CH3)2 H H 2-N02-4-S02CH3 mp 88-90( trans)

-199 5-CH3-5-C02C2H5 H H 2-N02-4-S02CH3

-200 5-CH3 H H 2-C1-3-CH3-4-S02CH3 powder (cis)

-201 5-CH3 H H 2-N02-4-S02CF2H mp 176-8(dec) (trans)

-202 5-CH3-5-C02C2H5 H H 2-C1-3-0CH3-4-S02CH3 nD 24.5 1.5649(trans)

-203 5-0CH3 H H 2-N02-4-S02CH3 powder (trans)

-204 5-CH3 H H 2-C1-4-S02CH3 powder (cis)

-205 5-CH3 H H 2-CH3-3-C1-4-S02CH3 mp 165-7(trans)

-206 5-CH3 H H 2-N02-4-C0CH3 mp 146-8(traπs)

-207 5-CH3 H H 2-C1-4-0CHF2 nD 24 1.5592(trans)

-208 5-CH3 H H 2-CH3-3-Br-4-S02CH3 m p 1 72 - 4 ( c i s )

-209 5-CH3 H H 2-C1 -3-C 1 -4-S02CH3 p o w d e r ( c i s )

-210 5,5-(CH3)2-6-CH3 H H 2-N02-4-S02CH3 mp 175 - 7

Nα ( R 2)n R 3 R 4 X Phys i cal Proper ties

-211 1-CH3 H H 2-N02 -3-0CH 3-4-C1 powder

-212 5-CH3 H H 2-N02 -3-0CH3-4-C1 powder ( trans)

-213 1-SCH3 H H 2-N02 -4-C1 mp 168-170

-214 5-CH3 H H 2-C1- 3-C1-4 -S02CH3 Na salt 180(dec) ( trans)

-215 5-CH3 H H 2-C1- 4-0CF2 CHF2 nD '25.5 1.5276(traπs)

-216 5-CH3 H H 2-N02 -4-CHF 2 mp 163-5(trans)

-217 5-CH3 H H 2-N02 -4-S02 CH3 powder (cis)

-218 5-CH3 H H -CH3 -3-N02 -4-S02CH3 mp 197-9(trans)

-219 5-CH3-5-S02CH3 H H N02 -4-C1 mp 184-6

-220 5-CH3-5-SCH3 H H ^• N02 -4-C1 mp 144-5

-221 5-CH3 H H ^• N02 -4-CF3 mp 90-2 (cis)

-222 5-CH3 H H ^• N02 -3-CH3 -4-S02CH3 mp 139-141 ( trans)

-223 5-CH3-5-C02C2H5 H H ^• N02 -4-CF3 oil

-224 5-CH3 H H ^• N02 -4-C1 mp 104-8 (cis)

-225 5-CH3 H H 2-0CH 3-3-OC H3-4-0CH3 powder ( trans)

-226 5-CH3 H H 2-C 1 - 3-C1-4 -CI rap 111 -2( trans)

-227 5-CH3 H H 2-C I - 3-C1-4 -0CH3 mp 113-4 ( trans)

-228 5-Br H H 2-N02 -4-C1 mp 158- 160 ( trans)

-229 5-CH2CH20CH3 H H 2-N02 -4-C1 nD 23 1.5850(trans)

-230 5-SCH2CH3 H H 2-N02 -4-C1 mp 119-120( trans)

-231 5-CH3 H H 2-N02 -4-S02 N(CH3)2 mp 142-5(dec) (trans)

-232 5-CH3 H H 2-CH3 -3-CH3 -4-S02CH3 H2NCH3 salt mp 139-140 (dec) ( trans)

-233 5-CH3 H H 2-CH3 -3-CH3 -4-S02CH3 Na salt mp 168 (dec) ( trans)

-234 5-CH3 H H 2-C 1 - 3-0CH3 -4-S02CH3 Na salt mp 158(dec) (cis)

-235 5-CH3 H H 2-CH3 -3-CH3 -4-C1 mp 117-8 ( t rans)

-236 5-CH3 H H 2-N02 -4-N02 mp 151-2(trans)

-237 5-CH3 H H 2-N02 -4-SCH 3 mp 129-132 ( trans)

-238 1-CH3 H H 2-N02 -4-SCH 3 mp 70-4

-239 5,5-(Br)2 H H 2-CH3 -3-CH3 -4-S02CH3 mp 129-131

-240 5-SCH2CH3 H H 2-CH3 -3-CH3 -4-S02CH3 mp 140-2(trans)

Nα ( R2)n R3 R4 Xm Physical Properties

-241 5-CH2CH20CH3 powder (trans)

-242 5-CH3 powder (trans)

-243 5-CH3 mp 115-7(trans)

-244 5-CH3 powder (trans)

-245 5-CH3 powder (trans)

-246 5-CH3 powder (trans)

-247 5-CH3 mp 147-150( trans)

-248 5-S02CH2CH3 mp 163-5( trans)

-249 5-CH3 powder ( trans)

-250 1-CH3 powder

-251 1-CH2CH20CH3 nD 23 1.5842

-252 1-CH3 powder

-253 1-CH3 powder

-254 1-CH3 powder

-255 1-CH3 powder

-256 5-CH3 powder ( trans)

-257 -(N=0) powder

-258 5-CH3 mp 152-6(cis)

-259 -(N=0) powder

-260 oil

-261 5-CH3 mp 172 4( trans)

-262 5-CH3 Na sa 1 t mp230(dec) (cis)

-263 5-CH3 Na sal t mpl80-2(dec) (cis)

-264 5-CH3 Na sal t mp223(dec) (cis)

-265 5-CH3 powder (trans)

-266 5-CH3 p 148 -9(trans)

-267 5-CH3 mp 169 -171(dec)(trans)

-268 5-CH3 K salt mp 198-200(dec)(trans)

-269 5-CH3 Li sal t mp> 260(trans)

-270 5-CH3 1/2 Ca salt mp> 260( trans)

-271 5-CH3 1/2 Cu salt mp> 260(trans)

-272 5-CH3 K salt mp 188-190 (dec) (cis)

-273 5-CH3 Li sal t mp 178-180(dec)(cis)

-274 5-CH3 1/2 Ca salt mp> 225(dec) (cis)

-275 5-CH3 1/2 Cu salt mp 210-212(cis)

Table 2

Structural Formula

No. ( R 2)n R 3 R 4 Hetero ring Xm Phys i cal Properties

H H 2-pyr idine 5-CF3 H H 2-pyr idine 5-CH20CH3 H H 2-pyr idine 5-CH2SCH3 H H 2-pyr idine 5-SCH3 H H 2-pyr idine 5-S0CH3 H H 2-ρyr idine 5-S02CH3 H H 2-pyr idine 5-SC2H5 H H 2-pyridine 5-S0C2H5 H H 2-ρyr idine 5-S02C2H5 H H 2-pyr idine 5-CH3 H H 2-pyr idine 5-N02 H H 2-pyr idine 5-CN H H 2-pyr idine 5-CF3 H H 2-pyr idine 5-CH20CH3 H H 2-pyr idine 5-CH2SCH3 H H 2-pyr idine 5-SCH3 H H 2-pyridine 5-S0CH3 H H 2-pyr idine 5-S02CH3 H H 2-pyridine 5-SC2H5 H H 2-pyridine 5-S0C2H5 H H 2-ρyridine 5-S02C2H5 H H 2-pyr idine 5-CH3 H H 2-pyr idine 5-N02 H H 2-pyr idine 5-CN H H 2-pyridine 5-CF3 H H 2-pyridine 5-CH20CH3 H H 2-pyr idine 5-CH2SCH3 H H 2-pyr idine 5-SCH3 H H 2-pyr idine 5-S0CH3 H H 2-pyridine 5-S02CH3

R 3 R 4 Hetero ring Xi Phys i ca1 Properties

CH3 CH3 2-pyridine 5-CF3

CH3 CH3 2-pyridine 5-CH20CH3

CH3 CH3 2-pyridine 5-CH2SCH3

CH3 CH3 2-pyridine 5-SCH3

CH3 CH3 2-pyridine 5-S0CH3

CH3 CH3 2-pyridine 5-S02CH3

CH3 CH3 2-pyridine 5-SC2H5

CH3 CH3 2-pyridine 5-S0C2H5

CH3 CH3 2-pyridine 5-S02C2H5

CH3 CH3 2-pyridine 5-CH3

CH3 CH3 2-pyridine 5-N02

CH3 CH3 2-pyridine 5-CN

CH3 CH3 2-pyridine 5-CF3

CH3 CH3 2-pyridine 5-CH20CH3

CH3 CH3 2-pyridine 5-CH2SCH3

CH3 CH3 2-pyridine 5-SCH3

CH3 CH3 2-pyridine 5-S0CH3

CH3 CH3 2-pyridine 5-S02CH3

CH3 CH3 2-pyrid ^* ine 5-SC2H5

CH3 CH3 2-pyridine 5-S0C2H5

CH3 CH3 2-pyridine 5-S02C2H5

CH3 CH3 2-pyridine 5-CH3

CH3 CH3 2-pyridine 5-N02

CH3 CH3 2-pyridine 5-CN

H H 3-pyridine 2-CF3

H H 3-pyridine 2-CF3-6-C1

H H 3-pyridine 2-CH20CH3

H H 3-pyridine 2-CH20CH3-6-CH3

H H 3-pyridine 2-CH20CH3-6-C1 H H 3 - p y r i d i n e 2 - CH20C H3 - 6 - S C H3

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H H 3-pyr d ine 2-CH2S 02CH3-6-CH3

H H 3-pyr dine 2-CH2S 02CH3-6-C1

H H 3-pyr dine 2-CH2S 0CH3-6-C1

H H 3-pyr dine 2-CH3

H H 3-pyr dine 2-CH3- 6-CH20CH3

H H 3-pyr dine 2-CH3- 6-CH2SCH3

H H 3-pyr dine 2-CH3- 6-CH3

H H 3-pyr dine 2-CH3- 6-C1

H H 3-pyr d ine CH3- 6-CN

H H 3-pyr d i ne CH3- 6-0CH3

H H 3-pyr dine CH3- 6-SCH2C1

H H 3-pyr di ne CH3- 6-SCH20CH3

H H 3-pyr dine CH3- 6-SCH3

H H 3-pyr dine CH3- 6-S02CH2C1

H H 3-pyr dine CH3- 6-S02CH3 oil

H H 3-pyr dine CN

H H 3-pyr d ine CN-6 -CH3

H H 3-pyr d i ne CN-6-CI

CH3 CH3 3-pyr d i ne CF3

CH3 CH3 3-pyr d ine CF3- 6-C1

CH3 CH3 3-pyr dine CH20 CH3

CH3 CH3 3-pyr dine CH20 CH3-6-CH3

CH3 CH3 3-pyr d ine CH20 CH3-6-C1

CH3 CH3 3-pyr dine 2-CH20 CH3-6-SCH3

CH3 CH3 3-pyr d ine 2-CH2S CH3

CH3 CH3 3-pyr dine 2-CH2S CH3-6-CH3

CH3 CH3 3-pyr d ine 2-CH2S CH3-6-C1

CH3 CH3 3-pyr dine 2-CH2S 02CH3

CH3 CH3 3-pyr dine 2-CH2S 02CH3-6-CH3 CH3 CH3 3-pyr dine 2-CH2S 02CH3-6-C1

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No. ( R 2)n R 3 R 4 Hetero ring Xm Physical Properties

E -271 -(n=0) H H 5-pyrimidine 4-SCH3-2-C2H5 E -272 H H 5-pyr imidi ne 4-CF3-2-SCH3 E -273 H H 5-pyrimidine 4-CF3-2-0CH3 E -274 H H 5-pyrimidine 4-CF3-2-CH3 E -275 H H 5-pyrimidine 4-CF3-2-CF3 E -276 H H 5-pyrimidine 4-CF3-2-C2H5 E -277 5-CH3 H H 3-pyridine 2-CH3-6-C1 mp 93-6 ( c i s ) E -278 5-CH3 H H 5-thiazoIe 2-0CH3-4-CH3 powder ( trans) E -279 1-CH3 H H 3-pyrazole l(N)-CH3-4-N02 mp 158-160

Table 3

Structural Formula

Na R 1 ( R 2)n R 3 R 4 Phys i ca 1 Proper t i es

1, 5, 5-(CH3)3 1, 5, 5-(CH3)3 1, 5,5-(CH3)3 5, 5-(CH3)2 5.5-(CH3)2 5, 5-(CH3)2 5-CH3 5-CH3 5-CH3 1-CH3 1-CH3 1-CH3 -(n=0) nD 25.0 1.5489 nD 25.0 1.5260

nD 25.0 1.5810

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 tngceajdifint. may be formulated by mixing suitable carriers in. a form generally used in agricultural chemicals such as wettable powder, water soluble powder, granule, emulsifiable concentrate and flowable. As solid carriers, talc, white carbon (silica), 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 recomended of benthiocarb, molinate, MY-93(S-(2,2-dimethylbenyil) 1- piperidinecarbothioate) or other carbamate-type herbicides; thiocarbamate-type herbicides; butachlor, pretilachlor, mefenacet or other acid amide-type herbicides; chlormethoxynil, bifenox or other

diphenylether-type herbicides; atrazine, cyanazine or other triazine- type herbicides; chlorsulfurnon, sulfometuron-methyl or other sulfonylurea-type herbicides; MCP, MCPB or other phenoxy alkane carboxylic acid-type herbicides; diclofop-methyl or other phenoxy propionic acid-type herbicides; benzoylprop-ethyl, flamprop-ethyl or other benzoylaminopropionic acid-type herbicides; and, as others, piperophos, dymron, bentazon, difenzoquart, naproanilid, HW-52 (4-ethoxy methoxy benzo-2' , 3*-dichloroanilide) , KNW-242 (l-(3-methylphenyl)-5- phenyl-lH-l,2,4-triazole-3-carboxamide), quinclorac (3,7-dichloro-8- quinoline carboxylic acid), and further, 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 5-70 weight percent, preferably 10-30 weight percent, in wettable powder; 3-70 weight percent, preferably 5-20 weight percent, in emulsifiable concentrate; 0.01-30 weight percent, preferably 0.05-10 weight percent, in granule.

A wettable 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 granule may be directly applied for soil or mixed with soil.

Non-limiting examples of herbicidal composition are illustrated by the following Examples:

Example 3: Wettable powder parts by weight Compound of this invention 20

White carbon 20

Diatomaceous earth 2

Sodium alkylsulfate 8

These are mixed homogeneously and reduced to fine particles to provide a wettable powder containing 20% of active ingredient. In use, it is diluted to a desired concentration with water, and is sprayed as suspension.

Example 4: Emulsifiable concentrate parts by weight Compound of this invention 20

Xylene 55 dimethylformamide 15

Polyoxyethylene phenyl ether 10

These are mixed and dissolved to provide an emulsifiable concentrate containing 20% of active ingredient. In use, it is diluted to a desired concentration with water, and sprayed as an emulsion.

Example 5: Granule

Bentonite 10 sodium alkyl sulfate 7

These are mixed homogeneously to provide a granule containing 5% of active ingredient.

Industrial Applicability:

The herbicidal effects of compounds are illustrated by the following test:

Test 1: Postemergence treatment test

Seeds of Henry crabgrass, giant foxtail, rice flatsedge,

2 velvetleaf, redroot pigweed and corn were planted in clay pots (200cm ) containing clay loam soil and were allowed to grow in greenhouse. When the plants were grown to a 5-10 cm height, aqueous suspensions, prepared by diluting an emulsifiable concentrate with water to specified concentration (250 ppm), were sprayed on the foliage of the plants at a rate of 100 1/lOa by using a micro-sprayer.

Three weeds 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 - 40% 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.

'fresh weight \ /Fresh weight in untreated plot/ ^~ in treated plot.

Degree of damage (%) = —— x 100

Fresh weight in untreated plot

The results are shown in Table 4.

Table 4

Comparative Compound A:

Comparative Compound B:

(DE 3902818)