CA1111062A

CA1111062A - Diphenyl ether derivatives, process for preparing the same and herbicidal compositions containing the same

Info

Publication number: CA1111062A
Application number: CA308,293A
Authority: CA
Inventors: Shigeki Nagai; Hakobu Sekioka; Mitsuaki Takenaka; Masazumi Sakata; Yosio Kawaguchi; Seiji Takamura; Minoru Nishimura
Original assignee: Ube Industries Ltd
Current assignee: Ube Corp
Priority date: 1977-07-28
Filing date: 1978-07-27
Publication date: 1981-10-20
Also published as: BR7804864A; NL7807967A; IT7826201A0; JPS6054954B2; GB2001635A; JPS5424851A; SU843695A3; FR2398728A1; DE2833021A1; IT1097782B; FR2398728B1; GB2001635B

Abstract

ABSTRACT OF THE DISCLOSURE:

New diphenyl ether derivatives having one to three substituents selected from a halogen atom and a trifluoromethyl group at any optional one to three positions of the 2'-, 3'-, 4'-, 5'- and 6'- positions in one phenyl moiety and notro group at the 4-position and unsubstitued or substitued aminosulfonylgroup at the 3-position in another phenyl moiety. They have a superior herbicidal effect and can be prepared starting from a know 3-benzyl-mercapto compound through three steps.

Description

This invention relates to a new group of diphenyl ether derivatives, to a process for preparing the ~ame and also to the new use of the said diphenyl ether derivative~ a~ a herbicide.
More particularly, it is concerned with a new diphenyl ether derivative having the formula ., Xn~ ~ N2 S02NHR (I) wherein X is a halogen atom or a trifluoromethyl group, n is an integer of 1 to 3 inclusive and ~ i9 a hydrogen atom, a lower al~oxycarbonyl group, an acetyl group, a chloroacetyl group or an N,N-dimethyl carbamoyl group, as well as with a proces~ for preparing the said diphenyl ether derivative and a herbicidal oomposition containing as an actlve ingredient at least one of the above-defined diphenyl ether derivatives.
In the above formula (I), a halogen atom represented by X may be exemplified by chlorine, bromineg fluorine or iodine;
and R may be illustrated by a hydrogen atom, a lower alko~ycar- -bonyl group, preferably of 1 to 3 carbon atoms in the alkoxy ` 20 moiety, e.g. methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, an acetyl group, a chloroacetyl group or an N,N-dimethylcarbamoyl group~ Also, where n in an integer of 2 or ~, X's may be the same or different.
It is also to be noted that the diphenyl ether deriva-tives (I) o~ this invention are intended to include to correspon-ding alkali metal salts, in particular sodium ualts.
Accorcling to an aspect of the present invention, there is provided a prc~cess for preparin~g a compound having the f ormula " Xn . ~

: `
wherein X is a halogen atom or a trifluoromethyl group, n is an integer of 1 to 3 inclusive and R is a hydrogenatom, a lower alkoxycarbonyl group, an acetyl group, a chloroacetyl group or an N,N-dimethylcarbamoyl group, which comprises reacting a compound having the formula Xn ~ O--~N02 wherein X and n have the same meanings as defined above, with chlorine in an aqueous acetic acid to obtain a compound having the formula Xn --O~ N02 S02Cl wherein X and n have the same meanings as defined above, reacting the thus obtained compound with an excess amount of ammonia to obtain a compound having the formula (Ia) Xn - - ~ -NO2 (Ia)

2 H2 wherein X and.n have the same meanings as defined above, said compound of formula. (Ia) being a compound of formula I
wherein~R is hydrogen and then if desired, treating the thus obtained compound of formula (Ia) with a compound having the formula:
R'-Cl wherein R' `is a lower alkoxycarbonyl group, an acetyl group, a chloroacetyl ~roup or an N,N-dimethylcarbamoyl group, in an organic solvent or an alkaline water in the presence of a base to obtain a compound of formula (I) as defined above wherein R is a lower alkoxycarbonyl group, an acetyl group, a chloro-ac~ yl group or an N,N-dimethylcarbamoyl group.

- la -.

There have been hexeto~oxe proposed a ~ide variety of diphenyl ether derivatives as agricultural herbicides and a considerable number of them has b~ien on the market for practi-cal use: for example, such herbici.des as "NIP" (active ingre-dient: 2',4'-dichloro-4-nitrodiphenyl ether), "CNP" (active ingredient: 2',4', 6'-trichloro-4-notrodiphenyl ether) and "TOPE" (active ingredient:

f ~
.
- lh -

3~-methyl-4-nitrodiphenyl ether) may be mentioned. These previously know diphenyl ether type herbicides can generally show a superior herbicidal effect in soll -treatment agalnst annuaI
weed~ o~ the family Gramineae devèloped in a paddy field, but they have a common characteristic of having an inferior herbicidal effect against variou3 weeds in foliar treatment or annual broad-leaved weeds and perennial weeds. Further, it can be frequently seen in those derivatives of such a type that it ma~ unexpectedly be different, upon differences in their chemical structures such as those in the sort, number or position of substituents, whether . a herbicidal e~fect may be exerted, how high a herbicidal effect may be? how rapidly a herbicidal..effect may be developed or how a phytox-icity may be to crop~ and so on.
: ~he present inventors have made earne~t studie~ to find out new diphenyl ether derivatives having a commercial usefulness and, as a result, they have successfully synthesized a new group of the diphenyl ether.derivatives of the above formula (I) and also found such new diphenyl ether derivatives (I) can show a remarkable herbicidal effect against various weed~, without any 20 phytotoxycity to crops and toxicity to human beings and domestic animals as well as fish and shellfi~hes and do not have any other harm~ul properties such as a naty smell and the like, This in-vention has been, therefore, completed upon these findings.
~ he diphenyl ether derivatives (I) of this invention can show a superior weed-killing activity by pre- and post-emergence treatment in soil; in other words, they have both soil treating activities and foliar treating activities. ~hen,-they are effective aga:inst various weeds such as annual or perennial weeds of the fami:Ly Gramineae growing in a paddy or upland field, broad-leaved weed~3 and the like.
Accordingly, the herbicidal diphenyl ether derivatives (I) of this invention can be e~fectively applied to a paddy field . ~ .

: as a pre-emergent herbicide before or after rice planting or a post-emergent herbicide against perennial weeds or broad-leaved weeds after 1 - 2 weeks from rice planting, and, further, they can be effectively employed as a soil treatment herbicide before or after sow.ing in an upland field or as a foliar treatment herbi-cide against variou~ weeds in an orchard, a tea garden, a mulber-ry field or a non-crop land. In addition, the diphenyl ether derivativee (I) of this invention has a particular oharacteri3tic that they can exert an extremely hlgh herbicidal activity against weedg of the family Caryophyllaceae which those previou~ly known . diphenyl ether type derivative~ could not contro.L.
It i~, accordingly, primary object of thi~ invention to ......... provide new diphenyl ether derivatives of the above.formula (I) which show an excellent herbicidal effect. Another object of this invention i9 to provide a process for preparing the above-mention-ed diphenyl ether derivatives.
A further object of this invention i~ to provide a her-bicidal composition ~hich comprises a~ an active ingredient a-t lea~t one of the diphenyl ether derivatives (I).
According to one aspect of this invention, there is provided a group of new diphenyl~ether derivatives of the above formula`(I). Representative examples of the diphenyl ether deri-vatives (I) are given in the following Table 1 for illustrating . purpose only.
~ A~ explained above, alkali metal salt~ of the diphen~l `~ ether derivatives (I) also fall within the scope of this invention and, as illustrat:ive examples, sodium ~alt of 2',4',6'-trichloro-3-methoxycarbonylaminosulfonyl-4-notro-diphenyl ether and sodium salt of 2',4~-dichloro-3-methoxycarbonylaminosulfonyl-4-nitrodi-phenyl ether are given in ~able 1, designated as Compound ~o. 25 and No. 36, respectively.

~ ' Among the diphenyl ether derivatives according to this - invention, compounds repre~ented by formula (I) wherein Xn repre-sents a 2~4-dichloro-, 2,496-trichloro-, 2,4-dichloro-6-fluoro-, 2-chloro-4-bromo- or 2-chloro-4-trifluoromethyl-~ubstituent, are preferable in ~iew o~ the herbicidal e~ect upon perennial weeds, particularly upon "Mizugayatsuri (cyper s serotinus Rottb.~, the price for production and the phytotoxicity.
~` As particularly preferable compounds may be mentioned 2',4'-dichloro-3-methoxycarbonylaminosulfonyl~4-nitro-diphenyl ether (Compound No. 9), . 2',4',6'-trichloro-3-methoxycarbonylamino~ulfony:L-4-nitrodiphenyl ether (Compound No 23), 2',4'-dichloro-6-fluoro-3-methoxycarbonylaminosulfonyl-4-nitrodi-phenyl ether ~Compound No, 38), .
2'-chloro-4'-bromo-3-methoxycarbonylamino~ulfonyl-4-nitrodiphenyl ether (Compound No. 47), 2'-chloro-4 t -trifluoromethyl-3-methoxycarbonylamino-sulfonyl-4-nitrodiphenyl ether (Compound No. 52) and ; 2'-chloro-4'-trifluoromethyl-3-ethoxycarbonylamino-sulfonyl-4- -nitrodiphenyl ether (Compound No. 53).

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~ he diphenyl ether derivatives of this invention can be prepared, for example, according to the ~ollowing reaction steps.
- ~he 1st step:

2 2 + C~2 Acetic Xn ~ ~ 2 ~ ~ CE2C~ + HC

: S0 The 2nd ~tep:

~ 2 + NH3 . so2ce 2 + HC~
' ~he 3rd 9 tep:

X~ ~N2 + RCR
S 021~H2 X
Alkali~ ~ O ~ N02 ~ HC
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- In the first step, the 3ulfonyl chloride can be prepared by introducing chlorine gas into a solution of the star-ting ~-benzylmercapto compound which can be obtained by a well-known method as illustrated below:
ce ~N2 ~ ~CH25H~oe4~o2 + ~c~

`~ Xn C ~ 2 + ~ OH
YSCH2~

Xn ~ 2 HC b A~q the solvant ma~ preferably be employed an aqueous acetic acid. ~he aqueous acetic acid to be used contains 5-- 50 wt.%, preferably 10 - 15 wt.~ of water. The reaction time may be more than l hours, preferably 3 - 6 hours. ~he reaction temperature may preferably be in the range of 10 - 15a. At a hig-ger temperature, substitution on the nucleu~q tends to occur. ~he thus produced compound may be recovered from the reaction medium by ordinary procedures.~
In the second step, the product in the firqt step is reacted easily with an excess amount of ammonia. As the solvent for the reaction may be used ~n organic solvent, e.g.~ an aromatic solvent such as benzene, toluene, xylene, etc. ~nd an e~ter such as ethyl acetate, methyl acetate, etc. ~he desired product can - also be obtained in high yield without any solvent by adding the starting ~ulfonyl chloride to a 5 - 28% a~ueous ammonia ~he reaction temperature may preferably be maintained at 10 - 30C with cooling, since the reaction is exothermic.

. . ' ' .

In the third step, the desired compound of this invention can be obtained by adding an acid chloride to a solution of the starting sulfonamide compound in an organic solvent or an alkaline water in the presence of a base. Whe~ the acid chloride - is ~mstable against water or has ;poor reactivity, the reaction may pre~erably be conducted by using an organic solvent and by heating the reaction system.
While any organic solveIlt can be usea for the purpose if it does not react with the acid chloride, there may preferably be mentioned a~ a solvent acetone, dimethylsulfoxide, dime thylformamide, dimethylacetamide, etc.
In particular, acetone may most advantageousl~ be employed for the purpose.
As the base, potassium hydroxide and sodium hydroxide ~- may preferably be employed when the reaction is carried out in an aqueous medium. These hydroxides may advantageously be employ-ed as a 1 - 5 wt.% a~ueou~ olutionO When the reaction is carried out in an organic medium, potassium carbonate or sodium carbonate may advantageously be used. ~he reaction is carried out at 10 -20C in an alkaline aqueou~ medium and at a temperature between room temperature and 150C in an organic medium. While the reac-tion period depends on the kind of the reagent to be used9 it i8 in the range of about 1 - 10 hours.
The desired product can easily be recovered by an ordi-nary method.
~ he above-depicted reaction steps will be more fully illustrated by the following examples.
Example 1.
S~nthesis of ben~l-2-nitro-5_chlorophen~1 sulfide ~o a solution of 86 g. (0,4 mole) of l-nitro-2,4-dichlorobenzene a~d 56 g. (0.45 mole) of benzylmercaptan in 1.4 ~. of i~opropyl alcohol was gradually added dropwis~ a solution of 30 g. of potassium hydroxide in 20 m~. of water and 70 m~. of ethanol.
After completion of the dropwise addition, the resulting mixture was refluxed on a water bath for 3 hours. After ~tanding o~er-night, the crystalline substance thus geparated wa~ recovered by filtration and then recrystalli~ed from a mixture of ethanol with a small amount of benzens~to give 87 g. (yield, ~0~0) of benzyl-2-~itro-5-chlorophenyl sulfide as yellow prisms of M.P. 131 - 134C.
~ample 2 . . .
., .
- 10 Synthesis of 2~,4l-dichloro-3-benzylmercapto-4-nitrodi-. _ _ . , .. . , .. . _ .
~ phenyl ether :. - - . .
- ~o a ~olution of 16.3 g. (0.1 mole) of 2,4-dichlorophenol in 30 me.
of dimethylacet mide were added 5.6 g. (0.1 mole) of potasgium hydroxide and then the resulting mixture was heated to 120C. to dissolve the potassium hydroxide, After it wa~ allowed to cool, 28 g. (0.1 mole) of benzyl-2-nitro-5-chlorophenyl sulfide were added thereto. ~he resulting mixture was hèated at about 155C.
while stirring for 6 hours and then cooled. After addition of water, the oily sub3tance thus separated was extracted with benzene. lhereafter, the extract was washed with a dilute aqueous ~olution of sodium hydroxide and water, dried over anhydrous s~odium sulfate and then the benzene was distilled off. ~he resi-due was recrystallized from ethanol to give 27 g. (Yield, 67~o) of 2',4'-dichloro-3-benzylmercapto-4-nitrodiphenyl ether as yellow pouwdery crystals of M.P. 104 - 105C.
Example 3.
S,ynthesis in t_e_lst and~
., .
Into a su~pen~ion of 33 g. (0.008 mole) o~ 2~,4~-dichloro-3-benzyl-mercapto-4-nitrodiphenyl ether in 200 me. of glacial acetic acid and 30 m~. of water was bubbled chlorine gas while stirring at about 12C. and the mixture wa~ then le~t at ordinary temperature overnight. ~hem, the mixture was poured into water, the oily ~ .

substance thus separated was ex-tracted with benæene, the extract was washed with water and dried over anhydrou~ sodium sulfate.
~he solvent was distilled off to leave 2',4!-dichloro-3-ch~oro-sulfonyl-4-nitrodiphenyl ether as a dark red oily substance.
Then, the product thus obtained was dissolved in ethyl acetate and the resulting solution was added dropwi~e to ammonia-saturated ethyl acetate. After completion of the dropwi~e addi-~ tion, the mixture was stirred at ordinary temperature for 30 minu-; tes and water was added thereto. The resulting mixture was washed with water and dried over anhydrous sodium suliate. ~he solvent , was dlstilled off and the residue was recrysta]lized from ethanol to afford 22.7 g. (~ield, 78%) of 2',4'-dichloro-3-aminosulfonyl-

4-nitrodiphenyl ether (Compound No. 8) as pale yellow powdery crystals of M.P. 95 - 98 C.
E~a_ple 4.
S~nthesis in the 3rd step n ~ ichloro-3-ethox.ycar~onylamino-sulfon~l-4-nitrodiphen~l ether ( a ompound No. 10) ~o a solution of 3.6 g. (0.01 mole) of 2',4'-dichloro-3-amino-sulfonyl-4-nitrodiphenyl ether in 40 m~. of a 1.25 w/v% aqueous solution of sodium hydroxide were added dropwise by turns, wh-ile stirring at about 25C., 3.6 g. (0.033 mole)-of ethyl chlorof~r-mate and a 10 w/~ a~ueous solution of sodium hydroxide to adjust its pH to 10 - 11. After completion of the dropwise addition, the mixture was stirred for 30 minutes and adjus-ted to pH 6.5 by the dropwise addition of a dilute aqueous æolution of hydrochloric acid. Insoluble materials were filtered off and the filtrate was made acidic with a strong hydrochloric acid. ~he so separated ; crystalline substance was recovered by filtration, dried and then recrystallized from benæene to afford 2.5 g. (Yield, 57%) of 2~,4'-dichloro-3-ethoxycarbonylaminosulfonyl-4-nitrodiphenyl ether as pale yellow prisms of M.P. 138 - 140C.
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.
.'. ~ .

- (2) Synthesis of 21 ,4'-dichloro-3-chloroacetylamlnosulfonyl-4 ; -nitrodiphen~l ether ~Compou~d No~ 12) ~o a solution of 3.6 g. (0.01 mole) of 2',4'-dichloro-3-amino~ul-fonyl-4-nitrodiphenyl ether in 2.5 m~. of a 2 w/v~0 aqueous solu-tion of sodium hydroxide were added dropwise by turns, while stirring at about 20~., 4.5 g. (0.04 mole) of chloroacetyl chlo-; ride and a 10 w/v~0 aqueou~ ~olution of sodium hydroxide to ad~ust its pE to 10 - 11. After completion of the dropwise addition, the mixture was stirred for 30 minutes, 200 ~. of water were added thereto to dissolve insolub:Le material~, the mixture was adjusted it~ pH to 4 with the dropwise additio~ of a dilute aque-OU8 solution of hydrochloric acid and then insolu~le materials were filtered off. ~hen, the filtrate was made acidic with a strong hydrochloric acid~ the so separated cry3talline substance was recovered by filtration, dried and recrystallized from a mix-ture of benzene with n-hexane to give 3.3 g. ~yield, 75%) of 2',4'-dichloro-3-chloroacetylaminosulfonyl-4-nitrodiphenyl ether as pale brown prism~ of M.P. 141 - 143 C.
(3) Synthesis of sodium salt of 2'~4'~6'-~r~c-l~r~-~-met~o~ycarbo-nvlaminosu1fonyl-4-nitrodi~henyl ether (Compound ~o. 25 : ~o a solution of 7.2 g. (0.0~8:mole) of 2',4',6'-trichloro-3-aminosulfonyl-4-~-itrodiphenyl-ether in 40 m~. of a 2.5 w/v~
a~ueous solution of sodium hydro~ide were added dropwise by turns, ~hile stirring at about 20C., 7.5 g. (0.08 mole) of methyl chloroformate and 10 wt.% of aqueous solution of sodium hydroxide ~- to adjust its pH to 10 - 11. After completion of the dropwise addition, the mixture was stirred for 30 minutes. ~hen, the so separated substance was recovered by filtration, washed with water, dehydrated and dried to give 6.6 g. (yield, 7.7~) of sodium 3~ salt of 2',4',6'-trichloro-3-methoxycarbonylaminosulfonyl-4-nitro-diphenyl ether as colorless powdery cr~stals of M~P, above 105C
(with decomp.).

,~ Z

(4) Synthesi~ of 2',4'~'-trichloro-3-N,N-dimethyl - aminocarbonvlaminosul~onvl-4-nitrodiphenyl ether (Compound ~o~ 26) ~o a solution of 2 g. (0.005 mole) of 2',~',6'-trichloro-3-amino-sulfonyl-4-nitrodiphenyl ether in 80 m~. of acetone were added 1.1 g. (0.008 mole) of potassium carbonate and 0.9 g. (0.008 mole) of N~N-dimethylcarbamoyl chloride iand the resulting mixture was heated under reflux for 12 hours~ Ihereafter, the acetone was di~tilled offy the residue was dis301ved in a dilute aqueous solu-1~ tion of sodium hydroxide, the resulting solution was ad~usted to p~ 5.8 with a dilute hydrochloric acid and insoluble materials were filtered off. The filtrate was made acidic with a strong hydrochloric acid, the so separated crystalline substance was recovered by filtration, dried and recrystallized from a mixture of benzene with n-hexane to give 1 g. (yield, 43~) of 2',4',6'-trichloro-3-N,N-dimethylaminocarbonylaminosulfonyl-4-nitrodiphenyl ether as colorless powdery crystals of M.P. 186 - 190 C~

(5) Synthesis of 2',4'-dibromo-3-methoxycarbonylaminosulfonyl-4-.. . . . . .. . . . .
nitrodiphen~l ether (Compound No. 33) ~o a solution of 2.3 g. (0.005 mole) of 2',4'-dibromo-3-aminosul-fonyl-4-nitrodiphenyl ether in 80 m~. of acetone were added 1.1 g.
(0.0075 mole) of potassium carbonate and further dropwise 0.7 g.
(0.0075 mole) of meth~l chloroformate with stirring. ~he result-ing mixture was heated under reflux for 3 hours. ~hen, the reac-tion mixture was cooled, the inorganic salts thus separated were filtered off, the solvent was distilled off from the filtrate and then the residue was dissolved in a dilute aqueou~ solution of sodium hydroxide. Insoluble substances were filtered off and the filtrate was adjusted to pH 6.0 with the dropwise addition of a dilute aqueous ~olution of hydrochloric acid. ~he crystalline substance thus separated was recovered by filtration, dried and recrystallized from a myxtilre of benzenne with n-hexane to give .

l.l g. (yieldJ 44%) of 2',4'-dibromo-3-methoxycarbonylamino3ul-fonul-4-nitrodiphenyl ether a~ pale yellow needles of M.P. 167 -172C.

(6) Synthesi~ of 2~,4'-dichloro-6'-~ uro-3-methox~carbon~ amino-sulfonyl-4-nitrodiphenyl ether (Compound No 38) ~o a solution of 2.0 g. (0.005 mole) of 2'4'-dichloro-6'-fluro-3-aminosulfonyl-4-nitrodiphenyl ether in 80 m~. of acetone were addea 1.2 g. (0.008 mole) of pota~sium carbonate and 0.8 g.
(0.008 mole) of methyl chloroformate and the resulting mixture was heated under reflux for 6 hours. After cooling, the inorga-nic salts thu~ separated were filtered off, the olvent was distil-led off from the filtrate, the residue was di~olved in a dilute aqueous solution of sodium hydroxide. Then, in~oluble ~ubstances were filtered off, the filtrate was adjusted to~pH 6 with the dropwise addition of a dilute aqueous-solution of hydrochloric acid and the so separated crystalline substance was filtered off.
The filtrate was made acidic with a ~trong hydrochloric acid, the crystalline ~ubstance thus separated was recovered by fil-tration, dried and recrystallized from benzene to give 1.3 g. (yield, 57%) of 2',4~-dichloro-6~-fluoro-3-methoxycarbonylaminosulfonyl-4-nitro-diphenyl ether as pale yellow prisms of M.P. 152 - 156 C.
In another aspect of this invention, there is provided a herbicidal composition which comprises as an active ingredient the diphenyl ether derivative of the above formula (I) and an agriculturally acceptable carrier.
When the diphenyl ether derivative of this invention is to be applied a~ herbicide~, the derivative may be formulated for u~e to the preparat~ns commonly employed as a herbicide, for example, dusts, granules, wet-table powders, emulsi~iable concen-trate~, water soluble powders, liquid formulations and so on, with admixture of an inert carrier and, if required, other auxi-liary agents.

. .

:, ~ . .
. , ~

A~ the inert carrier, there may be mentioned any of solid, liquid or ga~eou~ carriers ordinarily employed in the art fox herbicide~ and, for example, talc, clay9 kaolin~ diatomaceou~
earth, calcium carbonate, bentonite, white carbon, benzene, xyle-ne, n-hexane, methylnaphthalene, cyclohexanone, isophoron and the like.
The herbicidal compo~ition of this imvention may al~o optionally be blended with any a~iliary agent~ for preparation, for example, spreaders, diluent~, ~urface acti~re agent~, ~olvents ` 10 and the like as u~ually done in the art.
Moreover, the herbicidal compo~ition of this invention may also be admixed with other herbicides, fungicides, insectici-de~, other agricultural chemical~, fertilisers, e.g. urea, ammo-nium sulfate, ammonium pho~phate, pota~sic fertili~er~, soil conditioners and the like.
As the herbicides which may advantadeously be admixed with the compound of formula (I), there may be mentioned a thiocarbamate type herbicide such a~ ~enthiocarb (Saturn*
the ehemical name of whieh is S-(4-chlorobenzyl)-N,N-diethyl-thiolearbamate.), Molinate (Ordram*--the chemieal name of ` whieh is S-ethyl-N,N-hexamethylenethiolcarbamate),ete.; an aeid amide type herbieide such as Alachlor (Rasso*--the chemi-eal name oE whieh is ~-ehloro-2,6-diethyl-N-methoxy~ethyla-eetanilide), Butaehlor (Maehete*-- the ehemieal name of whieh is ~-ehloro-2,6--diethyl-N-butoxymethylaeetanilide), ete.; a phenoxy type herbieide sueh as 2,4-PA,*(the ehemieal name of which is 2,4-dichlorophenoxyacetic aeid), MCP, ete.: a diphenyl ether type herbieide sueh as Ni-trofen (NlP,* the ehemieal name of which is 2,4-dichloro-4 -ni-trodiphenyl ether), Chlornitrofen (MO*, the ehemieal name of whieh is 2,4,6-trichlorophenyl-4 -nitrodiphenyl ether), e-tc.: a urea *trademark ~ i -2~-, "..~

~- .

type herbicide such as Diuron (Karmex D,* the chemical name of which is 3-(3,4-dichlorophenyl)-1,1-dimethylurea), Linuron (Afalon*, the chemical name of which is 3-(3,4-dichlorophenyl)-l-methoxy-l-methylurea),etc.; a triazine type herbicide such as Simazin (Princep,* the chemical name of which is 2-chloro-4,6-bis(ethylamino)-1 r 3,5-triazine), Atrazin (Gesaprim,*the chemical name of which is 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine),etc.; and other herbicides such as Trifluralin (Treflan,* the chemical name of which is 2,6-dinitro-N,N-dipropyl-4-trifluoromethylanaline), Oxadiazon (Ronstar* the chemical name of which is 5-tert-butyl -3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-oxadiazol-2 one), ACN (Mogeton,*the chemical name of which is 2-amino-3-chloro-1,4 napthoquinone), Bentazon (Basagran,* the chemical name of which is 3-isopropyl-(lH)-benzo-2,1,3-thiadiazin-4-one-2,2-dioxide), etc.
The above mentioned carriers and various auxilia-ry agents may be optionally utilized alone or in combination therewith for desired purposes.
In general the herbicidal composition of this invention may contain the diphenyl ether derivative in an amount of :. /
*Trademark -24a-..
"~t~`) 0.1 - 99% by weight, based upon the finished compo~ition and the content of the active derivative in a herbicidal composition may usually depend upon the preparation form to be formulated, for instance, ordinarily 1 - 25 part~ by weight for dusts, 25 -90 parts by weight for wettable powders, 1 - 35 parts by weight for granules, 5 - 50 parts by weight for emul~ifiable concentra-te~ and the like.
The amount of the herbicidal composition to be applied usually to a field is 1 - 100 g/a with respect to the active ingredient of this invention.
Examples of the prepation of the pre~ent herbicidal ~` composition are given below. All parts are gi~en by weight here-inafter unless otherwi~e stated.
Example 5. Granules - 8 parts of 2',3'-dichloro-3-aminosulfonyl-4-nitrodiphenyl ether (Compound No. 5), 30 parts of bentonite, 59 parts of talc, 1 part of "Neopolex powder" (trade n~me of surfactant from Kao-Atlas K.X.) and 2 parts of sodium ligno~ulfonate were homogeneously blended. ~o the blend was added a small amount of water and the mixture was kneaded, granulated and dried to give granules.
Æxample 6. ~Yettable powders 50 parts of 2t~4'-dichloro-3-methoxycarbonylaminosulfonyl-4-nitro-diphenyl ether (Compound No. 9), 48 parts of ~aolin and 2 part~
of ~eopelex powder were homogeneously blended and pulverized to give wettable powders~
Example 7. mulsifiable concentrates 50 parts of 2',~'-dichloro-3-ethoxycarbonylaminosulfonyl-~-nitro-diphenyl ether (Compound ~o. 10), 40 part~ of xylene, 5 parts of dimethylformamide and 5 parts of "~oxanon" (trade name of surfac-tant from Sanyo Ka~ei Kogyo K.K) were homogeneously blended anddissolved to give emulsifiable concentrates.

. , .
-.

Example 8. Dusts 5 part~ of 2',4',6'-trichloro-3-methoxycarbonyla~inosulfonyl-4-nitrodiphenyl ether (Compound ~o. 23, 50 parts of talc and 45 parts of Kaolin were homogeneously blended to give dusts.
Experimental example~ of the present herbicidal compo-sitions are given below in order t;o illustrate herbicidal effects of the present composition more fully. In these Experiments, the test compounds' number~ are the same Compound No~. as designated hereinabove and the test compound~ are applied n the form of the ;~ 10 wettable powder prepared according to the procedures of the above Example 6~ which is used after dilution with water to a concentra-tion of the active ingredient of 1000 ppm.
Experiment 1.
Water surface application (soil treatment) test for padd~ field wedd control Wagner pots, each having the surface of 1/5000 are, were packed with Ube soil (alluvial soil) and transplanted with seeds of bar-~ nyardgras~, tubers of "Mizugayatsuri" (C~perus_serotinus Rottb.) ; and o~ "Urikawa" (Sa~ittaria E~ a Miq.) and stock~q of slender spikerush. ~henr the pots were slightly covered with soil andseeds of monochoria and of "Hotarui" (Scirpus hotarui Ohwi)-~erè
~owed thereover and rice plant seedlings at 2 leaf stage (variety:
Nihonbare) were also transplanted. ~hen, the pots were filled with water to a depth of 3 cm.
At the date of germination of weeds, each test compound - in the indicated dose was applied dropwi~e with a pipette and the were kept in a gla~s chamber at an average temperature of approximately 25C.
After ~ week~ from the treatment, herbicidal effects, of each test compound were investigated.
The re~ults are ~ummarized in the following ~able 2 wherein herbicidal effects were evaluated according to the rating 3ystems as defined below:

-26_ 5 = All killed; 4 = Severely damaged;
3 = Moderately damaged; 2 = Sligh-tly damaged;
1 = Minor damaged; O = None (normal development) .. .
~able 2.
Test Dose Rice Barn- _ _ _ Slender ~cirpus Mono- Sagi-com- seed- yard- serotl- sp:ike otaruilchoria ttarlc pound g/a lings grass nus rush pymaec ; 1 25 O 3 2 3 5 5 3 12.5 O 2 1 1 5 5 3 O ~ 5 15 5 5 5 5 12.5 0 * 4 3 5 5 4 ' - 3 25 O 4 5 4- 5 5 5 ; 12.5 O 4 4 3 5 5 4 o 4 3 3 5 5 4 ~, 4 25 O 2 2 3 5 5 3 12.5 O 2 1 2 5 5 2 ; 50 O 4 3 3 5 5 4 , 5 25 O 3 2 3 5 5 4 ~`` 12.5 O 2 2 2 5 5 2 O 5 - 5 ~ 5 5 5 5 ' 12.5 O - 4 4 4 ~ 5 5 4 ` 7 25 O 5 5 4 5 5 5 ~` 12.5 O -3 4 - 3 5 5 4 : 50 O 3 ~3 2 5 5 4 ~; 12.5 O 1 2 O 5 5 1 12.5 O 5 5 5 5 5 5 ,-:
.

`:

Table 2. (cont'd) Test Dose Rice Barn- Cyperu e Slender cirpus Mono- ~
com- seed- yard- seroti- spike lotarui choria ttarlc poOund g/a lings grass nus rush _ pymaec O 5 5 'j 5 5 5 12.5 O 5 5 5 5 5 5 .. ' _.

12.5 O 5 5 5 5 5 5 12 25 `O 5 5 4 ` 5 5 5 ` 12.5 O 4 3 3 5 5 4 12.5 O 3 4 2 5 5 4 .

12.5 O 4 3 2 5 5 4 .

` 15 25 O 5 5 4 5 5 5 ' 12.5 O 4 3 3 5 5 . _ _ ; 12.5 O 2 1 1~ 5 5 3 12.5 O 1 1 1 5 5 2 _ .

12.5 O 2 1 1 5 5 2 .

.. . .

. . ~ . , ` :

- Table 2. ~cont'd) Test Dose Rice Barn- Cyperuc Slender Scirpuc Mono- Sa~_-com- seed- yard- seroti- spike hotarui choria ttaria No. g/a lin~s grass nus ru~sh _ - pymaea -` 19 25 0 54 3 5 5 5 ` 12.5 0 3 2 2 5 -- 5 4 0 5 5 5` 5 5 5 :- 20 25 0 ~ 4 3 5 5 5 ~" 12.5 0 4 2 2 5 5 4 .. . ....

`; 12.5 0 1 1 1 5 5 ''.' . . ..
`~` 50 0 3 3 2 5 5 4 22 25 0 2` ` 2 1 5 5 2 12.5 0 1 1 1 - 5 5 2 ; 23 25 0 5 5 5 5 5 5 12.5 0 5 5 5 5 5 5 . .

12.5 0 5 5 5 5 5 5 .. .. ..
~; 50 0 5 5 5 5 5 5 12.5 0 5 5 5 5 5 5 :........................... ._. ._ ._ 12.5 0 3 3 2 5 5 4 ...

12,5 0 5 5 - 5----- 5 5 5 `

~6~:

Table 2. ~cont'd) Test Dose Rice Barn~ 'yperusl Slender Scirp~ Mono- Sagi-com- seed- yard- ~ieroti-¦ spike hotarui: choria ttaric .~ poOund g/a lings grass lus ¦ rush _ pymaec . _ .. 50 O 4 3 3 5 5 4 i 28 25 O 3 2 3 5 5 2 `` 12,5 O 3 1 _ 1 5 5 1 O 5 4 `4 5 5 5 `` ` 29 25 O 4 3 3 5 5 4 12.5 O 3 2 2 5 - 5 3 . 50 O 5 4 5 5 5 5 ` : 30 25 O 4 3 5 5 5 4 :. 12.5 O 3 . 2 2 5 5 3 ~`
: . 50 O 4 3 2 5 5 3 :~` 12.5 O 2 1 1 5 5 2 . 50 O 3 3 3 5 5 3 . 32 25 O 2 2 2 5 5 2 12.5 O 2 1 2 5 5 1 ~:
~- 50 O 5 5 5 ~5~ 5 5 `~ 33 25 O 5 5 5 5 5 5 .
. 12.5 O 5 5 5 5 5 5 : 50 O 5 5 5 5 5 5 12.5 O 5 5 5 5 5 5 . 35 25 O 5 4 3 5 5 5 1?.5 O 3 3 2 5 5 4 12.5 O 5 5 5 5 5 5 .

, --3-- `

. . .

T`able 2. (cont'd) : Test ; co~- Dose Rice Barn- _ype.rus Slender ~cirpus Mono- agi-pound seed- yard- :; roti- spike ilotarui. choria tt~rlc . No. y/a lin~s ~rass lUS rush . ~ymac~
`` 50 O 5 ~ 4 5 S 5 12.5 O 4 2 2 5 5 4 O 5 5 ~ 5 5 5 5 12.5 O 5 5 5 --5 5 5 _ ~` 39 25 O 5 5 5 5 5 5 12.5 O 5 5 5 5 5 5 12.5 O 4 3 4 5 5 4 12.5 O 4 3 4 5 5 5_ `

12.5 O 4 4 3 5 5 4 _ 12.5 O 5 4 4 5 5 4 :~

12.5 O 2 1 2 4 5 4 .
O 5~ 5 4 5 5 5 12,5 O 4 2 3 5 5 4 , . , .

--3:1--::
:
Table 2. (cont'd) com- Dose Rice Barn- Cyperus Slender Scirpuc Mono- ,aqi-pound seed- yard- ser~ spike notaru: choria ttari~
No. g/a lings grass nus rush ymaec O 4 4 4 5 5 . 4 ~` 46 25 O 2 2 3 5 5 2 12.5 O 2 1 2 4 - 5 2 12.5 O 5 4 5- ` 5 ~ 5 4 O` 5 5 5 5 5 5 , 48 25 O 5 4 5 5 5 5 12.5 O- 4 4 4 4 5 3 49 25 O 3 2~ 4 5 5 2 12.5 O 2 2 2 3 4 1 12.5 O 4 3 3 4 5 3 ` 51 25 O 3 3 3 5 5 3 12.5 O 2 2 2 5 4 2 _ 50- O 5 5 - 5 5 5 5 12.5 O _5 _ 5 ~ 5_ 5 ~ ~ 5_ _ 5 ` 50 O 5 ~ ~ 5 5 5 5 5 12.5 O 5 5 5 5 5 5 12,5 O 3 4 3 5 5 4 : , .
, . . .

, .

.~ . .
' . ' ' ' '' . ' ':

6~

Table 2. (cont'd) - Test Dose Ricë Barn- Cyperus ISlendër ~ ¦Sagi com- seed- yard- seroti-- spike hotarui¦chorlz ttaria NpOund g/a lings gras~ nus rush l ~maea . . . ............. . _ . _ ~, .. . , ~ ~ . _ NIP* 25 O 5 4 4 5 ¦ 5 2 12 5 0 5 2 4 4 l5 0 * 2',4'-Dichloro-4-nitro-diphenyl ether Experiment 2.
- ~ests against perinrial weeds_at various growth sta~s ~ Wagner pots, each having the surface of 1/5000 are, were packed i with Ube soil and tubers of "Mizuga~atsuri (Cyperus serotinus Rottb.~" and of "Urikawa (Sa~ittaria ~aea Miq.)" were planted and then the pots were filled with water to a depth of 3 cm.
Before germination and at the dates of grown heights of 5 cm. and 10 cm. in C~perus serotinus and before germination and at 2 and 4 leaf stages in Sa~ittaria p~maea, each test compound at the indicated dose was applied dropwise with a pipette. Then, the pots were kept in a glass chamber at an average -temperature of approx~mately 25C.
After 2 weeks from the treatment, herbicidal effects of each test compound were in~estigated.
The results are summarized in ~able 3 wherein the same rating sy~tems as in the Experiment 1 were applied.

.

Table 3.

Cyperus serotinus I Sagittaria pymaea TestDose . I .
com- Treatment pound g/a No. Before 5 cm 10 cm Before 2 leaf 4 leaf qerm . qerm . stage stage .
. , 9 20 S 5 5 5 .5 .4 .
. 10 5 5 4 5 S 3 . 40 5 5 5 5 5 5 10 20 5 5 5 5 5 . 5 . 10 5 5 5 5 5_ 5 : . 40 5 5 4 5 5 2 11 20 5 5 3 55 ~ 1 : 10 5 5 2 5 - 5 1 . 5 5 4 5 5 5 . 23 20 5 ` 5 3 5 .5 5 . 10 .5 4 `2. 5 5 4 24 20 5 4 2 . 5 5 4 -..... . 40 5 5 4 5 5 5 . 25 20 5 5 3 5 5 5 ~ 2 5 5 2 40--~5 4 2 5 5 : 33 20 5 2 . 1 5 4 0 ., 10 5 1 0 5 2 . 0 52 20 5 . 5 5 5 5 4 .
. 40 5 5 5 5 5 5 .

. 10 5 5 3 5 5 2 NIP. 203 . 0 0 1 0 0 10 _ O O O O O O

--3'~--.

f~
.

Experiment 3.
Soil treatment tests for upland weed control Waf~ner potæ, each having the surface of 1/5000 are, were packed with Ube soil and then seeds of wheat (variety:
Kobushikomugi), of soybean ~variety: ~atsudaizu No. 1), of manna-grass, of barnyardgraf~fæ, of common purslane, o~ pearlwort and of wavy bittercre~s were sowed. After covering with soil, each test compound was sprayed under pressure onto the soil sur~ace at the indicated dose and then the pots were kept in a glass chamber at an average temperature of approximately 25C.
After 2 weeks-from the treatment, herbicidal e~fectæ
of each test compound were in~estigated.
~ he rèsults are summarized in ~able 4 wherein the same rating system as in the E2periment 1 were applied.
Table 4.
..._ .. . . ..` ~
Test Dose ~heat Sog- ~anna- ~a~n_ Com- Pearl- Wa~y :: com-- bean ~rass yard- mon wort bitter-pound g/a grass purs- creæfs ; No. gras lane ~ 50 -~-~ 0 - --o ~ _ ~ 5 - - 4 4 12.5 0 0 1 4 3 0 3 . ._. . . . .

; 2 25 0 0 3 5 5 5 5 12.5 0 0 2 5 5 5 ~ 5 , . . _ . _ 12.5 0 0 3 5 5 5 5 _ __ . ~ .. , 2.5 0 0 1 5 5 5 --5 ~35-:' a6~

.

Table 4. (cont'd) Test Dose Wheat Soy- Manna- Barn~ mon Pearl- Wavy pound g/a bean grass Ygarc~lds PUne~ wort bitter-. 50 O O 3 . ~ 5 3 5 12.5 O O 1 4 2 0~ 2 . ~ .
. 50 O O 4 5 5 5 5 12.5 O O 3 5 5 5 5

7 25 O O 3 5 5 5 5 12.5 O O 2 5 5 - 5 5 O ` O 3 5 5 2 3 ! 8 25 O O 1 4 4 1 2 12.5 O O O 3 3 - o 1 12.5 O O 4 5 5 5 5 12.5 O O 4 5 S 5 5 12.5 O O 3 5 5 5 5 12.5 O O 2 5 5 5 5 _ _ 12.5 O O 2 5 S 5 5 . ' .

- - ~

Table 4. (cont'd) _ .
Test Dose Wheat bean Manna- arn- purs- wort bitter-0 0 ~ 5 5 5 5 ` 14 25 0 0 3 5 5 5 5 ` 12.5 0 0 2 5 5 _ 5 5 12.5 0 0 2 5 5 S 5 . ~ _.

`~ 16 25 0 0 2 4 4 1 ~
12.5 0 0 1 4 4 0 3 ~' 12.5 0 _ 0 2 3 __3 _ 0 4 12.5 0 0 1 4 3 0 3 50 ` 0 3 -5 5 ~ 5 ~

.5 0 0 1 5 5 5 5 . .

12,5 0 0 3 S 5 5 S

12.5 0 0 0 5 5 5 5 _ .

12.5 0 0 0 4 4 0 3 . ~ , ' .

6~
. . , Table 4. (cont'd) ~omt Dose Wheat Soy- Manna- Barn- Com- Pearl- Wavy bean ~rass yard- wort bitter-pound g/a , grass lane~ cress ; 12.5O O 5 I~ 5 5 S

12.5O O 5 5 5 -5 S

2.5O O 5 S 5 5 5 . 50 O O 4 5 5 5 5 12.5O O 3 5 5 5 5 ` 27 25 O O 5 5 5 5 5 12.5O - o 5 5 5 5 5 _ 50 ~O O 3 5 4 2 5 12.5O O 1 _ 3 3 O 3 O O ~ 5 5 5 5-12.5O O 3 5 5 5 5 12.5O O 2 5 5 5 5 - o ; ~o 2 5 5 5 1 ~ 5--12.5 O O O 5 5 5 5 ''~ .

~ -38-.

r!~2 Table 4. (cont'd) :
Test Dose Wheat Soy- Manna- Barn- mon Pearl- Wavy .~ pOund g/a bean grass Ygrads PUane~ wort cbrets . .

32 25 O O 1 ~ 3 13 : 12.5 O O O ~ 2 O3 ,., 12.5 O O 4 5 S 55 _.

12.5 O O 3 5 5 S5 12.5 O O 3 5 5 55 12.5 O O 4 5 5 55 O O 5 5 ` 5 5 5 12.5 O O 2 4 4 31_ 5 50-`- O O 5 - S~ 5 55 :; 38 25 O O 5 5 S SS
` 12.5 O O 5 S 5 55 12.5 O O 5 5 5 55 12.5 O O 4 5 5 44 .
, . `

:
. Table 4. (cont'd) ...
: TcOes_ Dose Wheat Soy- Manna- Bc~rn- mon Pearl- Wavy ~ pound bean grass yard- purs- wort bltter-.~ No. g/a grass lane cress , 41 25 O O 5 5 5 5 5 ~ 12.5 O O 5 5 S 5 S
.. ,. _ 12.5 O O 4 5 5_5 I S

12.5 O ' O _ 5 5 5 S 5 12.5 O O 1 3 2 2 2 12.5 O O 3 4 4 3 -3 12.5 O O 1 2 2 3 2 j. _ 12.5 O O 4 4 5 4 4 . . .

48 25 O O 4 5 S 4 5 .
` 12.5 O O 3 3 4 3 3 .: , . .. ..

` 49 25 O O 4 4 5 4 4 - 12.5 O O 2 2 3 2 2 .'' _ ..
.: .

' . ' .
~~~

' .
. .

:

Table 4. tcont'd) Test Dose Wheat Soy- Manna- Barn- Com- Pearl- Wavy pound g/a bean graRs yard- lane wort bitter-. 50 O O 5 S 5 S S
`: 50 25 O O S 5 S 5 5 12.5 O O 4 4 4 3 4 _ Sl 25 O O 2 3 4 3 4 12.5 O O 1 2 3 ~ 4 . 50 O O 4 5 5 5 -5 12.5 O O 2 4 5 5 5 _ : 12.5 O O 2 4 S S 5 : 54 25 O O 2 3 S S S
. 12.5 O O 1 2 4 5 S
.~. 50 O O 5 5 5 O 5 12.5 I O I ~ ~ ~

, ..
':, .

;. -, . .
. - : . ' ! EXperiment 4, Foliar treatment -tests for upland weed control Wagner pots, each having the surface of 1/5000 are, were packed with Ube soil and seedlings of manna-gras~ at 3 lea~
stage, of cocklebur at 2 leaf stage, of white goose-foot at 2 leaf stage and of nutgrass at 3 lo~af ~tage were planted and grown.
~ heny a wettable powder of each test compound was dilu-ted with water containing 100 ppm of "Ne~esterin" (trade name of spreader available from Kumiai Kagaku E.K.) to-a concentration of the active ingredient of 1000 ppm and the result,ing preparation was uniformly applied to seedlings by foliar spraying under pres-; sure at a dose of 5 m~. per pot. Then, the pots were kept in a glass chamber at an average temperature of approximately 25 C.
After 2 weeks from the treatment, herbicidal effects ofeach test compound were investigated.
~ he results are summarized in ~able 5 wherein the same rati~g systems as in the Experiment 1 were applied.
~able 5.
Manna-gras~ Cockle- White ~utgrass compound _ bur goose-foot 1 ; 2 _ 3 7 ~ 4 ___ 9 5 _ ~ _ _ _ 5 ,~ - ~5-- - _ _ _ _ _ _ __ _ 3 6 ~ - 4 -~ ~. - 5 - - 3 ,, . . .

.

; -42-~;

- Table 5. (cont'd) ~r ~n;' Manna-grass Onamomi 'White Nutgragg 7 5~ ~ 5 - 3

8 2 3 3 2 -- 5 _ - 5 ` 11 5 . 5 - - 5 : 12 4 5 5 4 .. 15 4 . . 5 55 ~ 1 ., .
. 16 . 3 4 : 4 2 17 2 . 4 5 3 : 19 . 4 5 . 5 - 3 . 5 5 - 3 21 . 4 5 . 5 3 ~ 22 3 ~ .4 2 .: 23 5 5 5 S
24 5 . 5 5 . 25 . 5 5~ 5 ., . _ . . 28 2. . _ __. 4 2 : 29 _ 3 . - 5 _ 5 3 4 . 5 5 3 ':
.~
., .

: ' ', .

: - ' ~ ' : , $~

: T~bLe S. (cont'd) :` ~o ~ound Manna-grass Onamomi goose-foot Nutgrass `: ~2 - - 4 5 3 1- _ _ _ __ _ _ 5 6 5 L.~

.. ~7 = 3 ~ _ ~ _ ~ ~ =~
. 51 2 4 5 3 .. , _ ._ : . 52 5 5 5 5 . ~ - _ 4 4 . ` .' ~ .

4~

~rom the above-recited results, it can be seen that the diphenyl ether derivatives of thi~ invention can effectively control a wide of weeds by soil or foliar application without any phyto-toxicity to crops and thu~ are practically useful as an excellent herbicide.

. .

::

-~1-5-. . , :

.

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A compound having the formula (I):

(I) wherein X is a halogen atom or a trifluoromethyl group, n is an integer of 1 to 3 inclusive and R is a hydrogen atom, a lower alkoxycarbonyl group, an acetyl group, a chloroacetyl group or an N,N-dimethylcarbamoyl group.

2. A compound according to claim 1 wherein Xn represents a 2,4-dichloro-, 2,4,6-trichloro-, 2,4-dichloro-6-fluoro-, 2-chloro-4-bromo- or 2-chloro-4-trifluoromethyl-substituent.

3. A compound according to claim 1 wherein R is a hydrogen atom, an alkoxycarbonyl group having 1 to 3 carbon atoms in the alkoxy moiety, an acetyl group, a chloroacetyl group or an N,N-dimethylcarbamoyl group.

4. A compound according to claim 1 wherein Xn represents 2,4,6-trichloro-, 2,4-dichloro-6-fluoro- or 2-chloro-4-trifluoromethyl- and wherein R is an acetyl group a methoxycarbonyl group or an N,N-dimethylcarbamoyl group.

5. A process for preparing a compound having the formula (I):

(I) wherein X is a halogen atom or a trifluoromethyl group n is an integer of 1 to 3 inclusive and R is a hydrogen atom, a lower alkoxycarbonyl group, an acetyl group, a chloroacetyl group or a N,N-dimethylcarbamoyl group, which comprises reacting a compound having the formula:

wherein X and n have the same meanings as defined above, with chlorine in an aqueous acetic acid to obtain a compound having the formula:

wherein X and n have the same meanings as defined above, reacting the thus obtained compound with an excess amount of ammonia to obtain a compound having the formula (Ia):

(Ia) wherein X and n have the same meanings as defined above, said compound of formula (Ia) being a compound of formula I wherein R is hydrogen and then if desired, treating the thus obtained compound of formula (Ia) with a compound having the formula:
R'-C1 wherein R' is a lower alkoxycarbonyl group, an acetyl group, a chloroacetyl group or an N,N-dimethylcarbamoyl group, in an organic solvent or an alkaline water in the presence of a base to obtain a compound of formula (I) as defined above wherein R is a lower alkoxycarbonyl group, an acetyl group, a chloro-acetyl group or an N,N-dimethylcarbamoyl group,

6. A process according to claim 5 wherein Xn represents a 2,4-dichloro-, 2,4-,6-trichloro, 2,4-dichloro-6-fluoro-, 2-chloro-4-bromo- or 2-chloro-4-trifluoromethyl-substituent.

7. A process according to claim 5 wherein R is a hydrogen atom, an alkoxycarbonyl group having 1 to 3 carbon atoms in the alkoxy moiety, an acetyl group, a chloroacetyl group or an N,N-dimethylcarbamoyl group.

8. A compound having the formula (I):

(I) wherein X is a halogen atom or a trifluoromethyl group, n is an integer of 1 to 3 inclusive and R is a hydrogen atom, a lower alkoxycarbonyl group, an acetyl group, a chloroacetyl group or an N,N-dimethylcarbamoyl group, and the alkali metal salts thereof.

9. A compound of formula (I) according to claim 8 wherein it is in the form of an alkali metal salt.