CA2001964A1 - Aryloxy benzotriazole herbicidal agents and methods for the preparation thereof - Google Patents

Abstract

ARYLOXY BENZOTRIAZOLE HERBICIDAL AGENTS AND
METHODS FOR THE PREPARATION THEREOF

ABSTRACT OF THE INVENTION
This invention is directed to certain substi-tuted aryloxy benzotriazole compounds which are herbi-cidal agents. The invention is further directed to methods for the preparation of the aryloxy benzo-triazole compounds.

Description

~0,972 2~964 ARYLOXY B~NZOTRIAZOL~ HBRBICIDAL AG~ ~ND
M~T~OD8 FOR T~ PR~PAR~TIO~ TH~RRQF

It ha~ now been found that when aryloxy benzotriazole3 are substituted at the N1 position by certain substituted alkyl moieties, an unexpectedly increased level of her~icidal aativity is obtained.
The present invention is directed to certain substituted aryloxy benzotriazole compounds that are highly effective as herbicidal agents. The present invention is also directed to methods for preparing the aryloxy ben~otriazole ~ompounds.
The aryloxy benzotriazole ~ompounds of the present invention have the structure:

z ~ o ~ /N or z ~ ~ /C-(CHR2)n-R3 R~C~(CHR2)n R3 2C)~9~

wherein the benzotriazole portion of the formula I com-pound is substituted by aryloxy in the 5 or 6 position;
M is C-X, N, or N+-O ;
W, X, Y, and Z are each independently hydrogen, halo-halogen, nitro, cyano, C1-C~ haloalXyl or Cl-C4 haloalkoxy:
n is 0, 1 or 2;
R is hydrogenJ Cl-C4 alkyl, aryl or when taken together with Rl, R an~ Rl may form a ring in which RRl are represented by the structure -~CH2)m- where m is an integer of 2, 3, 4 or 5;
R1 and R2 are each independently hydrogen, Cl-C4 alkyl or when taken together Rl and R2 may form a ring in which R1R2 are represented by the structure -~C~2)m where m is an integer o~ 2, 3, 4 or 5:

O A O
R3 i~ cyano, C-Q, C~, CH2OCR7, CH2OR8 or CH(OR9~2;
Q iq OH, OR4 or NR5R6:
A is O, NOR5, NCOR5, NNR5R6 or NNHCO~H2;
R7 is hydrogen, Cl-C4 alkyl or aryl;
R8 is hydrogen or C1-C4 alk~l:
Rg is C1-C4 alkyl;
R4 is Cl-C6 alkyl optionally interrupted by O

':

2~9~

or S or optionally substituted with C
C~ alkoxy, halogen, hydroxy, C3-C6 cycloalkyl, furyl, or optionally substi-tuted phenyl; C3-C6 alkenyl optionally sub~tituted with one or two Cl-C3 alkoxy, halogen, substituted phenyl or C3-C6 cycloalkyl; C3-C6 al~ynyl option-ally ~ubstituted with Cl-C~ alXoxy or halogen: C3-C6 cycloalkyl; ammonium; C1-C6 dialkylammonium; C1-C6 trialkylam-monium: a metal cation: or a moiety of formula R
N = ~R
R5 and R6 each independently rapresent hydro-gen, Cl-C6 alkyl, phenyl or halophenyl:
the benzotriazole N-oxides and ~-methosulfat~s: and when R1 or R2 is C1-C4 alkyll the optical isomer~
thereof.
æurprisingly~ it has been found that the 3ub~tituted aryloxy benzotri~zoles are herbicidal agents, whioh e~hibit control of a broad ~pectrum o$
monoootyledonous a~d dicotyledonous plants. The compou~ds are effective at lo~ application rate~ for cGntrolling ~eed~ indige~ou~ to both dry and ~et land ar~a~.

Z6) [1~9~i4 A preferred group of the substituted aryloxy benzotriazoles of the present invention are illustrated by above formula I, wherein the benzotriazole is substituted in the 6 position by aryloxy; M is C-X; X, Y, and Z each independently represent Cl, F, or CF3: W
is hydrogen, n is O; R and Rl are each i~dependently hydrogen or methyl; and R3 i5 Cl-C~ carboalkoxy or carboxy.
Compounds of formula I (wherein the ben~o-triazole i~ substituted in the 5 or 6 position~ or formula II are prepared as ~hown below in flow diagram I wherein B is halogen and M, W, Y, Z, n, R, R1, R2 and R3 are as hereinabova describsd for formula I and II
with the proviso that at least one of R or R1 is hydrogen.

FLOU D I RGRP~n I

Z~B ~ H ~ 3 Z~o~ HNo3~ D2 lV 111 Z~ ~2 NaN02 _~

V ` VI

IR
K2C03 ~ C-tCHRz)n~R3 R Rl Z ~O ~CN ~Rl ~ ~N~ - ~ C HR2 ~ R3 ~C~~t HR2~n-R3 2 t31~1L964 The appropriately substituted halobenzene is reacted with m~nitrophenol ~o give the phenyl ether III
which i3 then nitrated to give compound IV, which in turn is reduced to give the diamino compound, V. The compound V i3 ring closed in the presence of sodium nitrite and the re~ultant phenoxy benzotriazole, VI, is reacted with a haloalkyl electrophile to yield com-pound~ of formula I and II as shown above wherein at least one of R or R1 is hydrogen.
1~ Alternatively, the compound~ of foxmula I, wherein the benzotriazole is substituted in position 6, are prepared as shown below in flow diagram II.

FLOU DlRBRR11 11 IRl R ,C~ ( CHR2 )n~R3 U Y NOz 11 U Y NH R
~< ~=< H2N~C~CHR2)n~R3 ~< /=~
20~ n ~ No2 ~ ~ Z ~ \ ~ ~ NO2 IV Vl I

,Rl ~Rl R~C~~CHR2)n~R3 ~C-(CHR2)n-R3 25 Z~O~N NaNO2 z~O~NHz ( 6-subs t i tuted V 111 benzotriazole) 20~I964 The appropriately substituted dinitro com-pound ~IV) is reacted with an amine nu~leophile to give compound~ of formula VII. ~eduction of VII affords the diamine VIII, which is ring-clo~ed through th~ agency o~ sodium ~itrite to a~ford compounds of formula I, wherein ths aryloxy group is attached to position 6 of the benzotriazole. This method of preparation is most effectively carried out when n i~ O and R3 i8 C~(ORg)~.
Another method useful for preparing compounds of formula I wherein the benzotriazole is substitute~
in position 6 is shown in flow diagram IIIo FLOW DIRGRR~1 11 I
Rl R-C - ( CHRZ ) n~R3 Z~B + H o~N

¦ IX
R~
R-C-(CHRz)n-R3 2 S Z~o~N

The appropriately substituted halobenzene is reacted with the 6-hydroxy ben~otxia~ole compound IX to give compou~ds of formula I.
The intermediate 6-hydroxy ben~otriazole compound IX wherein when n is O, R3 is C~ORg)2 is prepared a~ shown in flow diagram IV.

L9~4 FLOU DIRGRRM IV

C5H5CH O~ t H2N-C-~CHR2~ -R3 1 C6H5CH2~N-C- ~cHR2)n-RJ C6H5CH2~ -C- ~ CHR2~ n-R3 Xl X

R~C~(CHRZ)n~R~ HO R~C~(CHR2)n~R3 C6H5CH2~CN~N Pd~C ~N/N
Xl I IX
The amine nucleophile as hereinabove des~ribad is reacted with 4-benzyloxy-2-halo-nitro-benzene to give the intermediate compound X. Reduction o~ sompound X in the presence of Raney Nickel affords the diamine XI which is ring ~losed using nitrou acia to give the benzotriazole compound XII. Reductive oleavage of the benzyl group yields the intermediate ~-hyaroxy be~zotriazole compound IX.
Advantageously, it has been found that the above-desoribed proces illustrated in flow ~iagrams ITI and IV is most ef~ecti~ely aarried out for those formula I compounds ~herein n is 0 and R3 is carbo~y when the amine nucl00phile is proteoted as the dialkyl aaetal of the ~orresponding aminoaldehyde. ~ubse~ue~t 2G1~9~4 hydrolysis and oxidation of the thus-obtained 6-aryloxy ben~otriazole intermediate XIII affords compounds of ~ormula I wherein n is O and R3 is carbo~y. An example of this prooess is sho~n in flo~ diagram V wherein the dimethyl acetal of an aminoacetaldehyde i~ u ed as the amine nucleophile.

FLOI.I DIRGRRM V

R-C-CH t OCH ~ ) 2 R-C-CHO
U Y _~N + ~_ _ ~N

~ o~,1 R-C - COOH

~ ~ N

The formula I and II aryloxy benzotriazoles of the pre~ent i~vention are useful for the control of a wide variety of herbaceous and woody, annual and perennial, ~onocotyledonous and dicotyledonous plants.
Th0se compounds ~re ~ffective in controlli~g the above-said plants when applied to the foliage there~f or to soil, or water, containing seeds or propagating organY of said plants suoh as tubers, rhizomes, or stolons at rates of about O.OD5 to 5.0 ~g/ha and preferably at rate~ of about 0~01 to 4.0 kg~ha.
Among the plants which may be controlled with the compounds of this invention are Abutilon theo-20~9~4 phra~ti, Sesbania exaltata, I~omoea æp., Sida spinosa,Cassia obtusifolia, Setaria qlauca, Sorghum halepense, and Echinocholoa crusqalli.
~he formula I compounds are applied in agronomically acceptable carriers which are formulated as wettable po~ders, dust conce~trates, granular formulations, suspension concentrates, microemulsions, emulsifiabls concentrates, solutions, emulsion~ and the like.
Wettable powders are prepared by grinding together about 20~ to 45% by weight of a finely divided solid carrier such as kaolin bentonite, diatomaceous earth, attapulgite, or the like, 45% to 8D% by weight of the active compound, 2% to 5% by weight of a dis--persing agent ~uch as sodium lignosulfate, and 2% to 5%
by weight of a nonionic surfactant such as octylphenoxy polyethoxy ethanol, nonylphenoxy polyethoxy ethanol or the like.
A typiGal emulsifiable concentrate is pre-pzred by dissolving about 5% to 25% by weight of theactive compou~d in about 65% to 90% ~y weight of a carrier such as N-methylpyrrolidone, isophorone, butyl cellosolve, methyl acetate or the like and dispersing therein a~out 5% to 10% by weight of a ~onionic surfa~tant such as an alkylphenoxy polyetho~y alcohol.
This concentrate is di~p~r~ed in water for application as a liquid spray.
Preparation of a granular formulation is achieved by dissolving the active compound in a solvent such a~ methylene chloride, N-methylpyrroli~one, or the like and spraying the thus-prepared ~olution on a granular carrier ~uch as corncob grits, sand, attapul-gite or kaolin. The granular produat, thu~ prepared, generally comprises about 3% to 20% by weight of the , o active compound and about 97% to 80% by weight of t~e granular carrier.
In order to faailitate a further under-standing of the invention, the following exampleR are pre-~ented primarily for the purpose of illustrating certain more specific details thereof. The invention ic not to be deemed limited thereby except as defined in the claims. Unless otherwise noted, all parts are by weight, all temperatures are expressed as degrees centigrade, NNR designates proton nuclear magnetic resonance spectroscopy, and HPLC dQsignates high pressure liquid chromatography.

2~l964 PreParation of 3-chloro-5-fluoro-4-(3-nitrophenoxy)-benzotrifluoride cl No2 CF s~F ~ HO~

F , K2C~
Cl N2 CF3 ~ ~ ~

F
A mixture of 36.7 g of 3-nitrophenol, 54.1 g of 3,4-difluoro-5-chlorobenzotrifluoride, and 41.5 g of powdered potassium carbonate in 300 mL dimethylsulfox-ide is stirred at room temperature for 16 hours, then at 50C for 5 1/2 hours. The mixture is cooled, poured onto lL of water and extracted with methylene chloride.
The organic phase is washed thoroughly with water, dried, and concentrated in vacuo to give 81.1 g of a residue, which is an isomeric mixture. Chromatography on silica gel using 7:3 hexane-ether as eluant affords 72O7 g of the desired product; HPLC analysis indicates >90% purity-2~964 Preparation of 3-chloro-5-fluoro-4~ ~initrophenoxy)-benzotrifluoride C~ ~ C~

A solution of 72.7 g of 3-chloro-5-fluoro-4-(3-nitrophenoxy)benzotrifluoride in 200 mL of acetic acid is stirred at 10C and 108 g of 13% nitric acid in sulfuric acid is added over a 4 hour period. During the addition, more acetic acid is added so as to keep 15 the reaction homogeneous. The reaction is stirred at room tamperature for 21 hours, then 50 mL of acetic anhydride is added in 3 portions over 3 days with water bath cooling. The final reaction mixture is poured onto ice and extracted with methylene chloride. The combined extracts are washed with water followed by aqueous carbonate, then dried and concentrated 1n vacuo to give 73.5 g of a residue. This material is dissolved in 50 mL of acetic anhydride and cooled to 0C. A solution of 8.5 mL of fuming nitric acid in 45 mL sulfuric acid is added alternately with 35 mL of acetic anhydride and 10 mL of acetic acid over a 4 hour period. After stirring for an additional one-half hour, the reaction is poured onto ice and worked up as above to afford ~9 g of a residue. Column chromato-graphy of this material on silica gel using hexane-chloroform mixtures affords 13.2 g of the title product as an oil, identified by NMR.

2~ 96~

Preparation of 6-r(2-chloro~ .6-tetrafluoro-p_ tolyl~o~ lH-benzotriazole CF3~~NO2 - 2 ~ C~O~NH2 1N~NO2 CF~O~

A mixture of 13.2 g of 3-chloro-5-fluoro-4-(3,4-dinitrophenoxy)benzotrifluoride, 0.3 g of 5~
Pd/C and 150 mL of ethanol is shaken in a Parr hydro-genation apparatus under 50 psi of H2. During the course of the reaction, 0.8 g of 5% Pd/C is added in 2 portions over a 5 hour period. After a total of 23 hours, when the uptake of H2 appears to cease, the reaction is filtered and concentrated in vacuo to give a residue. This residue is dissolved in 100 mL of acetic acid and added, slowly over 3 hours, to a solution of 2.64 g of NaNO2 in 30 mL of water and 50 mL
of acetic acid at 5C. After stirring at 5 to 20C
30 for an additional 1 1/2 hours, the reaction mixture is concentrated in vacuo to afford the title product, 20.~ g Z0~9~i~

Preparation of methyl 6-C(2-chloro-~ -trifluoro-p-tolyl~oxyl-l~I-benzotriazole-l-acetate and methyl 5-r(2-chloro-~ -trifluoro-P-tolyl)oxYl-lH-benzo-triazole-1-acetate rC02CH~

0 CF:5~0~N 1, CF~o~ +

~o ~ N~

A mixture of 2.5 g of 6-(2-chloro-4-tri-fl~oromethylphenoxy)-lH-benzotriazole, 1.59 g of methyl bromoacetate, and 2.07 g of powdered potassium carbonate in 30 mL of dimethylformamide is stirred at room temperature for 24 hours. The mixture is concen-trated ln vacuo, and the resultant residue is parti-tioned between methylene chloride and water. The organic phase is washed with water, dried, and concen-trated in vacuo, and this residue, which contains a mixture of alkylated products, is purified by HPLC
using hexane-methyl-t~butyl ether as eluant to afford 0.92g of Ia as a gum, 97.6% pure by HPLC, id~ntified by NMR, and 0.74g o~ Ib as a gum, 96.2% pure by HPLC, identified by N~.
Using essentially the same procedure, and substituting methyl-~-bromopropionate as electrophile, affords 1.05g of methyl 6-[(2-chloro~ trifluoro-p-tolyl~-oxy]~-methyl-lH-benz~triazole 1-acetate as a 26)~ 964 gum of 97.3% purity, identified by NMR; 1.09g of methyl 5-[(2-chloro-~ -trifluoro-p-tolyl)oxy]-~-methyl-2H-benzotriazole-l-acetate as a gum o,f 93.9% purity, identified by NMR; and 0.77g of methyl 5-~.(2-chloro-Q,-~,~-trifluoro-p-tolyl)oxy]-~-methyl-lH-benzotriazole-l-acetate as a gum of 96.0% purity, identified by NMR.
Using essentially the same procedure, and substituting methyl-~-bromopropionate and 5-(2-chloro 6-fluoro-4-trifluoromethylphenoxy)-1,2,3-benzotriazole as reactants, afEords 0.87g of methyl 6-[(2-chloro-~,-~, Ct, 6-tetrafluoro-p-tolyl)oxy]-~-methyl-lH-benzotria-zole-l-acetate as a gum, identified by NMR; 1.68g of methyl 5-[(2-chloro-~ ,6-tetrafluoro-p-tolyl)oxy]--~-methyl-2H-benzotriazole-l-acetate as a gum, identified by NMR; and 1.38g of methyl 5-[(2-chloro-~,-~,~,6-tetrafluoro-p-tolyl)oxy]-~-methyl-lH-benzotria-zole-l-acetate as a gum, identified by NMR.

Preparation of 3-f5-r2-chloro-~ trifluoro-p-tolyl)-oxy]-2-nit.roanilino~eropionitrile C l N2 C I ~ CN
CF3 ~ ~ No2 H2RCH2cH~cN CF~ ~ ~ No2 A solution of 2.8g of 3 chloro-4-(3,4-dini-trophenoxy)benzotrifluoride and l.O9g of ~-aminopropio-nitrile in 10 mL acetonitrile is heated at reflux temp-erature for 8 hours. The solution is concentrated in vacuo, and the residue is dissolved in methylene chloride, washed twice with water, and concentrated ln 2~ 36~

vacuo to give solid residue. Recrystallization from methanol affords the title compound, 3.08g HPLC
indicates 95.7% purity, mass spectral analysis indicates MW 385.
Using essentially the same procedure and sub-stituting 3-chloro-5-fluoro-4-(3,4-dinitrophenoxy)-benzotrifluoride and the appropriate amino alcohol, amino aldehyde, dimethylacetal or amino acid, the following compounds are obtained.

H

CF3~ ~N02 F
R Rl R3 _ C6H5 (R-isomer) 2 C6H5 (S-isomer) 2 H
CH~ H CH(OCH3)2 The above compounds are identified by NMR
analysis.

9~

Preparation of 3-~6- r ( 2-chloro-~ trifluoro-p-tolyl?oxy1~ropionitrile HH
C I N CNC I N CN

CFS~O~N02 ~ CF~NH2 ¦N~HO2 ~CN

C F;S~ o ~ N

A solution of 3.0g of 3-chloro-4-~3-~-cyano-ethylamino-4-nitrophenoxy)benzotrifluoride in 100 mL
absolute methanol containing 0.3g of 5% Pd/C is shaken in a Parr hydrogenation apparatus, initially at 40 psi H2, for 5 hours. The resulting mixture is filtered and concentrated in vacuo to afford the crude diamine, identified by mass spectral analysis.
2~ This material is dissolved in 40 mL acetic acid, cooled to 5C, and 0.59g NaNO2 dissolved in 5 mL
water is added over 4 minutes. The resulting mixture is stirred at room temperature for 1 hour and concentrated in vacuo to give a residue. The residue is dissolved in methylene chloride, washed sequentially with aqueous Na2CO3 and water, dried and concentrated in vacuo to afford the title product 2.45g, as a gum:
HPLC analysis indicates 92.8% purity; the product is further identified by mass spectral analysis (MW 366).

2q:1 ~19~4 Using essentially the same procedure and employing the appropriate N-substituted 5-~2-chloro-,6-tetrafluoro-~-tolyl)oxy]-2-nitroaniline com-pound as starting material, the following compounds are obtained.

~C~R

C F ,~ O--~

R Rl R3 mp C
CH3 CH2OH gum C6H5 (R-isomer) CH2H 85-86 C6H5 (S-isomer) CH2H 83-84 CH3 H CH(OCH3)2 go-97.5 The above compounds are identified by NMR
and elemental analyses.

Preparation o~ 2-aminopro~ionaldehyde dimeth~l acetal N-OH NH
ll Ran~y Nl 1 2 CH3-C-CH(OCH3)2 + 2H2 ~ CH3-cHcH(ocH3)2 A mixture of pyruvic aldehyde dimethyl acetal oxime (38 g) and Raney nickel (5.63 g) in methanol is shaken in a Parr hydrogenator under 17-54 psig hydro-gen. An additional 5.5 g of Raney nickel is added as needed and hydrogenation at 27-45 psig is continued until about 90% of the theoretical quantity of hydrogen 9~i4 is absorbed. The reaction mixture is filtered, and the filtrate is concentrated by distillation through a 30-cm column. When the distillate boiling point reaches 78C, 75 ml of absolute ethanol is added and distillation is continued to give a 26 g (78%) fraction boiling at 138-140C. A twice-distilled sample of the title compound, bp 98-100C (145 mm), is identified by elemental and N~R analyses.

Preparation of benzyl 3-chloro-4 nitrophenyl ether HO~ K2CO, \~NO~
A mixture of 3-chloro-4-nitrophenol (10 g, 0.058 mole}, benzyl bromide (11.8 g, 0.069 mole), and potassium carbonate (16 g, 0.116 mole) in acetone is stirred, heated at reflux temperature for 17 hours, cooled and filtered. The filtrate is concentrated 1n vacuo to give a solid residue which is recrystallized from absolute ethanol to give the title compound, mp 82-84.5C, identified by elemental and NMR analyses.

2~ YL9~4 PreParation of 2-r5-(benzyloxy!-2-nitroanilinol-pro-pionaldehyde dimethyl acetal C~H5CH2o ~ Cl lH2 + CH3-CH-CH(OCH3)2 ~ K2CO3 Cll, ~ .
C6H5CH20~NH -CH-CH ( OCH3 ) 2 A mixture of benzyl 3-chloro-4-nitrophenyl ether (48.2 g, 0.183 mole), 2-aminopropionaldehyde dimethyl acetal (65.3 g, 0.55 mole), potassium carbonate (101 g, 0.73 mole) and toluene in dry dimethyl sulfoxide, under nitrogen, is stirred at 99-105C for 20 hours, cooled to room temperature and filtered. The filter cake is washed with ether. The combined filtrates are mixed with ice water. The phases are separated and the aqueous phase is extracted with ether. The ether extracts are combined with the organic phase. The combined organic phase is washed with six portions of water, dried (Na2S04) and concentrated in vacuo to give an oil residue which is crystallized in methanol to afford the title product as a yellow solid, 39.6 g (64.5%). A sample is recrystallized from methanol to afford a yellow solid, mp 57-6~-C, identified by elemental and NM~ analyses.

Pre~aration_o~ 2- r 2-amino-5-(benzyloxy)anilino1propion-aldehvde dimetnyl acetal H ~ C H, CsHsCH20 ~ ~ ~ NH CH-CH(OCH~) C61!sCHzO ~ ~ ~ NU CH-CH(OCH~)2 A solution of 2-[5-(benzyloxy)-2-nitro-anilino~propionaldehyde dimethyl acetal (24.0 g, 0.071 mole) in tetrahydrofuran is treated with Raney nickel (10 g) and placed in a Parr shaker hydrogenation apparatus under 20.S-37 psig hydrogen at ambient temperature. After the uptake of the theoretical quantity of hydrogen, the mixture is filtered and the filtrate is concentrated ln vacuo to afford the title product as a dark-colored syrup. The product is identified by infrared and mass spectral analyses.

2~

: ' 9~j~

Preparation of 6-(benzyloxy)-~-methyl-lH-benzotriazole-1-acetaldehyde dimethyl acetal C3HsCH2 NH -CH-CH ( OCH~ ) 2 NH2 ~ N~N02~CH;~COOH

C~H5CH20 N;CH-CH(OCH~) ~N
A solution of NaN02 (34 g, 0.492 mole) in water is added to a cold (3C) solution of acetic acid and water. A cold (4C) solution of 2-[2-amino-5-(ben-zyloxy)anilino]-propionaldehyde dimethyl acetal in dimethoxyethane is then added in one portion to the vigorously-stirred NaNQ2 acetic acid solution. The reaction temperature rises to 22C. The reaction mixture is stirred at 18-22C for 20 minutes, cooled to 5C, and filtered. The solid filter cake is washed with water and dried at 50C, to give the title product as a white solid, 75.7 g (65.7%). A sample is re-crystallized twice from 1:1 toluene-heptane solution to a white solid, mp 101-103C (sinter 100C), identified by elemental and NMR analyses.

3~

~5 ;4 EXAMPLE_12 Pre~aration of 6-(benzyloxy)-~-methvl-l~I-benzotriazole-l-acetic acid C,jHsCH20~ 3 ~N-CH-CH(OCH3)~ C~N~CH20 ~ N-CH-cHo 0 CH~ ¦
C~H5CH20~CN_cH_cooH ~ KMnO~

N

A solution of 6-(benzyloxy)-~-methyl-lH-benzotriazole-1-acetaldehyde dimethyl acetal (95 g, 0.272 mole) and concentrated sulfuric acid (20 ml) in acetic acid and water is heated at 72C for 20 hours, cooled to room temperature and concentrated ln vacuo.
The concentrated solution is diluted with acetone and water and treated with KMnO4 (140 g) in portions over a three hour period at 18-30C with stirring.
The reaction mixture is decanted and filtered. The filtrate is concentrated ln vacuo to remove acetone, diluted with water, cooled in an ice bath, and the resulting precipitate is removed by filtration to give the title product. A sample of this solid is recrystallized twice from aqueous ethanol to afford a white solid, mp 213-215C, identified by elemental and NMR analyses.

:

; ~ :
,:
, 2~ 96~

Preparation of methyl 6-(benzYloxY~ methvl-lH-benzo-triazole-1-acetate C6H5CH20~CN-CH-COON C6HsCH20~N-CH-COOCH;~

A mixture of 6-(benæyloxy~ methyl-lH benzo-triazole-1-acetic acid (36.6 g, 0.123 mole) and concentrated sulfuric acid (2.7 ml) in methanol is stirred at reflux temperature for 6 hours, cooled in an ice bath and treated with K2C03 (25 g). The resulting mixture is stirred vigorously until a thick slurry results, diluted with methylene chloride and filtered. The filtrate is concentrated in vacuo to give a solid residue. Recrystallization of the residue from methanol affords the title product as a white solid, 27 g, mp 88-91.5C, identified by N~ and elemental analyses. Another 4.2 g (81076 total yield) of the title product is obtained from the mother 1i~uor.

PreParation of methyl 6-hydroxy-~-methyl-lH-benzotria-zole-l-acetate CH~ HO N-CH-COOCH3 C ,; H 5 C H 2 ~C N - C H - C O O C H 3 / \[~C '/ ' ~o~9~

A solution of methyl 6-(benzyloxy)-~-methyl-lH-benzotriazole-l-acetate (31 g, 0.1 mole) in dimethoxyethane and methanol is shaken with 10%
palladium on carbon catalyst (8 g, 50% wat,er wet) under 24-33 psig of hydrogen in a Parr apparatus until approximately 0.1 mole of H2 is absorbed (2 1/2 hours).
The reaction mixture is filtered and the filtrate is concentrated }n vacuo to give the title compound as an off-white solid, 21.7 g, mp 132.5-134.5C, identified by NMR and elemental analyses.

EX~MPLE 15 Preparation of methyl ~-methyl-6 -r (2-nitro-~J~ tri-fluoro-~-tolyl)oxyl-1H-benzotriazole-1-acetate N02 l H3 F 3 C F H o ~[~ c H - c o o c H

F C J~ C H - C O O C H 3 ~
A mixture of methyl 6-hydroxy-~-methyl-lH-benzotriazole-l-acetate (2.21 g, 0.01 mole), 4-fluoro-3-nitrobenzotrifluoride (2.09 g, 0.01 mole), and ~2C03 ~5.5 g, 0.04 mole) in dry dimethyl sulfoxide is stirred at 22C for 16 hours, diluted with chloroform and filtered. The filtrate is washed with two portions o~
water and two portions of saturated a~ueous NaCl, dried over Na2S04 and concentrated i vacuo to give a gum residue. The residue is crystallized from 60~ aqueous ethanol to give 3.8 g of the title product as a 9~4 yellow ~olid. A ~ample i~ recrystallized twice from 80% aqueous ethanol to give a yellow solid, mp 84.5-88.2C, identified by elemental and NMR analyses.
Using e~entially the same procedure and substituting the appropriate haloaryl starting material, the ~ollo~ing compound~ are obtained.

CH-COOCH
U Y N~
Z ~ o ~ N
M W Y Z mpC
C-NO2 Cl H CF3 107-112 N H H CF3 gum N H Cl Cl gum N -o H H CF3 N~-O H Cl Cl ~XA~PL~ 16 PreParation of 6-[(2-~hloro~ ,6-tetrafluoro-p-tolyl~o~y~-~-methyl-lH ben~otr;a~ole-l-a~etic a~i~

~[~ ~N- C H - C H ( O C H3 ) 2 F3C 12. KMnO4 F CH
F3C ~cN-CH- COOH

A ~olution of ~-t~2-~hloro~ ,6 tetra-fluorQ-p-tolyl)oxy]-~-methyl-l~-benzotriazole-~-ace-z~

taldehyde dimethyl acetal (23.0 g, 0.053 mole) in acetic acid is treated with 54 ml of 2.5 N H2SO4 and heated at 70C for 12 hours. A portion of the reaction solution is concentrated, diluted with acetone and treated portionwise, at 25-38C, with an aqueous solu-tion of KMnO4 (23.7 g, 0.15 mole). Addition is con-tinued until a persistent pink color is obtained at 27C. The reaction mixture is filtered to remove MnO2 and the filtrate is concentrated ln vacuo to give a residue. Addition of water to the thus-obtained resi-due precipitates the title compound as a pale yellow solid, 16.6 g. A sample is recrystallized twice from 75~ aqueous ethanol to afford a crystalline solid, mp 174-175.5C, identified by elemental and NMR analyses.

Preparation of 6- r f2-chloro-Q,~.~.6-tetrafluoro-p-tolyl)oxvl-e-methYl-lH-benzotriazole-l-acetic acid compound with isoproPvlamine (1:1) CH~
F f-COOH

F 3 C ~o ~

F CH-COOH H2N-~H ~ CU3 ~ 2 F 3 C C ~ ~

Isopropylamine (0.5 g, 0.0085 mole) is added to a solution of 6-[(2-chloro~ ,6-t~trafluoro-p-tolyl)oxy]-~-methyl-lH-benzotriazole-l-acetic acid (2.0 g, 0.005 mole) in methylene chloride and the resultant solution is concentrated ln vacuo to afford a gum which is dissolved in toluen~. The toluene solution is 2~ 9~D~

concentrated to afford the title compound as a white solid, mp 103.5-105.5, identified by elemental and NMR
analyses.

~XAMP~
Preparation of methyl 6-~f2-chloro-~,~L~ 6-tetrafluoro-p-tolyl)oxyl-~ ~-dimethyl-lH-benzotriazole-1-acetate 0 C H 3 C ~
FCH~-c-cH2oH ~ CH3-C-COOH

F ~ C C ~11C U C 110 N F C/~ C
CH~
F CH~-c-c~ocH3 CH2N2 A solution of 6-[(2-chloro-~ ,6-tetra-fluoro-p-tolyl)oxy]-~,~-dimethyl-lH-benzotriazole-l-ethanol (2.2 g, 0.00545 mole) in acetic acid and water is stirred at 56-80C, treated portionwise with solid KMnO4 (8.5 g, 0.054 mole) ov~r a 3 hour period, cooled and filtered. The filtrate i5 concentrated ln vacuo to give a gum residue. The residue is chromatographed on silica gel with 15% tetrahydrofuran in chloroform to afford a white solid, 1.2 gO The solid is dissolved in methanol, treated with a solution of diazomethane in tetrahydrofuran, heated on a steam bath and concentrat-ed in vacuo to give a solid residue. Chromatography of the residue using silica gel and 5% tetrahydrofuran in carbon tetrachloride as eluant affords the title ;~:V~l9~qL

product as a white solid, 0.65 g, mp 76.8-80C, identified by elemental and NMR analyses.

PreDaration of 6-r(2-chloro-~ ,6-tetrafluoro-p-tolyl)oxv~ methyl-lH-benzotriazole-l acetaldehyde I H3 CH~
F CH-CH~OCH~)2 F CH-CHo 0 I ~C cX3~N ~$~c~c ~N

A solution of 6-[(2-chloro-~ ,6-tetra-fluoro-p-tolyl)oxy]-~-methyl-lH-benzotriazole-l-ace-taldehyde dimethyl acetal (20 g, 0.046 mole) in acetic acid is treated with 47 ml of 2.5 N H2S04, heated for 12 hours at 70C, cooled and diluted with water and methylene chloride. The phases are separated and the aqueous phase is extracted with methylene chloride.
The combined organic phases are dried (MgS04), filtered through a pad of A1203, and concentrated in vacuo to afford the title compound as a solid, mp 107-108C, characterized by elemental and NMR analyses.

.

~ 1 :

96~

EXA~PLE 20 Preparation of 6-~2-chloro-~ ,6-tetrafluoro-p-tolyl)oxy~ methyl-lH-benzotriazole-l-acetaldehyde oxime S

CH; CH3 N-OH
F CH-CH(OCH,)2 ~ CH-CH

c~ ~ c~C~

A solution of 6-[(2-chloro-~ ,6-tetra-fluoro-p-tolyl)oxy]-~-methyl-l~-benzotriazole-l-ace-taldehyde dimethyl acetal (23.0 g, 0.053 mole) in acetic acid is treated with 54 ml of 2.5N H2SO4 and stirred at 70 C for 12 hours. A 15 ml portion of the reaction solution is diluted to a total vclume of 100 ml with water, the resulting precipitate is separated, washed with water, treated with a solution of hydroxylamine hydrochloride (1.0 g, 0.014 mole) in pyridine and ethanol, heated at 85C for several hours, cooled and concentrated in vacuo to give a solid residue. Recrystallization from aqueous ethanol, ethanol and toluene gives the title compound mp 148-151C, identified by elemental and NMR analyses.

2[)~ L96~

~ EXAMPLE 21 Preparation of 6-r(2-chloro-~ 6-tetrafluoro-p-tolyl~oxy~ methyl-lH-benzotriazole-l-acetonitrile (I) and 6- r f2-chloro-e,~,~ 6-tetrafluoro-p-tol~l)ox~
methyl-lH-benzotriazole-l-acetaldehyde O-acetyloxime rII) CH3 N-OH fH3 F CH-CI-I F CH-CN
lC ~C~C"N J~C\¢~CN~N '' ( I ) o ll C H ~ N - O C C H 3 F 3 C ~ "

( I I ) A solution of 6-[(2-chloro-~ ,6-tetra-fluoro-p-tolyl)oxy]-~-methyl-lH-benzotriazole-1-ace-taldehyde oxime (5.0 g, 0.012 mol) in acetic anhydride is allowed to stand at 22 C for 20 hours and concen-trated in vacuo to give an oil residue. The residue is chromatographed on silica gel using chloroform as eluant to afford the title compound (I); 2.0 g, mp 118-119C, identified by elemental and NMR analyses and the title compound (II), 2.1 g, mp 95-97C, identified by elemental and NMR analyses.

3~

2~96~

Preparation of 6-~(2-chloro-~ 6-tetrafluoro-p-tolyl)oxy]-~-methyl-lH-benzotriazole-l-acetaldehyde semicarbazone l H3 FCH-CHO

F 3 C ~CN~N --1 0 F CH-C

F ~ C C ~C ~
A mixture of 6-[(2-chloro-~ ,6-tetra-fluoro-p-tolyl)oxy]-~-methyl-lH-benzotriazole-l-ace-taldehyde (0.0295 mole), semicarbazide hydrochloride (4.0 g, 0.035 mole), and sodium acetate (5.8 g, 0.071 mole) in aqueous ethanol is heated to reflux temperature, cooled and filtered. The solid filter cake is recrystallized from ethanol to give the title compound as a solid, mp 170-171C, identified by elemental and NMR analyses.

Preparation of 6-r(2-chlor ~ .6-tetrafluoro p-tolyl)oxy~-~-methyl-lH-benzotria~ol-l-acetaldedhyde (2,4-dinitrophenyl)hydrazon~

3 lC HH 3 C H o F C H - C N 2 F ~ C C ~"~ ' ~ ~N"N

96~

A solution of 6-[(2-chloro~ ,6-tetra-fluoro-p-tolyl~oxy]-~-methyl-lH-benzotriazol-1-ace-taldedhyde (0.0294 mole) in ethanol is added to a solution of 2,4-dinitrophenylhydrazine (7 g, 0.035 mole) and conc. H2SO4 (35 ml, 0.63 mole) in H2O at 50 C, allowed to come to room temperature and filtered.
The solid filter cake is recrystallized from aqueous acetic acid and from ethanol to afford the title compound, mp 148-149C, identified by elemental and NMR analyses.

Preparation of (S)-6 r t2-chloro-~ ,6-tetrafluoro-p-tolvl)oxyl-~-phenyl-lH-benzotriazole-l-acetaldehyde l 6Hs C6Hs ~ C~N/ CH C I ~ C~ "N
A mixture of (S)-6-[(2-chloro-~ ,6-tetra-fluoro-p-tolyl)oxy]-~-phenyl-lH-benzotriazole-1-ethanol tl.0 g, 0.0022 mole) in chloroform is treated with MnO2, (1.0 g, 0.0115 mole) stirred at 40C for 18 hours and filtered through a bed of diatomaceous earth.
The filtrate is concentrated in vacuo to give a residue which is chromatographed using silica gel and 10~ tetrahydrofuran in carbon tetrachloride to yield the title product as a white solid, 0.42 g, mp 84-85C, characterized by elemental and NMR analyses.

L96~

Preparation of 6- ~2-chloro~ ,6-tetrafluoro-p-tolvl)oxvl-~-methyl-lH-benzotriazole-1-acetyl chloride CH~ CH;~
F CH-COOH F CH-COC I

0 ~,c c~' N - ~ ~CN/N

A mixture of 6-~(2-chloro-~ ,6-tetra-fluoro-p-tolyl)oxy]-~-methyl-lH-benzotriazole-1-acetic acid (2.0 g, 0.005 mole), SOCl~ (3 ml, 0.04 mole), methylene chloride and dimethylformamide (2 drops) is heated at reflux temperature for 2 hours, cooled and concentrated in vacuo to give a residue and which is chased twice with xylene at 65C. The resultant residue is identified as the title product by infrared analysis.

, .

~19~i4 Preparation of N-butyl-6-~(2-chloro-~ 6-tetra-fluoro-p-tolyl)oxy~ methYl-lH-benzotriazole-l-acetamide f H 3 F CH-COC I

~ 3 C C ~CN"N

F CH-CONH-C4Hg F ~ C C ~--N
A solution of 6-[(2-chloro-~ ,6-tetra-fluoro-p-tolyl)oxy]-~-methyl-lH-benzotriazole-1-acetyl chloride (0.0084 mole) in toluene is added to n-butylamine (1.22 g, 0.0167 mole) at 22C, stirred for 1 hour at a~bient temperature and filtered. The solid filter cake is recrystallized from aqueous ethanol to afford the title compound as a white solid, mp 142-143C, identified by elemental and NMR analyses.
Using essentially the same procedure and sub-stituting the appropriate amine, the following compounds are obtained.

F3C -- ~CN-CH-CONR5R6 . _ mPC

C6H5 175.5-176 c~3 C6H5 132-133 C2~5 C2H5 gum The above compounds are identified by NMR
analysis.
~ XANPL~ 27 Preparation of ~ethylallyl 6-~2-chloro-~ 6-tetra-fluoro-p-tolyl~o~y]-~-methyl-~H-be~zotria~ole-l-acetate F CH-COOH
F3C C ~ N~N

F3C C ~ N/N

~ mixture of ~-~(2-chloro-~ ,6-tetra-fluoro p-tolyl)oxy~ methyl-lH benzotriazole-l acetic acid, thionyl chloride ~C.8 ml, O.oll mole~, and 2 ~rops of dimekhylfoxmamide in methyle~e ahloride is heated at reflu~ temperature for 2 hours, cooled and concentrated in vacuo to give a xe idue which i~

re-evaporated four times with toluene at 60. The resultant residue is treated with 2-methylallyl alcohol and pyridine, shaken until reaction is complete by infrared spectral analysis and concentrate~ ln vacuo to give a residue. The thus-obtained residue is dissolved in 1% acetonitrile in carbon tetrachloride and filtered through a pad of silica. The filtrate is concentrated in vacuo to give a solid residue. The solid residue is recry~tallized from warm heptane to afford the title compound as a white solid, mp 71-74C, identified by elemental and NMR analyses.
Using essentially the same procedure and substituting n-hexyl alcahol affords n-hexyl 6-[(2-chloro-~ ,6-tetrafluoro-p-tolyl)oxyJ-~-methyl-lH-benzotriazole-l-acetate as a gum, characterized by - elemental and NMR analyses.

~ XAMPLE 28 Postemerqence herbicidal evaluation of test compounds The postemergence herbicidal activity of the compounds of the present invention is demonstrated by the following tests wherein seeds or tubers of each species are planted 6 to 21 days prior to treatment, depending on the rate of growth of the seedlings. Each species is planted in an individual container and then all species assembled into an 11 x 11 inch tray for treatment. Planting is timed so that monocot species have 2 to 4 leaves and dicots have cotyledons plus 1 to 3 leaves at treatment. After planting, trays are watered with an overhead mis and/or sub-irrigation to maintain moisture until ready ~or treatment. After treatment plants are watered by sub-irrigation only during the evaluation period.

3~

.

~ 38 -In most cases the data are for a single test, but in several instances, they are average values obtained from more than one test.

Plant Species Used Velvetleaf Abutilon theophrasti Oats, cultivated Avana sativa Sicklepod Cassia obtusifolia Nutsedge, yellow Cyperus esculentus Barnyardgrass Echinochola crusqalli Soybeans ~lycine max Morningglory Ipomea Sp.
Sebania, hemp Sesbania exaltata Foxtail, yellow Setaria alauca Sida, prickley Sida spinosa Johnsongrass Sorghum halapense Corn, cultivated Zea maYs Lambsquarters Chenopodium album Jimsonweed Datura stramonium 9~4 DescriPtion of Symptoms Major Rating , Rating Category Symbol Subcateqory Symbol Desiccation D a. New growth occurring Z
of Tissue b. Extreme variation in V
individual plant response Inhibition I a. Break of axillary buds X
b. Bleach or loss of color B
c. Malformed seedlings M

Abnormal A a. Abnormal leaves L
Growth b. Twisting and bending T
of stems c. Elongation of internodes E
d. Rosetting or Shortening R

Color Change C a. Loss of green color with Y
yellow appearing tissue b. Loss of green color with W
white appearing tissue c. Increased red or pink P
pigments with or with-out loss of green 26~9Çi~

Severitv of Iniurv Rating Scale Cateqory of Inlury No regenerative tissue present Death 9 No leaves expanded Severe Injury 8 Leaves smaller than cotyledons Severe Injury or <1 inch 7 Leaves larger than cotyledons Severe Injury or >1 inch 6 Normal growth would not be Moderate Injury expected 5 Normal growth would not be Moderate Injury expected 4 Normal growth would not be Moderate Injury expected 3 Temporary (maximum acceptable Slight Injury for crops) 2 Superficial (obvious but no Slight Injury stunting) 1 Minimum apparent injury Slight Injury O Not different from untreated No effect reference The potting media for postemergence testing was either TERRA-LITE~, Metro-Mix 300, 300, from W. R.
Grace & Co., Cambridge, Mass., containing peat moss, vermiculite, perlite, composted pine bark, granite sand, and a wetting agent or a custom blend of natural silt loam soil:HYPONEX~ top soil:perlite, 1:1:8 (v/v/v), plus 20-20-20 soluble fertilizer equivalent to 1,121 kg/ha.
The test compounds o~ the invention are 1 dissolved in a solvent system of acetone:methanol:
dimethylformamide, 90:8:2 (v/v/v) and the solution is atomized onto the plants at a rate equivalent to 561 per hectare. Atomizing is accomplished by using air pressure to force the solution through a standard even-fan agricultural spray nozzle. Rate of application is controlled by placing the experimental units on a constant speed belt which carries them under the spray nozzle. After spraying, the plants are placed on greenhouse benches and are cared for in the usual manner commensurate with conventional greenhouse practices. From 1 to 3 weeks after treatment the seedling plants are examined and rated according to the rating system provided below. The data obtained are recorded in Table I below.

2~g~4 ~, ~1 a a a a a a O a '~1 a a O aO O O a H H H~

~ ~1 a 8 aO a a a H ~3 0 0 H
a a a a a a H Ha o o 01 a a a a a H a H H H
a a a a a H H ,~ O

a ~ a a a j~ o I o o . ~ g Oa g 8 g H ;~ ~ 1 8~ aO ~ o H~

~1 ~ rl g o o ~ o ~ ~1 H H
;~ ;~ ~ ~a o ~8 o ~o ~ ~8 8 a g ~ 8 8 g ~

a 8 8 8 8 8 ~ H
a a a ~ a 1 o o o o o a a ,~ . ~1 ~' i ~1 o 'I ,~ On O
~a ~ oo$ogg ~;
u.~1oooooooo ~ ~ ~ L '~

Z~IL964 ~a ,~¦ ,, co ~1 1 1 1 1 1 1 ~1 o g a g a a a H H

~Ig O H ~ a Q ~ H O
a a o~ a a ~ a u~
;~ I a a a g Q a æ ~H~ U~

~ I ~ ~I g a ~ a a a a a H
.~ ~ ~ O ~ O ~a a O a Oa O

~ a O g a a a a ~ H
;~ Q ~ a a a ~ ~ aa~ a ~ a ~a H
a o H
a ~a ~ a ~æ ~

Q ~ l t l ~ ~1 o g o g ~1 ~ ~1 o ,~ o ~ ~ ,~
~1 o r~J ~I Ln ~1 0 0 ,i o o - ,i ,i o o o o I~ b ,~ o ~ ~ ~ ~ o ~

20~96gL
~4 --X a ~ ~
In '~1 a ~ ~3 a o I I I I I I I
a a o a g g ~o ~ ~3 o ~¦ ~ a a a o a a a a a ~ ~
a H a a a a ~ H H
g ~ a a H a a a a a H H

~-- ~; O i~ ,H~ H ~ H Cl O O O

g g a a C~ g ~ ~g a ~31 Oa g g g H ,0~ ~ ~a ~a ~ ~ ,g~ n g~ ~ ~ æ ~ ~ H~

~ ~ ~ ~ a a ~ H ~ i H O

H ~ Hn ~D H a H ~ H O
0 ~5 a a g ~ ~ H~

~ H a ~ H

O ~D O ~i ~ O ~ O ~ ~ O
O ~ ~1 ~ 1 0 ~ ~
o ~r ~ ~1 ~1 o ~r ~ ~o ~ u~ ~1 ~1 ~ O ~ ~ ~1 0 0 u~ t~3 ,i o o ~ i o o o o E q~ X ;~
o ~ o ~ o ~ b ~ b ~ ~ ~

2V~)~3L96 ~1 o u~ a~ Q U~
~1 a ~ a H H H
a c~ a H H O
a a~i a a H

.~ ~ ,~ O O O ~ ~I H O

;~ ~ ~ Oa ~ ~ I o H U~

79 1 l~i ~1 Oa a a a H H ~

8 ~ Oa 8 aOa a H ~ :
l U~
I ~ Oa a H
g . ~ ,~
~ ~ ~ a ~ a,Oa H ~ ~H
U~

~ ~¦ ,a ~
i, ~
a aO ~ i H
U~
O d' ~ O O
~1 o ~ ~r ~1 o ~
~1 0 ~ ~O ~1 ~i 0 0 ~ ~ O O

,~ ~ O ~ N
~ ~ ~ ~ b ~
, ~ , o ~
~ ~ h~

~0~L96 ~1 O ,H~

~1 a o o o gl 1 a o ~ o ~r ~
~,11 a o o o .C ~ o o o o ;~ ~ ?~ aO oHo ~

~ H

-- ~ C~ 1--1 H H
I u~
;~ H~ ,H~

~ ~ H H H H

~¦ On ~1 a o H O

CO ~
~ ,~000 2~ 9~

Preemer~ence herbicidal evaluation of test compounds The preemergence herbicidal activity of the compounds of the present invention is exemplified by the following tests in which the seeds or tubers are pressed into the surface of the potting media in individual sections of an 11 x 11 inch tray, then covered with approximately 0.25 inch of coarse sand. A
solution of the test compound in acetone:methanol:di-methylformamide, 90:8:2 (v/v/v) is sprayed onto the sand surface at a rate equivalent to 561 L per hectare in the manner described above for postemergence test-ing, then approximately 0.5 inch of water is added to leach the test compound into contact with the seeds, or tubers, and into the potting media. The potting media for preemergence testing was either a blend consisting of 3 parts (by volume) of pasteurized silt loam top soil ~ca. 1.5% O.M.) and one part coarse sand or the same as that described for postemergence testing above.
The treated trays are placed on greenhouse benches and cared for in accordance with conventional greenhouse procedures. From 2 to 3 weeks after treatment, the trays are examined and rated according to the rating scale system set forth above. The herbicidal prociency of the active ingredients of the present invention is evident from the test results which are recorded in Table II below. When more than one test is involved for a given compound, the data are averaged.

o H H H H 1--1 ~
~1 Oa a Oa ~ H ~ ~ O

O a a ~ H H O O
~ H ~ ~
~31 a a o o H O H H

21 o Oa a æ a H H O
x_{ a a a ~ H H H ,H~ H O

~ ~,~ o a ~i o o o o o '~ ~ Oa ~ H & &

~¦ o ~ ~ H H O O
t~ 1~ ~H
~ ~ '~1 a a a a U~ ~ ~UH~ H o o oH oH H H H H u~

~ ~ ~ a ~a a ~ o c, o ,~ ~i H ~ ~ O

o o ~ H O i~3 H O
~$ ~nl '' ';1' ~HD ' O O d' 1 0 ~
O ~ ~ ~I Ln ~ O O
I ~ O O O O
p:
In~OOOOOO

2~01gL9~4 H H H

~1 Cl ~a ~3 H g ~1~ a ,H~ ~j ~1 a H H H

1~ ¦ ~H ,_~ ~
C ~ o o Cl ~ ~ ~H a I a)q~
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--~ ~¦ ,, ~ ,, O

H H H o O ~

~ ~1 8 H 1-1 O
~ O ~1 ,~ CO
~ ~l ~ o ,i o o j 7 ~ o 2~ 964 a ~ ~ a ~ a a o ~1 a a O H
a a H a a ~ a H

I a H a a ~ a a ~!

r ~ O O O H O O O
. ~ ~ H H ~ l H
;~ ~ ~¦ a a H ~ H H O

~ ~¦ a a H ~ H H H H
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~ ~ ~ ~ In ~HI O O O O
~ ~¦ , , , æ a H ~ ~

1~ ~D¦ H H i~ H
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In ~ ~i In N ~i O O

1 ~ ~ L ~ L ~ p ~ b ~

2~ 96 ~¦ O O H

~¦ O H H

H a a a o o o ~¦ H ~ ~ H O a o U~
H H H H H H H

~-~¦ H H H H 1--1 H H

O H H H a ~ ~

~~ ~ & O O H ~ a H
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~ H H O H

;~ ~ I I I H H ~ O

O O H H O o i~

H H ~H ~i H O O
g o ~1 0 o ,~

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20v~9~i~
.

~1 ~1 ~i ~ ~ 1--1 H H
H H
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N

O O O

o O O

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H H O
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H H ~! ~

d' ~--I O N
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o ~ In ~1 O O
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:,

Claims (14)

1. A compound having the structure:

or I II
wherein M is C-X, N or N+-O-;
W, X, Y and Z each independently represent hydrogen, halogen, nitro, cyano, C1-C4 haloalkyl or C1-C4 haloalkoxy;
n is 0, 1 or 2;
R is hydrogen, C1-C4 alkyl, aryl or when taken together with R1, R and R1 may form a ring in which RR1 are represented by the structure -(CH2)m- where m is an integer of 2, 3, 4 or 5;
R1 and R2 are each independently hydrogen, C1-C4 alkyl or when taken together R1 and R2 may form a ring in which R1R2 are represented by the structure -(CH2)m- where m is an integer of 2, 3, 4 or 5;

R3 is cyano, , ,, CH2OR8 or CH(OR9)2;
Q is OH, OR4 or NR5R6;
A is O, NOR5, NCOR5, NNR5R6 or NNHCONH2;
R7 is hydrogen, C1-C4 alkyl or aryl;
R8 is hydrogen or C1-C4 alkyl;
R9 is C1-C4 alkyl R4 is C1-C6 alkyl optionally interrupted by O or S or optionally substituted with C1-C4 alkoxy, halogen, hydroxy, C3-C6 cycloalkyl, furyl, or optionally sub-stituted phenyl; C3-C6 alkenyl option-ally substituted with one or two C1-C3 alkoxy, halogen, substituted phenyl or C3-C6 cycloalkyl; C3-C6 alkenyl option-ally substituted with C1-C4 alkoxy or halogen; C3-C6 cycloalkyl; ammonium;
C1-C6 dialkylammonium; C1-C6 trialkylam-monium; a metal cation; or a moiety of formula ;
R5 and R6 each independently represent hydrogen, C1-C6 alkyl, phenyl or halophenyl;
the benzotriazole N-oxides and N-methosulfates; and when R1 or R2 is C1-C4 alkyl, the optical isomers thereof.

2. The compound according to claim 1 having the structure:

I

wherein the benzotriazole portion of said compound is substituted by aryloxy in the 5 or 6 position and M, Y, W, Z, n, R, R1, R2 and R3 are as described in claim 1.

3. The compound according to claim 1 having the structure:

wherein M, Y, W, Z, n, R, R1, R2, and R3 are as described in claim 1.

4. The compound according to claim 2 wherein the benzotriazole is substituted in the 6 position by aryloxy; M is C-X; W is hydrogen: X, Y, and Z each independently represent Cl, F, or CF3; n is O; R
is hydrogen or C1-C4 alkyl;

R1 is hydrogen or methyl; R3 is ; Q is OH or OR4; and R4 is C1-C4 alkyl.

5. The compound according to claim 2, methyl 6-[(2-chloro-.alpha.,.alpha.,.alpha. -trifluoro-p-tolyl)oxy]-1H-benzotriazole-1-acetate, methyl 6-[(2-chloro-.alpha.,.alpha.,.alpha.-tri-fluoro-p-tolyl)oxy]-.alpha.-methyl-1H-benzotriazole-1-acetate, 6-[(2-chloro-.alpha.,.alpha.,.alpha.,6-tetrafluoro-p-tolyl )oxy]-.alpha.-methyl-1H-benzotriazole-1-acetic acid, methyl 6-[(2-chloro-.alpha.,.alpha.,.alpha.,6-tetrafluoro-p-tolyl)oxy]-.alpha.-methyl-1H-benzotriazole-1-acetate, 6-[(2-chloro-.alpha.,.alpha.,.alpha.,6-tetra fluoro-p-tolyl)oxy]-.beta.-methyl-1H-benzotriazole-1-propionic acid, methyl 6-[(2-chloro-.alpha.,.alpha.,.alpha.,6-tetra fluoro-p-tolyl)oxy]-.alpha.,.alpha.-dimethyl-1H-benzotriazole-1-acetate, methyl 6-[(.alpha.,.alpha.,.alpha.,-trifluoro-2-nitro-p-tolyl)oxy]-.alpha.-methyl-1H-benzotriazole-1-acetate, (2-chloro-.alpha.,.alpha.,.alpha.,6-tetrafluoro-p-tolyl)oxy]-.alpha.-methyl-1H-benzotriazole-1-acetamide, isopropylammonium 6-[(2-chloro-.alpha.,.alpha.,.alpha.,6-tetrafluoro-p-tolyl)oxy]-.alpha.-methyl-1H-benzotriazole-1-acetate and 6-[(2-chloro-.alpha.,.alpha.,.alpha.,6-tetrafluoro-p-tolyl)oxy]-.alpha.-methyl-1H-benzotriazole-1-acetonitrile.

6. A method for the control of monocotyle-donous and dicotyledonous annual, perennial and aquatic plant species which comprises applying to the foliage of said plants or to the soil or water containing seeds or other propagating organs of said plants, a herbi-cidally effective amount of a substituted aryloxy benzotriazole compound.

7. The method according to claim 6, wherein the compound is as described in claim 1.

8. The method according to claim 7, wherein said compound is 6-[(2-chloro-.alpha.,.alpha.,.alpha.,6-tetrafluoro-p-tolyl)oxy]-.alpha.-methyl-1H-benzotriazole-1-acetic acid and methyl 6-[(2-chloro-.alpha.,.alpha.,.alpha.,6-tetrafluoro-p-tolyl)oxy]-.alpha.-methyl-1H-benzotriazole-1-acetate.

9. A composition for controlling mono-cotyledonous and dicotyledonous annual, perennial and aquatic plant species comprising an agronomically acceptable carrier containing a herbicidally effective amount of a substituted aryloxy benzotriazole compound.

10. The composition according to claim 9, wherein the compound is described in claim 1.

11. A process for the preparation of a compound having the structure:
or I II
wherein M is C-X, N or N+-O-;
W, X, Y and Z each independently represent hydrogen, halogen, nitro, cyano, C1-C4 haloalkyl or C1-C4 haloalkoxy;
n is 0, 1 or 2;
R is hydrogen, C1-C4 alkyl, aryl or when taken together with R1, R and R1 may form a ring in whioh RR1 are represented by the structure -(CH2)m- where m is an integer of 2, 3, 4 or 5;
R1 and R2 are each independently hydrogen or C1-C4 alkyl with the proviso that at least one of R or R1 is hydrogen;

R3 is cyano, , , , CH2OR8 or CH(OR9)2;
Q is OH, OR4 or NR5R6;
A is O, NOR5, NCOR5, NNR5R6 or NNHCON2;
R7 is hydrogen, C1-C4 alkyl or aryl;
R8 is hydrogen or C1-C4 alkyl;
R9 is C1-C4 alkyl;

R4 is C1-C6 alkyl optionally interrupted by O
or 8 or optionally substituted with C1-C4 alkoxy, halogen, hydroxy, C3-C6 cycloalkyl, furyl, or optionally sub-stituted phenyl; C3-C6 alkenyl option-ally substituted with one or two C1-C3 alkoxy, halogen, substituted phenyl or C3-C6 cycloalkyl; C3-C6 alkynyl option-ally substituted with C1-C4 alkoxy or halogen; C3-C6 cycloalkyl;
R5 and R6 each independently represent hydro-gen, C1-C6 alkyl, phenyl or halophenyl;
and when R1 or R2 is C1-C4 alkyl, the optical isomers thereof, which comprises reacting a compound having the struc-ture:

wherein M, W, Y and Z are as described above with about 1.0 to 1.5 molar equivalents of a haloalkyl compound having the structure:

wherein B is halogen and n, R, R1, R2 and R3 are as described above, in the presence of an alkali metal carbonate and a polar solvent at a temperature of about 20°C to 50°C whereby the desired products having structure I and II, as described hereinabove, are formed.

12. A process for the preparation of a compound having the structure:

IA

wherein M is C-X, N or N+-O-;
W, X, Y and Z each independently represent hydrogen, halogen, cyano, C1-C4 haloalkyl or C1-C4 halo-alkoxy;
n is 0, 1 or 2;
R is hydrogen, C1-C4 alkyl, aryl or when taken together with R1, R and R1 may form a ring in which RR1 are represented by the structure -(CH2)m- where m is an integer of 2, 3, 4 or 5;
R1 and R2 are each independently hydrogen, C1-C4 alkyl or when taken together R1 and R2 may form a ring in which R1R2 are represented by the structure -(CH2)m- where m is an integer of 2, 3, 4 or 5;

R3 is cyano, , , or CH2OR8;
Q is H, OH, OR4 or NR5R6;
A is O, NOR5, NCOR5, NNR5R6 or NNHCONH2;
R7 is hydrogen, C1-C4 alkyl or aryl;
R8 is hydrogen or C1-C4 alkyl;
R4 is C1-C6 alkyl optionally interrupted by O
or S or optionally substituted with C1-C4 alkoxy, halogen, hydroxy, C3-C6 cycloalkyl, furyl, or optionally sub-stituted phenyl; C3-C6 alkenyl option-ally substituted with one or two C1-C3 alkoxy, halogen, substituted phenyl or C3-C6 cycloalkyl; C3-C6 alkynyl option-ally substituted with C1-C4 alkoxy or halogen; C3-C6 cycloalkyl;
R5 and R6 each independently represent hydrogen, C1-C6 alkyl, phenyl or halophenyl;
with the proviso that when n is O, R3 is CH(OR9)2;
and when R1 or R2 is C1-C4 alkyl, the optical isomers thereof; which comprises reacting a compound having the structure:

wherein M, W, Y, and Z are as described hereinabove with 1.0 to 2.0 molar equivalents of an amine nucleo-phile having the structure:

wherein n, R, R1, R2 and R3 are as described above in the presence of a polar solvent at a temperature of about 80° to 150°C to form 3-(substituted)-amino-4-nitrophenyl ether, removing the solvent from and catalytically hydrogenating the 3-(substituted)-amino-4-nitrophenyl ether in the presence of a C1-C4 alcohol to form 3-(substituted)-amino-4-aminophenyl ether, reacting the 3-(substituted)-amino-4-aminophenyl ether with about 1.0 to 1.1 molar equivalents of sodium nitrite as an aqueous solution in the presence of acetic acid at a temperature of about 5° to 10°C to form a reaction mixture and heating the reaction mixture to a temperature of about 20° to 50°C to form the compound having the structure 1A.

13. A process for the preparation of a compound having the structure:

IB

wherein M is C-X, N or N+-O-;
W, X, Y and Z each independently represent hydrogen, halogen, cyano, C1-C4 haloalkyl or C1-C4 halo-alkoxy;
n is 0, 1 or 2;
R is hydrogen, C1-C4 alkyl, aryl or when taken together with R1, R and R1 may form a ring in which RR1 are represented by the structure -(CH2)m- where m is 2 an integer of 2, 3, 4 or 5;
R1 and R2 axe each independently hydrogen, C1-C4 alkyl or when taken together R1 and R2 may form a ring in which R1R2 are represented by the structure -(CH2)m- where m is an integer of 2, 3, 4 or 5;
R3 is cyano, , , , CH2OR8 or CH(OR9)2;
Q is H, OH, OR4 or NR5R6;
A is O, NOR5, NCOR5, NNR5R6 or NNHCONH2;
R7 is hydrogen, C1-C4 alkyl or aryl;
R8 is hydrogen or C1-C4 alkyl;
R9 is C1-C4 alkyl;
R4 is C1-C6 alkyl optionally interrupted by O
or S or optionally substituted with C1-C4 alkoxy, halogen, hydroxy, C3-C6 cycloalkyl, furyl, or optionally sub-stituted phenyl; C3-C6 alkenyl option-ally substituted with one or two C1-C3 alkoxy, halogen, substituted phenyl or C3-C6 cycloalkyl; C3-C6 alkynyl option-ally substituted with C1-C4 alkoxy or halogen; C3-C6 cycloalkyl;
R5 and R6 each independently represent hydrogen, C1-C6 alkyl, phenyl or halophenyl;

the benzotriazole N-oxides and N-methosulfates; and when R1 or R2 is C1-C4 alkyl, the optical isomers thereof; which comprises reacting a compound having the structure:

wherein R, R1, R2 and R3 are as described hereinabove with about 1.0 to 2.0 molar equivalents of a compound having the structure:
wherein B is halogen and M, W, Y and Z are as described hereinabove in the presence of a solvent at a tempera-ture of about 20°C to 100°C to form the compound having the structure IB.

14. A process for the preparation of a compound having the structure:

wherein R and R1 are each independentaly hydrogen or C1-C4 alkyl or when taken together R and R1 may form a ring in which RR1 are represented by the structure -(CH2)n- where n is an integer of 2, 3, 4 or 5; R9 is C1-C4 alkyl which comprises reacting a compound having the structure:

wherein B is halogen with 1.0 to 2.0 molar equivalents of a compound having the structure:

wherein R, R1 and R9 are as described hereinabove in the presence of a solvent at a temperature of about 80°
to 150°C to form 6-benzyloxy-2-(substituted)-amino-nitrobenzene, removing the solvent from and hydrogenat-ing said nitrobenzene intermediate in the presence of Raney nickel and a solvent to form 6-benzyloxy-2-(sub-stituted)-amino-aniline, reacting said aniline with about 1.0 to 1.1 molar equivalents of aqueous nitrous acid at a temperature of about 5° to 10°C to form a reaction mixture, heating the reaction mixture to form 6-benzyl-oxy-1H-benzotriazole-.alpha.,.alpha.(disubstituted)-11-ace-taldehyde dialkyl acetal and catalytically hydrogenating said 6-benzyloxy-1H-benzotriazole in the presence of a solvent to form the compound having the structure 1C.