CA1120744A

CA1120744A - .beta.-NAPHTHYL AND .beta.-TETRAHYDRONAPHTHYL-PHENYL EHTERS

Info

Publication number: CA1120744A
Application number: CA000314561A
Authority: CA
Inventors: Gerhard Horlein; Hans J. Nestler; Helmut Kocher; Peter Langeluddeke
Original assignee: Hoechst AG
Current assignee: Hoechst AG
Priority date: 1977-10-29
Filing date: 1978-10-27
Publication date: 1982-03-30
Also published as: GR72089B; DE2748658A1; BR7807102A; PL210577A1; DD145363A5; AU4106978A; JPS5470250A; ES474447A1; DE2861852D1; AR225887A1; EG13577A; PL112149B1; AT365406B; EP0001804A1; EP0001804B1; AU522476B2; ZA786077B; PT68713A; OA06080A; ATA768378A

Abstract

Abstract of the disclosure:

Substituted .beta.-naphthyl and .beta.-tetrahydronaphthyl-phenyl ethers of the formula

Description

2~

. _ . . .
It is known that B-naphthoxy-propionic acid deriva-tives have a selective herbicidal action against dicotyle-donous weeds and are being used especially for the control of undesired plant growth in the cultivation of rice (cf.
JA-OS 125,740-76). Like all hormon-type weed killers , these products, too, have no e:ffect against weed grasses.
It is the object of the present invention to provide herbicidal compositions containing a compound of the for-mula I

~ - O - ~ - O- CH - (CH2)~ Z

in which ~ = ~ or X Y

X is hydrogen or halogen, Y is hydrogen, (C1-C4)-alkyl or halogen, R1 is hydrogen or (C1-C4)-alkyl, q is a whole number from zero to 2, 0 0 Il 11 Z lS a group of the formula -C-oR2~ -C-SR3, 1l / R4 R6 / R7 S

-C-N \ , -C-N-N \ , -C-NH2, " . R8 : . . . :. : -: :

'. ; ' ", .' : ,~
': - ~ '' ' : ''`: , : :.' - ' . ..

- 3 - HOE 77/F 218 -CN, -CH20H, -C , -C / , -CH2-0-g-Rll, -CH2-0-G-N or -CH2--S02-R12' R2 is hydrogen, (C1-C12)alkyl which may be substituted one to six times by halogen and/or once by hydroxy, (C1-C6)-alkoxy, (C1-C4)alkylthio, (C1-C6)alkoxy-(C2-C6)alkoxy, halo(C1-C2)alkoxy, methoxy-ethoxyethoxy, (C1-C4)alkyl-amino, di(C1-C4)alkylamino, phenyl, oxiranyl, or phen-oxy, (the latter optionally being substituted once or - twice by halogen and/or (C1-C4)alkyl); (C5-C6)cycloal-kyl, halo(C5-C6)alkyl, (C3-C6)alkenyl, halo(C3-C6)al-kenyl, (C5-C6)cycloalkenyl, (C3-C4)alkinyl which may be substituted once or twice by (C1-C6)alkyl, phenyl, halo-gen and/or (C1-C2)alkoxy; phenyl which may be substi-tuted one to three times by (C1-C4)alkyl, (C1-C4)alkoxy, halogen, N02 and/or CF3; furfuryl, tetrahydrofur~uryl, or a cation equivalent of an organic or inorganic base;
R3 is (C1-C6)alkyl which may be substituted by (C1-C4)al-koxy, halogen or phenyl (optionally mono- to tri-sub-stituted by (C1-C4)alkyl and/or halogen); (C3-C6)alke-nyl, or phenyl (optionally substituted one to three times by (Cl-C4)alkyl and/or halogen);
R4 and R5, which are .identical or different, are hydrogen, (C1-C4)alkyl, hydroxy(C1-C6)alkyl, (C5-C6)cycloalkyl, or phenyl (optionally substituted one to three times by ~i 4)alkyl~ tCl~C4)alkoxy, halogen and/or CF3); with - , .:. .. ,::, , : ,,, ~IZs~7~9~
_ 4 _ HOE 77/F ?18 the proviso that R4 and R5 cannot both be phenyl; or R4 and R5 together form a methylene chain with 2, 4 or 5 members in which one CH2 group may be replaced by oxygen, NH or N(CH3);
R6 is H or CH3, R7 is H, CH3 or C2H5~

R8 is H, CH3 7 C2H5 or phenyl, - Rg and R10, which are identica:l or different, are (C1-C4)-alkoxy, (C1-C4)alkylthio, ~C1-C4)alkylamino, or di(C1-C4)alkylamino, or together are a radical of the for-mula =N-R12;
R11 is tC1-C6)alkyl, (C1-C6)haloalkyl, C3-, C5- or C6-cycloalkyl, (C3-C6)alkenyl, phenyl, (C1-C4)alkylphenyl, (C1-C4)alkoxyphenyl, halophenyl, trifluoromethylphenyl, 15 nitrophenyl or a radical of the formula R
-CH-O ~ O-and R12 is (C1-C4)alkyl or phenyl optionally substituted one to three times by halogen, CF3, N02 and/or (C1-C4)-alkyl.
The alkyl, alkenyl and alkinyl radicals in R1 to R5, R11 and R12 may be straight or branched, and halogen pre-ferably means chlorine or bromine. The naphthyl-(2) ra-dical is preferably unsubstituted or substituted in l- or 1,6-position by Cl, Br, or CH3. Preferred radicals Z are -COOR2, -CH20H and -CH20-COR11 (q = O) in which R2 pre-ferably is alkyl or alkoxyalkyl and R11 is alkyl. Most of LZ1;~'7~

the compounds o~ fo~mu~a I are noyel, with the exception of 2- ~4-(2-naphthoxy~-phenoxy-~-propionic acid which is known from DE-OS 2,136,828 as compound having lipide-reducin~ properties.
Compounds of the formula I - with the exception of those in which R2 is hydrogen - are therefore also claimed.
In a further aspect, the invention relates to a method of controlling the growth of undesired plants which comprises applying to the plants or the area to be treated an effective amount of a compound of the formula I Rl ~ _ o ~ - O-CH-(CH2)q~Z (I) in which ~ is X~-~y ~3/

X is hydrogen or halogen, Y is hydrogen, (Cl-C4)-alkyl or halogen, Rl is hydrogen or (Cl-C4~-alkyl, q is a whole number from zero to 2, O O

Z is a group of the formula -C-oR2~ -" / R~ ~1 ,6 / 7 S
-C-N , -C~N-N \ , -C-NH2 ~ 0 / Rg -CN, -CH20~ C ~ r~CH ~ ~CH2r`0rlC-~

Rlo -CH2-0-C-N or -CH2-0-s0~2 R12 R5 ;:
R2 is hydrogen, (Cl-C12) alkyl which may be substituted one to six times by halogen and/or once by hydroxy, (Cl-C6) alkoxy, (Cl-C4) alkylthio, (Cl-C6) alkoxy-(C2-C6) alkoxy, halo (Cl-C2) alkoxy, methoxy-ethoxyethoxy, (Cl-C4) alkylamino, di(Cl-C4) alkyalmino, phenyl, oxiranyl, or phenoxy, (the latter optionally being sub-stituted once or twice by halogen and/or (Cl-C4) alkyl); (C5-C6) cycloalkyl, halo (C5-C6) alkyl, (C3-C6) alkenyl, halo (C3-C6) alkenyl, (C5-C6) cycloalkenyl, (C3-C4) alkinyl, which may be sub-stituted once or twice by (Cl-C6~ alkyl, phenyl, halogen and/or (Cl-C2)alkoxy; phenyl which may be substituted one to three times by (Cl-C4) alkyl, (Cl-C4) alkoxy, halogen, NO2 and/or CF3; furfuryl, tetrahydrofurfuryl, or a cation equivalent of an organic or inorganic base-R3 is (Cl-C6) alkyl which may be substituted by (Cl-C4) alkoxy, halogen or phenyl (optionally mono- to tri-substituted by (Cl-C4) alkyl and/or halogen);
(C3-C6) alkenyl or phenyl (optionally substituted one to three times by (Cl-C4) alkyl and/or halogen);
R4 and R5, which a:re identical or dif~erent, are hydrogen, (Cl-C4) alkyl, hydroxy (Cl~C6) alkyl, (C5~C6) cycloalkyl~ or phenyl - 5a -74~

(optionally subskit~ted one to three ti~es b~ (Cl~C4) alkyl, (Cl-C4) alkoxy, halogen and~or C~3~; With the p~oviso that R4 and R5 cannot both be p~en~l; or R4 and R5 together form a methylene chain with 2, 4 or 5 members in which one CH2 group may be replaced by oxygen, NH or N(CH3);
R6 is H, or CH3, R7 is H, CH3 or C2~5;
R8 is H, CH3, C2H5 or phenyl, Rg and Rlo, which are identical or different, are (Cl-C4)-alkoxy, (Cl-C4) alkylthio, (Cl-C4) alkylamino, or di(Cl-C4) alkylamino, or together are a radical of the formula =N-R12;
Rll is (Cl-C6) alkyl, (Cl-C6) haloalkyl, C3-, C5- or C6- cycloalkyl, (C3-C6) alkenyl, phenyl, (Cl-C4) alkylphenyl, (Cl-C4) alkoxyphenyl, halophenyl, trifluoromethylphenyl, nitrophenyl or a radical of the formula CH - O ~ - O - ~

and R12 is (Cl-C4) alkyl or phenyl optionally substituted one to three times by halogen, CF3, NO2 and/or (Cl-C4)-alkyl.
In yet a further aspect, the invention relates to a herbicidal compos~tion comPrising 2 to 95% by weight of a compound of the formula II ;

[~ X ~ ~ 0 ~ C~ ~ C - ~2 - 5b -wherein Y rep~esents hyd~ogen, (cl-c4)-alkyl or halo~en, Rl represents (Cl~C4)-alkyl, and R2 represents hydrogen, (Cl-C10)-alkyl, or a cation equivalent of an organic or inorganic base, in admixture with 5 to 98% by weight of an agriculturally suitable carrier, selected from the group consisting of emulsifiers, wetting and dispersing a~ents, finely divided solid dusting agents, and granular inert materials.
The compounds of formula I can be synthesized from known compounds or from compounds prepared by processes by reacting lo compounds of formula II
~ _ 0 ~ OH II

or the alkali metal salts thereof with compounds of the formula Rl IV
IRl III S
M-CH-(CH2)q~Z or r in which Rl and Z have the aforesaid meanings and M is chlorine bromine, mesyloxy or a benzenesulfonyloxy group which may be sub-stituted in the aromatic nucleus, and, if desired, transforming the compounds of formula I obtained into corresponding derivatives of formula I by saponification, esterification, transesterification, salt formation, reduction, amidation, acylation, dehydration, sulfhydration, acetalization, or oxime formation.
The reaction of compound II with compound III can be carried out in a p~QtiC or aprotic solyent, for example water, - 5c -, -- .

dimethyl ~ormamide, di~ethYl ~ oxide~ sul~olan, N~ethyl~
pyrrolidone, hexamethyl~phosphoric acid tria~ide, acetonitrile, acetone, methylethylketone, benzene, toluene, xylene, chloro-benzene, or dichlorobenzene. For this reac~

5d ,, ,,~ ;, , t " ' ` ':
, tion either the salts of the R-naphthoxyphenols are used or acid-binding agents are added to the free phenols, in order to bind the acids formed. As acid binding agents alkali metal carbonates, such as sodium or potassium car-bonate, are especially preferred. The reaction tempera-tures and reaction times largely depend on the solvent used.
The reaction of free ~-naphthoxyphenols with halo~
alkane-carboxylic acid derivatives in the presence of acid-binding agents generally requires aprotic, dipolar solvents such as acetone, methylethylketone or acetonitri-le. The reaction is preferably carried out at reflux tem-peratures and is generally complete after 3 to 30 hours;
if sulfonic acid esters of formula III, for example the mesylates or tosylates, are used as etherification com-ponent, the reaction time may be up to 70 hours.
When high boiling aprotic, dipolar solvents, such as dimethyl formamide, dimethyl acetamide, dimethyl sulf-oxide, sulfolan, N-methylpyrrolidone, or hexamethyl-phos-phoric acid triamide, reaction temperatures should be keptbelow the respective boiling temperature since some of the solvents start decomposing at the boiling point and atmos-pheric pressure, especially in the presence of bases. Here, the temperatures are preferably 90 to 160C. In these cases the reaction times are between a few minutes only and about 2 to 3 hours. Besides the alkali metal carbona-tes alkali metal and alkaline earth metal hydroxides, espe-cially sodium and potassium hydroxide may be used as bases, 29 preferably in equimolar proportions.

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

., ' ' , .
" ~' ~ ' " `"~

~2i~

r - HOF. 77/F 218 If phenols are used as starting compounds, salts, for example sodium or potassium phenolates, aromatic solvents such as benzene, toluene or xylene, or chlorinated aroma-tic compounds such as chlorobenzene or o-dichlorobenzene are suitable as reaction medium. At temepratures of from ôO to 160C the reaction time is generally from 1 to 6 hours.
The R-naphthylphenyl ethers prepared by the afore-said methods may be converted, if desired, into other derivatives by means of secondary reactions. These are also carried out in accordance with processes known per se.
Thus, the free acids of formula I (Z = ~COOH) may be subsequently converted into aldehydes (Z = -CHO), esters (Z =COOR2), salts tZ = -COOcat), amides (Z =

-CON\ ), hydrazides (Z = -CONR6-~ ), or thiol esters (7 = -COSR3). For this purpose, for example acid halides may be prepared from free acids; these may then be reduced catalytically according to the Rosenmund reaction (~alde-hydes) or reacted with alcohols (-~esters), amines (~ami-des), hydrazines ( ~ hydrazides), or mercaptans ( -~ thiol-esters). Acid esters (Z = -COOR2) may be saponified to form free acids. Nitriles (Z = -CN) can be obtained by dehydration of amides (Z = -CONH2) by means of POCl3 or P205, and may in turn be transformed into thioamides (Z =
-CSNH2) with H2S. Am;des or hydrazides can be obtained 29 directly from esters by reaction with correspondingly sub-, : ' ~

stituted amines or hydrazines. Reduction of the esters with metal hydrides, for example LiAlH4, yields alcohols (Z = -CH20H), which can be transformed with corresponding acylation agents into carboxylic acid esters (Z =

-CH2-0-COR~ carbamic acid esters (Z = -CH2-0-CO-N \ ), or sulfonic acid esters (Z = -CH2-OS02R12). When aldehydes (Z = -CHO) are reacted with alcohols, mercaptans, primary or secondary amines, the respective acetals, mercaptals, Schiff's bases or aminals (Z = -CH/ 9 \ ) are obtained.

In all cases in which R1 is not hydrogen the R-naph-thylphenyl ethers of formula I are racemates, i.e. opti-cally inactive mixtures of two enantiomeric ~optically active) components with opposite sense of rotation, the center of chirality being the carbon atom between O and (CH2)q. It has been found that the d-enantiomers have a particularly strong herbicidal effect. Hence, the present invention relates to the optically inactive racemates and to the optically active enantiomers, especially the d-form.
- The optically active isomers of formula I can be ob-tained, for example, by using as starting compound of for-mula III an optically active compound in which the center of chirality is adjacent to the radical M.
The enantiomeric compounds I can also be obtained by splitting the racemates into their antipodes with the use - of optically active auxiliaries. To carry out this opera-tion the derivatives are transformed into a form suitable 29 for resolution, in most cases the free acids. A subsequent .: . , .

' ' '~ ;' ', retransformation ~nto the startin~ deriyatiyes o~ other desired derivatives can be carried out according to known chemical pro-cesses.
The compositions according to the invention are character-ized by a good herbicidal effect a~ainst week grasses in pre- and post-emergence application~ The novel compounds differ from the phenoxyphenoxyalcanecarboxylic acid derivatives known from DE-OS 2,223,894 and 2,601,548 by an additional and pronounced effect against dicotyledonous weeds.
Even if used in high doses the compositions do no harm to a great number of important crops. They are, therefore, suitable as selective herbicides in agriculture and horticulture.
They can be combined with other herbicides, insecticides and fungicides.
The compositions of the invention contain preferably 2 -95~ of the active compounds of the formula I. They are customarily formulated as wettable powders, emulsifiable concentrates, sprayable solutions, dusting agents, or granules.
Wettable powders are formulations which are uniformly dispersible in water and which, in addition to the active compound, also contain diluents or inert materials, wetting agents, for example, polyoxyethylated alkylphenols, polyoxyethylated oley-lamines or stearylamines, alkylsulfonates or alkylphenylsulfonates and dispersing agents, ~or example sodium ligninsulfonates, sodium 2,2'-dinaphthylmethane-6,6'~disul$onate, or the sodium salt of oleylmethyl~taurine.

_ g _ ,, , ., . - ,, -- -3t~ ~

Emulsifiable concentrates are obtained by dissolving the active compound in an organic solvent, for example, butanol, cyclohexanone, dimethyl formamide, xylene or even higher-boiling aromatics, and adding a non-ionic wetting agent, for example, a polyoxyethylated alkylphenol or a polyoxyethylated oleylamine or stearylamine.
Dusting agents are obtained by grinding the active compound with finely divided solids, for example talc, natural clays, such as kaolin, bentonite, pyrophillite or diatomaceous earth.
Granules can be manufactured either by spraying the active compound onto absorbent, granular inert material or by applying active compound concentrates by means of adhe-sives, for example polyvinyl alcohol, sodium polyacrylate or even mineral oils, onto the surfaces of carriers, such as sand, kaolinites or granular inert material. Suitable formulations can also be manufactured by the customary methods of manufacture of fertilizer granules, if desired in admixture with fertilizers.
In the case of herbicidal agents, the concentrations -of the active compounds in the commercial formulations can vary. In wettable powders, the active compound concentra-tion varies, for example, between about 10 and 95 %, the remainder consisting of the abovementioned formulation ad-ditives. In the case of emulsifiable concentrates, the active compound concentration is about 10 % to 80 %~ Dust formulations usually contain 5 - 20 % of active compound, and sprayable solutions about 2 - 20 %. In the case of 29 granules, the active compound content in part depends on : . - . .

: : , : ,.. .
- . , ~ . :
..

whether the active compound is in a liquid or solid form and what granulating auxiliaries, fillers and the like are used.
If necessary or desired the commercial concentrates may be diluted prior to application in the usual manner, for example by means of water in the case of wettable powders and emulsifiable concentrates. Dusts, granules and sprayable solutions are generally ready for use with-out further dilution. The amount of active ingredient necessary for obtaining the desired result depends on ex-ternal conditions such as temperature, humidity and the like. It can vary within wide limits, for example between 0.05 and 10.0 kg/ha of active substance but is preferably between 0.1 and 5 kg/ha.
EXAMPLES OF PREPARATION:
Most of the compounds of the invention are highly viscous oils that are difficult to distill. For their iden-tification the NMR data are indicated in Table 2. For the solid substances the melting point is indicated.
E X A M P L E 1:
-2-~4-(2-naphthoxy)-phenoxy~-propionic acid methyl ester Over a period of 15 minutes 12.3 g (0.1 mol) of 2-chloro-propionic acid methyl ester were added dropwise -to a suspension, stirred at 100C, of 25.8 g (0.1 mol) of dry sodium 4-(2-naphthoxy)-phenolate in 100 ml of xylene. When the addition was complete, the temperature was slowly raised to 140C and the mixture was refluxed for 5 hours.
After coolingv the sodium chloride formed was extracted 29 with water, the solvent was removed by distillation and .. . ..

the residue was fractionated in a high vacuum.
29.6 g (92 % of the theory) of 2-/ 4-(2-naphthoxy)-pheno~y 7-propionic acid methyl ester, m.p. 91 to 93C were obtained.

O ~ OCH-COOCH3 E X A M P L E 2:
2-/ ~-(2-naphthoxy)-phenoxy 7-propionic acid isobutyl ester A mixture of 11.8 g (0.05 mol) of 4-(2-naphthoxy)-phe-nol, 10.5 g (0.05 mol) of 2-bromopropionic acid isobutyl ester and 6.9 g (0.05 mol) of pulveri7ed, anhydrous potas-sium carbonate in 100 cc of acetone were refluxed for 18 hours. After cooling, the potassium bromide/potassium bi-carbonate salt mixture was filtered off with suction, the acetone was removed by distillation and as residue 16.9 g (93 ~ of the theory) of 2-/ 4-(2-naphthoxy)-phenoxy 7-pro-pionic acid isobutyl ester were obtained.
The crude product can be purified by distillation in a high vacuum or by chromatography. As for the NMR data cf. Table 2.

O ~ O-CH-COOCH2CH

~ .

, .

: ' ' ' ~, ::i: ` ' . . , ~-IZ~

E X A M P L E 3:

2-/ 4-(1-chloro-2-naphthoxy) phenoxy 7--propionic acid ethyl .
ester A mixture of 16.3 g (0.060 ml) of 4-(1-chloro-2-naph-thoxy)-phenol, 11.4 g (0.063 mol) of 2-bromopropionic acid ethyl ester and 8.7 g (0.063 mol) of pulverized, anhydrous potassium carbonate in lOO ml of acetone was refluxed for 30 hours. After cooling, the potassium bromide/potassium bicarbonate salt mixture formed was filtered off with suc-tion and the solvent was evaporated. The residue was takenup in chloroform and, for purification, the mixture was filtered through a silica gel layer.
After removal of the chloroform by distillation, 20.6 g (93 % of the theory) of 2-/ 4-(1-chloro-2-naphthoxy)-phen-oxy 7-propionic acid ethyl ester were obtained. As for the NMR data cf. Table 2.

~ ~ O-cH-cooc H

E X A M P L E 4:
d-(+)-2-/ 4-(2-naphthoxy)-phenoxy 7-propionic acid ethyl .
ester A mixture of 11.5 g (48.7 mmols) of 4-(2-naphthoxy)-phenol, 13.7 g (50.4 mmols) of 1(-)~lactic acid ethyl ester tosylate and 7.4 g (53.6 mmols) of pulverized, anhydrous potassium carbonate in 80 cc of acetonitrile were refluxed - : :,,: .: .. . : ~

for 25 hours. After cooling, the potassium toluene-sul-fonate/potassium bicarbonate salt mixture was filtered off with suction, the solvent was removed by evaporat on and after having been taken up in ethylene chloride the crude d(+)-2-/ 4-(2-naphthoxy)-phenoxy 7-propionic acid ethyl ester was purified by chromatography on silica gel. 12.9 g (79 ~ of the theory) of purified product were obtained having a rotation /C~725 of 18.4 (1 m in chloroform) in the form of a non crystalline substance. As to the NMR
data cf. Table 2.

H ~D C~e~ o ~ O

~CH

E X A M P E E 5:
_ _ 2-/ 4-(1-methyl-2-naphtoxy)-phenoxy 7-propionic acid .
16.8 g (50 mmols) of 2-/ 4-(1-methyl-2-naphthoxy)-phenoxy 7-propionic acid methyl ester (Example 36) were dissolved in 100 cc of methanol and saponifled at boiling temperature by adding 200 cc of 2N sodium hydroxide solu-tion. After distillation of the methanol and acidification, 15;4 g of 2-/ 4-(1-methyl-2-naphthoxy)-phenoxy 7-propionic acid, m.p. about 112C were obtained.

o ~ OCH-COOH

E X A M P L E 6:
2-/ 4-(2-naphthoxy)-phenoxy 7-propionamide .
30.8 g (0.01 mol) of 2-/ 4-~2-naphthoxy)-phenoxy 7-propionic acid (Example 60) were dissolved in 200 ml of benzene, 14.3 g (0.12 mol) of thionyl chloride were added and the compound was transformed into the acid chloride by boiling under reflux ~or 8 hours. By distilling off the excess amount of thionyl chloride and benzene 32.7 g of crude acid chloride were obtained. The acid chloride was dissolved ln 60 ml of toluene and the solution was added dropwise at room temperature to an ammoniacal toluene solution. Stirring of the mixture was continued for 2 hours while continuously introducing ammonia; towards the end of the reaction the mixture was heated to about 80C. After t5 cooling, the precipitate was filtered off, washed with water and dried. 24.3 g (83 % of the theory) of 2-/ 4-(2 naphthoxy)-phenoxy 7-propionamide melting at 147 to 148C were obtained.
A further 3.6 g (12 %) of the compound could be iso-lated from the filtrate.

CH
0~ OCH-CONH2 .`

E X A M P L E 7:

2-/ 4-(2-naphthoxy)-phenoxy 7-n-propanol .
32.2 g (0.1 mol) of 2-/ 4-(2-naphthoxy)-phenoxy 7-propionic acid methyl ester (Example l) were dissolved in . ~ ... .- -. . . i .. .
:. . . .
.
~, ., . . , ! , ' , , 1 ' .:, , ,, ~." .. ' ' :
" ' ' . , ; ', , ' 100 ml of tetrahydrofurane and the solution was added dropwise over a period of 1.5 hours to a suspension, heat-ed to 65G, of 3.8 g (0.1 mol) of lithium aluminum chlori-de in 50 ml of tetrahydrofurane. The mixture was then re-fluxed for l hour, cooled and, for decomposing the excess amount of lithium aluminum hydride, 20 ml of ethyl ace-tate ànd then 60 ml of water were added dropwise. After acidification with sulfuric acid and separation of the aqueous phase, the tetrahydrofurane was evaporated, the residue was taken up in chloroform, washed with water, and dried and the solvent was removed. 24.8 g t84 % of the theory) of 2-/ 4-(2-naphthoxy)-phenoxy 7-n-propanol were obtained, nD = 1.6173.

~ O ~ OCH-C~20 E X A M P L E 8:_ 2-/ 4-(2-naphthoxy)-phenoxy 7-n-propyl chloroacetate -- 10.0 g (34 mmols) of 2~/ 4-(2-naphthoxy)-phenoxy 7-n-propanol and 4.0 g (40 mmols) of triethylamine were dis-solved in 50 cc of toluene. Over a period of 40 minutes a solution of 4.2 g t37 mmols) of chloroacetyl chloride was added dropwise at room temperature and, after the addi-tion, the mixture was heated for 6 hours at 100C. After cooling, the triethylammonium hydrochloride precipitate was filtered off with suction7 the filtrate was washed with .. ! :,,,,, .. '~ " ' ' ' . . . . ..

2N hydrochloric acid and water and the toluene solution was filtered over 50 g of silica gel. Thereafter the sol-vent was distilled off under reduced pressure whereupon 10.7 g (85 ~ of the theory) of 2-/ 4-(2-naphthoxy)~phen-oxy 7-n-propyl chloroacetate were obtained in the form of a non crystalline substance; nD 1.5980.

~O~OCH-CH20C-C32Cl E X A M P L E 9:

N-methyl-0-~2-/ 4-~2-naphthoxy)-phenoxy 7-n-propyl~-__ _ _ __ J
carbamate 10.3 g (35 mmols) of 2-/ 4-(2-naphthoxy)-phenoxy 7-n-propanol were dissolved in 50 cc of toluene and, after addition of 2 cc of triethylamine, 2.2 g (39 mmols) of N-methylisocyanate were added at room temperature. The mix- -ture was heated to 100C within 1 hour and stirring was continued at that temperature for 6 hours. After cooling, the reaction mixture was diluted with 100 cc of toluene and then washed with 2N hydrochloric acid and water. ~After drying and evaporation of the solvent~ 11.7 g (95 ~ of the theory) of N-methyl-0-~2-/ 4-(2-naphthoxy)-phenoxy 7-n-pro-pyl~-carbamate were obtained in the form of a non crystal-line substance; n20 = 1.5981.

~ ~ 32 C N3CH3 , " . .. : ~ ~ :

~213~7~
- 18 - HOE 77/F ?18 -2-/ 4-(2-naphthoxy)-phenoxy 7-propionitrile 2.0 g (6.5 mmols~ of 2-/ 4-(2-naphthoxy)-phenoxy 7-propionamide were dissolved in 30 cc of toluene while heat-ing and, after addition of 9.6 g (8.0 mmols) of thionylchloride, the amide was transformed into the nitrile by refluxing the mixture for 20 hours. The unreacted thio-nyl chloride was distilled off~ the residue was taken up in 260 cc of chloroform and filtered over 20 g of silica gel. After evaporation of the chloroform, 1.8 g (96 % of the theory) of 2-/ 4-(2-naphthoxy)-phenoxy 7-propionitrile were obtained; m.p. 93 to 94C.

~ ~ -O ~ OCH-CN

E X A M P L E 11:
2-/ 4-(1-chloro-2-naphthoxy)-phenoxy 7-propionic acid-2-methoxyethyl ester t4.3 g (40 mmols) of 2-/ 4-(1-chloro-2-naphthoxy)-phenoxy 7-propionic acid methyl ester (Example 39) in 150 cc of ethylene glycol monomethyl ether were heated for 7 hours to 100C in the presence of 1 cc of concentrated sulfuric acid, while the methanol formed was continuously distilled off. The excess amount of ethylene glycol mono-methyl ether was removed by distillation under reduced pressure, the residue was taken up in chloroform and wash-37~

ed with water unt~ was ~ree ~rom acid. A~ter evaporationof the solvent, 15.6 g (97% o~ the theory) o~ 2-~ 4~ choro~2-naphthoxy)-phenoxy_/-propionic acid 2-methoxyethyl ester were obtained in the form of a non crystalline substance; n20 = 1.5872.

~ O ~,._ OcH-coQcH2cH2ocH3 E X A M P L E 12:
Sodium salt of 2-/ 4-(1-bromo-2-naphthoxy)-phenoxy_~-propionic acid 9.0 g (23.3 mmols) of 2- ~4-(1-bromo-2-naphthoxy)-phenoxy ~-propionic acid (Example 71) were dissolved in 70 cc of ethanol and 3.5 g (23.6 mmols) of 27~ aqueous sodium hydroxide solution were added. The sodium salt of 2- ~4-(1-bromo-2-naphthoxy) -phenoxy_7-propionic acid, m.p. 170C, was distilled.

Br CH
~ ~ ~ _ OCH~COONa E X A M P L E i3:

2- / 4-(2-naphthoxy)-pheno~y _~acetic acid 24.9 g (79 ~mols) of the sodium salt of 2- / 4-(2-naph-thoxy)-phenoxy _ 7 ~acetlc acid (~xample 58) were suspended ,.

- 1 9 - , .~, .

.... :~. , : . ., ~ ,: -'7'~L

in 250 ml of 2N sulfuric acid and by heating the suspen-sion for 15 minutes to 90C the salt was transformed into the free acid. By suction filtration 23.4 g (100 %) of 2-/ 4-(2-naphthoxy)-phenoxy 7-acetic acid, m.p. 142.5 -143C were obtained.

OE~' O{~OCH2 CooH

E X A M P L E 14:
. .
2-/ 4-(2-naphthoxy)-phenoxy 7-propionic acid propargyl .
ester 13.2 g (43 mmols) of 2-/ 4-(2-naphthoxy)-phenoxy 7-propionic acid (Example 60) were dissolved in 100 cc of benzene and, after addition of 6.1 g (52 mmols) of thionyl chloride, the compound was transformed into its acid chlo-ride by refluxing the mixture for 8 hours. By distilia-tion of the excess amount of thionyl chloride and the ben-zene 14.0 g of crude acid chloride were obtained. The acid chloride was dissolved in 30 cc of toluene and the solution was added dropwise, at room temperature over a period of 30 minutes, to a solution of 2.9 g (52 mmols) of propargyl alcohol and 6.5 g (65 mmols) of triethylamine in 30 cc of toluene. The mixture was refluxed for 2.5 hours, cooled, the precipitate was filtered off with suction and the filtrate was washed with water. After drying and eva-poration of the solvent~12.8 g (86 % of the theory) of 2-/~4_(2-naphthoxy)-phenoxy 7-propionic acid propargyl ester , ... .

~:

' ! ' 7~

were obtalned; nD = 1.5915. Traces of the free acid, if any, were removed by filtration over silica gel of a solu-tion of the ester in chloroform.

~o~ocH-co2c~l2c-cH

E X A M P L E 15:

2-/ 4-(1-bromo-2-naphthoxy)-phenoxy 7-propionic acid . _ .
2-chlorocyclohexyl ester 29.0 g (75 mmols) of 2-/ 4-(l-bromo-2-naphthoxy)-phenoxy 7-propionic acid (Example 71) were dissolved in 150 ml of toluene, 10.6 g (75 mmols) of 2-chlorocyclohexanol and 0.5 cc of concentrated sulfuric acid were added and the mixture was refluxed for 4 hours with separation of the water formed by means of a water separator. After cooling and diluting with 100 cc of toluene, the reaction mixture was washed with water until it was neutral and, ~ after drying over sodium sulfate, the toluene was distil-led off. 30.4 g (80 % of the theory) of the desired ester were obtained. As to the NMR data cf. Table 2.

r OCH-CO-O

,~
' ' -"

-- ~L -il 2~1~ 7~
- 22 ~ HOE 77/F 218 E X A M P L E 16:

4-/ 4-(2-naphthoxy)-phenoxy 7~n-butyric acid The sodium salt of 4-(2-naphthoxy)-phenol was prepar-ed by heating 23.6 g (0.10 mol) of 4-~naphthoxy)-phenyl with 50 cc of 2N sodium hydroxide solution (0.10 mol) in 100 cc of dibutyl-diglycol ether to t20C and distilling off the water. ~.5 g (0.11 mol) of ~v-butyrolactone were then added and the mixture was heated for 6 hours to 150C.
The dibutyldiglycol ether was distilled off under reduced pressure and the residue was taken up in water while heat-ing. By acidification 4-/ 4-(2-naphthoxy)-phenoxy 7 n-bu-tyric acid was obtained.

~C--~ OcH2cH~H2cooH

E X A M P L E 17:
.
4-/ 4-(2-naphthoxy)-phenoxy 7-n-valeric acid In the manner described in Example 16 the above com- ~`
pound was obtained using 11.0 g (0.11 mol) of ~ valerolac-tone and heating for 6 hours to 180C.

~ O~DCH-CH2C112COOH

The following compounds were prepared in analogous manner with the use of the respective sta~rting materials.

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FORMULATI~N ExAM~LES
E X A M P L E A;
An emulsifiable concentrate is obtained from 15 parts by weight of active substance 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxethylated nonyl phenol (10 EO) as emulsifier.
E X A M P L E B:
A wettable powder which is easily dispersible in water is obtained by mixing 25 parts by weight of active substance 64 parts by weight of quartz containing kaolin as inert material 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleyl-methyl-taurine as wetting and dispersing agent and grinding the mixture in a pin mill.
E X A M P L E C:
A dusting powder is obtained by mixing 10 parts by weight of active substance and 90 parts by weight of talc as inert material and comminuting the mixture in a hammer mill.
E X A M P L E D:
A granular formulation consists, for example, of about 2 to 15 parts by weight of active substance and 98 to 85 parts by weight of inert granular materials such as attapulgite, pumice and quartz sand.

.. , .:. :

f~ ~

BIOLOGICAL EXAMPLES
E X A M P L E I:
Weeds were sown in flower pots and the pots were sprayed with compositions according to the invention in 5 the form of aqueous suspensions of wettable powder in different concentrations.
The herbicidal efficiency of the compounds of the in-vention was evaluated visually according to the scheme of Bolle (Nachrichtenblatt des Deutschen Pflanzenschutzdien-10 stes, 16, 1964, 92 - 94).

Evaluation Damaging action in % on number Weeds Crops ... ..

2 97.5 to<100 ~0 to 2.5 3 - 95 to ~97.5 >2.5 to 5 4 90 to <95 >5 to 10 to <`90 ~10 to 15 -;
6 75 to <85 >15 to 25

7 65 to <75 > 25 to 35

8 32.5 to <65 >35 to 67.5

9 0 to <32.5 >67.5 to 100 The test results in the following Table Ia show that the compounds of the invention exhibit an outstanding her-bicidal action against many weeds.
In the same manner many crop plants were sown in pots and, prior to emergency, the seeds were treated with the compounds of the invention. It was found that even with high doses of 2.4 kg of active substance per hectare the ' ' , '' ~....... : ' ' , ':
' ' ` : ' . ' ' . ~'' " ,~ ; ' ' ' ' :`

' ' .

-" ~L l;~ Jt~

crop plants were at most damaged to a minor extent only.
The plants were evaluated about 4 weeks after application of the compounds. The results are listed in the following Table Ib. The pots were kept under greenhouse conditions.
E X A M P L E II:

.
Various weeds and crop plants were sown in pots and the plants were grown in the greenhouse to a height of 15 to 25 cm. The plants were then treated in a post-emergence process with the compounds of the invention. The visual evaluation about 4 weeks after application showed that the weeds were well combated, i.e. killed, while many crop plants were not damaged at all or to an insignificant de-gree only (cf. Table II).
T a b l e Ia Herbicidal effect in pre-emergence against weed grasses and weeds Compound dose ALM SAL LOM ECG AMR
according to Example kg_AS/ha 1 2.4 0.6 2 2 2.4 1 1 1 1 2 0.6 2 3 1 2 3 21 2.4 1 1 1 1 - ;
0.6 2 2 1 1 -- 22 2.4 0.6 1 2 2 1 3 ALM = Alopecurus myosuroides ECG - Echinochloa crus gali SAL = Setaria lutescens AMR = Amaranthus retroflexus LOM = Lolium multiflorum AS = Active substance ,....- ''" .-:' '~ ~ '; ~ .,, : . .
... . . ....

- 32 - ~iOE 77/F 218 Q` 3~1 o~
~s~ .
(D ~ 3 ~ ~ 1 3 ~ S:: ~ ., O ~ ~ ~t ¦ ~1~1 ~1 E~

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Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Method of controlling the growth of undesired plants which comprises applying to the plants or the area to be treated an effective amount of a compound of the formula I

(I) in which is or X is hydrogen or halogen, Y is hydrogen, (C1-C4)-alkyl or halogen, R1 is hydrogen or (C1-C4)-alkyl, q is a whole number from zero to 2, Z is a group of the formula , , , , , , , or -CH2-O-SO2-R12 R2 is hydrogen (C1-C12) alkyl which may be substituted one to six times by halogen and/or once by hydroxy, (C1-C6)-alkoxy, (C1-C4) alkylthio, (C1-C6) alkoxy-(C2-C6) alkoxy, halo (C1-C2) alkoxy, methoxy-ethoxyethoxy, (C1-C4) alkylamino, di(C1-C4) alkyalmino, phenyl, oxiranyl, or phenoxy, (the latter optionally being substituted once or twice by halogen and/or (C1-C4) alkyl);
(C5-C6) cycloalkyl, halo (C5-C6) alkyl, (C3-C6) alkenyl, halo (C3-C6) alkenyl, (C5-C6) cycloalkenyl, (C3-C4) alkinyl, which may be substituted once or twice by (C1-C6) alkyl, phenyl, halogen and/or (C1-C2) alkoxy; phenyl which may be substituted one to three times by (C1-C4) alkyl, (C1-C4) alkoxy, halogen, NO2 and/or CF3; furfuryl, tetrahydrofurfuryl, or a cation equivalent of an organic or inorganic base;
R3 is (C1-C6) alkyl which may be substituted by (C1-C4) alkoxy, halogen or phenyl (optionally mono- to tri-substituted by (C1-C4) alkyl and/or halogen);
(C3-C6) alkenyl or phenyl (optionally substituted one to three times by (C1-C4) alkyl and/or halogen);
R4 and R5, which are identical or different, are hydrogen, (C1-C4) alkyl, hydroxy (C1-C6) alkyl, (C5-C6) cycloalkyl, or phenyl (optionally substituted one to three times by (C1-C4) alkyl, (C1-C4) alkoxy, halogen and/or CF3);
with the proviso that R4 and R5 cannot both be phenyl; or R4 and R5 together form a methylene chain with 2, 4 or 5 members in which one OH2 group may be replaced by oxygen, NH or N(CH3);
R6 is H, CH3, R7 is H, CH3 or C2H5;
R8 is H, CH3, C2H5 or phenyl, R9 and R10, which are identical or different, are (C1-C4)-alkoxy, (C1-C4) alkylthio, (C1-C4) alkylamino, or di(C1-C4) alkylamino, or together are a radical of the formula =N-R12;
R11 is (C1-C6) alkyl, (C1-C6) haloalkyl, C3-, C5- or C6- cycloalkyl, (C3-C6) alkenyl, phenyl, (C1-C4) alkylphenyl, (C1-C4) alkoxyphenyl, halophenyl, tri-fluoromethylphenyl, nitrophenyl or a radical of the formula and R12 is (C1-C4) alkyl or phenyl optionally substituted one to three times by halogen, CF3, NO2 and/or (C1-C4)-alkyl.

2. A herbicidal composition comprising 2 to 95% by weight of a compound of the formula II
(II) wherein Y represents hydrogen, (C1-C4)-alkyl or halogen, R1 represents (C1-C4)-alkyl, and R2 represents hydrogen, (C1-C10)-alkyl, or a cation equivalent of an organic or inorganic base, in admixture with 5 to 98% by weight of an agriculturally suitable carrier, selected from the group consisting of emulsifiers, wetting and dispersing agents, finely divided solid dusting agents, and granular inert materials.

3. A herbicidal composition according to claim 2 wherein the compound of formula II is in the form of its d-enantiomer relative to the carbon atom between 0 and C=0 as center of chirality.

4. A herbicidal composition according to claim 2 or claim 3 wherein in the compound of formula II, Y is hydrogen or chlorine, R1 is CH3 and R2 is hydrogen, (C1-C4)-alky1, or a cation equivalent of an organic or inorganic base.

5. A herbicidal composition according to claim 2 wherein the compound of formula II is

6. A herbicidal composition according to claim 2 wherein the compound of formula II is

7. A herbicidal composition according to claim 2 wherein the compound of formula II is

8. A herbicidal composition according to claim 2 wherein the compound of formula II is

9. A herbicidal composition according to claim 2 wherein the compound of formula II is

10. A herbicidal composition according to claim 2 wherein the compound of formula II is

11. A herbicidal composition according to claim 2 wherein the compound of formula II is