CA1150267A

CA1150267A - Heterocyclic ether type phenoxy fatty acid derivatives and herbicidal composition

Info

Publication number: CA1150267A
Application number: CA000417839A
Authority: CA
Inventors: Yasukazu Ura; Gozyo Sakata; Yuzi Kawamuar; Kenzi Makino; Yasuo Kawamura; Takasi Ikai; Toshihiko Oguti
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 1979-02-22
Filing date: 1982-12-15
Publication date: 1983-07-19

Abstract

ABSTRACT OF THE DISCLOSURE
The invention provides a herbicidal composition which comprises an adjuvant and as active ingredient a heterocyclic ether type ohenoxy fatty acid derivative having the formula (I) wherein X represents a halogen atom;
n is 0, 1 or 2; R1 represents a hydrogen atom; a lower alkyl group; R2 represents -OH; an -O- alkyl group; an -OM group where M is an inorganic or organic salt moiety; an group;

an -O- lower alkenyl group; an -O- benzyl group; an -O- lower alkylalkoxy group; the -O- phenyl group; the -O-cyclohexyl group, an -O-haloalkvl group, an -O- lower alkynyl or an -O-cyanoalkyl group; and R3 and R4 respectively represent a hydrogen atom or a lower alkyl group.

Description

~L~5~ii7 The present invention relates to heterocyclic ether type phenoxy fatty acid derivatives and herbicidal compositions containing them.
Various compounds have been used as herbicides for many years. These herbicides have been used to eliminate labour and to improve the productivity of agricultural and horticultural crops.
Herbicides having superior herbicidal characteristics are always required. Herbicides for agricultural and horti-cultural use are preferably compounds which selectively controlthe weeds in a small dose without toxicity to the crops. The known herbicides do not always have optimum herbicidal characteristics.

-2- *

Substituted pyridyloxyp~enoxy fatty acid herbicides which are heterocyclic ether type phenoxy fatty acid derivatives have been disclosed in Japanese Unexamined Patent Publication Wo. 106735/1976. Benzimidazole, bPnzthiazole, and benzoxazole derivatives~and herbicidal effect of these compounds have been disclosed in Japanese Unexamined Patent Publication No.
40767/1978.
The present invention provides heterocyclic ether type phenoxy fatty acid derivatives which are useful in herbicidal compositions having excellent herbicidal activity against various weeds, especially gramineous weeds and substan-tially non-phytotoxicity to broad leaf crop plants.
The present invention also provides a process for producing such herbicidal compounds.
According to the present invention there are provided compounds having the formula (X)n ~ f H ~ O-CH-COR (I) wherein X represents a halogen atom;
n is 0, 1 or 2; Rl represents a hydro~en atom or a lower alkyl group; R represents -OH; an -O- alkyl group; an -OM group wherein M is an inorganic or organic salt moiety; an N ~ R3 \ R4 group, an O-lower alkenyl group; an O- benzyl group; an O-lower alkylalkoxy group; the O-phenyl group; the -O- c~_lohexyl group;
an -O- haloalkyl group, an -O- lower alkynyl group or an -O-cyanoalkyl group; and R3 and R respectively represent a hydrogen atom or a lower alkyl group.

Z~7 In the formula (I), R2 can be an -OM group which includes-CNa, -OK, --2 Ca, -0-12 Mg, an -OH lower alkylamino group, an -OH ethanol-amino group, an -OH lower alkyl ethanolamino group or the -ONH4 group. Such compounds are water soluble and can be used in an aqueous solution.
The heterocyclic ether type phenoxy fatty acid derivatives having the quinoline ring and having the formula (I) of the present invention are the novel compounds.
The heterocyclic ether type phenoxy fatty acid derivatives (I) of the present invention are unique compounds which are effective for controlling gramineous weeds without any phytotoxicity to broad leaf crop plants as well as broad leaf weeds especially in a post-emergence treatment.
Typical compounds of the present invention having the formula (I) are shown in Table (1) together with their physical properties.

3Z~7 Table 1 C ' Rl ( )n ~ N ~ O - CH - COR

Comp. X R ¦ R2 I Physical property _ 1 H CH3 OH mp 188-189 C W.C.
o 2 H CH OCH3 mp 98-99 C W.C.

3 H CH3 C2H5 oily at room temp.

4 6-Cl CH3 C2H5 nD ~ = 1.5814 _ o H CH3 ONa mp >280 C W.C.
_ 6 H CH3 N(CH3)2 mp 108-109 C W.C.
_ 7 H H OCH3 oily at room temp.
_ _ 8 6-F CH OH mp 158-159 C W.C.
3 _ 9 6-F CH3 OCH3 mp 97C W.C.
6-F CH3 C2H5 mp 60-61 C W.C.
o 11 6-Br CH3 OH _ mp 171-172 C W.C.
_ _ O
12 6-Br CH3 OCH3 mp 117 C W.C
o -13 6-Br CH3 C2H5 mp 96-97 C W.C.
20 14 6-I CH3 OCH3 mp 126-127 C W.C.
_ 20 colorless 6-I CH3 C2H5 nD = 1.6237 liqîd 16 6-Cl CH3 OH mp 176-177 C W.
17 6-Cl CH3 OCH3 - mp 94-95 C W.C.
18 6-Cl CH3 N(CH3)2 mp 122-123 C W.C.
. 19 pale yello~
19 6-F CH3 oC3H7n nD = 1.5700 liquid 20 colorless 6-F CH3 oC3H7-i nD = 1.5632 liquid 21 6-F CH3 Oc4H-gn mp 45.5-47 C W.C.

22 6-F CH3 oC4H-gi nD 1.5593liquid pale yello~
23 6-F CH3 OC4H-gt nD = 1~5580 liquid . 20.5 colorless 24 6-F CH3 5 11 nD --1 5572liquid .

~ 5~3Z6~7 Comp. ¦ X l Rl l R2 Physical property No ~ ~ ¦ OCH2 ~ nD = 1.5972 yellow 26 6-F CH3 O(CH2)2OCH3 mp 62-63 C W.C.
27 ~ ~ jOCH2CH=CH2 n21= 1.5728 cllrldSs Optical rotation Physical temp. property Compound [a ] D
(solvent concen-tration) _ 28 COOCH3 F [~]32= +31.2so 91 H -C- O ~ ~ (CHC13; C=1.18%) W.C.

___ CH3 l 29 COOCH3 ~ [a] 32= +36.4 m.p.
H- C-~O ~ O~~ ~ (CHC13; C=0.99%) 91-92 C
_ W. C .

NMR SPECTRUM OF COMPOUNDS
Compound _ No.
1 (~ ppm, DMSO-d6); 1.55(3H,d), 4.7(1H,q), 6.7-8.2 (10H,m), 11.0(lH) 2 (~ ppm, CDCQ3); 1.6(3H,d)~ 3.7(3H,s), 4.7(1H,q), 6.7-8.0(lOH,m) 3 (~ ppm, CDCQ3); 1.2(3H,t), 1.6(3H,d), 4.15(2H,q), 4.65(lH,q), 6.75-8.05(lOH,m) _ _ .
4 (~ ppm, CDCQ3); 1.2(3H,t), 1.6(3H,d), 4.15(2H,q), 4.65(lH,q), 6.8-8.0(9H,m) _ _ 6 (~ ppm, CDCQ3); 1.6(3H,d), 3.0(6H,d), 4.9(1H,q), 6.8-8.1(lOH,m) 7 (~ ppm, CDCQ3); 3.75(3H,s), 4.55(2H,s), 6.7-8.1 (lOH,m) 11~26~

Compound No.
8 (~ ppm, DMS0-d6); 1.55(3H,d), 4.8(1H,q), 6.8-8.4 (9H,m), 12.9(1H,b s) g (~ ppm, CDCQ3); 1.6(3H,d), 3.7(3H,s), 4.7(lH,q), 6.75-8.0(9H,m) (~ PEm~CDcQ3); 1.25(3H,t), 1.6(3H,d), 4.2(2H,q), 4.7(lH,q), 6.7-8.0(9H,m) 11 ~ ppm, DMSO-d6); 1.55(3H,d), 4.8(1H,q), 6.8-8.4 (9H,m), 13.0(1H,b s) l _ 12 (~ ppm, CDCQ3); 1.6(3H,d), 3.7(3H,s), 4.7(lH,q), 6.7-8.0(9H,m) 13 (~ ppm, CDCQ3); 1.2(3H,t), 1.6(3H,d), 4.15(2H,q), 4.7(1H,q), 6.7-8.0(9H,m) 14 (~ ppm, CDCQ3); 1.6(3H,d), 3.7(3H,s), 4.7(1H,q), 6.7-8.0(9H,m) (~ ppm, CDCQ31; 1.2(3H,t), 1.6(3H,d), 4.2(2H,q), 4.7(lH,q), 6.7-8.0(9H,m) 16 (~ ppm, DMSO-d6); 1.56(3H,d), 4.84(lH,q); 16.80-8.40, 9H-6.91(2H,d), 7.17(2H,d), 7.57(2H, s), 7.96 (lH, s), 8.27(lH, d)]
17 (~ ppm, CDCQ3); 1.57(3H,d), 3.68(3H,s), 4.68(1H,q);
[6.75-8.10, 9H-6.83(2H,d), 7.13(2H,d), 7.96(1H,d)]
18 (~ ppm, CDCQ3); 1.59(3H,d), 2.92(3H,s), 3.08~3H,s), 4.91(1H,q); ~6.75-8.05, 9H-6.84(2H,d), 7.13 (2H,d), 7.91tlH,d)]
19 (~ ppm, CDCQ3); 0.85(3H,t), 1.60(3H,d), 1.71(2H,m), 4.11(2H,t), 4.72(1H,q); [6.75-8.15, 9H-6.88(2h,d), 7.14(2H,d), 7.94(lH,d)]
(~ ppm, CDCQ3); 1.19(3H,d), 1.26(3H,d), 1.59(3H,d), 4.65(1H,q), 5.04(1H,m); [6.75-8.10, 9H-6.84(2H,d), 7.13(2H,d), 7.92(lH,d)]
_ _ 21 (~ ppm, CDCQ3); 0.88(3H,t), 1.00-2.10(4H,m), 1.60 (3H,d), 4.15(2H,t), 4.73(1H,q); [6.70-8.15 ,9H-6.90 (2H,d), 7.15(2H,d), 7.95(1H,d)]
_................. _ .
22 (~ ppm, CDCQ3); 0.88(6H,d), 1.62(3H,d), Ca. 1.85 (lH,m), 3.92(2H,d), 4.73(1H,q); ~6.75-8.10, 9H-6.86 (2H,d), 7.11(2H,d), 7.95(1H,d)]

Compound No.
23 (~ ppm, CDCQ3); 1.43(9H,s), 1.58(3H,d), 4.63(lH,q);
[6.80-8.10, 9H-6.91(2H,d), 7.18(2H,d), 7.94(1H,d)]
24 (~ ppm, CDCQ3); 0.87(3H,t), 1.05-1.55(6H,m), 1.62 (3H,d), 4.17(2H,t), 4.74(1H,q); ~6.80-8.15, 9H-6.91 (2H,d), 7.19(2H,d), 7.99(1H,d)]
(~ ppm, CDCQ3); 1.62(3H,d~, 4.78(1H,q), 5.20(2H,s);
[6.75-8.15, 14H-6.88(2H,d), 7.15(2H,d), 7.97(1H,d)]
26 (~ ppm, CDCQ3); 1.63(3H,d), 3.33(3H,s), 3.60(2H,t), 4.32(2H,t), 4.77(1H,q); [6.75 8.20, 9H-6.90(2H,d), 7.15(2H,d), 8.00(lH,d)]
27 (~ ppm, CDCQ3); 1.63(3H,d), 4.67(2H,d), 4.78(lH,q);
(5.00-6.20, 3H,m); ~6.80-8.10, 9H-6.91(2H,d), 7.08(2H,d), 7.90(lH,d)]
28 (~ ppm, CDCQ3); 1.63(3H~d), 3.76(3H,s), 4.75(1H,q);
[6.80-8.20, 9H-6.91(2H,d), 7.17(2H,d), 8.02(1H,d)]
29 (~ ppm, CDCQ3); 1.61(3H,d), 3.75(3H,s), 4.76(lH,q);
~6.80-8.20, lOH-6.92(2H,d), 7.18(2H,d), 8.07(lH,d)]
_ ~1~15~2~7 The compound (I) of the present invention can be produced by the following processes:-A) By the condensation of a compound having theformula ( )n ~ ~ (II) N Hal wherein X and n are defined above, and Hal designates a halo-~en atom; with 4-hydroxyphenoxy fatty acid derivative havins the formula Rl HO ~ OCH -- COR ( I I I ) wherein Rl and R2 are defined above, in the presence of an inorganic or organic base, such as sodium hydroxide, potassium hydroxide or potassium carbonate, at a suitable temperature.
The reaction can be carried out in an inert solvent such as dimethylformamide, dimethylsulfoxide~ or acetonitrile;
B) By the condensation of a compound having the formula (II) with a hydroquinone monobenzyl ether naving the formula HO~ O CH~ ( IV) in the presence of an inorganic or organic base to produce a compound having the formula (X)n ~ o ~3 oCH2~3 _ 9 _ wherein X and n are defined above; then hydrogenation of the product in the presence of a catalyst, such as palladium-carbon catalyst, to cause debenzylation and to yield a com-pound having the formula ~ N ~ ~30~ (VI) wherein X and n are defined above; and then condensation of the product with an ~-halofatty acid derivative having the formula R
2 (VII) Hal - CH - COR
wherein R1, R2 and Hal are defined above; in the presence of an inorganic or organic base, such potassium carbonate in a polar organic solvent, such as methyl ethyl ketone, acetoni-trile or dimethylformamide;
C~ The product obtained by the process A) or B) may be converted into the other compounds of formula I by hydrol-ysis, esterification, ester interchange, salt formation or amidation.
In the process A), the reaction is preferably car-ried out at 50 to 200C, especially at 80 to 100C, at a molar ratio of the compound (II): 4-hydroxyphenoxy fatty acid derivative (III) of 1:0.2 to 5.0, preferably 1:0.5 to 2.0 and especially 1:0.8 to 1.5. The inorganic or organic bases include in any base which is useful for the condensation of the compound (II) and the compound (III). The concentration of the starting materials in the inert solvent may be in a range of 5 to 50 wt. %, preferably 10 to 30 wt. %.
In the process B), the reaction is preferably car-ried out at 50 to 200C, especially at 100 to 150C, at a molar ratio of a compound (II): a hydroquinone monobenzyl ether (IV) of 1:0.2 to 5.0 ~L~ 67 preferably 1:0.5 to 2.0, especially 1:0.8 to 1.5. The inorganic or organic base includes any base which is useful for the condensation of the compound (II) and the compound (IV). The reaction is preferably carried out in an inert solvent at a concentration of the starting material of 5 to 50 wt.%, preferably 10 to 30 wt.%. The hydrogenation of the resulting intermediate (V) is carried out under conditions for the debenzylation to yield the compound (VI). The hydrogen pressure is preferably in the range of 1 to 5 atm., more preferably 1 to 2 atm. The reaction of the compound (VI) with the ~halofatty acid derivative (VII) is preferably carried out at 80 to 100C at a molar ratio of the compound (VI): the compound (VII) of 1:0.2 to 5.0, preferably 1:0.5 to 2.0, and especially 1:0.8 to 1.5. The inorganic or organic base may be the same. The concentration of the starting materials in the inert solvent may be in a range of 5 to 50 wt.~, preferably 10 to 30%.
In the process C), the conditions of the hydrolysis, the esterification, the ester interchange, the neutralization and the amiaation can be selected as desired. These conditions are known by a person skilled in the art.
The present invention will be further illustrated by way of the following Examples.

Zf~7 Example l:

Methyl i-t4_ ( 2- quinolyloxy)phenoxy)propionate (Compound No. 2) In 50 ml of dimethylsulfoxide, 12 g of hydroquinone mono-benzyl ether, 8. 2 g of 2-chloroquinoline and 8. 3 g of potassium carbonate were dissolved and the mixture was heated at 150 to 160C
for 4 hours to ~ause reaction. AftercooliD~ the reactionmlx~ure.was poured into water and the product was extracted with ether for several times. The ether layer was washed with an aqueous solution of sodium hydroxide and then with water and the ether layer was the dehydrated over sodium sulfate. The solvent was distilled off.
The resu~ting crude crystal was washed with diisopropyl ether to yield 12 g (yield 75''70) of 2-(4-benzyloxyphenoxy)quinoline. All of the intermediate was dissolved in 200 ml of a mixed solvent consisting of tetrahydrofuran and ethanol (5:1) and 1. 5 g of palladium-carbon type catalyst was added. 880 ml of hydrogen gas was fed into the mixture to effect hydrogenation at the atmospheric pressure. After hydrogenation, the catalyst was separated by suction filtration and the solvent was distilled off. The residue was washed with chloro-form-n-hexane type solvent to yield 6. 3 g ~yield 74~0) of white crystal of 2-(4-hydroxyphenoxy)quinoline (m.p. 177C).
In 50 rnl of methyl ethyl ketone, 2. 37 g of the product, 2.1 g of methyl c~-bromopropionate and 2. O g of potassium carbonate were added and the mixture was refluxed for 5 hours to effect reaction.
After cooling to the room temperature, the precipitated product was separated by filtration and the solvent was distilled off to yield 2.2 g (yield 68%) of the object compound.

Example 2 2-[4-t2-q~inolvloxy)phenoxy]propionic acid N,N-dimethylamide (Compound No. 6) In 100 ml of methyl ethyl ketone, 2.3 g of the inter-mediate of Example 1 of 2-(4-hydroxyphenoxy)quinoline, 1.8 g of N,N-dimethyl-~-bromopropionic acid amide and 1.4 g of potassium carbonate were added and the mixture was refluxed for 5 hours. After the reaction, the precipitated crystal was separated by filtration and the so]vent was distilled off.
The product was dried under reduced pressure. The resulting crude crystals were recrystallized from a solvent of methanol-water to yield 3.6 g (yield 88%) of white crystal of the object compound.
The compound of formula I can be used in the form of a herbicidal composition.
In the preparation of the herbicidal compositions, the compound of formula I can be uniformly mixed with or dissolved in suitable adjuvants including solid carriers such as clay, talc, bentonite and diatomaceous earth; liquid carriers such as water, alcohols (e.g. methanol and ethanol), aromatic hydrocarbons (e.g. benzene, toluene, or xylene), chlorinated hydrocarbons, ethers, ketones, esters (e.g. ethyl acetate), acid amides (e.g. dimethylformamide).

~Z6~7 if desired also with an emulsifier, a dispersing agent, a suspending agent, a wetting agent, a spreader, or a stabilizer to form a solution, an emulsifiable concentrate, a wettable powder, a flowable suspension, a dust or a granule, which is applied if desired, by diluting it with suitable diluent.
It is possible to combine the compound of the present invention with another herbicide, or an insecticide, a fungicide, a plant growth regulator or a synergistic agent.
Examples of the herbicidal compositions of the present invention are given in which parts are parts by weight.
Solution:
Active ingredient: 5 to 75 wt.%, preferably 10 to 50 wt.%, especially 15 to 40 wt.%.
Solvent: 95 to 25 wt.%, preferably 88 to 30 wt.%, especially 82 to 40 wt.%.
Surfactant: 1 to 30 wt.%, preferably 2 to 20 wt.%.
Emulsifiable concentrate:
.
Active ingredient: 2.5 to 50 wt.%, preferably 5 to 45 wt.%, especially 10 to 40 wt.%.

Surfactant: 1 to 30 wt.%, preferably 2 to 25 wt.%, especially 3 to 20 wt.%.

Liquid carrier: 20 to 95 wt.%, preferably 30 to 93 wt.%, especially 57 to 85 wt.%.

Dust:

Active ingredient: 0.5 to 10 wt.%.

Solid carrier: 99.5 to 90 wt.~.

Flowable suspension:
. .
Active ingredient: 5 - 75 wt.%, preferably 10-50 wt.%

~ater: 94 - 25 wt.%, preferably 90-30 wt.%

Surfactant: 1 - 30 wt.%, preferably 2-20 wt.

5~Z67 Wettable powder:
Active ingredient: 2.5 to 90 wt.%, preferably 10 to 80 wt.%, especially 20 to 75 wt.%.
Surfactant: 0.5 to 20 wt.%, preferably 1 to 15 wt.%, especially 2 to 10 wt.%
Solid carrier: 5 to 90 wt.~, preferably 7.5 to 88 wt.%! especially 16 to 56 wt.%
Granule:
Active ingredient: 0.5 to 30 wt.%
` 10 Solid carrier: 99.5 to 70 wt.%
The emulsifiable concentrate is prepared by dissolving the active ingredient in the liquid carrier together with the surfactant. The wettable powder is prepared by admixing the active ingredient with the solid carrier and the surfactant and the mixture is~pulverized. The flowable suspension is prepared by suspending and dispersing a finely divided active ingredient in an agueous solution of a surfactant. The dust, the solution, the granule etc. are prepared by mixing the active ingredient with the adjuvant.
In the following compositions, the following ad~uvants are used.
So~pol-2680*
POE-hormylnonylphenolether 50 wt. parts POE-nonylphenolether 20 "
POE-sorbitan alkyl ester 10 "
Ca-alkylbenzenesulfonate 20 "
Sorpol-5039*
POE-alkylarylether sulfate 50 "
Silica hydrate 50 "
Carplex*
Silica hydrate 100 "
Zeeklite*
Clay 100 "

~15~267 Sorpol W-150*
POE-nonylphenolether 100 wt. parts * Trademark~
Composition 1: Wettable powder:

Compound No. 1 50 wt.parts Zeeklite A* 46 "
Sorpol 5039*~Toho Chem.) 2 "
Carplex 2 "
* Trademark These components were uniformly mixed and pulverized to prepare a wettable powder. The wettable powder was diluted with water at 50 to 1, 000 times and the diluted solution was sprayed at a dose of 5 to 1000 g of the active ingredient per 10 ares.

Corriposition 2: Emulsifiable concentrate:

Compound No. 4 20 wt.parts Xylene 7 5 Sorpol 2680~Toho Chem.) 5 "
* Trademark The components were uniformly mixed to prepare an emul-sifiable concentrate. The emulsifiable concentrate was diluted with water at 50 to 1, 000 times and the diluted solution was sprayed at a dose of 5 to 1000 g of the active ingredient per 10 ares.

Composition 3: Aqueous solution-Compound No. 5 30 wt. parts Sorpol W-150*~Toho Chem.) 10 "
Water 6 0 "
* Trademark ~5~267 The component~ were mixed to dissolve them and to prepare an aqueous s'olution. The aqueous solution wa~ diluted with water at 50 to 1, 000 times and the diluted solution was sprayed at a dose OI 5 to 1000 g. of the active ingredient per 10 ares.

As the other herbicides, the following he~bicid'es were respectively used 2-(2, 4-dichloropheno:~y)propionic acid, 2, 4 - dichlorophenoxyacetic acid, 3 - ( 3 - trifluoromethylphenyl~ - l, 1-dimethylurea,3-(4-methylphenethyloxyphenyl)- l-methyl- 1 -methoxy urea, 3-(methoxycarbonylamino~phenyl-N-(3-methylphenyl) carbamate, 3-(ethoxycarbonylamino)-phenyl-N-phenylcarbamate, 3-isopropyl-lH-2,1, 3-benzo thiadiazine-(4)-3H- one-2, 2-dioxide, 5-amino-4-chlor 2-phenylpyridazine- 3-one, 3- cycl'ohexyl- 5, 6-trimethyleneuracil, 2-chloro-4-ethylamino-6-isopropylamino-1, 3, 5-triazine, 2-chloro-4, 6-di(ethylamino~-1, 3, 5-triazine, 2-methylthio-4, 6-bistisopropyl-amino)-1, 3, 5-triazine, 4-amino-4, 5-dihydro-3-methyl-6 phenyl-l, 2, 4-triazine- 5- one, 4-amino-6-t-butyl-4, 5-dihydro- 3 -methylthio-l, 2, 4-triazine- 5-one, 2-chloro-4-trifluoromethylphenyl-3' -ethoxy-4-nit_ rophenyl ether or sodium-5-¦2-chloro-4-(trifluoromethyl) phenoxy~-2-nitro benzoate.
It is also possible to combine the compound of the present invention with the other herbicidal compounds such as are described in "Weed Control Handbook'l (Vol. I 6th edition 1977; Vol. II 8th edition 1978) issued by the British Crop Protection Council edited by J.D.
Fryer l~A & R.J. Makepeace BSc . Blackwell Scientific Publication~

The heterocyclic ether type phenoxy fatty acid derivatives of the present invention have an excellent herbi-cidal effect on various weeds especially gramineous weeds in soil treatment or in foliage treatment, without any phytotoxicity to broad leaf crop plants such as cotton, soy-bean, radish, cabbage, eggplant, tomato, sugar beet, ground nut, peas, beans, linseed, sunflower, safflower, potato, tobacco, alfalfa and onion etc. Therefore, the heterocyclic ether type phenoxy fatty acid derivatives of the present invention are suitable for selective control of gramineous weeds in a culture of a broad leaf crop plant as herbicide for agricultural and horticultural fields especially up-land fields.
The heterocyclic ether type phenoxy fatty acid derivatives of the present invention are also effective as herbicides for controlling various weeds in the agricultural and horticultural fields such as up-land, paddy fields and orchards as well as non-cultivated lands such as playground, vacant land, and railway sides.
The herbicidal composition usually contains 0.5 to 95 wt. % of the compound of the present invention as the ac-tive ingredient and the remainder of the adjuvants in con-centrated form. The dose of the compound of the present in-vention depends on the weather conditions, soii conditions, form of the composition, season of an application, type of crop plant and types of weeds. It is usually in a range of 1 to 5000 g, preferably 5 to 1000 g, of the compound of the invention per 10 acres~
The herbicidal activities of the hcterocyclic cther type phenoxy fatty acid derivatives of the prcsent invention are illustrated in the following Tests.

~S~2~7 In the following tests, the herbicidal effects of the compounds of the present invention on gramineous weeds including rice are shown together with non-phytotoxicity of the same compounds to broad leaf crop plants as well as broad leaf weeds especially, non-phytotoxicity of the same compounds to broad leaf weeds in ?ost-emergence. These remarkable selectivities have not been found by other compounds.
Test 1: Tests for herbicidal effect in soil treatment:
Each of a plurality of plastic boxes having a length of 15 cm, a width of 22 cm and a depth of 6 cm was filled with a sterilized diluvium soil and seeds selected from rice (Oryza sativa), barnyard grass (Echinochloa crus-galli), large crab-grass tDigitaria adscendens), lambsquarters (Chenopodium ficifolium), common purslane (Postuloca oleracea), hairy gal-insoga (Galinsoga ciliata), yellow cress (Rorippa atrovirens) seeds were sown to a depth of about 1.5 cm. Each solution of each herbicidal composition was uniform~y sprayed on the surface of the soil to give the specific dose of the active ingredient.

_19 _ ~ 3~5~267 The solution was prepared by diluting, with water, a wettable powder, an emulsifiable concentrate or a solution described in Examples of the composition except varying the active ingredient~
The solution was sprayed by a small spray. Three weeks after the treatment, the herbicidal effects to rice and various weeds were observed and rated by the following Standar~s. ~h6 results are shown in Table 2.

Standard rating:
5: Growth control of more than 90%
(subsantial suppression) 4: Growth control of 70 to 90%
3: Growth control of 40 to 70%
2: Growth control of 20 to 40%
1: Growth control of 5 to 20%
0: Growth control of less than 5%
(non-herbicidal effect) Note: Ri: Rice Ba.: Barnyard grass L. C.: Large crab grass La.: Lambsquarters 2 0 C . P .: Common pur slane H. G .: Hairy galin soga Y. C.: Yellow cress _ 20 --Table 2-1 ~ ¦ L, C, ¦ L~. ¦ C. P, ¦ H. G. ¦ Y. C
11 5ooo 5 55 5 2 22 2 32 100 1 5 . 5 5 v 5 a 2 3 3 5 lO0 5 S 4 2 2 2 2 100 5 5 . 5 2 0 2 2

6 50 5 5 4 1 0 1 1 50. 4 1 5 4 0 __ 1 2ti7 Table 2-2 Dose of CNmo.P Comp. Ri B~ L C, La C. P. H, G. Y, - 1200 5 5 5 3o 2 3o 3 ~ 5 5 0 0 0 0 . lO0 5 5 5 - 3 3 4 4 Table 2-3 comP.¦ Comp. Ri Ba L.C. C.A. C.P. H.G. Y.C
No .(~ /a) _ 55_ 5_ - o 0 0 ~0 . 1 25 5 5 5 0 0 0 0 ~ 25 5 5 5 0 . .. 0 .

~5~267 Table 2-4 Comp, Dose oi- Ri Ba L, C, La. C. P. H. G. Y. C

100 5 . 5 5 2 2 2 2 0 _ 0 0 0 I 00 5 5 5 2 2 -- ~-- 2 2 17 ` 50 5 5 5 1 1 1 1 5 _ 5 0 0 0 0 . 100 5 5-- 5----2 2 2 2 5 5 _ 0 0 0 0 100 5 5 5 2 . 2 2 2 . 100 5 . 5 5 2 2 2 2 . 2250 5 5 5 .1 1 1 5_ 5 S 0 0 0_ 0 1 00 5 5---5 ~ 2 2 2 2 24 50 - 5 5 5 1 I l. I
5_ 0_0 0 .. 1 00 5 5 5 - 2 2 2 2 0 0 0 __ 0_ 0 0 z~

Table 2-5 Comp. Dose of Ri ¦ Ba L.C. ha. ¦ C.P. H.G. Y.C.
No Comp;

12.5 S 5 5 0 0 0 0 12.5 4 ~ 4 0 0 0 0 Test 2: Tests for herbicidal effect in foliage treatment:
Each of a plurality of plastic boxes having a length of 15 cm, a width of 22 cm, a depth of 6 cm was filled with a sterilized diluvium soil and seeds selected from rice, large crab-grass, lambsquarters L. var. common purslane, hairy galinsoga, yellow cress and tomato seeds were sown in the form of spots to a depth of about 1.5 cm. When the weeds had grown to 2 to 3 leaf stage, each solution of each herbicidal composition was uniformly sprayed to foliages at each dose of each active ingredient shown in Table 3. The solution was prepared by diluting, with water, a wettable powder, an emulsi-fiable concentrate or a solution described in the Examples of the composition except varying the active ingredient and the solution was uniformly sprayed by a small spray on all of foliages of the plants.
Two weeks after the spray treatment, the herbicidal effects on the weeds and tomato were observed and rated by the standard shown in Test 1. The results are shown in Table 3.

Table 3-1 Dose of Comp. Comp. Ri L.C. La. C.P. H.G. Y.C. Tomato No. I (g/a) 1~ ~ 3 1 52 _ ~ 3 0 .

4 3 ~ 2 ~ 0 .

_ _ .

_ .

l 150 ~ 2 2I 0 I 1 1 2 0 .

~15~Z67 Table 3-2 Comp. ¦ Comp ¦ Rl ¦ L. C . ¦ La- C . P . H . G . Y . C .
-- ¦ (g/a) ¦ l _ 1 00 5 5 2 1 2 3 5_ 5 I l 1 2 1 1 -2 _ 2 Table 3-3 Comp. C mp. ¦ Ri L . C . La. C . P. H . G . Y. C

11 50 5 5 0 0 ' 1 1 0 0 0_ 0 1200 4 5 0 1 -~ 2 2 -Table 3-4 . Comp. ¦ Dose of Ri ~ L.C. La. ~ C.P. H.G. ~ Y.C.

5_ _0 0 0 0 100 5. 5 ~ 2 2 2 2 _ 0 0 0 0 . 25 5 5 0 0_0 0 5_ 0 0 0 0 . .... 25 5 5 0 0 0 0 100 5 5 2 22` 2 _ 0 _ 0 0 _1 00 5 5 1 2 . 25 5 5 0 0 0 0 ~5~267 Table 3-S

Dose of _ Comp . Comp . RiL . C .La . C . P . H . G . Y . C .
No .( g/a ) 12.5 5 5 0 0 0 0 12.5 5 5 0 0 0 0 Z~7 Test 3: Tests for phytotoxicity to crop plants (foliage treatment:
Each of a plurality of plastic boxes having a length of lS cm, a width of 22 cm, and a depth of 6 cm was 'illed with a sterilized diluvi~m soil and seeds selected .rom cotton, soybean, radish, cabbage and egsplant seeds were sown in the form of spots to a depth of about 1.5 cm. When the plants had grown to lea.-emergence stage, each solution of each her-bicidal composition was uniformly sprayea on the foliage at each dose of each active ingredient shown in Table 4. The solution was prepared by diluting, with water, a wettable pow~er, an emulsifiable concentrate or a solution described in the Examples of the composition except varying the active ingredient and the solution was unifor~iy sprayed by a smal' spray on all foliage of the plants.
Two weeks after the spray treatment, the phytotox-icities to the plants were observed and rated by the following standard. The results are shown in Table 4.
Stanaard rating-5: Co~plete death of plant 4: Serious phytotoxicity to plant 3: Fair phytotoxici'y to plant 2: Slight phytotoxicity to plant 1: Only slight phytotoxicity to plant 0: Non phytotoxicity Note: Cot.: Cotton Cab.: Cabbage Soy.: Soybean Egg.: Eggplant Rad.: Radish _ 30 -~ ~ 5~267 Table 4- 1 Dose of N o ( g / a ) C ot . S oy . Et a d . C ab . E g g .

4 S0 1 1 I ~ 1 _able 4-2 ¦ Dose of l Compound Compound Cot. Soy. Rad. Cab . Egg.
No. (g¦a~ _ ~ 1 1 0 1 0 0 0 1 0 0 1 0 0 . .

0 i 0 0 1 0 0 _ Table 4-~

. Dose of Compound C ompound Cot . Soy. Rad. Cab . Egg .
No. (~/a) _ 0 ~ 1 0--- ___--0-__ 2 5 0 - 0 0 0 0 1 0 1 0 0 _ 0 S0-~-- 1 0 1 0 j 0 0 0 1 0 1 0 1 0 0 0 _ ~s~z~i7 Table 4- 4 -Dose of Compound Compound Cot. Soy. Rad. Cab . Egg.
No . (~ /a ) 1650 0 1 ~ 0 19 255 1 1 1 1 l 0 ~ I 0 0 0 0 1 0 1 I !

23 50 0 1 1 i 0 I ! I

26 50 1 0 1 ` 0 0 0 27 50 1 0 1 ` 1 0 0 2S I o 0 0 0 0 Table 4-5 Dose of _ Compound Compound Cot. Soy. Rad. Ca~. Egg.
No.(g/a) 10~ O O O O O

' 100 O O O O O

Claims

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

1. A heterocyclic ether type phenoxy fatty acid derivative having the formula (I) wherein X represents a halogen atom: n is 0, 1 or 2: R1 represents a hydrogen atom or a lower alkyl group: R2 repre-sents -OH, an -O-alkyl group, an -OM group wherein M is an in-organic or organic salt moiety, -NR3 R4 group, an -O- lower alkenyl group, an -O-benzyl group, an -O- lower alkyl-alkoxy group, the -O-phenyl group, the -O-cyclohexyl group, an -O-haloalkyl group, an -O- lower alkynyl group, or an -O-cyano-alkyl group; R3 and R4 respectively represent a hydrogen atom or a lower alkyl group.

2. A heterocyclic ether type phenoxy fatty acid derivative having the formula (VIII) wherein X1 and X2 respectively represent a halogen atom or a hydrogen atom; R5 represents -OH, an -O-alkyl group, an -OM group wherein M is an inorganic or organic salt moiety, an -O- lower alkenyl group, an -O-benzyl group, an -O- lower alkylalkoxy group, the -O-phenyl group, the -O-cyclohexyl group, an -O-haloalkyl group, an -O- lower alkynyl group, or an -O-cyanoalkyl group.

3. Methyl 2-[4-(2-quinolyloxy)phenoxy]propionate.

4. Methyl 2-[4-(6-fluoro-2-quinolyloxy)phenoxy]
propionate.

5. Ethyl 2-[4-(6-fluoro-2-quinolyloxy)phenyl]
propionate.

6. Methyl 2-[4-(6 chloro-2-quinolyloxy)phenyl]
propionate.

7. Ethyl 2-[4-(6-chloro-2-quinolyloxy)phenoxy]
propionate.

8. n-Propyl 2-[4-(6-chloro-2-quinolyloxy)phenoxy]
propionate.

9. i-Propyl 2-[4-(6-chloro-2-quinolyloxy)phenoxy]
propionate.

10. n-Butyl 2-[4-(6-chloro-2-quinolyloxy)phenoxy]
propionate.

11. Methyl 2-[4-(6,7-dichloro-2-quinolyloxy)phenoxy]
propionate.

12. Ethyl 2-[4-(6,7-dichloro-2-quinolyloxy)phenoxy]
propionate.

13. A derivative of the formula selected from the following compounds where X, R1 and R2 are as below

14. A method of killing weeds which comprises applying thereto a heterocyclic ether type phenoxy fatty acid derivative as defined according to claim 1, 2 or 3.

15. A method of killing weeds which comprises apply-ing thereto a heterocyclic ether type phenoxy fatty acid derivative as defined according to claim 4, 5 or 6.

16. A method of killing weeds which comprises apply-ing thereto a heterocyclic ether type phenoxy fatty acid derivative as defined according to claim 7, 8 or 9.

17. A method of killing weeds which comprises apply-ing thereto a heterocyclic ether type phenoxy fatty acid derivative as defined according to claim 10, 11 or 12.

18. A method of killing weeds which comprises apply-ing thereto a heterocyclic ether type phenoxy fatty acid derivative as defined according to claim 13.

19. A process for producing a heterocyclic ether type phenoxy fatty acid derivative having the formula (I) wherein X represents a halogen atom; n is 0, 1 or 2; R1 repre-sents a hydrogen atom or a lower alkyl group; R2 represents -OH, an -O-alkyl group, an -OM group wherein M is an inorganic or organic salt moiety, -NR3 R4 group, an -O- lower alkenyl group, the -O-benzyl group, an -O- lower alkyl-alkoxy group, the -O-phenyl group, the -O-cyclohexyl group, an -O-haloalkyl group, an -O- lower alkynyl group, or an -O-cyanoalkyl group;
R3 and R4 respectively represent a hydrogen atom or a lower alkyl group which comprises reacting a compound having the formula (VI) wherein X and n are defined above, and a halide having the formula (VII) wherein X and n are defined above and Hal represents a halo-gen atom; or reacting a compound having the formula (II) wherein X, n, and Hal are defined above; with a 4-hydroxy-phenoxy fatty acid derivative having the formula (III) wherein R1 and R2 are defined above, in the presence of an inorganic or organic base.