CA1044912A - Herbicidal compositions - Google Patents
Herbicidal compositionsInfo
- Publication number
- CA1044912A CA1044912A CA234,775A CA234775A CA1044912A CA 1044912 A CA1044912 A CA 1044912A CA 234775 A CA234775 A CA 234775A CA 1044912 A CA1044912 A CA 1044912A
- Authority
- CA
- Canada
- Prior art keywords
- herbicidal
- group
- parts
- chloro
- urea
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
- A01N35/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen containing a carbon-to-nitrogen double bond
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
Mixture of a compound of the formula wherein R1 is selected from the group consisting of hydrogen, alkyl and phenyl, R2 is selected from the group consisting of alkyl, straight or branched chain lower alkenyl, lower alkynyl, lower alkoxy lower alkyl, lower alkylthiomethyl, lower alkoxycarbonyl lower alkyl and benzyl, X is a same or different substituent which is selected from the group consisting of alkyl, lower alkoxycarbonyl, halogen, cyano, phenyl, phenyl substituted with halogen, methyl or methoxy, styryl, furyl, thienyl, 5,5-pentamethylene and 4,5-tetramethylene, n is 0 or an integer from 1 to 6;
or a hydrate or a metal salt of the compound defined herein above; and a well-known herbicide; have greater herbicidal activity.
Mixture of a compound of the formula wherein R1 is selected from the group consisting of hydrogen, alkyl and phenyl, R2 is selected from the group consisting of alkyl, straight or branched chain lower alkenyl, lower alkynyl, lower alkoxy lower alkyl, lower alkylthiomethyl, lower alkoxycarbonyl lower alkyl and benzyl, X is a same or different substituent which is selected from the group consisting of alkyl, lower alkoxycarbonyl, halogen, cyano, phenyl, phenyl substituted with halogen, methyl or methoxy, styryl, furyl, thienyl, 5,5-pentamethylene and 4,5-tetramethylene, n is 0 or an integer from 1 to 6;
or a hydrate or a metal salt of the compound defined herein above; and a well-known herbicide; have greater herbicidal activity.
Description
DFT~I_ D DF,.SCRIrTTON OF Tll INVENTION:
This invention relates to new herbicidal compositions having enhanced effeotiveness and to an improved method of killing weeds. Thc.invention consists ; in providing mixtures of herbicidal compounds which are more effective tllan the indivldual componellts. More ~flrticularly, this inventioll is directed to composi-tions containing, as active helbicidal ingredient, thc mixture of at least one `- ~0~912 -2-, compound selected from the group consisting of:
(a) the compound of the fo].lowing formula 1 [I]
O
wherein Rl is.selected from the group consisting of hydrogen, alkyl and phenyl, . R2 is selected from the group consisting of alkyl, straight or branched chain lower alkenyl, lower alkynyl, lower alkoxy lower alkyl, lower alkylthiomethyl, lower alkoxycarbonyl . lower alkyl and benzyl, . .X $s a same or differ~nt subst$t~lent wh$ch is selected Prom the group consigt$ng oE alky-L, lower alkoxycarbonyl, halogell, cyano, . phenyl, phenyl substLtuted with halogen, methyl or methoxy, styryl, furylg thienyl, 5,5-pentame~hylene and 4,5-tetramethylene, n is 0 or an integer from 1 to 6;
or a hydrate or a metal salt of the compound defined herein above; and ~ (b) at least one herbicide selected fro~ the group consisting of urea, triazine, `'carbamate, diphenylether, phenoxyacetlc acid, acid amide, diazine and fatty acid derivatives and 3-isopropyl-2,].,3-benzotlliadiazine-4-one-2,2 dioxide.
PrePerred for use of their herbic:ldal effectivcness are the mlxture of a compo~lnd of the formula C-Ri CH3 ~ 1 . ~ ~ C-R
CH3 ~ 0 , CH/ CH ~
[II] [III] [IV]
wherein Rl is ethyl or propyl group, R2 is ethyl, propyl, allyl or propargyl group and . R3 is methyl or ethyl;
~' ' ' .
~V4~9~ 3-and at least one herbiciAe selected from the group consisting of 3-me~hoxycarbonylaminophenyl-N-(3'-methylphenyl)-carbamate, 3-isopropyl-2,1,3-ben~othiadiazine-4-one-2,2-dioxide, l-phenyl-4-amino-5-chloro-pyridazone-(6), N-(3-chloro-5-methoxyphenyl)-N',N'-dimethylurea, N-(3,4-dichlorophenyl)-N',N'-dimethylurea, N-(3,4-dichlorophenyl)-N'-methoxy-N'-methylurea, 1,3-dimethyl-(3-benzothiazole-2-yl)urea, 1,3-dimethyl-3~(5-methylbenzothiazole-2-yl)urea, 1,3-dimethyl-3-(5-t-butylbenzothiazole-2-yl)urea, 1,1,3-trimethyl-3-(5-methylbenzothiazole-2-yl)urea, 1,1,3-~rlmethyl-3-(5-ethylbenzothlazole-2-yl)llrea, 1,3 dimethyl-3-(5,7-dlmethylben~othiazole-2-yl)urea and '. . .
. 1,1,3-trimethyl-3-(5,7-dimethylbenzothiazole-2-yl)urea.
Rspecially preferred for use of their herbicidal effectiveness are the mixture of a compound selected from the group consisting of , 2-[1-(allyloxyamino)propylidene]-5,5-dimethylcyclohexane-1,3-dione,
This invention relates to new herbicidal compositions having enhanced effeotiveness and to an improved method of killing weeds. Thc.invention consists ; in providing mixtures of herbicidal compounds which are more effective tllan the indivldual componellts. More ~flrticularly, this inventioll is directed to composi-tions containing, as active helbicidal ingredient, thc mixture of at least one `- ~0~912 -2-, compound selected from the group consisting of:
(a) the compound of the fo].lowing formula 1 [I]
O
wherein Rl is.selected from the group consisting of hydrogen, alkyl and phenyl, . R2 is selected from the group consisting of alkyl, straight or branched chain lower alkenyl, lower alkynyl, lower alkoxy lower alkyl, lower alkylthiomethyl, lower alkoxycarbonyl . lower alkyl and benzyl, . .X $s a same or differ~nt subst$t~lent wh$ch is selected Prom the group consigt$ng oE alky-L, lower alkoxycarbonyl, halogell, cyano, . phenyl, phenyl substLtuted with halogen, methyl or methoxy, styryl, furylg thienyl, 5,5-pentame~hylene and 4,5-tetramethylene, n is 0 or an integer from 1 to 6;
or a hydrate or a metal salt of the compound defined herein above; and ~ (b) at least one herbicide selected fro~ the group consisting of urea, triazine, `'carbamate, diphenylether, phenoxyacetlc acid, acid amide, diazine and fatty acid derivatives and 3-isopropyl-2,].,3-benzotlliadiazine-4-one-2,2 dioxide.
PrePerred for use of their herbic:ldal effectivcness are the mlxture of a compo~lnd of the formula C-Ri CH3 ~ 1 . ~ ~ C-R
CH3 ~ 0 , CH/ CH ~
[II] [III] [IV]
wherein Rl is ethyl or propyl group, R2 is ethyl, propyl, allyl or propargyl group and . R3 is methyl or ethyl;
~' ' ' .
~V4~9~ 3-and at least one herbiciAe selected from the group consisting of 3-me~hoxycarbonylaminophenyl-N-(3'-methylphenyl)-carbamate, 3-isopropyl-2,1,3-ben~othiadiazine-4-one-2,2-dioxide, l-phenyl-4-amino-5-chloro-pyridazone-(6), N-(3-chloro-5-methoxyphenyl)-N',N'-dimethylurea, N-(3,4-dichlorophenyl)-N',N'-dimethylurea, N-(3,4-dichlorophenyl)-N'-methoxy-N'-methylurea, 1,3-dimethyl-(3-benzothiazole-2-yl)urea, 1,3-dimethyl-3~(5-methylbenzothiazole-2-yl)urea, 1,3-dimethyl-3-(5-t-butylbenzothiazole-2-yl)urea, 1,1,3-trimethyl-3-(5-methylbenzothiazole-2-yl)urea, 1,1,3-~rlmethyl-3-(5-ethylbenzothlazole-2-yl)llrea, 1,3 dimethyl-3-(5,7-dlmethylben~othiazole-2-yl)urea and '. . .
. 1,1,3-trimethyl-3-(5,7-dimethylbenzothiazole-2-yl)urea.
Rspecially preferred for use of their herbicidal effectiveness are the mixture of a compound selected from the group consisting of , 2-[1-(allyloxyamino)propylidene]-5,5-dimethylcyclohexane-1,3-dione,
2-[1-(allyloxyamino)butylidene~-5,5-dimethylcyclohexane-1,3-dione, and 2-[1-(allyloxyamlno)btltylidene]-4-methoxycarbonyl-5,5-dimethylcyclohexane-1,3-dione;
and at least one herbicide selected from the group consisting of 1. .
and at least one herbicide selected from the group consisting of 1. .
3-methoxycarbonylaminophenyl-N-(3'-methylphenyl)-carbamate, ; 3-isopropyl-2,1,3-benzothiadiazine-4-one-2j2-dioxide and l-phenyl-4-amino-5-chloro-pyridazone-(6).
The herbicidal composition is chosen with view oE the crop plant and the problem weed in that area. Frequently, the~mixing of herbicides required to control certain combinations of~weeds present produces a composition not only toxic ! to the ob~ectionable weeds but also to the crop plants.
The purpose of the present invention is to provide mixtures of herbicides . ' ' ' ' ' .
- . .. j .....
~ 2 -4-.; .
which have complementary effects and will therefore control a broader number of weed but do so at lower levels of application.
In one aspect, the present invention is a novel composition comprising two kinds of selective herbicides for grass weeds and for broadleaf weeds.
It is a further object to provide an improved cmd more efficacious method for killing weeds.
The compound of above for~ula EI] is particularly effect-ive in the control of grass weeds.
It is expected that the said compound represen~ed by the above formula [I]
has the following three chemical formulae because oE tautomerism:
U IH-O-R2 ~ O_Rz Xn ~ Xn - ~ C-R
R2 ~/
[VI]
The compounds of the formula [I] can be prepared in accordance with the ~ following equation;
I OH O O NH-~-R
Xn ~ -Rl ~ NH2-O-R2 > Xn_ ~ -Rl [VII] LVIII] ~ [I] ~
wherein Rl, R2, X and n are as previously deEined.
Whén above formula[VLI]represents 5,5-dimethyl-2-acyl-3-hydroxy-2-cyclohexane-l-one, above starting compound can be prepared in accordance with the following equation:
, - r ~ -~04~ Z
(CH )2C=CHCOCH + CH2~CCH3 NaOCH3 ~
3 3 COOCH3 in CH3011 C~13- ~
. CH3 3 NaOH ~ HCQ ~ RlcocQ OH O
=7 1 ~ I ~ ~ -R
lD U2 CU ~ a CH3 ~ ~n yridine ~ o . wherein Rl is as previously defined.
It is also expected that the starting compound represented by the formula [VII~
. has the same three chemical formulae as the formula [I] because of tautomerism.
. The sodium and potassium salts are prepared by treating a compound of formula I] above with a sodium or potassiu~ hydroxide in aqueous solution or an organic olvent such as acetone, methanol, ethanol or dimethylEormamlde. The salts are isolated by filtration or by evaporation of the resulting solutlon.
The calcium, barium, manganese, copper, zinc, nickel, cobalt, iron and silver salts are prepared from the sodium salt by treatment with the appropriate inorganic . metal salt,, e.q. calcium chloride, barium chloride, copper sulfate, zinc, chloride, ~' nickel chloride, and cobalt nitrate.
.
Some of the compound of this invention may form hydrate thereof as follows:
p ~H-O-R2 NH-O-R2 Xn- ~ l 2 ~ l H O
.
- : II] [IX]
wherein Rl, R2, X and n are as previously defined.
` Some typical compounds of formula II] which can be employed in combination in the composition of .his invention are listed in Table 1.
~ '~ ' . .
,~ .
, ' ' .
,; " ~,,, - . Table :1.
. Colr,pd. No. Chc~ical l~ame Physical C:onstant __ ~
. 2-ll-(al.lyloxyamino)methyl.idenc~-5,5- m p 55 - 60C
. dimcthylcyclollexane-1,3-dione . .
~____. ____ _ ___~
2 2-[1-(et:hoxyamino)t!thy].idcne]-cyclo- m p 48 - SO~C .
. hexane-l, 3-dione . .
__ _ . 2-[1-(ethoxyalnino)etllyli.dene]~ -cyano- n 23`. 5l 5280 . 5,5-dilllcthylcyclollexRne-1~3-di()ne D ' . _ _ ___ ~
. . 4 2 [1-(cthoxyami.no)ct}lylidcne]-4-iso- n 241.5115 propylcyclohexane-].,3-dione D
_ _ __ 2-[1-(ethoxyamino)ethylidene]-4~ .- .
. ~ 5 ethoxycarbonyl-4-ethylcyclohexane- nD22 51.5047 . 1, 3-dione . ,~_ ____ . G 2- ~1- tcthoxyamino)ethylidtclle]-4-bromo- n ~ 3~ .5405 5,5-dimet:hylcyc].c-llexalle-1,3-dione D
~ . _~ .................. ~. ~_ ~ .
. . 2- [ 1- tcthoxyamillo) ethylidcne ~ -4- .
7 ethoxycarbonyl-$,5-dll~lethylcyclo- nD~Il.SOSO
hexane-1,3-di.ont _. _ ................... _ _ _~
8 2-~1-(ethoxyan~ino)ethylidene]-5- n 241.5132 ethylcyclohexanc-1,3-dione D
__~
. 2-~1-tethoxyalDino)ethylidene~-4-methoxycarbonyl--5;5-dimet}lylcyclo- nD2 51. 5065 . hexane-1,3-dione . . ~
2-~l-tethoxyamino)cth~lident!J-5,5- n 2l'51.5094 dimcthylcyclollt!xanc-1,3-di.onc D
_ _______~____ _____~
11 2~[1-tetho~xyamino)etlly]i(lelle]-5- m.p. 56 - 57C .
phenylcyclollcxanc-l,3-diolle ~ ~ __ __ ___ _ 2 2-.[1-tallyloxyamino)etllylidene]- m p 55 - 57C
cyclohcxane-1,3-dione _~ ~
2-[1-(allyloxyalllino)etllyli.dt-lle]-4- .
13 bromo-5,5-dir.lethylcyclohe~ane-1?3- ~ nD311.5468 . ~ dione .
_ . 2-[1-(allyloxyamino)ethyliàene].-4- .
. 14 cyano-S,S-dimcthylcyclohtexan~e-1,3- m.p. 78 - 80C
dione _, _ _.
. 2-[1-(allyloxyamino)ctnylidt~ne]-4-ethoxycarbonyl-5,5-diMethylcyclo- nD2~1.5128 . hexane-1,3-di.one . .
,. , __ _ _ .,.
.
. ~ -- ----. ~-11 (a~ oxy~ o ) t t~ ] i~elle ] -~l- , 16 Dle~ho~ycar~tny~-5,5-dinici}lylcyclo- nD251.5095 .
hexane-l,3-dionc ~
17 2-[1- (allyl:o~;y~mi.no) etl yli.c!ene]-5- n 2~1. 5203 ethylcyclohexant!-1,3-diollt-~ D
~ . .
1~ 2-[1-(allyloxyamino)ethylidene]-5,5- m.p. 30.5 - 31.5C
dimethylcyclohexant!-l,3-dione _ .. . 19 2-[1 (ally].oxyamino)ethy~ldt!ne]-5- m.p. 34 - 35C
.. ,. _ phenylcyclohexant-~-l,3-dione .
2 [1-(propoxyamino)et1ly].idtelle~-5,5- n '~ 51 5088 dimel:hylcyclohexane-l~ 3-dlon 21 2- [1- (etlloY.yan i.no)propyli.dene]- n 24~5l 5]88 ., . cyclollexane-l,3-dione D
__ _ .. _~ .. , ,., . ~_ _ _ . 22 2- [l- (ethoxyamitlo)propylidcene]-5- m 65 66C
. (4--Dlc~ lpllcny~.)cyc,].o~ x~llle.~1,3--di.OllC .p. --... ........ _~ ~ ___~ ..
'23 2-[1-(et:hoxyami.llo)propy~ .clcll e]-5- (3~ m ' l ~ C
. chlorophcnyl)cycloilc7:ane.1,3-cli'one .p. ~
I~ ~
24 2- [1~ (cthoY.yalilino)propylidene]-5- (4- 59 60C
. . mei-,hoxyp}lenyl) cyclohexane-1,3-dione m. p . _ . ~ ~
2 . 2-[l-(ethoxyamino)propy].idtenc]-5-(4- m 92 - 93C
chlorophenyl) cyclohcxanc -l,3-dione . p .
_ ~ .
. . 26 2-[l-(ethoxyal!i3.no)plopyi.idene]-5- . m.p. 67 - 6~C
phenylcyclohexane-1,3-dione . , .
' . .. _.. ,.
27 2- [ l- (etl oxyamlno) propyli.dene ] -5- m . p . 92 - 96 C
_ . ~styrylcyclphcY.,ille-l, 3-dlone _ ..
28 2-[1-telho.xyaillino)propyl-lclenc]-5-(2- i .p. 50-52C .
__ :~ ryl)cyclohcxana-1,3-d~.one .____ . 29 2-[1-(ethoxyalllino)propylldene]-5-(2- m. . 68- 69C
. thienyl) cyclollexane-1,3-di.olie . P
. __ _ _ __ 2-[1-(etlloxyanlino)propylidene]-5- n 201.5045 methyl.cyclohexane-1,3-dio, ne ~ D
. _ ,,. ..
31 2-ll-(ethoxyamino)propylidene]-5,5- i41 5027 . dimethylcycloht xane-l,3-di.one nD
. ~
32 2- ll- (ethoxy =amino)propylidene]-5-iso- n l 51.5111 propylcyclohe7:aFIe-1 ~ 3-tlione D . .
2- [l- (ethoxy~mino)prt,pylidene]-5- n l 8~s 1.5019 33 hexylcyclollt xane-l,3-dione D
.' . . ' ~. '--,.
~,. ' , ' .
... . ~ j ~ ~
. . ~ ~
2-~ (etlloxyalllino)propylidene]-4- .
34 methyl-5,5-dimetllylcyclohe~ne-1,3- nD2ll.5081 . . ~ dione . . .
. ___ , ._ _.
2-[].- (ethoxyfmlino)propy] idcnc] --4,4- n 18~ . 4946 ilQ~tllylcyclo~lcxan~ 3-~lionc D .
. _ _ _ _ _ 2-[l-(cthoxyamino)propylidcne]-4- .
36 cyano-5,5-dimcthylcyclohcxane-1j3- m.p. 47 -48C
. . dione .
2--[1-(ethoxyamino)propylidcnc]-4-37 methoxycarbonyl-5,5-dimc~hyl.cyclo- nD241.5070 . hexane-]., 3-dimle .
_ _ _ ~_~ _, . 2-[1-(ethoxyamino)propylidene]-/!-( 38 ethoxycarbonyl-5,5-dime~hyl.cyc].o- nnl B 1.5040 .
.. hexane-1,3-dione _._~ __ _ . 39 2-[1-(ctho~:ya!llino)propylidenc]-4-n- n 251.5078 . pro~ylcyclohcxane-1,3--dione . D
_ ~
2-[].-(etlloxyamino)prol7ylidcnc]-4-iso- n 2 ~l 5055 I . hutylcyclollcxan~ 3-dicllc D
~ . _~____ ~1 2-[1-(n~tl~xy.liethoY~yamino)prol)y].idenc]- n 271.501i ., 5,5-dimethylcyc;Lol)cxallc-1.,3-di.one D
_~ ~ ____ --. . 2-~1-(butlloxymethoxyaloillo)propyli- .
42 dcne}-5,5-dimethylcyclohexane-1,3- nD271.4927 dione .
__ . 2-ll- (me thylt1liometl-oxyamino)~ropyli- . .
43 dene~-5,5-dimetllylcyclohexanc-1,3- nD271.5582 dione .
~. . _ ~ . ~
`~. ~ 2-[1-(methylthio;nethoxyaniino)propyli- n 271 5328 ~4 dene]-5-isopropylcyclollcYnne-l,3-dione D
___ _ _.~
2-[l-(metlloxycthoxyamino)propylidene]- n 20l.5100 . 5~5-dimctllylcyclohexane-1,3-diolle D
. _ __ ~ _ _ _ ._ 2-[1-(et.hoxyc~rbonyl.metlloY.yalllino)plo-46 pylidenc]-4,4-dimethylcycloheY.ane-1,3- nD21.50l9 dione -. ~
_ 2-[l~(propoxyamino)propylidelle]-5,5- n 261.4994 . ~7 dimethylcyclohexane-1,3-dione D .
, _ __ . ~8 2-[l-(~llyloxyamino)propylidene]- n 251.5265 . ~ cyclohexane-1,3-divne D
_ __ .. 49 2-[1-(allyloxyamino)propylidene]-5-n 2D-5 1.5200 . methylcyclohexane-1,3-dionc D . . ..
.
. 2-~1-(allyloxyamino)propylidcnc]-5,5- 2 41 5Ll9 dimethy'.cyclollcxanc-1,3-dionc D ' __ _ ' , . . _ . _ .
.. .
:~
~3~ , 9 _ ____.__ . . __~
5l 2-[1-(allyloxyamillo)propylidene]-5- n 23-51 ~ 0 . isopropylcyclohcxane-1,3-dione D .
. ~ ~ _._ . 2 2~ (al].yloxyalllino)propylidcnc] 5- n le 51.5082 .5 11exy].cycl~llexanc-1,3-lione D
___ ~ . .. ~
53 2 [1-(allyloxyamino)prn~)ylidene3-5- 221.5bS2 .
(2-furyl)cyclohcxlllc-1,3-dionc D
_ _ 5' 2-[1-(allyloxyamino)propylidene]-5- m p 48- 50C
. ~ phenyl.cyclohcxane-1,3-dione , .
., . _ _ . 55 2-[1-(allyloxyalr~ o)propylidene]-5- n 211.5851 fityrylcyclohexane-1,3-dione D
2-[1-(allyloxyamino)propyli.dcne~-4-f 56 bromo-6,6-dimethylcyc]ohexane-1,3- nD271.5338 . . dione .. _ . 2-[1-(allyloxylmino)propylidcne]-4-. 57 bromo-5,5-dimethylcyc].ohexane-1~3- nD261.53G5 dione ~ ~
. . 2-[1-(~llyloxyami.n(-)pfol~yliclene]--4- .
. . 58 cyano-5,5-di.rncLl)ylcy:lohexalle-i,3- m.p. 62-63C
. . dione . ~ , ._ . 2-[1-(allyloxya~ino)propylidene]-"-59 methoxycar~onyl-5,5-dir.lethylcyclo- n~2 I.S 1. 5088 hexane-1,3-dione _ . _ . 2-11-(a].].yloxyamino)propylidene]-4- .
cthoxycar~onyl-5-mcthylcyclohcxane- nD2Dl.5146 . .
. . 1,3-dione .
. _ _ . _ .. . ....... ~
2-[1-(allyloxyaDIino)propylidene]-4- .
61 etlloxycarbonyl-5,5-dimetllylcyclo- nDI81.5079 hcxanc-1,3-dione .
. , _ ~
62 2-[1-~ally}.oi;yami.llo)prc-pylidene]-4-etllo- . 1 22l 5078 xycarbonyl-4-ethylcyclohexane-1,3-dion ID
. . _ . ,.
2-[1-(ally].oxyamino)propylidene]-'l- .
63 methyl-5,5-dimethylcyclohcxanc-1,3- nD2'1.5138 dione ~
_ . _ . 64 2-[1-(allyloxyamino)propylidene]-4,4- n 1~1.5138 dimethylcyclohexane-1,3-dione D
. _ _ . - -65 2-[1-(ailyloxyamino)propylidene]-4- n 21.5152 . -. i~opropylcyclohexane-1;3-dione D
~--~_ ___._ 66 2-[1-(allyloxyamlno)propylidene]-'l~n n 2 5l . 5103 .
. propylcyclohexane-1,3-d~.one . I) . _ _ _ _ ~
67 2-[1-(allyloxyamino)propylidene]-'~-n- n 2 I- 5 1, si34 . . butylcyclohexane-].~3-lionc D
. . __~ _ _ ~ ' .
.
.
., .~ . .
~` ¢
~ -- -68 2-[1-(allyloxyan~ o)propyl.i~lene]-4- n 2 5l, 5091 n-pentylcyclohexana-1,3-diona D
69 ~-[I.-(I)ropargyloY.y.;~ ino)propylidene]- n la- 51 , 5218 595-dimetllyleyclohexane-1,3--dione D
~ .
2-ll-(methallyloxyamino)propy].idene]- n 231 5107 . 5,5-dimethylcyelohexane-1,3-clione D
__ ~ .
71 2-ll-(n-butoxyamino)propy~.idene]-5,5- n ~8-51.5027 . . dimat.hyleyelollexane-1,3-diolle . D
.... .. . __ _ _ 72 2-[1-(isobutoxyami.no)propylitlene]- n 2 31 4976 . 5,5-dimethyleyelohexane-1,3-dione D
_ _ _ . 3 2-[1-(benzyloxyamillo)propy].i.delle]-5,5- m p ~58-59C
I 7 dimethylcyelohexane-1,3-di.one . .
~_ . _ 7~ 2-[].-(methoxyamlllo)l)~ltylidene]-5,5-- n 2 31. ~l940 . ~ dimethylcyelolle~:ane-1,3-diona D .
--~ . ~__ 2-~1-(el:l~oxyamillo)blltyli;d~lle]~5,5- l~ 2l1.49GS
. dlma~hyleyclollexalla-1,3-di.ollo D
. _ _____________ ~_ ~
. . 2-[1-~ethoxyamino)butylidene]-5- n 151 5068 . 76 isopropyleyelohexane-1,3-diolle D
. .. . . _ . _ __ 77 2-~1-(ethoxyamino)l-utylidene]-5- n ~ 8~S 1. 5005 hexyleyelohexane-1,3-dione D
. _~ .
. 2-[1-(ethoxyamino)l~utylidene]-4-78 eyano-5,5-dimethylcyelohexane-1,3- m.p. 83-87~C .
dione . .
.. . __ 2-[1-(ethoxyamino)butylidellQ]-4- .
79 ~etlloxyearbonyl-5,5-dlmethyl- nD2 4~5 1- 5007 . eyelolla~ne-1,3-dione .
__ ______ _ ._ . 2-[1-(etl~oxyamino)butyli.dene]-.'~- .
etlloxycarbonyl-5,5-dimetllylcyclo- . nD2l 51.4990 . hexana-1,3-dione _ _ 2-ll-(etlloxyamino)b~ltylidene~-4,4- n 201.5050 . . . 81 dimethylcyclollexane-1,3-dione . D
_ _ ~
. 82 2-[1-(isopropor.yamino)butylidenel- n 3l1.4939 ..
, . . 5,5-dimethylcyclohexane-1,3-dione D
. .
2-[l-(allyloxyamino)b~tylidene]-5,5- n 2l1.50S9 33 dimethyleyc].ohexane-1,.3-dione D
. . . ._ 2-[1-(allyloxyamino)butylide.ne]-5- n 181. 5135 .
84 isopropylcyclohexane-1,3-dione . D
'. ' _ . ,-- . _ .'.
~, ' ' ' ' ' ,.
~. . . .
3~
, _ ~ _ ___ __ ~____ _ . -2-[1--(al].yloxyam~ o)b~ltylidenc]-5- n la S 1.5051 . hexylcyelolle:~ane-1,3-dione D
_ ~
86 2~ (ally].oxyal!lino)b~lty:l.idcne]-5- m p 52 - 53C
(4-mcthoxyi henyl)cyclohex~ne-l.,3-dionc _.~
2-~ nl.lyloxyar.lino)butylidelle~--5- n 25.5 l 5657 87 (3-ch].orophenyl)cyclohtexalle-].,3-dione D
_ . 2-ll-(a].lyloxyamino)bntylidene]-5-m p 36 - 37~C
88 (~I-ch].orophcnyl)cyclohexanc-1,3-dionc. . .
. __ ~ . . __ .. . 2 ~ allyloxyamino)butylidelle]-4-89cyano--5,5-dimet:llylcyclohc:xane-1,3- m.p. 105 - lO~C
. dione .
_ ~___ .. . 2-[1-(allyloxyamino)but:ylidene]-4-J,~etho~:ycarl~onyl-5,5-dimethylcyclo- nD24-~ ].. 50G3 hexane-1,3-dion.
. ~ ~ . . _ 2-[1-(allyloxyamino)butyli(lene]-4- 2~
91 ethoxyca~bonyl-5,5-dimcthylcyclo- nD 1.5066 . . hexanc--1,3-dionc .
__ ~ ___ _._~ __ . 2-[1-(,ll].yloxyal~ lo)bll~;yli.clcllc]-ll-92 et:hoxycarbonyl-~l-cChylayclollcxane- nD2~-5 1.5078 1,3-dionc . 2-[l-(allyloxya~ llo)hul:ylidellc]-ll~4- n ~ 7$3 93 dimethylcyclollexane-1,3-di.onc D
_ _ _ . _ _ __ 94 2-[1-(allyloxyalrlino)butylidcnc]-4- n 2 3~5 1, 5058 isopropylcyclollcxane-1,3-diolle D .
2-[1- (propar~yloxyamino)l)utyl.i.dene]- n 3~1.5132 5,5-dimcthylcyclolle-,:ane-1,3-dione D
., _ __ _ ___ ___ .
96 2-[1-(hcxyloxyamillo)butylidene]-5,5- n 251 ll725 . dioe~:hylcyclolle~ ane-l,3-dionc D
_~_~_ .~_ ~,,~ .
2-[1-(etlloxyamirlo)isol)~ltylidene]- n 2 31 5013 97 5,S-dimethylcyclohcxane-1,3-dione D
. _~ __., 2-[1-(et:lloxyamlno)llcxylidenc]-5,5- n 3l~ 4~81 98 dimethylcyclohcxallc-1,3-dionc ` D
. . . _ . 99 2-[1-(~llyloxyamino)hexylidene~-5,5- ~ 3l1.5040 dimethylcyclollexane-1,3-dione D .
_ .
lO0 2~ (ethoxyamino~b~nzylidcne]-5,5- m p. lS0-151C
di.methylcyclohexane-1,3-dione .
. _ .
101 2-¦1- (allyloxyamino)bcnzylidcne]-5,5- m.p 169 - 170C
dimethylcyclohexanc-1,3-dione .
.. . . ,~ . .' ' ' ' ..
~ , .. .
~ 12- . .
.
. ~ . ______ 102 2-[l--(e~hoxyaGIino)pro~yl.i(lelle]--5~5- n 2l1.527? .
pentamcthylenccyclollexane-1,3-dlone ~ I
' _ _ __.................... _ _ _ 103 2-El-(allyloxyanillo)propylidene]-5,5- n 2~1.5336 pentame~llylenecyclohexanc-],3~dione D
, ~ __ _ __ __ .__ _ 104 2-[1-(ethoxyamino)propylidene]~ 5- n 2 ~1.5282 tetrameLllylcnecyc].ol-eYane-1,3-dione D
. _ ~_ 105 2-[1-(a~.lyloxysmino)propylidelle]-4,5- n 211.5347 .
. te~rametllylenecyclohexane-1,3-di.one D
~ _ . _~ __~
.- ~langanese salt of 2- [1- (ethoxyamino)-106 . ethylidene]-5,5-dimethylcyclollexanc~ m.p.225-226 DC (d.) 1,3-dione .- ~~ 1----Potassium salt o~ 2-[1-(cthoYyamino)- ~
~ 107 et}~yli.dcne]-5,5-dilnethylcyclohexane- m.p.110-112C(d.) .
: 1,3-dionc . ___ ~
Copper ~alt o 2-[.1.-(ethoxyam:i.no)- .
108 etl-ylidealc]-5,5-dimcthy~jcyclollexane- m.p.].56-157C(d.) 1,3-di.onc . __ _ __ _ __~_ _____ . Copper sal~ of 2--[l--(cthoxy~millo)-ios ethylidcne]-4-cyano-$,5-diD)ethylcycl.o- m.p.l61-164C(d.) hexane-1,3-dione . _ _ _ . . Sodium salt o~ 2-[1-(etlloxyamillo)- .
. 110 ethylidene~-4-methoxycarbonyl-5,5- m.p.llO-120DC(d ).
di.methylcyclohexane-1,3-dione . _ . Copper salt of 2-[1-(allyloxyan~i.no)-111 ethylidene]-5-ethylcyclohexane-1,3- m.p.l64-165DC(d.) dione . : .
.. . , ______ . Coppcr salt o~ 2-[l-(allyloxyamino)-112 ethyli.dene]-5-phe~ylcyclohexar,e 1,3- m.p.l88-l.89~C(d.). dione . _ _ .
Copper salt o~ 2-[l-(allyloxyar.~ino) 113 etl-ylidcne]-4-cyano-5,5-dimethylcyclo- m.p.l54-158 DC ~d.)-hexane-1,3-dione .
. . ~
Sodium salt o~ 2-[1-(al~yloxyalnino)- -`
.114 ethylidene]-4-methoxycarbonyl-5,5- m.p.l~3-194C(d.) . . dimethylcyclohexane-1,3-dione _ ._ . Sodium salt of 2-[1-(allyloxyamino)-115 ethylidene]-4-ethoxycarbonyl-5;5- m.p.llO-120DC(d.) .
dimethylcyclolleXanc-1,3-diol c _ Copper salt of 2-11-(methyltllio-116 metho~yamino)propyl.idene]-5,5- m.p. 110 D C (d.) . dimethylcyclohexane-1,3-dione .
_ - '. __ ... .... .. . ... . . ..
( , _~_ _ Co~-pcr salt of 2-[l-(el:hoxyamino)-117 propyli~cne]-5-(2-furyl~cyclchexane- m.p.l97-1~8C(d.j . 1,3-dione .___.__ . _, ._ Copper salt of 2-Ll-(ethoxyalllirlo)-118 propylidenc]-~5-(2-~hienyl)c~clollexane- m.p.]84'-]85Ctd.) ~3-dlone .
_ ___ __._ __~
opper salt of 2-[1-(ethoxya~ino)-119 propylidene~-S-(4-chlorophenyl)- m.p.lS6-188C(d.) ~ cyc]ohexanc-1,3-dione ___ __ .- , . Copper sa~t of 2-[1-(cchoxya~lino)-120 p~op)~lidene~-~-(3--chlororhenyl)- m.p.l84-185C(d.) cyclohexanc-1,3-clione _ __~__ ___ .' Copper salt or 2-[1-(ethoxyalnino)~
121 , propyliderle3-5-(4-methylphellyl)- m.p.l83-184C~d.) cyclohexane-1,3-di,one _ . _~ ~
. Copper ~alt o 2-[1-tcthoxynmlno)-122 propyli~lenc] 4-cyano-5,5 di~ne~llyl- m.p. ôl~83Dt:(d.) _ _ cyclohexane-1,3-diona Sodiun~ salt Or 2-[l-(c~hoxyrlml;lo)-123 propylidene]-4-e~lloxycal~olly]--5,5- m.p.l88-190C(d.) dime~hylcyclolleY~ane-1,3-dione . ~ ~ __ 124 Copper salt of 2-~1-(al]yloxyamino)- m.p.146-147C(d.) propylidene~-cyclohexane-1,3-dione :.- . _~ _ _ Copper salt of 2-~1-(al]yloxya~lino)- .
125 propylidene]-5-methylcyclol~exane- m.p.129-130C(d.) 1,3-dione ___ . . ___.~
Nicliel sal~ of 2-El-(allyloxyamillo)~
126 propylidene3-5,5-dime~llylcyclohexanc- m.p.169-170C(d.) 1-,3-dione.
_ _,_____ ~--__ Calcillm salt of 2-[1-(allyloxyamino)-' 127 propylidenc]-5~5-dimel:llylcyclohexalle- m!p.107-108C(d.) . 1,3-~lione __ _ _ _ _ Cobalt ~alt of 2-[1-(al],yloxyamino)-120 propylidene3-5,5-dimethylcyclollexane- ~ m.p.l51-152C(d.) 1,3-dione . , -_ _ _ .
Copper salt of 2-~1-(allyloxyamino)-. 129 propylidelle]-5-isopropylcyclohexane- m.p.l45-146C(d.) 1,3-dione _ _ ____ ~__ Copper ~,alt of~2-[1-(allyloxyamino)-130 propylidene]-4-cyano-5,5-dimethyl- m.p. 78-80C(d.) . eycloliexane-1,3-dione .
.' , ' .
, .
r : L~4~
_. . ~ . . ' Sodiu~ salt o 2-~1-(allyloxyamino)-131 propylid~ne]-4~methoxycarl,onyl-5,5- m.p.l75-178C(d.) dimetllylcyclollexane 1,3-dione . . ~ _ __ Sodium salt of 2-[1-(al]~loxyarlino)-132 propylidelle]-ll-e~lloxycar~ollyl-5,5- m.p.110-120C(d.) dimethylcyc]ohexane-1,3-dione .
_ ~_ . .
Calcium salt of ~-[l-(allyloxyamino)-133 propylidene]-4-propylcyclohexalle- m.p.l50-152C(d.) 1,3-dione ~_ _ _ _ . Copper salt of -?-[l-~proparsyl~xy-.
134 amino)pro~ylidene~-5,5-dimethylcyclo- m.p.l26-127C(d.) . hexane-1,3-dione . __ Barlum salt of 2-[1-(propoxyamino)-135 propylidene]-5,5-dimethylcyc]ohexane- m.p. 75-7~C(d.) 1,3-dione . _ ,, ~.__ __ Calcium salt o~ 2-[1-(i~ol~i!toxyamlllo)-136 propylidene]-5,5--dillletl~y]cyc]ollexane- m.p.l95-200C(d.) 1,3-dione _ . ~ ~
. Copp~ salt of 2-[l~(bu~oxyamitlo)--137 propyllclene]-5,$-dimethylcyc~ohexane- m.p.l23-12$C(d.) 1,3-dione -. _ _ . Calcium salt of 2-~1-(ethoxyamino)-138 butylidene3-$,5-dimethylcyclohexane- m.p. 180~C(d.
1,3-dione _ ,___ _ Copper salt of 2-~1-(ethoxy~mino)-139 butylidenel-4-cyano-5,5-dimethyl- m.p. 98-101C(d.) cyclohexane-1,3-c;ione ,. . , , , .._ .; Sodium salt of 2-El-(ethoxyamino)-140 butylidene]-4-methoxycarbonyl-5,$- m.p.lS3-18$C(d.) . dimethylcyclohexane-1,3-diorle __ _ __ _ _ _.___ Nickel salt of 2-[1-(ally~oi:yamino)-141 butylidene]-5,5-dimethylcyclollexane- >~ p. 250C(d.) 1,3-dione . __ _ Cobalt salt of 2-[1-(allyloxyamino)- ~
142 butylidene]-5,5-dimetllylcyclohexane- - m.p.l53-154C(d.) 1,3-dione ~
_ Sodium ~al~ of 2-[1-(allyloxyamino)-143 butylidene]-5,5-dimethylcyGlohe~:ane- m.p. 80-82C
1,3-dione .
. -_ ______ Copper sa]t of 2-[1-(allyloxyamino)-144 butylidene]-5-isopropylcyclohexane- m.p.l45-146C(d.) . 1,3-dione '. , . ,_ _ ,, . .
, ' . ~ .
z . Copper salt o~ 2~ (ally~oY~yal,llno)- 0 145 butylidcnc~--5-hcxcylcyclollcxan~-1 3- m.p.105-106 C~d.) dione __ ~
. . Copper salt oL 2~~1- (allyloxyamino)-146 butylidenel-5--(fi-motlloxypl~enyl)cyclo- m.p.l82-183C~d.) hexane-1,3-dione . _ Copper salt o 2-11-(allyloxyamino)- O
147 butylidene]-4-cyano-5,5-dimethyl- m.p. 92-95 C(d.) cyc]ohexane-1,3-dione . __ _ . . ~_ _ ~
Sodium sall: of 2-[1- (allyloxyamino)-148 butylidenel-4-mctiloxycarbonyl-5 5- m.p. 192C(d.) . dimcthylcyclohexane-1,3-dione . _ __ ~ _ _ .- Sodium salt of 2-[1-(allylo-. yamino)-~- 149 buty]idene]-4-etlloxycarbony]-5 5- m.p.llO~ 120C(d.) dimethylcyclollexalle-1,3-dione _ _ ___ _ _ Copper salt of 2-[1-(benzyloxyamino)- O
150 buty]idene]-5j5-dimetllylcyclollexane- ~ m.p.126--127 C(d.) 1,3-dione _ ~ . _ _ Coppcr ~alt of 2 ~l-(all)~]oxyanlino)- O
151 propylidene]-4~5-tel:rame~llylellccyclo- m.p.l78-179 C(d.) hexanc-1,3-dionc _ ___ . _____ _ ____.
2 2-~1- (allylo :yantino)but-y]idclle]-5,5- m.p. 47-l~9C
dimethylcyclohcxane-1,3-d-ionc hydrate .
~ _ ~____ ~ .
153 2-[1-(allyloxyamino)propylidenc]-5,5- m.p 52-54C
. dimethylcyclohexane-1,3-d;cne hydratf ~ _ _.
2-~1- (allyloxyamino)p~opylidenc]-5~ m.p. 46-48C
154 meth~,lcyclohexane-1,3-dione hydrate . _ __~__ ~ _ _ r 2-[1-(allyloxyamillo)propylidene]-5- m.p 48-50C
15.~ phenylcyclohexanc-1,3-dione hydrate .
__ __ . ~
156 2-[1-(ethoxyamillo)propylidene]-5- m.p. 67-68C
~_ plienylcyclollcxane-1,3-dione hydrate .__... ~ I
' . . .
- . m.p.: n~el~in~ polnt nD: re~Xactive index d. : decomposition .
.
.
. ~' ' ' ' ' ' , - ' ' ' .
.
. ~16-f~",~
}lereinater, the compounds of this inventioll are represented by Compound No. in Table 1.
As mentioned previously, it has been found that the mixture of a compollrld of formula [I] and a well-~nown herbicide may have a synergetic herbiciclal activity in addition to a ~umu].atively increased activity of those each selective herbicidal.
functions.
The paragraphs which follow describe in more detail the utility of this invention.
Suitable urea derivatives for the practice of this in~ention are:
.
Chemical Name Common Name N-(3 chloro-4-metllcxyphenyl)~N.',N'~di.metllylllrea metoxuro N-(3,~-dlchlorophc-nyl)-N~,N'-dimethylure~ diuron N-(3,4-dichlorophenyl)-N'~metlloxy-N'~methylurea linuron 1,3-dimethyl-(3-benzothiazole-2~yl)urea methabenztlliazuron 1,3~dimethyl~3~(5-methylbenzo~hiazole-2-yl)urea (abbreviation : ~) 1,3-dimethyl~3-(5-t-butylbenzothiazole-2-yl)urea (abbrevlation : B) 1,1,3-trimethyl-3-(5-methylbenzothiazole-2-yl)urefl (abbreviation : C) 1,1,3-trimethyl-3-(5-ethylben~othiazole~2~yl)urea (abbreviation : D) 1,3-dimethyl-3-(5,7-dimethylbenzothia~ole-2-yl)urea (abbrevi~ti.oll : E) Ill.p. 131-13~C
1,1,3-trimetl-yl--3-($,7-dimethylbenzothi~ole-2-yl~urea (abbrevi.fl~lon : F) . m.p. 95-96C
These metoxuron, dîuron and linuron etc. are used for controlling mainly broad-leaf weeds in numerous crops such as soybean, po~atoes and ca`rrots etc., bu~ thei.r herbicidal effect for grass weeds is inferior and there is high possibility to cause phyto-toxicity in case of fol.iar trefltment.
~ lowever, by means of blending a compound of formula [I] with above-mentioned ureas herbicide~ the mi~ed herbicidal composition-is able to kill comple~ely both ' , , lU~lZ -17-grass and broad leaf weeds in smaller amount of application rate compared with the individual components and ~urthermore, the said mixed herbicidal composition does not show phyto-toxicity to the crops, mainly because of reduced amount of compound applied.
Suitable triazine derivatives herbicides for the practice of this invention are:
Chemical Name Common Name 2-chloro-4,6-diethylamino-1,3,5-triazine simazine 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine atrazine 2-chloro-4,6-diisopropylamino-1,3,5-triazine propazine 2-methyimercapto-4-ethylamino-6-isopropylamlno-1,3,5-tria~lne ametryne 2-methylmercapto-~,6-dilsopropylamlno-1,3,5-~rlazlne prometryne , These triazine herbicide are mainly used as a selective herblcide for control of broadleaf weeds in wheat, rice and corn etc., but their herbicidal - effect for grass weeds is inferior and there is high possibility to cause phyto-toxicity to crops ln case of foliar treatment.
~ lowever, by means of blending a compound of formula [I] with above-mentioned triazlne herbicides, the mixed herbicidal composition is not only able to kill comp:letely both grass and broadleaf weeds ln smaller amoun~ oE application rate compared with tlle individual components, but also the sald mixed herblcidal com--position does n~t show phyto-toxicity to the crops, mainly because of reduced amount of compound applied.
Suitable carbamate herbicides for the practice of this invention are:
Chemical Name Common Name 3-methoxycarbonylaminophenyl-N-(3'-methylphenyl)-carba~ate phenmedipham methyl N-(3,4-dichlorophenyl)carbamate swep ~` ~V~,~9~
isopropyl N-(3-chlorophenyl)calbamatc ch].oropropham s-(4-chlorobenzyl.)-N,~-dietllyltlliol carbamate bentlliocarl
The herbicidal composition is chosen with view oE the crop plant and the problem weed in that area. Frequently, the~mixing of herbicides required to control certain combinations of~weeds present produces a composition not only toxic ! to the ob~ectionable weeds but also to the crop plants.
The purpose of the present invention is to provide mixtures of herbicides . ' ' ' ' ' .
- . .. j .....
~ 2 -4-.; .
which have complementary effects and will therefore control a broader number of weed but do so at lower levels of application.
In one aspect, the present invention is a novel composition comprising two kinds of selective herbicides for grass weeds and for broadleaf weeds.
It is a further object to provide an improved cmd more efficacious method for killing weeds.
The compound of above for~ula EI] is particularly effect-ive in the control of grass weeds.
It is expected that the said compound represen~ed by the above formula [I]
has the following three chemical formulae because oE tautomerism:
U IH-O-R2 ~ O_Rz Xn ~ Xn - ~ C-R
R2 ~/
[VI]
The compounds of the formula [I] can be prepared in accordance with the ~ following equation;
I OH O O NH-~-R
Xn ~ -Rl ~ NH2-O-R2 > Xn_ ~ -Rl [VII] LVIII] ~ [I] ~
wherein Rl, R2, X and n are as previously deEined.
Whén above formula[VLI]represents 5,5-dimethyl-2-acyl-3-hydroxy-2-cyclohexane-l-one, above starting compound can be prepared in accordance with the following equation:
, - r ~ -~04~ Z
(CH )2C=CHCOCH + CH2~CCH3 NaOCH3 ~
3 3 COOCH3 in CH3011 C~13- ~
. CH3 3 NaOH ~ HCQ ~ RlcocQ OH O
=7 1 ~ I ~ ~ -R
lD U2 CU ~ a CH3 ~ ~n yridine ~ o . wherein Rl is as previously defined.
It is also expected that the starting compound represented by the formula [VII~
. has the same three chemical formulae as the formula [I] because of tautomerism.
. The sodium and potassium salts are prepared by treating a compound of formula I] above with a sodium or potassiu~ hydroxide in aqueous solution or an organic olvent such as acetone, methanol, ethanol or dimethylEormamlde. The salts are isolated by filtration or by evaporation of the resulting solutlon.
The calcium, barium, manganese, copper, zinc, nickel, cobalt, iron and silver salts are prepared from the sodium salt by treatment with the appropriate inorganic . metal salt,, e.q. calcium chloride, barium chloride, copper sulfate, zinc, chloride, ~' nickel chloride, and cobalt nitrate.
.
Some of the compound of this invention may form hydrate thereof as follows:
p ~H-O-R2 NH-O-R2 Xn- ~ l 2 ~ l H O
.
- : II] [IX]
wherein Rl, R2, X and n are as previously defined.
` Some typical compounds of formula II] which can be employed in combination in the composition of .his invention are listed in Table 1.
~ '~ ' . .
,~ .
, ' ' .
,; " ~,,, - . Table :1.
. Colr,pd. No. Chc~ical l~ame Physical C:onstant __ ~
. 2-ll-(al.lyloxyamino)methyl.idenc~-5,5- m p 55 - 60C
. dimcthylcyclollexane-1,3-dione . .
~____. ____ _ ___~
2 2-[1-(et:hoxyamino)t!thy].idcne]-cyclo- m p 48 - SO~C .
. hexane-l, 3-dione . .
__ _ . 2-[1-(ethoxyalnino)etllyli.dene]~ -cyano- n 23`. 5l 5280 . 5,5-dilllcthylcyclollexRne-1~3-di()ne D ' . _ _ ___ ~
. . 4 2 [1-(cthoxyami.no)ct}lylidcne]-4-iso- n 241.5115 propylcyclohexane-].,3-dione D
_ _ __ 2-[1-(ethoxyamino)ethylidene]-4~ .- .
. ~ 5 ethoxycarbonyl-4-ethylcyclohexane- nD22 51.5047 . 1, 3-dione . ,~_ ____ . G 2- ~1- tcthoxyamino)ethylidtclle]-4-bromo- n ~ 3~ .5405 5,5-dimet:hylcyc].c-llexalle-1,3-dione D
~ . _~ .................. ~. ~_ ~ .
. . 2- [ 1- tcthoxyamillo) ethylidcne ~ -4- .
7 ethoxycarbonyl-$,5-dll~lethylcyclo- nD~Il.SOSO
hexane-1,3-di.ont _. _ ................... _ _ _~
8 2-~1-(ethoxyan~ino)ethylidene]-5- n 241.5132 ethylcyclohexanc-1,3-dione D
__~
. 2-~1-tethoxyalDino)ethylidene~-4-methoxycarbonyl--5;5-dimet}lylcyclo- nD2 51. 5065 . hexane-1,3-dione . . ~
2-~l-tethoxyamino)cth~lident!J-5,5- n 2l'51.5094 dimcthylcyclollt!xanc-1,3-di.onc D
_ _______~____ _____~
11 2~[1-tetho~xyamino)etlly]i(lelle]-5- m.p. 56 - 57C .
phenylcyclollcxanc-l,3-diolle ~ ~ __ __ ___ _ 2 2-.[1-tallyloxyamino)etllylidene]- m p 55 - 57C
cyclohcxane-1,3-dione _~ ~
2-[1-(allyloxyalllino)etllyli.dt-lle]-4- .
13 bromo-5,5-dir.lethylcyclohe~ane-1?3- ~ nD311.5468 . ~ dione .
_ . 2-[1-(allyloxyamino)ethyliàene].-4- .
. 14 cyano-S,S-dimcthylcyclohtexan~e-1,3- m.p. 78 - 80C
dione _, _ _.
. 2-[1-(allyloxyamino)ctnylidt~ne]-4-ethoxycarbonyl-5,5-diMethylcyclo- nD2~1.5128 . hexane-1,3-di.one . .
,. , __ _ _ .,.
.
. ~ -- ----. ~-11 (a~ oxy~ o ) t t~ ] i~elle ] -~l- , 16 Dle~ho~ycar~tny~-5,5-dinici}lylcyclo- nD251.5095 .
hexane-l,3-dionc ~
17 2-[1- (allyl:o~;y~mi.no) etl yli.c!ene]-5- n 2~1. 5203 ethylcyclohexant!-1,3-diollt-~ D
~ . .
1~ 2-[1-(allyloxyamino)ethylidene]-5,5- m.p. 30.5 - 31.5C
dimethylcyclohexant!-l,3-dione _ .. . 19 2-[1 (ally].oxyamino)ethy~ldt!ne]-5- m.p. 34 - 35C
.. ,. _ phenylcyclohexant-~-l,3-dione .
2 [1-(propoxyamino)et1ly].idtelle~-5,5- n '~ 51 5088 dimel:hylcyclohexane-l~ 3-dlon 21 2- [1- (etlloY.yan i.no)propyli.dene]- n 24~5l 5]88 ., . cyclollexane-l,3-dione D
__ _ .. _~ .. , ,., . ~_ _ _ . 22 2- [l- (ethoxyamitlo)propylidcene]-5- m 65 66C
. (4--Dlc~ lpllcny~.)cyc,].o~ x~llle.~1,3--di.OllC .p. --... ........ _~ ~ ___~ ..
'23 2-[1-(et:hoxyami.llo)propy~ .clcll e]-5- (3~ m ' l ~ C
. chlorophcnyl)cycloilc7:ane.1,3-cli'one .p. ~
I~ ~
24 2- [1~ (cthoY.yalilino)propylidene]-5- (4- 59 60C
. . mei-,hoxyp}lenyl) cyclohexane-1,3-dione m. p . _ . ~ ~
2 . 2-[l-(ethoxyamino)propy].idtenc]-5-(4- m 92 - 93C
chlorophenyl) cyclohcxanc -l,3-dione . p .
_ ~ .
. . 26 2-[l-(ethoxyal!i3.no)plopyi.idene]-5- . m.p. 67 - 6~C
phenylcyclohexane-1,3-dione . , .
' . .. _.. ,.
27 2- [ l- (etl oxyamlno) propyli.dene ] -5- m . p . 92 - 96 C
_ . ~styrylcyclphcY.,ille-l, 3-dlone _ ..
28 2-[1-telho.xyaillino)propyl-lclenc]-5-(2- i .p. 50-52C .
__ :~ ryl)cyclohcxana-1,3-d~.one .____ . 29 2-[1-(ethoxyalllino)propylldene]-5-(2- m. . 68- 69C
. thienyl) cyclollexane-1,3-di.olie . P
. __ _ _ __ 2-[1-(etlloxyanlino)propylidene]-5- n 201.5045 methyl.cyclohexane-1,3-dio, ne ~ D
. _ ,,. ..
31 2-ll-(ethoxyamino)propylidene]-5,5- i41 5027 . dimethylcycloht xane-l,3-di.one nD
. ~
32 2- ll- (ethoxy =amino)propylidene]-5-iso- n l 51.5111 propylcyclohe7:aFIe-1 ~ 3-tlione D . .
2- [l- (ethoxy~mino)prt,pylidene]-5- n l 8~s 1.5019 33 hexylcyclollt xane-l,3-dione D
.' . . ' ~. '--,.
~,. ' , ' .
... . ~ j ~ ~
. . ~ ~
2-~ (etlloxyalllino)propylidene]-4- .
34 methyl-5,5-dimetllylcyclohe~ne-1,3- nD2ll.5081 . . ~ dione . . .
. ___ , ._ _.
2-[].- (ethoxyfmlino)propy] idcnc] --4,4- n 18~ . 4946 ilQ~tllylcyclo~lcxan~ 3-~lionc D .
. _ _ _ _ _ 2-[l-(cthoxyamino)propylidcne]-4- .
36 cyano-5,5-dimcthylcyclohcxane-1j3- m.p. 47 -48C
. . dione .
2--[1-(ethoxyamino)propylidcnc]-4-37 methoxycarbonyl-5,5-dimc~hyl.cyclo- nD241.5070 . hexane-]., 3-dimle .
_ _ _ ~_~ _, . 2-[1-(ethoxyamino)propylidene]-/!-( 38 ethoxycarbonyl-5,5-dime~hyl.cyc].o- nnl B 1.5040 .
.. hexane-1,3-dione _._~ __ _ . 39 2-[1-(ctho~:ya!llino)propylidenc]-4-n- n 251.5078 . pro~ylcyclohcxane-1,3--dione . D
_ ~
2-[].-(etlloxyamino)prol7ylidcnc]-4-iso- n 2 ~l 5055 I . hutylcyclollcxan~ 3-dicllc D
~ . _~____ ~1 2-[1-(n~tl~xy.liethoY~yamino)prol)y].idenc]- n 271.501i ., 5,5-dimethylcyc;Lol)cxallc-1.,3-di.one D
_~ ~ ____ --. . 2-~1-(butlloxymethoxyaloillo)propyli- .
42 dcne}-5,5-dimethylcyclohexane-1,3- nD271.4927 dione .
__ . 2-ll- (me thylt1liometl-oxyamino)~ropyli- . .
43 dene~-5,5-dimetllylcyclohexanc-1,3- nD271.5582 dione .
~. . _ ~ . ~
`~. ~ 2-[1-(methylthio;nethoxyaniino)propyli- n 271 5328 ~4 dene]-5-isopropylcyclollcYnne-l,3-dione D
___ _ _.~
2-[l-(metlloxycthoxyamino)propylidene]- n 20l.5100 . 5~5-dimctllylcyclohexane-1,3-diolle D
. _ __ ~ _ _ _ ._ 2-[1-(et.hoxyc~rbonyl.metlloY.yalllino)plo-46 pylidenc]-4,4-dimethylcycloheY.ane-1,3- nD21.50l9 dione -. ~
_ 2-[l~(propoxyamino)propylidelle]-5,5- n 261.4994 . ~7 dimethylcyclohexane-1,3-dione D .
, _ __ . ~8 2-[l-(~llyloxyamino)propylidene]- n 251.5265 . ~ cyclohexane-1,3-divne D
_ __ .. 49 2-[1-(allyloxyamino)propylidene]-5-n 2D-5 1.5200 . methylcyclohexane-1,3-dionc D . . ..
.
. 2-~1-(allyloxyamino)propylidcnc]-5,5- 2 41 5Ll9 dimethy'.cyclollcxanc-1,3-dionc D ' __ _ ' , . . _ . _ .
.. .
:~
~3~ , 9 _ ____.__ . . __~
5l 2-[1-(allyloxyamillo)propylidene]-5- n 23-51 ~ 0 . isopropylcyclohcxane-1,3-dione D .
. ~ ~ _._ . 2 2~ (al].yloxyalllino)propylidcnc] 5- n le 51.5082 .5 11exy].cycl~llexanc-1,3-lione D
___ ~ . .. ~
53 2 [1-(allyloxyamino)prn~)ylidene3-5- 221.5bS2 .
(2-furyl)cyclohcxlllc-1,3-dionc D
_ _ 5' 2-[1-(allyloxyamino)propylidene]-5- m p 48- 50C
. ~ phenyl.cyclohcxane-1,3-dione , .
., . _ _ . 55 2-[1-(allyloxyalr~ o)propylidene]-5- n 211.5851 fityrylcyclohexane-1,3-dione D
2-[1-(allyloxyamino)propyli.dcne~-4-f 56 bromo-6,6-dimethylcyc]ohexane-1,3- nD271.5338 . . dione .. _ . 2-[1-(allyloxylmino)propylidcne]-4-. 57 bromo-5,5-dimethylcyc].ohexane-1~3- nD261.53G5 dione ~ ~
. . 2-[1-(~llyloxyami.n(-)pfol~yliclene]--4- .
. . 58 cyano-5,5-di.rncLl)ylcy:lohexalle-i,3- m.p. 62-63C
. . dione . ~ , ._ . 2-[1-(allyloxya~ino)propylidene]-"-59 methoxycar~onyl-5,5-dir.lethylcyclo- n~2 I.S 1. 5088 hexane-1,3-dione _ . _ . 2-11-(a].].yloxyamino)propylidene]-4- .
cthoxycar~onyl-5-mcthylcyclohcxane- nD2Dl.5146 . .
. . 1,3-dione .
. _ _ . _ .. . ....... ~
2-[1-(allyloxyaDIino)propylidene]-4- .
61 etlloxycarbonyl-5,5-dimetllylcyclo- nDI81.5079 hcxanc-1,3-dione .
. , _ ~
62 2-[1-~ally}.oi;yami.llo)prc-pylidene]-4-etllo- . 1 22l 5078 xycarbonyl-4-ethylcyclohexane-1,3-dion ID
. . _ . ,.
2-[1-(ally].oxyamino)propylidene]-'l- .
63 methyl-5,5-dimethylcyclohcxanc-1,3- nD2'1.5138 dione ~
_ . _ . 64 2-[1-(allyloxyamino)propylidene]-4,4- n 1~1.5138 dimethylcyclohexane-1,3-dione D
. _ _ . - -65 2-[1-(ailyloxyamino)propylidene]-4- n 21.5152 . -. i~opropylcyclohexane-1;3-dione D
~--~_ ___._ 66 2-[1-(allyloxyamlno)propylidene]-'l~n n 2 5l . 5103 .
. propylcyclohexane-1,3-d~.one . I) . _ _ _ _ ~
67 2-[1-(allyloxyamino)propylidene]-'~-n- n 2 I- 5 1, si34 . . butylcyclohexane-].~3-lionc D
. . __~ _ _ ~ ' .
.
.
., .~ . .
~` ¢
~ -- -68 2-[1-(allyloxyan~ o)propyl.i~lene]-4- n 2 5l, 5091 n-pentylcyclohexana-1,3-diona D
69 ~-[I.-(I)ropargyloY.y.;~ ino)propylidene]- n la- 51 , 5218 595-dimetllyleyclohexane-1,3--dione D
~ .
2-ll-(methallyloxyamino)propy].idene]- n 231 5107 . 5,5-dimethylcyelohexane-1,3-clione D
__ ~ .
71 2-ll-(n-butoxyamino)propy~.idene]-5,5- n ~8-51.5027 . . dimat.hyleyelollexane-1,3-diolle . D
.... .. . __ _ _ 72 2-[1-(isobutoxyami.no)propylitlene]- n 2 31 4976 . 5,5-dimethyleyelohexane-1,3-dione D
_ _ _ . 3 2-[1-(benzyloxyamillo)propy].i.delle]-5,5- m p ~58-59C
I 7 dimethylcyelohexane-1,3-di.one . .
~_ . _ 7~ 2-[].-(methoxyamlllo)l)~ltylidene]-5,5-- n 2 31. ~l940 . ~ dimethylcyelolle~:ane-1,3-diona D .
--~ . ~__ 2-~1-(el:l~oxyamillo)blltyli;d~lle]~5,5- l~ 2l1.49GS
. dlma~hyleyclollexalla-1,3-di.ollo D
. _ _____________ ~_ ~
. . 2-[1-~ethoxyamino)butylidene]-5- n 151 5068 . 76 isopropyleyelohexane-1,3-diolle D
. .. . . _ . _ __ 77 2-~1-(ethoxyamino)l-utylidene]-5- n ~ 8~S 1. 5005 hexyleyelohexane-1,3-dione D
. _~ .
. 2-[1-(ethoxyamino)l~utylidene]-4-78 eyano-5,5-dimethylcyelohexane-1,3- m.p. 83-87~C .
dione . .
.. . __ 2-[1-(ethoxyamino)butylidellQ]-4- .
79 ~etlloxyearbonyl-5,5-dlmethyl- nD2 4~5 1- 5007 . eyelolla~ne-1,3-dione .
__ ______ _ ._ . 2-[1-(etl~oxyamino)butyli.dene]-.'~- .
etlloxycarbonyl-5,5-dimetllylcyclo- . nD2l 51.4990 . hexana-1,3-dione _ _ 2-ll-(etlloxyamino)b~ltylidene~-4,4- n 201.5050 . . . 81 dimethylcyclollexane-1,3-dione . D
_ _ ~
. 82 2-[1-(isopropor.yamino)butylidenel- n 3l1.4939 ..
, . . 5,5-dimethylcyclohexane-1,3-dione D
. .
2-[l-(allyloxyamino)b~tylidene]-5,5- n 2l1.50S9 33 dimethyleyc].ohexane-1,.3-dione D
. . . ._ 2-[1-(allyloxyamino)butylide.ne]-5- n 181. 5135 .
84 isopropylcyclohexane-1,3-dione . D
'. ' _ . ,-- . _ .'.
~, ' ' ' ' ' ,.
~. . . .
3~
, _ ~ _ ___ __ ~____ _ . -2-[1--(al].yloxyam~ o)b~ltylidenc]-5- n la S 1.5051 . hexylcyelolle:~ane-1,3-dione D
_ ~
86 2~ (ally].oxyal!lino)b~lty:l.idcne]-5- m p 52 - 53C
(4-mcthoxyi henyl)cyclohex~ne-l.,3-dionc _.~
2-~ nl.lyloxyar.lino)butylidelle~--5- n 25.5 l 5657 87 (3-ch].orophenyl)cyclohtexalle-].,3-dione D
_ . 2-ll-(a].lyloxyamino)bntylidene]-5-m p 36 - 37~C
88 (~I-ch].orophcnyl)cyclohexanc-1,3-dionc. . .
. __ ~ . . __ .. . 2 ~ allyloxyamino)butylidelle]-4-89cyano--5,5-dimet:llylcyclohc:xane-1,3- m.p. 105 - lO~C
. dione .
_ ~___ .. . 2-[1-(allyloxyamino)but:ylidene]-4-J,~etho~:ycarl~onyl-5,5-dimethylcyclo- nD24-~ ].. 50G3 hexane-1,3-dion.
. ~ ~ . . _ 2-[1-(allyloxyamino)butyli(lene]-4- 2~
91 ethoxyca~bonyl-5,5-dimcthylcyclo- nD 1.5066 . . hexanc--1,3-dionc .
__ ~ ___ _._~ __ . 2-[1-(,ll].yloxyal~ lo)bll~;yli.clcllc]-ll-92 et:hoxycarbonyl-~l-cChylayclollcxane- nD2~-5 1.5078 1,3-dionc . 2-[l-(allyloxya~ llo)hul:ylidellc]-ll~4- n ~ 7$3 93 dimethylcyclollexane-1,3-di.onc D
_ _ _ . _ _ __ 94 2-[1-(allyloxyalrlino)butylidcnc]-4- n 2 3~5 1, 5058 isopropylcyclollcxane-1,3-diolle D .
2-[1- (propar~yloxyamino)l)utyl.i.dene]- n 3~1.5132 5,5-dimcthylcyclolle-,:ane-1,3-dione D
., _ __ _ ___ ___ .
96 2-[1-(hcxyloxyamillo)butylidene]-5,5- n 251 ll725 . dioe~:hylcyclolle~ ane-l,3-dionc D
_~_~_ .~_ ~,,~ .
2-[1-(etlloxyamirlo)isol)~ltylidene]- n 2 31 5013 97 5,S-dimethylcyclohcxane-1,3-dione D
. _~ __., 2-[1-(et:lloxyamlno)llcxylidenc]-5,5- n 3l~ 4~81 98 dimethylcyclohcxallc-1,3-dionc ` D
. . . _ . 99 2-[1-(~llyloxyamino)hexylidene~-5,5- ~ 3l1.5040 dimethylcyclollexane-1,3-dione D .
_ .
lO0 2~ (ethoxyamino~b~nzylidcne]-5,5- m p. lS0-151C
di.methylcyclohexane-1,3-dione .
. _ .
101 2-¦1- (allyloxyamino)bcnzylidcne]-5,5- m.p 169 - 170C
dimethylcyclohexanc-1,3-dione .
.. . . ,~ . .' ' ' ' ..
~ , .. .
~ 12- . .
.
. ~ . ______ 102 2-[l--(e~hoxyaGIino)pro~yl.i(lelle]--5~5- n 2l1.527? .
pentamcthylenccyclollexane-1,3-dlone ~ I
' _ _ __.................... _ _ _ 103 2-El-(allyloxyanillo)propylidene]-5,5- n 2~1.5336 pentame~llylenecyclohexanc-],3~dione D
, ~ __ _ __ __ .__ _ 104 2-[1-(ethoxyamino)propylidene]~ 5- n 2 ~1.5282 tetrameLllylcnecyc].ol-eYane-1,3-dione D
. _ ~_ 105 2-[1-(a~.lyloxysmino)propylidelle]-4,5- n 211.5347 .
. te~rametllylenecyclohexane-1,3-di.one D
~ _ . _~ __~
.- ~langanese salt of 2- [1- (ethoxyamino)-106 . ethylidene]-5,5-dimethylcyclollexanc~ m.p.225-226 DC (d.) 1,3-dione .- ~~ 1----Potassium salt o~ 2-[1-(cthoYyamino)- ~
~ 107 et}~yli.dcne]-5,5-dilnethylcyclohexane- m.p.110-112C(d.) .
: 1,3-dionc . ___ ~
Copper ~alt o 2-[.1.-(ethoxyam:i.no)- .
108 etl-ylidealc]-5,5-dimcthy~jcyclollexane- m.p.].56-157C(d.) 1,3-di.onc . __ _ __ _ __~_ _____ . Copper sal~ of 2--[l--(cthoxy~millo)-ios ethylidcne]-4-cyano-$,5-diD)ethylcycl.o- m.p.l61-164C(d.) hexane-1,3-dione . _ _ _ . . Sodium salt o~ 2-[1-(etlloxyamillo)- .
. 110 ethylidene~-4-methoxycarbonyl-5,5- m.p.llO-120DC(d ).
di.methylcyclohexane-1,3-dione . _ . Copper salt of 2-[1-(allyloxyan~i.no)-111 ethylidene]-5-ethylcyclohexane-1,3- m.p.l64-165DC(d.) dione . : .
.. . , ______ . Coppcr salt o~ 2-[l-(allyloxyamino)-112 ethyli.dene]-5-phe~ylcyclohexar,e 1,3- m.p.l88-l.89~C(d.). dione . _ _ .
Copper salt o~ 2-[l-(allyloxyar.~ino) 113 etl-ylidcne]-4-cyano-5,5-dimethylcyclo- m.p.l54-158 DC ~d.)-hexane-1,3-dione .
. . ~
Sodium salt o~ 2-[1-(al~yloxyalnino)- -`
.114 ethylidene]-4-methoxycarbonyl-5,5- m.p.l~3-194C(d.) . . dimethylcyclohexane-1,3-dione _ ._ . Sodium salt of 2-[1-(allyloxyamino)-115 ethylidene]-4-ethoxycarbonyl-5;5- m.p.llO-120DC(d.) .
dimethylcyclolleXanc-1,3-diol c _ Copper salt of 2-11-(methyltllio-116 metho~yamino)propyl.idene]-5,5- m.p. 110 D C (d.) . dimethylcyclohexane-1,3-dione .
_ - '. __ ... .... .. . ... . . ..
( , _~_ _ Co~-pcr salt of 2-[l-(el:hoxyamino)-117 propyli~cne]-5-(2-furyl~cyclchexane- m.p.l97-1~8C(d.j . 1,3-dione .___.__ . _, ._ Copper salt of 2-Ll-(ethoxyalllirlo)-118 propylidenc]-~5-(2-~hienyl)c~clollexane- m.p.]84'-]85Ctd.) ~3-dlone .
_ ___ __._ __~
opper salt of 2-[1-(ethoxya~ino)-119 propylidene~-S-(4-chlorophenyl)- m.p.lS6-188C(d.) ~ cyc]ohexanc-1,3-dione ___ __ .- , . Copper sa~t of 2-[1-(cchoxya~lino)-120 p~op)~lidene~-~-(3--chlororhenyl)- m.p.l84-185C(d.) cyclohexanc-1,3-clione _ __~__ ___ .' Copper salt or 2-[1-(ethoxyalnino)~
121 , propyliderle3-5-(4-methylphellyl)- m.p.l83-184C~d.) cyclohexane-1,3-di,one _ . _~ ~
. Copper ~alt o 2-[1-tcthoxynmlno)-122 propyli~lenc] 4-cyano-5,5 di~ne~llyl- m.p. ôl~83Dt:(d.) _ _ cyclohexane-1,3-diona Sodiun~ salt Or 2-[l-(c~hoxyrlml;lo)-123 propylidene]-4-e~lloxycal~olly]--5,5- m.p.l88-190C(d.) dime~hylcyclolleY~ane-1,3-dione . ~ ~ __ 124 Copper salt of 2-~1-(al]yloxyamino)- m.p.146-147C(d.) propylidene~-cyclohexane-1,3-dione :.- . _~ _ _ Copper salt of 2-~1-(al]yloxya~lino)- .
125 propylidene]-5-methylcyclol~exane- m.p.129-130C(d.) 1,3-dione ___ . . ___.~
Nicliel sal~ of 2-El-(allyloxyamillo)~
126 propylidene3-5,5-dime~llylcyclohexanc- m.p.169-170C(d.) 1-,3-dione.
_ _,_____ ~--__ Calcillm salt of 2-[1-(allyloxyamino)-' 127 propylidenc]-5~5-dimel:llylcyclohexalle- m!p.107-108C(d.) . 1,3-~lione __ _ _ _ _ Cobalt ~alt of 2-[1-(al],yloxyamino)-120 propylidene3-5,5-dimethylcyclollexane- ~ m.p.l51-152C(d.) 1,3-dione . , -_ _ _ .
Copper salt of 2-~1-(allyloxyamino)-. 129 propylidelle]-5-isopropylcyclohexane- m.p.l45-146C(d.) 1,3-dione _ _ ____ ~__ Copper ~,alt of~2-[1-(allyloxyamino)-130 propylidene]-4-cyano-5,5-dimethyl- m.p. 78-80C(d.) . eycloliexane-1,3-dione .
.' , ' .
, .
r : L~4~
_. . ~ . . ' Sodiu~ salt o 2-~1-(allyloxyamino)-131 propylid~ne]-4~methoxycarl,onyl-5,5- m.p.l75-178C(d.) dimetllylcyclollexane 1,3-dione . . ~ _ __ Sodium salt of 2-[1-(al]~loxyarlino)-132 propylidelle]-ll-e~lloxycar~ollyl-5,5- m.p.110-120C(d.) dimethylcyc]ohexane-1,3-dione .
_ ~_ . .
Calcium salt of ~-[l-(allyloxyamino)-133 propylidene]-4-propylcyclohexalle- m.p.l50-152C(d.) 1,3-dione ~_ _ _ _ . Copper salt of -?-[l-~proparsyl~xy-.
134 amino)pro~ylidene~-5,5-dimethylcyclo- m.p.l26-127C(d.) . hexane-1,3-dione . __ Barlum salt of 2-[1-(propoxyamino)-135 propylidene]-5,5-dimethylcyc]ohexane- m.p. 75-7~C(d.) 1,3-dione . _ ,, ~.__ __ Calcium salt o~ 2-[1-(i~ol~i!toxyamlllo)-136 propylidene]-5,5--dillletl~y]cyc]ollexane- m.p.l95-200C(d.) 1,3-dione _ . ~ ~
. Copp~ salt of 2-[l~(bu~oxyamitlo)--137 propyllclene]-5,$-dimethylcyc~ohexane- m.p.l23-12$C(d.) 1,3-dione -. _ _ . Calcium salt of 2-~1-(ethoxyamino)-138 butylidene3-$,5-dimethylcyclohexane- m.p. 180~C(d.
1,3-dione _ ,___ _ Copper salt of 2-~1-(ethoxy~mino)-139 butylidenel-4-cyano-5,5-dimethyl- m.p. 98-101C(d.) cyclohexane-1,3-c;ione ,. . , , , .._ .; Sodium salt of 2-El-(ethoxyamino)-140 butylidene]-4-methoxycarbonyl-5,$- m.p.lS3-18$C(d.) . dimethylcyclohexane-1,3-diorle __ _ __ _ _ _.___ Nickel salt of 2-[1-(ally~oi:yamino)-141 butylidene]-5,5-dimethylcyclollexane- >~ p. 250C(d.) 1,3-dione . __ _ Cobalt salt of 2-[1-(allyloxyamino)- ~
142 butylidene]-5,5-dimetllylcyclohexane- - m.p.l53-154C(d.) 1,3-dione ~
_ Sodium ~al~ of 2-[1-(allyloxyamino)-143 butylidene]-5,5-dimethylcyGlohe~:ane- m.p. 80-82C
1,3-dione .
. -_ ______ Copper sa]t of 2-[1-(allyloxyamino)-144 butylidene]-5-isopropylcyclohexane- m.p.l45-146C(d.) . 1,3-dione '. , . ,_ _ ,, . .
, ' . ~ .
z . Copper salt o~ 2~ (ally~oY~yal,llno)- 0 145 butylidcnc~--5-hcxcylcyclollcxan~-1 3- m.p.105-106 C~d.) dione __ ~
. . Copper salt oL 2~~1- (allyloxyamino)-146 butylidenel-5--(fi-motlloxypl~enyl)cyclo- m.p.l82-183C~d.) hexane-1,3-dione . _ Copper salt o 2-11-(allyloxyamino)- O
147 butylidene]-4-cyano-5,5-dimethyl- m.p. 92-95 C(d.) cyc]ohexane-1,3-dione . __ _ . . ~_ _ ~
Sodium sall: of 2-[1- (allyloxyamino)-148 butylidenel-4-mctiloxycarbonyl-5 5- m.p. 192C(d.) . dimcthylcyclohexane-1,3-dione . _ __ ~ _ _ .- Sodium salt of 2-[1-(allylo-. yamino)-~- 149 buty]idene]-4-etlloxycarbony]-5 5- m.p.llO~ 120C(d.) dimethylcyclollexalle-1,3-dione _ _ ___ _ _ Copper salt of 2-[1-(benzyloxyamino)- O
150 buty]idene]-5j5-dimetllylcyclollexane- ~ m.p.126--127 C(d.) 1,3-dione _ ~ . _ _ Coppcr ~alt of 2 ~l-(all)~]oxyanlino)- O
151 propylidene]-4~5-tel:rame~llylellccyclo- m.p.l78-179 C(d.) hexanc-1,3-dionc _ ___ . _____ _ ____.
2 2-~1- (allylo :yantino)but-y]idclle]-5,5- m.p. 47-l~9C
dimethylcyclohcxane-1,3-d-ionc hydrate .
~ _ ~____ ~ .
153 2-[1-(allyloxyamino)propylidenc]-5,5- m.p 52-54C
. dimethylcyclohexane-1,3-d;cne hydratf ~ _ _.
2-~1- (allyloxyamino)p~opylidenc]-5~ m.p. 46-48C
154 meth~,lcyclohexane-1,3-dione hydrate . _ __~__ ~ _ _ r 2-[1-(allyloxyamillo)propylidene]-5- m.p 48-50C
15.~ phenylcyclohexanc-1,3-dione hydrate .
__ __ . ~
156 2-[1-(ethoxyamillo)propylidene]-5- m.p. 67-68C
~_ plienylcyclollcxane-1,3-dione hydrate .__... ~ I
' . . .
- . m.p.: n~el~in~ polnt nD: re~Xactive index d. : decomposition .
.
.
. ~' ' ' ' ' ' , - ' ' ' .
.
. ~16-f~",~
}lereinater, the compounds of this inventioll are represented by Compound No. in Table 1.
As mentioned previously, it has been found that the mixture of a compollrld of formula [I] and a well-~nown herbicide may have a synergetic herbiciclal activity in addition to a ~umu].atively increased activity of those each selective herbicidal.
functions.
The paragraphs which follow describe in more detail the utility of this invention.
Suitable urea derivatives for the practice of this in~ention are:
.
Chemical Name Common Name N-(3 chloro-4-metllcxyphenyl)~N.',N'~di.metllylllrea metoxuro N-(3,~-dlchlorophc-nyl)-N~,N'-dimethylure~ diuron N-(3,4-dichlorophenyl)-N'~metlloxy-N'~methylurea linuron 1,3-dimethyl-(3-benzothiazole-2~yl)urea methabenztlliazuron 1,3~dimethyl~3~(5-methylbenzo~hiazole-2-yl)urea (abbreviation : ~) 1,3-dimethyl~3-(5-t-butylbenzothiazole-2-yl)urea (abbrevlation : B) 1,1,3-trimethyl-3-(5-methylbenzothiazole-2-yl)urefl (abbreviation : C) 1,1,3-trimethyl-3-(5-ethylben~othiazole~2~yl)urea (abbreviation : D) 1,3-dimethyl-3-(5,7-dimethylbenzothia~ole-2-yl)urea (abbrevi~ti.oll : E) Ill.p. 131-13~C
1,1,3-trimetl-yl--3-($,7-dimethylbenzothi~ole-2-yl~urea (abbrevi.fl~lon : F) . m.p. 95-96C
These metoxuron, dîuron and linuron etc. are used for controlling mainly broad-leaf weeds in numerous crops such as soybean, po~atoes and ca`rrots etc., bu~ thei.r herbicidal effect for grass weeds is inferior and there is high possibility to cause phyto-toxicity in case of fol.iar trefltment.
~ lowever, by means of blending a compound of formula [I] with above-mentioned ureas herbicide~ the mi~ed herbicidal composition-is able to kill comple~ely both ' , , lU~lZ -17-grass and broad leaf weeds in smaller amount of application rate compared with the individual components and ~urthermore, the said mixed herbicidal composition does not show phyto-toxicity to the crops, mainly because of reduced amount of compound applied.
Suitable triazine derivatives herbicides for the practice of this invention are:
Chemical Name Common Name 2-chloro-4,6-diethylamino-1,3,5-triazine simazine 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine atrazine 2-chloro-4,6-diisopropylamino-1,3,5-triazine propazine 2-methyimercapto-4-ethylamino-6-isopropylamlno-1,3,5-tria~lne ametryne 2-methylmercapto-~,6-dilsopropylamlno-1,3,5-~rlazlne prometryne , These triazine herbicide are mainly used as a selective herblcide for control of broadleaf weeds in wheat, rice and corn etc., but their herbicidal - effect for grass weeds is inferior and there is high possibility to cause phyto-toxicity to crops ln case of foliar treatment.
~ lowever, by means of blending a compound of formula [I] with above-mentioned triazlne herbicides, the mixed herbicidal composition is not only able to kill comp:letely both grass and broadleaf weeds ln smaller amoun~ oE application rate compared with tlle individual components, but also the sald mixed herblcidal com--position does n~t show phyto-toxicity to the crops, mainly because of reduced amount of compound applied.
Suitable carbamate herbicides for the practice of this invention are:
Chemical Name Common Name 3-methoxycarbonylaminophenyl-N-(3'-methylphenyl)-carba~ate phenmedipham methyl N-(3,4-dichlorophenyl)carbamate swep ~` ~V~,~9~
isopropyl N-(3-chlorophenyl)calbamatc ch].oropropham s-(4-chlorobenzyl.)-N,~-dietllyltlliol carbamate bentlliocarl
4-chloro-2-butynyl N~m-chlorophenyl)carbama~e barban methyl N-t4-aminobenzenesulfonyl)carbamate asulam Some of carbamate herbicide are used for control of broadleaf weeds in sugar beets, but their herbicidal effect for grass weeds is inferior.
Nowcver, the mixed herbicidal composition of a compound of formula [1] and carbamates is not only able to kill completely both grass and broadleaf weeds in smaller amount of application rate compared with tlle individual components, but also does not show phyto-toxicity against the crops.
Suitable diphenyl ethers herbicide for ~he practice of this inventlon are:
Chem:Lcn]. Name Cotmnon Name.
4'-nitro-2,4-dichloro-diphenyl ether nitrofen 4-nitro-2,4,6-trichloro-diphenyl ether . (abbreviation : MO) 2,4-dichloro-3'-methoxy-4'-nitrodiphenyl ether (abbrevi.ation : X-52) These diphenyl ether herbicides are used or control of weeds in paddy and upland fields, but their employment is rather limited to the soil treatment and phy~o-toxicity against crops occur iP spraying on thc 12af and stem.
~ lowever, by means of blending a compound of formula [I] with above-mcntiollQd diphenyl ethers herbicides, the mixed herblcidal composition is able to kill completely the objective weeds in smaller amount of application rate compared wi~h the individual components and further, phyto-toxicity against crops can be remark-ably mitigated.
Suitable phenoxyacetic acid derivatives for the practice of this invention are:
Chemical Name Co~non Name ~ . .
2-methyl-4-chloro-phenoxyacetic acid MCPA
2,4-dichloro-phenoxyacetic acid 2,4-D
` ~4~1f~
These phenoxyacetic ac:Ld herblcides are llsed for control oE broadleaE weeds in paddy and upland field by foliar treatment, but their her~icidal effect for grass weeds is inferior.
~ lowever, the m:ixed herbicidal composition compris:ing a compo~md o:E the formula [I] and above-mentioned phenoxyacetic acids herbicides is able to kill completely the object.ive weeds in smaller amount of application rate compared with the individual components.
Suitable acid amide derivatives for the practice of this invention are:
Chemical Name Common Name , _ 3,4-dichloropropionanilide propanil
Nowcver, the mixed herbicidal composition of a compound of formula [1] and carbamates is not only able to kill completely both grass and broadleaf weeds in smaller amount of application rate compared with tlle individual components, but also does not show phyto-toxicity against the crops.
Suitable diphenyl ethers herbicide for ~he practice of this inventlon are:
Chem:Lcn]. Name Cotmnon Name.
4'-nitro-2,4-dichloro-diphenyl ether nitrofen 4-nitro-2,4,6-trichloro-diphenyl ether . (abbreviation : MO) 2,4-dichloro-3'-methoxy-4'-nitrodiphenyl ether (abbrevi.ation : X-52) These diphenyl ether herbicides are used or control of weeds in paddy and upland fields, but their employment is rather limited to the soil treatment and phy~o-toxicity against crops occur iP spraying on thc 12af and stem.
~ lowever, by means of blending a compound of formula [I] with above-mcntiollQd diphenyl ethers herbicides, the mixed herblcidal composition is able to kill completely the objective weeds in smaller amount of application rate compared wi~h the individual components and further, phyto-toxicity against crops can be remark-ably mitigated.
Suitable phenoxyacetic acid derivatives for the practice of this invention are:
Chemical Name Co~non Name ~ . .
2-methyl-4-chloro-phenoxyacetic acid MCPA
2,4-dichloro-phenoxyacetic acid 2,4-D
` ~4~1f~
These phenoxyacetic ac:Ld herblcides are llsed for control oE broadleaE weeds in paddy and upland field by foliar treatment, but their her~icidal effect for grass weeds is inferior.
~ lowever, the m:ixed herbicidal composition compris:ing a compo~md o:E the formula [I] and above-mentioned phenoxyacetic acids herbicides is able to kill completely the object.ive weeds in smaller amount of application rate compared with the individual components.
Suitable acid amide derivatives for the practice of this invention are:
Chemical Name Common Name , _ 3,4-dichloropropionanilide propanil
5-chloro-~-methyl-2-propionamidothiazole T0-2 These acid amlde herb:Lcldes are generally used for control o~ weeds :Ln paddy and up.land Eields, but their herblc:ldal effect for grass weeds is unsa~is-Eactory :Ln some cases.
However, a mixed herbicidal composition comprising a compound of the formula [I] and above-mentioned acid amides herbicides is able to kill completely the objective weeds in smaller amount of application rate compared with~the individ-ual components.
Suitable fatty acid derivatives for the practice of this lnvention are:
Chemlcal Name Common Name sodium 2,2-dichlorapropionate dalapon sodium 2,2,3,3-tetrafluoroproplonate ~ TFP
Above fatty acid herbicides are used for control of Japanese pampas grass and bamboo-grass in uncultivated areas or a pasture, but their herblcidal effect is not satisfactory. ~owever, a mixed herbicidal composition obtained by blending a compound of the formula EI] with fatty acids herbicides is able to destroy satisfactorily the undesirable weeds by employing a smaller amount in comparison ~ 20~
with an amount by using individually compound [I~ alone or fatty acid herbicide.s alone.
Suitable diazine derivatives herbicides for the practice of this invention are:
Chemical Name Cotnmon Name l-phenyl-4-amino--5-chloro--pyrida7.one-(6) pyrazon 3-cyclohexyl-5,6-trimethyleneuracil lenacil Above pyra~.on is used for the control of broadleaf weed in sugar beets, but their herbicidal effect for grass weeds is inferior.
However, the mixed herbicidal composition obtained by blending a compound of formula [I] with dia~ines herbicide is able to kill the objective weeds in smaller amount of application rate compàrcd with ~he lnclividual componcnts and ~urther, said mixed composition does not show phyto-toxicity ~:o the crops.
Suitable other known herblcide for thc practlce o~ this invention are:
, Chemical Name Common Nanle 3-isopropyl-2~1,3-benzothiadiazine-4-one-æ,2-dioxide bentazon Bentazon is used for control of broadleaf weeds in paddies, soybean etc., and cereals respectively, but its herbicidal effect for grass weeds is remarkably inferior.
llowever, by means oE blending a compound of formula ~I] wlth benta~one, the mixed herbicidal composilion is not on:ly able to kill comple~ely both grass and broadleaf weeds in smaller amount of application rate compared with the indi-vidual components, but also shows a very slight phyto-toxicity to the crops.
In the practice of this invention mixtures of from 5 to 95% by weight oE
each component may be used, but with 30 to 70Y of each optimum results are ob-tained.
The mixcd composition of this invention can be applied directly to thc soil as preemerg~nce treatment or to plant foliage, as post-emergence trca~mcnt, or .
~ 3~ 21-they can be mixed intimately with the soil and may be applied to soil or plant fol.iar a~ rates of over 10 g of active ingredients per ~0 ~re, preferably over 25 g per 10 are.
The metnod of the pr~sent invention coml~rehends the employmerlt of a liquid or solid compositioll containing two or more of the compounds of formula [I] and well~known herbicides as an active ingredient.
The zctive ingredien~. of this invention may be formulated by mixing wi~h suitable carriers in a form gcnerally used in agricultural chemicals such as wettable powder, emulsifiable concentrate, dust formulation, granular formulation, water soluble powder and aerosol. ~s solid carri.ers, bentonite, diatomaceous earth, apatite, gypsum, talc, pyrophyllite, vern~-iculitc, clay and others are used.
As llquid carl~icrs, water, keroscnc, mincral oil, pctroleum, solvent n.3phtha, bcnY.enc, xylene, cyclohexane, cyclollexanorle, d:i.methyl.~ormalllide, alcohol, acelone~
and others are used. Sometimes surLace active agent is added ln.order to give a homogeneous and stable formulation.
The composi~-ion of this invention also can be applied admixed with othcr chemical.s which are used in agronomi.c and horticultural management. Such chemiczls can be, but are not restricted to, the classes of chemicals con~only known as plant nutrients, fertilizers, insecticides, acaricides, fungicides, he.rbicides and nematocides.
The concentrations of the ac~.ive ingrcclients in the herbici.clal compositi.on of this invention vary according to type of formulation, and they are, for example, used in a range of 5 - ~0 weigtlt percent, preferably 10 - 60 weight percent, in wettable powder, 5 - 70 weight percent, preEerably 20 - 60 weight ~ercent, in emulsifiable concentrates, and 0.5 - 30 weigllt percent, preferably 1 - 10 weigllt percent in dust for~ulaLion.
Thus, a wettable powder or an emul.sifiable conccntrate produced thereto is diluted with water to a specified concentration and thereby, it is used as a liquid suspension or a liquid emu].sion for treating soils or plant foliars.
1~
~ s~ ~Z -22-. ~ . .
urther, a dust formulation is direccly used for th~ soil Lrea~men~ or the foliar treatment.
The non-limiting examples for the herbicidal composition of ~he present invention are illustrated as 1 ollOW9:
Example 1. Emulsifiable Concentrate Parts by weight Compound 50 2a Linuron 20 Xylene 35 Dimethylformamide 15 ; Polyoxyethylene phenylether 10 These are mixed and dissolved.
Consequently~ emulslfiable concen~:rate containinp, 40% of the active in~re-dient is obtained. In practical use, it is diluted to certain concentratio with water and then is sprayed as an emulsior~.
E~ample 2. Wettable Powder Parts by wei~ht Compound 83 lS
Diuron 3 Diatomaceous earth 23 Sodium alkylsulfate 8 Talc 24 . These are mixed homogeneously and reduced to fine particles. Consequently, wettable powder containing 45% of active ingredient is obtained. In practical use, it is diluted to a certain concentratio~ with water and is sprayed as a suspension.
. ¢
r-~ 23-.. . .
Example 3. Dust Formulation '' Parts by weight - ~ Compound 32 5 ' Si~azine ' ' 3 "''' Talc 35 Bentonite t5 Clay 35 : Sodium alkylsulfate 7 These are mixed homogeneously and reduced to fine particles. Fine par-, ' ticles aré made into granules having the diameter in the range of 0.5 1.0 mm ,' by granulator.
' Consequently, dust formulation con~aining 8~ of the active ingredlent i8 obtained. In practical use it ls directly app~ied.
Example 4. Emulsifiable Concent,rate ~; Parts by weight ! Compound 83 , 20 ,: Phenmedipham 20 ' Xylene 35 , ' Dimethylformamide 15 Polyoxyethylene phenylether 10 These are mixed and dissolved.
' Consequently, emulsifiable-concentrate containing 40% of the active ingre-dient is obtained. In practical use, it is diluted to certain concentration with water and then is sprayed as an emulsion.
Example 5. Wettable Powder ~ ' Parts by weight Compound 32 ' 15 .
. ~, .
.
','~'.
~4~2 -24-; Nitrofen - 30 Diatomaceous earth 23 Sodium alkylsulfate 8 Talc 24 These are mixed homogeneously and reduced to fine particles. Consequently, wettable powder containing 45% of above ingredient is obtained. In practical use, it is diluted to a certain concentration with water and is sprayed as a suspension.
Example 6. Emulsiflable Concentrate Parts by weight . Compound 83 25i t ' Bentazon . 15 Xylene ~35 Dlmethylformamide 15 Polyoxyethylene phenylether 10 These are mixed and dissolved. , I Consequently, emulsifiable concentrate containing 40% of the active ingre-dient is obtained. In practical use, it is diluted to certain concentration with water and then is sprayed as emulsion.
Example 7. Wettable Powder Parts by weight Compound 83 ~ 15 Pyrazon 30 - .;
Diatomaceous earth 23 Sodium alkylsulfate 8 Talc 24 - r ~
~ 25-These are mixed homogeneously and reduced to fine particles. Consequently, wettable powder containing 45% of active ingredient is obtained. In practical use, it is diluted to a certain concentration with water and is sprayed as a suspension.
The following tests were carried out to compare the herbicidal effectiveness . of the mixed composition of the present invention with that of single active ingredient.
. .
1" , .1 .
' , ' .
.
Test 1 Foliar treatment (Post-emergence) Seeds of large crab-grass and lambs-cuarter were planted in a pot and - covered slightl.y with soil. The pots were kept in a green house.
When plants became the ~th leaf stage, an aqueous emulsion prepared by diluting an emulsifiable concentrate with water to a specified concentration was sprayed on the foliar of the plants in pots.
Three weeks after spraying, the fresh weight of the weeds above ground was measured and its result is shown in Table 2.
. ..... ... _ ... ............. .. -~.. .,.,.. ,.. -.. .... ~ .. -~ - - --- 1''---'-'' r-l ~ r~ ~ r-1 ~ r-- ~t ~ O O ~t r/~ ~ ~_ O
~_ O r-l r-l r-l C~l r-l r-l r-l r-l r-; 001 r-l r~ r-l L ~ n Ln ~ ____ _. ,. ..~ ~ __ .___... ~ __.._. __ __ __ O U~ ~ ~t ~1 ~) L~ O 1-- 0 ~D ~ ~L) ~ o r~ O O r-l O
r-l Or-l r-l r-1 rY O c~l O O rt r ) O O ~i ~0 r l O
1~ _ _ ~_ ____ , ___ _ __ _ .
a) ~dO O ~1 ~ ~ O ~1 ~ oo ~1 o i~ ~ ~ ~o O
01~ U ~ r-l r 1 r-l r-l r-l ~--I r-l r-l r-l r-l c~l ~ rr~i n rl--1 ------~--~---- ~---- ---------~--r-l r JO O ~n O O rl l ~0Ol 0~0 O C:~ ~ O
0~ .
: ~ 27 1~L49~LZ
~' _ . _ _ _ _ _ _ _ ~ e~.. ' ~,0 ~ O ~ cn ~7 ~D a~ ~ u~
. . o o -o ,o .~ .~ ~ o o _ ~ __ _ __ .
~ ~ ~-~ ~ ~o ~
. _ ____ __ _ u~ul ~ ~ o ~ ~ o ~ l~o l ~ j o ~
_ _ _ ___ , ~3.8 , .. .... . ... .. . .. . .. ... , .. .. . .. -- .. . ~ . . . ~ ... . ..
, .2 ' . ' _ _ ~ o ___ o __j__ ~ O ~
~ ~t ~1 ~1 ~¦ t~ ~1 co a~ I a~ o u~ I r O
1 - ~ I
~_ ~ -~ . O' I~ I_ 0~ ~ ~ ~ ~D ~ ~
O O ~ ,~ 0 ,~ ~ ~ c~i ~ I~ ~
. _ l ll e~l ~ o a~ a~ <~ I_ o ~;t ~1 loo oor~ u^, . o~j ~ ~ ~ ~ ,~ ~ 1~
. I
_ _ _ r :
0~ 0~ ~ ~ 0~ ~ ~ ~ ~0~ ~ ~ ,1 . .
, .~ l , ~ i i . 1;
2~ ~
.. .
.
z - - - ---- ~ -- ~ ~o~ ~
. u~ ,~ Q ~ ,~ ~ ~ ,~ ~ ~ 1 - - - -- ~ -. O ~D` "'u~ ~ ~J' O, ~ O. CO U~ 1~ ~
o o ~ ~l u~ o ~ ~ ~ ~l ~l~l ~l __ _ . _ _ ~ ~ I .
~. ~ oo ~ 'O O ~ oc~ ~. o .~ ou) ul ' u~ O~ '~i ~ u~ ~ o~u~ .~ ~ ~ Or~ ~D ,`
~ -- - l - ~
~ . ~ . ,, ~ .~ ~ i.,.
~ ~ . ,~ 1 ~ ~ . .
~ 1 ~o .~ .
~ _ 1~ lv~ ~ 1~ 1~ .
~ I~ cO~D ~1 ~1~ C~ ~ ~
__ ~ r __l ~ ~ ~ O ~ ~ ~
~ ~ ~ .~ ~ .~ ~
0 0~ ~ U~ 00 U~ O O ~, ~I
. 0~ ~ .~ ~ 0~ ~ ~ ., __ ~ __l , .
I~ t~ t ~
l ~,~, 1~o ~a ~ a j~ 1 ~; ~ ~ æ ,~ æ z; $ æ ~ .
8 R R ,C R R ~1 ~ V
~91~ ~
' , .: . `
However, a mixed herbicidal composition comprising a compound of the formula [I] and above-mentioned acid amides herbicides is able to kill completely the objective weeds in smaller amount of application rate compared with~the individ-ual components.
Suitable fatty acid derivatives for the practice of this lnvention are:
Chemlcal Name Common Name sodium 2,2-dichlorapropionate dalapon sodium 2,2,3,3-tetrafluoroproplonate ~ TFP
Above fatty acid herbicides are used for control of Japanese pampas grass and bamboo-grass in uncultivated areas or a pasture, but their herblcidal effect is not satisfactory. ~owever, a mixed herbicidal composition obtained by blending a compound of the formula EI] with fatty acids herbicides is able to destroy satisfactorily the undesirable weeds by employing a smaller amount in comparison ~ 20~
with an amount by using individually compound [I~ alone or fatty acid herbicide.s alone.
Suitable diazine derivatives herbicides for the practice of this invention are:
Chemical Name Cotnmon Name l-phenyl-4-amino--5-chloro--pyrida7.one-(6) pyrazon 3-cyclohexyl-5,6-trimethyleneuracil lenacil Above pyra~.on is used for the control of broadleaf weed in sugar beets, but their herbicidal effect for grass weeds is inferior.
However, the mixed herbicidal composition obtained by blending a compound of formula [I] with dia~ines herbicide is able to kill the objective weeds in smaller amount of application rate compàrcd with ~he lnclividual componcnts and ~urther, said mixed composition does not show phyto-toxicity ~:o the crops.
Suitable other known herblcide for thc practlce o~ this invention are:
, Chemical Name Common Nanle 3-isopropyl-2~1,3-benzothiadiazine-4-one-æ,2-dioxide bentazon Bentazon is used for control of broadleaf weeds in paddies, soybean etc., and cereals respectively, but its herbicidal effect for grass weeds is remarkably inferior.
llowever, by means oE blending a compound of formula ~I] wlth benta~one, the mixed herbicidal composilion is not on:ly able to kill comple~ely both grass and broadleaf weeds in smaller amount of application rate compared with the indi-vidual components, but also shows a very slight phyto-toxicity to the crops.
In the practice of this invention mixtures of from 5 to 95% by weight oE
each component may be used, but with 30 to 70Y of each optimum results are ob-tained.
The mixcd composition of this invention can be applied directly to thc soil as preemerg~nce treatment or to plant foliage, as post-emergence trca~mcnt, or .
~ 3~ 21-they can be mixed intimately with the soil and may be applied to soil or plant fol.iar a~ rates of over 10 g of active ingredients per ~0 ~re, preferably over 25 g per 10 are.
The metnod of the pr~sent invention coml~rehends the employmerlt of a liquid or solid compositioll containing two or more of the compounds of formula [I] and well~known herbicides as an active ingredient.
The zctive ingredien~. of this invention may be formulated by mixing wi~h suitable carriers in a form gcnerally used in agricultural chemicals such as wettable powder, emulsifiable concentrate, dust formulation, granular formulation, water soluble powder and aerosol. ~s solid carri.ers, bentonite, diatomaceous earth, apatite, gypsum, talc, pyrophyllite, vern~-iculitc, clay and others are used.
As llquid carl~icrs, water, keroscnc, mincral oil, pctroleum, solvent n.3phtha, bcnY.enc, xylene, cyclohexane, cyclollexanorle, d:i.methyl.~ormalllide, alcohol, acelone~
and others are used. Sometimes surLace active agent is added ln.order to give a homogeneous and stable formulation.
The composi~-ion of this invention also can be applied admixed with othcr chemical.s which are used in agronomi.c and horticultural management. Such chemiczls can be, but are not restricted to, the classes of chemicals con~only known as plant nutrients, fertilizers, insecticides, acaricides, fungicides, he.rbicides and nematocides.
The concentrations of the ac~.ive ingrcclients in the herbici.clal compositi.on of this invention vary according to type of formulation, and they are, for example, used in a range of 5 - ~0 weigtlt percent, preferably 10 - 60 weight percent, in wettable powder, 5 - 70 weight percent, preEerably 20 - 60 weight ~ercent, in emulsifiable concentrates, and 0.5 - 30 weigllt percent, preferably 1 - 10 weigllt percent in dust for~ulaLion.
Thus, a wettable powder or an emul.sifiable conccntrate produced thereto is diluted with water to a specified concentration and thereby, it is used as a liquid suspension or a liquid emu].sion for treating soils or plant foliars.
1~
~ s~ ~Z -22-. ~ . .
urther, a dust formulation is direccly used for th~ soil Lrea~men~ or the foliar treatment.
The non-limiting examples for the herbicidal composition of ~he present invention are illustrated as 1 ollOW9:
Example 1. Emulsifiable Concentrate Parts by weight Compound 50 2a Linuron 20 Xylene 35 Dimethylformamide 15 ; Polyoxyethylene phenylether 10 These are mixed and dissolved.
Consequently~ emulslfiable concen~:rate containinp, 40% of the active in~re-dient is obtained. In practical use, it is diluted to certain concentratio with water and then is sprayed as an emulsior~.
E~ample 2. Wettable Powder Parts by wei~ht Compound 83 lS
Diuron 3 Diatomaceous earth 23 Sodium alkylsulfate 8 Talc 24 . These are mixed homogeneously and reduced to fine particles. Consequently, wettable powder containing 45% of active ingredient is obtained. In practical use, it is diluted to a certain concentratio~ with water and is sprayed as a suspension.
. ¢
r-~ 23-.. . .
Example 3. Dust Formulation '' Parts by weight - ~ Compound 32 5 ' Si~azine ' ' 3 "''' Talc 35 Bentonite t5 Clay 35 : Sodium alkylsulfate 7 These are mixed homogeneously and reduced to fine particles. Fine par-, ' ticles aré made into granules having the diameter in the range of 0.5 1.0 mm ,' by granulator.
' Consequently, dust formulation con~aining 8~ of the active ingredlent i8 obtained. In practical use it ls directly app~ied.
Example 4. Emulsifiable Concent,rate ~; Parts by weight ! Compound 83 , 20 ,: Phenmedipham 20 ' Xylene 35 , ' Dimethylformamide 15 Polyoxyethylene phenylether 10 These are mixed and dissolved.
' Consequently, emulsifiable-concentrate containing 40% of the active ingre-dient is obtained. In practical use, it is diluted to certain concentration with water and then is sprayed as an emulsion.
Example 5. Wettable Powder ~ ' Parts by weight Compound 32 ' 15 .
. ~, .
.
','~'.
~4~2 -24-; Nitrofen - 30 Diatomaceous earth 23 Sodium alkylsulfate 8 Talc 24 These are mixed homogeneously and reduced to fine particles. Consequently, wettable powder containing 45% of above ingredient is obtained. In practical use, it is diluted to a certain concentration with water and is sprayed as a suspension.
Example 6. Emulsiflable Concentrate Parts by weight . Compound 83 25i t ' Bentazon . 15 Xylene ~35 Dlmethylformamide 15 Polyoxyethylene phenylether 10 These are mixed and dissolved. , I Consequently, emulsifiable concentrate containing 40% of the active ingre-dient is obtained. In practical use, it is diluted to certain concentration with water and then is sprayed as emulsion.
Example 7. Wettable Powder Parts by weight Compound 83 ~ 15 Pyrazon 30 - .;
Diatomaceous earth 23 Sodium alkylsulfate 8 Talc 24 - r ~
~ 25-These are mixed homogeneously and reduced to fine particles. Consequently, wettable powder containing 45% of active ingredient is obtained. In practical use, it is diluted to a certain concentration with water and is sprayed as a suspension.
The following tests were carried out to compare the herbicidal effectiveness . of the mixed composition of the present invention with that of single active ingredient.
. .
1" , .1 .
' , ' .
.
Test 1 Foliar treatment (Post-emergence) Seeds of large crab-grass and lambs-cuarter were planted in a pot and - covered slightl.y with soil. The pots were kept in a green house.
When plants became the ~th leaf stage, an aqueous emulsion prepared by diluting an emulsifiable concentrate with water to a specified concentration was sprayed on the foliar of the plants in pots.
Three weeks after spraying, the fresh weight of the weeds above ground was measured and its result is shown in Table 2.
. ..... ... _ ... ............. .. -~.. .,.,.. ,.. -.. .... ~ .. -~ - - --- 1''---'-'' r-l ~ r~ ~ r-1 ~ r-- ~t ~ O O ~t r/~ ~ ~_ O
~_ O r-l r-l r-l C~l r-l r-l r-l r-l r-; 001 r-l r~ r-l L ~ n Ln ~ ____ _. ,. ..~ ~ __ .___... ~ __.._. __ __ __ O U~ ~ ~t ~1 ~) L~ O 1-- 0 ~D ~ ~L) ~ o r~ O O r-l O
r-l Or-l r-l r-1 rY O c~l O O rt r ) O O ~i ~0 r l O
1~ _ _ ~_ ____ , ___ _ __ _ .
a) ~dO O ~1 ~ ~ O ~1 ~ oo ~1 o i~ ~ ~ ~o O
01~ U ~ r-l r 1 r-l r-l r-l ~--I r-l r-l r-l r-l c~l ~ rr~i n rl--1 ------~--~---- ~---- ---------~--r-l r JO O ~n O O rl l ~0Ol 0~0 O C:~ ~ O
0~ .
: ~ 27 1~L49~LZ
~' _ . _ _ _ _ _ _ _ ~ e~.. ' ~,0 ~ O ~ cn ~7 ~D a~ ~ u~
. . o o -o ,o .~ .~ ~ o o _ ~ __ _ __ .
~ ~ ~-~ ~ ~o ~
. _ ____ __ _ u~ul ~ ~ o ~ ~ o ~ l~o l ~ j o ~
_ _ _ ___ , ~3.8 , .. .... . ... .. . .. . .. ... , .. .. . .. -- .. . ~ . . . ~ ... . ..
, .2 ' . ' _ _ ~ o ___ o __j__ ~ O ~
~ ~t ~1 ~1 ~¦ t~ ~1 co a~ I a~ o u~ I r O
1 - ~ I
~_ ~ -~ . O' I~ I_ 0~ ~ ~ ~ ~D ~ ~
O O ~ ,~ 0 ,~ ~ ~ c~i ~ I~ ~
. _ l ll e~l ~ o a~ a~ <~ I_ o ~;t ~1 loo oor~ u^, . o~j ~ ~ ~ ~ ,~ ~ 1~
. I
_ _ _ r :
0~ 0~ ~ ~ 0~ ~ ~ ~ ~0~ ~ ~ ,1 . .
, .~ l , ~ i i . 1;
2~ ~
.. .
.
z - - - ---- ~ -- ~ ~o~ ~
. u~ ,~ Q ~ ,~ ~ ~ ,~ ~ ~ 1 - - - -- ~ -. O ~D` "'u~ ~ ~J' O, ~ O. CO U~ 1~ ~
o o ~ ~l u~ o ~ ~ ~ ~l ~l~l ~l __ _ . _ _ ~ ~ I .
~. ~ oo ~ 'O O ~ oc~ ~. o .~ ou) ul ' u~ O~ '~i ~ u~ ~ o~u~ .~ ~ ~ Or~ ~D ,`
~ -- - l - ~
~ . ~ . ,, ~ .~ ~ i.,.
~ ~ . ,~ 1 ~ ~ . .
~ 1 ~o .~ .
~ _ 1~ lv~ ~ 1~ 1~ .
~ I~ cO~D ~1 ~1~ C~ ~ ~
__ ~ r __l ~ ~ ~ O ~ ~ ~
~ ~ ~ .~ ~ .~ ~
0 0~ ~ U~ 00 U~ O O ~, ~I
. 0~ ~ .~ ~ 0~ ~ ~ ., __ ~ __l , .
I~ t~ t ~
l ~,~, 1~o ~a ~ a j~ 1 ~; ~ ~ æ ,~ æ z; $ æ ~ .
8 R R ,C R R ~1 ~ V
~91~ ~
' , .: . `
Claims (26)
1. A herbicidal composition comprising (a) from 5 to 95 parts by weight of at least one compound selected from the group consisting of the compound of the following formula wherein R1 is selected from the group consisting of hydrogen, alkyl and phenyl, R2 is selected from the group consisting of alkyl, straight or branched chain lower alkenyl, lower alkynyl, lower alkoxy lower alkyl, lower alkylthiomethyl, lower alkoxy-carbonyl lower alkyl and benzyl, X is a same or different substituent which is selected from the group consisting of alkyl, lower alkoxycarbonyl, halogen, cyano, phenyl, phenyl substituted with halogen, methyl or methoxy, styryl, furyl, thienyl, 5,5-pentamethylene and 4,5-tetramethylene.
n is 0 or an integer from 1 to 6;
or a hydrate or a metal salt of the compound defined herein above'; and (b) from 95 to 5 parts of at least one herbicidal compound selected from the group consisting of urea, triazine, carbamate, diphenyl ether, phenoxyacetic acid, acid amide, diazine and fatty acid derivatives.
and 3-isopropyl-2,1,3-benzothiadiazine-4-one-2,2-dioxide.
n is 0 or an integer from 1 to 6;
or a hydrate or a metal salt of the compound defined herein above'; and (b) from 95 to 5 parts of at least one herbicidal compound selected from the group consisting of urea, triazine, carbamate, diphenyl ether, phenoxyacetic acid, acid amide, diazine and fatty acid derivatives.
and 3-isopropyl-2,1,3-benzothiadiazine-4-one-2,2-dioxide.
2. A herbicidal composition comprising from 5 to 95 parts by weight of at least one compound selected from the group consisting of the formula:
wherein R1 is selected from the group consisting of hydrogen, alkyl of 1 to 5 carbon atoms and phenyl, R2 is selected from the group consisting of alkyl of 1 to 6 carbon atoms, straight or branched chain alkenyl of 3 to 4 carbon atoms, propargyl, alkoxymethyl of 1 to 4 carbon atoms, methoxyethyl, methyl-thiomethyl, alkoxycarbonylmethyl of 1 to 2 carbon atoms and benzyl, X is a same or different substitutent which is selected from the group consisting of alkyl of 1 to 6 carbon atoms, alkoxycarbonyl of 1 to 2 carbon atoms, bromo, cyano, phenyl, chlorophenyl, methoxyphenyl, styryl, 2-furyl, 2-thienyl, 5,5-pentamethylene and 4,5-tetramethylene, n is 0 or an integer from 1 to 6;
or a hydrate or a metal salt of the compound defined herein above, wherein metal is selected from the group of sodium, potassium, calcium, barium, copper, manganese, cobalt and nickel;
and from 95 to 5 parts of at least one herbicidal compound selected from the group consisting of N-(3-chloro-4-methoxyphenyl)-N',N'-dimethylurea, N-(3,4-dichlorophenyl)-N',N'-dimethylurea, N-(3,4-dichlorophenyl)-N'-methoxy-N'-methylurea, 1,3-dimethyl-(3-benzothiazole-2-yl)urea, 1,3-dimethyl-3-(5-methylbenzothiazole-2-yl)urea, 1,3-dimethyl-3-(5-t-butylbenzothiazole-2-yl)urea, 1,1,3-trimethyl-3-(5-methylbenzothiazole-2-yl)urea, 1,1,3-trimethyl-3-(5-ethylbenzothiazole-2-yl)urea, 1,3-diméthyl-3-(5,7-dimethylbenzothiazole-2-yl)urea, 1,1,3-trimethyl-3-(5,7-dimethylbenzothiazole-2-yl)urea, 2-chloro-4,6-diethylamino-1,3,5-triazine, 2-chloro-4-ethylamino-6-isopropylamino-1.,3,5-triazine, 2-chloro-4,6-diisopropylamino-1,3,5-triazine, 2-methylmercapto-4-ethylamino-6-isopropylamino-1,3,5-triazine, 2-methylmercapto-4,6-diisoproyylamino-1,3,5-triazine, 3-methoxycarbonylaminophenyl-N-(3'-methylphenyl)-carbamate, methyl N-(3,4-dichlorophenyl)carbamate, isopropyl N-(3-chlorophenyl)carbamate, s-(4-chlorobenzyl)-N,N-diethylthiol carbamate, 4-chloro-2-butynyl N(m-chlorophenyl)carbamate, methyl N-(4-aminobenzenesulfonyl)carbamate, 4'-nitro-2,4-dichloro-diphenyl ether, 4-nitro-2,4,6-trichloro-diphenyl ether, 2,4-dichloro-3'methoxy-4'-nitrodiphenyl ether, 2-methyl-4-chloro-phenoxyacetic acid, 2,4-dichloro-phenoxyacetic acid, 3,4-dichloropropionanilide 5-chloro-4-methyl-2-propionamidothiazole sodium 2,2-dichloropropionate sodium 2,2,3,3-tetrafluoropropionate 1-phenyl-4-amino-5-chloro-pyridazone-(6) 3-cyclohexyl-5,6-trimethyleneuracil and 3-isopropyl-2,1,3-benzothiadiazine-4-one-2,2-dioxide.
wherein R1 is selected from the group consisting of hydrogen, alkyl of 1 to 5 carbon atoms and phenyl, R2 is selected from the group consisting of alkyl of 1 to 6 carbon atoms, straight or branched chain alkenyl of 3 to 4 carbon atoms, propargyl, alkoxymethyl of 1 to 4 carbon atoms, methoxyethyl, methyl-thiomethyl, alkoxycarbonylmethyl of 1 to 2 carbon atoms and benzyl, X is a same or different substitutent which is selected from the group consisting of alkyl of 1 to 6 carbon atoms, alkoxycarbonyl of 1 to 2 carbon atoms, bromo, cyano, phenyl, chlorophenyl, methoxyphenyl, styryl, 2-furyl, 2-thienyl, 5,5-pentamethylene and 4,5-tetramethylene, n is 0 or an integer from 1 to 6;
or a hydrate or a metal salt of the compound defined herein above, wherein metal is selected from the group of sodium, potassium, calcium, barium, copper, manganese, cobalt and nickel;
and from 95 to 5 parts of at least one herbicidal compound selected from the group consisting of N-(3-chloro-4-methoxyphenyl)-N',N'-dimethylurea, N-(3,4-dichlorophenyl)-N',N'-dimethylurea, N-(3,4-dichlorophenyl)-N'-methoxy-N'-methylurea, 1,3-dimethyl-(3-benzothiazole-2-yl)urea, 1,3-dimethyl-3-(5-methylbenzothiazole-2-yl)urea, 1,3-dimethyl-3-(5-t-butylbenzothiazole-2-yl)urea, 1,1,3-trimethyl-3-(5-methylbenzothiazole-2-yl)urea, 1,1,3-trimethyl-3-(5-ethylbenzothiazole-2-yl)urea, 1,3-diméthyl-3-(5,7-dimethylbenzothiazole-2-yl)urea, 1,1,3-trimethyl-3-(5,7-dimethylbenzothiazole-2-yl)urea, 2-chloro-4,6-diethylamino-1,3,5-triazine, 2-chloro-4-ethylamino-6-isopropylamino-1.,3,5-triazine, 2-chloro-4,6-diisopropylamino-1,3,5-triazine, 2-methylmercapto-4-ethylamino-6-isopropylamino-1,3,5-triazine, 2-methylmercapto-4,6-diisoproyylamino-1,3,5-triazine, 3-methoxycarbonylaminophenyl-N-(3'-methylphenyl)-carbamate, methyl N-(3,4-dichlorophenyl)carbamate, isopropyl N-(3-chlorophenyl)carbamate, s-(4-chlorobenzyl)-N,N-diethylthiol carbamate, 4-chloro-2-butynyl N(m-chlorophenyl)carbamate, methyl N-(4-aminobenzenesulfonyl)carbamate, 4'-nitro-2,4-dichloro-diphenyl ether, 4-nitro-2,4,6-trichloro-diphenyl ether, 2,4-dichloro-3'methoxy-4'-nitrodiphenyl ether, 2-methyl-4-chloro-phenoxyacetic acid, 2,4-dichloro-phenoxyacetic acid, 3,4-dichloropropionanilide 5-chloro-4-methyl-2-propionamidothiazole sodium 2,2-dichloropropionate sodium 2,2,3,3-tetrafluoropropionate 1-phenyl-4-amino-5-chloro-pyridazone-(6) 3-cyclohexyl-5,6-trimethyleneuracil and 3-isopropyl-2,1,3-benzothiadiazine-4-one-2,2-dioxide.
3. A herbicidal composition comprising from 5 to 95 parts by weight of at least one compound selected from the following formula consisting of:
, and wherein R1 is selected from the group consisting of ethyl and propyl, R2 is selected from the group consisting of ethyl, propyl, allyl and propargyl, R3 is selected from the group consisting of methyl and ethyl, and from 95 to 5 parts of at least one herbicidal compound selected from the group consisting of N-(3-chloro-4-methoxyphenyl)-N',N'-dimethylurea, N-(3,4-dichlorophenyl)-N',N'-dimethylurea, N-(3,4-dichlorophenyl)-N'-methoxy-N'-methylurea, 1,3-dimethyl-(3-benzothiazole-2-yl)urea, 1,3-dimethyl-3-(5-methylbenzothiazole-2-yl)urea, 1,3-dimethyl-3-(5-t-butylbenzothiazole-2-yl)urea, 1,1,3-trimethyl-3-(5-methylbenzothiazole-2-yl)urea, 1,1,3-trlmethyl-3-(5-ethylbenzothiazole-2-yl)urea, 1,3-dimethyl-3-(5,7-dimethylbenzothiazole-2-yl)urea, 1,1,3-trimethyl-3-(5,7-dimethylbenzothiazole-2-yl)urea, 2-chloro-4,6-diethylamino-1,3,5-triazine, 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine, 2-chloro-4,6-diisopropylamino-1,3,5-triazine, 2-methylmercapto-4-ethylamino-6-isopropylamino-1,3,5-triazine, 2-methylmercapto-4,6-diisopropylamino-1,3,5-triazine, 3-methoxycarbonylaminophenyl-N-(3'-methylphenyl)-carbamate, methyl N-(3,4-dichlorophenyl)carbamate, isopropyl N-(3-chlorophenyl)carbamate, s-(4-chlorobenzyl)-N,N-diethylthiol carbamate, 4-chloro-2-butynyl N(m-chlorophenyl)carbamate, methyl N-(4-aminobenzenesulfonyl)carbamate, 4'-nitro-2,4-dichloro-diphenyl ether, 4-nitro-2,4,6-trichloro-diphenyl ether, 2,4-dichloro-3-methoxy-4'-nitrodiphenyl ether, 2-methyl-4-chloro-phenoxyacetic acid, 2,4-dichloro-phenoxyacetic acid, 3,4-dichloropropionanilide 5-chloro-4-methyl-2-propionamidothiazole sodium 2,2-dichloropropionate sodium 2,2,3,3-tetrafluoropropionate 1-phenyl-4-amino-5-chloro-pyridazone-(6) 3-cyclohexyl-5,6-trimethyleneuracil and 3-isopropyl-2,1,3-benzothiadiazine-4-one-2,2-dioxide.
, and wherein R1 is selected from the group consisting of ethyl and propyl, R2 is selected from the group consisting of ethyl, propyl, allyl and propargyl, R3 is selected from the group consisting of methyl and ethyl, and from 95 to 5 parts of at least one herbicidal compound selected from the group consisting of N-(3-chloro-4-methoxyphenyl)-N',N'-dimethylurea, N-(3,4-dichlorophenyl)-N',N'-dimethylurea, N-(3,4-dichlorophenyl)-N'-methoxy-N'-methylurea, 1,3-dimethyl-(3-benzothiazole-2-yl)urea, 1,3-dimethyl-3-(5-methylbenzothiazole-2-yl)urea, 1,3-dimethyl-3-(5-t-butylbenzothiazole-2-yl)urea, 1,1,3-trimethyl-3-(5-methylbenzothiazole-2-yl)urea, 1,1,3-trlmethyl-3-(5-ethylbenzothiazole-2-yl)urea, 1,3-dimethyl-3-(5,7-dimethylbenzothiazole-2-yl)urea, 1,1,3-trimethyl-3-(5,7-dimethylbenzothiazole-2-yl)urea, 2-chloro-4,6-diethylamino-1,3,5-triazine, 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine, 2-chloro-4,6-diisopropylamino-1,3,5-triazine, 2-methylmercapto-4-ethylamino-6-isopropylamino-1,3,5-triazine, 2-methylmercapto-4,6-diisopropylamino-1,3,5-triazine, 3-methoxycarbonylaminophenyl-N-(3'-methylphenyl)-carbamate, methyl N-(3,4-dichlorophenyl)carbamate, isopropyl N-(3-chlorophenyl)carbamate, s-(4-chlorobenzyl)-N,N-diethylthiol carbamate, 4-chloro-2-butynyl N(m-chlorophenyl)carbamate, methyl N-(4-aminobenzenesulfonyl)carbamate, 4'-nitro-2,4-dichloro-diphenyl ether, 4-nitro-2,4,6-trichloro-diphenyl ether, 2,4-dichloro-3-methoxy-4'-nitrodiphenyl ether, 2-methyl-4-chloro-phenoxyacetic acid, 2,4-dichloro-phenoxyacetic acid, 3,4-dichloropropionanilide 5-chloro-4-methyl-2-propionamidothiazole sodium 2,2-dichloropropionate sodium 2,2,3,3-tetrafluoropropionate 1-phenyl-4-amino-5-chloro-pyridazone-(6) 3-cyclohexyl-5,6-trimethyleneuracil and 3-isopropyl-2,1,3-benzothiadiazine-4-one-2,2-dioxide.
4. A herbicidal composition comprising from 5 to 95 parts by weight of at least one compound selected from the group consisting of the formula:
wherein R1 is selected from the group consisting of ethyl and propyl, R2 is selected from the group consisting of ethyl, propyl ally and propargyl;
and from 95 to 5 parts of at least one herbicidal compound selected from the group consisting of 3-methoxycarbonylaminophenyl-N-(3'-methylphenyl)-carbamate, 3-isopropyl-2,1,3-benzothiadiazine-4-one-2,2-dioxide and 1-phenyl-4-amino-5-chloro-pyridazone-(6)
wherein R1 is selected from the group consisting of ethyl and propyl, R2 is selected from the group consisting of ethyl, propyl ally and propargyl;
and from 95 to 5 parts of at least one herbicidal compound selected from the group consisting of 3-methoxycarbonylaminophenyl-N-(3'-methylphenyl)-carbamate, 3-isopropyl-2,1,3-benzothiadiazine-4-one-2,2-dioxide and 1-phenyl-4-amino-5-chloro-pyridazone-(6)
5. A herbicidal composition comprising from 5 to 95 parts by weight of at least one compound selected from the group consisting of the formula:
wherein R1 is selected from the group consisting of ethyl and propyl, R2 is selected from the group consisting of ethyl, propyl, allyl and propargyl;
and from 95 to 5 parts of at least one herbicidal compound selected from the group consisting of 3-methoxycarbonylaminophenyl-N-(3'-methylphenyl)-carbamate, 3-isopropyl-2,1,3-benzothiadiazine-4-one-2,2-dioxide and 1-phenyl-4-amino-5-chloro-pyridazone-(6)
wherein R1 is selected from the group consisting of ethyl and propyl, R2 is selected from the group consisting of ethyl, propyl, allyl and propargyl;
and from 95 to 5 parts of at least one herbicidal compound selected from the group consisting of 3-methoxycarbonylaminophenyl-N-(3'-methylphenyl)-carbamate, 3-isopropyl-2,1,3-benzothiadiazine-4-one-2,2-dioxide and 1-phenyl-4-amino-5-chloro-pyridazone-(6)
6. A herbicidal composition comprising from 5 to 95 parts by weight of at least one compound selected from the group consisting of the formula:
wherein R1 is selected from the group consisting of ethyl and propyl, R2 is selected from the group consisting of ethyl, propyl, allyl and propargyl, R3 is selected from the group consisting of methyl and ethyl;
and from 95 to 5 parts of at least one herbicidal compound selected from the group consisting of 3-methoxycarbonylaminophenyl-N-(3'-methylphenyl)-carbamate, 3-isopropyl-2,1,3-benzothiadiazine-4-one-2,2-dioxide and 1-phenyl-4-amino-5-chloro-pyridazone-(6)
wherein R1 is selected from the group consisting of ethyl and propyl, R2 is selected from the group consisting of ethyl, propyl, allyl and propargyl, R3 is selected from the group consisting of methyl and ethyl;
and from 95 to 5 parts of at least one herbicidal compound selected from the group consisting of 3-methoxycarbonylaminophenyl-N-(3'-methylphenyl)-carbamate, 3-isopropyl-2,1,3-benzothiadiazine-4-one-2,2-dioxide and 1-phenyl-4-amino-5-chloro-pyridazone-(6)
7. A herbicidal composition comprising from 5 to 95 parts by weight of a compound selected from the group consisting of 2-[1-(allyloxyamino)propylidene]-5,5-dimethylcyclohexane-1,3-dione, 2-[1-(allyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione, 2-[1-(allyloxyamino)butylidene]-4-methoxycarbonyl-5,5-dimethyl-cyclohexane-1,3-dione and sodium salt of above compounds and from 95 to 5 parts of at least one herbicidal compound selected frcm thc group consisting of N-(3-chloro-4-methoxypilenyl)-N',N'-dimethylurea, N-(3,4-dichlorophenyl)-N',N'-dimethylurea, N-(3,4-dichlorophenyl)-N'-methoxy-N'-methylurea, 1,3-dimethyl-(3-benzothiazole-2-yl)urea, 1,3-dimethyl-3-(5-methylbenzothiazole-2-yl)urea, 1,3-dimethyl-3-(5-t-butylbenzothiazole-2-yl)urea, 1,1,3-trimethyl-3-(5-methylbenzothiazole-2-yl)urea, 1,1,3-trimethyl-3-(5-ethylbenzothiazole-2-yl)urea, 1,3-dimethyl-3-(5,7-dimethylbenzothiazole-2-yl)urea, 1,1,3-trimethyl-3-(5,7-dimethylbenzothiazole-2-yl)urea, 3-methoxycarbonylaminophenyl-N-(3'-methylphenyl)-carbamate, 3-isopropyl-2,1,3-benzothiadiazine-4-one-2,2-dioxide, and 1-phenyl-4-amino-5-chloro-pyridazine-(6)
8. A herbicidal composition comprising 30 to 70 parts by weight of 2-[l-(allyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione or sodium salt thereof and from 70 to 30 parts of 3-methoxycarbonylaminophenyl-N-(3'-methylphenyl)carbamate.
9. A herbicidal composition comprising 30 to 70 parts by weight of 2-[1-(allyloxyamino)butylidene]-4-methoxycarbonyl-5,5-dimethylcyclohexane-1,3-dione or sodium salt thereof from 70 to 30 parts of 3-methoxycarbonyl-aminophenyl-N-(3'-methylphenyl)-carbamate.
10. A herbicidal composition comprising 30 to 70 parts by weight of 2-[1-(allyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione or sodium salt thereof and from 70 to 30 parts of 3-isopropyl-2,1.3-benzothiadiazine-4-one-2,2-dioxide.
11. A herbicidal composition comprising 30 to 70 parts by weight of 2-[1-(allyloxyamino)butylidene]-4-methoxycarbonyl-5,5-dimethylcyclollexane-1,3-dione or sodium salt thereof and from 70 to 30 parts of 3-isopropyl-2,1,3-benzothiadiazine-4-one-2,2-dioxide.
12. A herbicidal composition comprising 30 to 70 parts by weight of 2 (allyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione or sodium salt thereof and from 70 to 30 parts of 1-phenyl-4-amino-5-chloro-pyridazon-(6)
13. A herbicidal composition comprisiilg 30 to 70 parts by weight of 2-[1-(allyloxyamillo)butylidene]-4-methoxycarbonyl-5,5-dimethylcyclohexane-1,3-dione or sodium salt thereof and from 70 to 30 parts of 1-phenyl-4-amino-5-chloro-pyridazone-(6)
14. A method for the control of weeds comprising applying a herbicidal com-position of claim 1 in an amount sufficient to exert herbicidal action to A locus to be protected.
15. A method for the control of weeds comprising applying a herbicidal com-position of claim 2 in an amount sufficient to exert herbicidal action to a locus to be protected.
16. A method for the control of weeds comprising applying a herbicidal com-position of claim 3 in an amount sufficient to exert herbicidal action to a locus to be protected.
17. A method for the control of weeds comprising applying a herbicidal com-position of claim 4 in an amount sufficient to exert herbicidal action to a locus to be protected.
18. A method for the control of weeds comprising applying a herbicidal com-position of claim 5 in an amount sufficient to exert herbicidal action to a locus to be protected.
19. A method for the control of weeds comprising applying a herbicidal com-position of claim 6 in an amount sufficient to exert herbicidal action to a locus to be protected.
20. A method for the control of weeds comprising applying a herbicidal com-position of claim 7 in an amount sufficient to exert herbicidal action to a locus to be protected.
21. A method for the control of weeds comprising applying a herbicidal com-position of claim 8 in all amount sufficient to exert herbicidal action to a locus to be protected.
22. A method for the control of weeds comprising applying a herbicidal com-position of claim 9 in an amount sufficient to exert herbicidal action to a locus to be protected.
23. A method for the control of weeds comprising applying a herbicidal com-position of claim 10 in an amount sufficient to exert herbicidal action to a locus to be protected.
24. A method for the control of weeds comprising applying a herbicidal com-position of claim 11 in an amount sufficient to exert herbicidal action to a locus to be protected.
25. A method for the control of weeds comprising applying a herbicidal com-position of claim 12 in an amount sufficient to exert herbicidal action to a locus to be protected.
26. A method for the control of weeds comprising applying a herbicidal com-position of claim 13 in an amount sufficient to exert herbicidal action to a locus to be protected.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP49107654A JPS5931481B2 (en) | 1974-09-20 | 1974-09-20 | Cyclohexanedione herbicide composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1044912A true CA1044912A (en) | 1978-12-26 |
Family
ID=14464651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA234,775A Expired CA1044912A (en) | 1974-09-20 | 1975-09-04 | Herbicidal compositions |
Country Status (30)
| Country | Link |
|---|---|
| JP (1) | JPS5931481B2 (en) |
| AR (1) | AR218213A1 (en) |
| AT (1) | AT347174B (en) |
| AU (1) | AU477150B2 (en) |
| BE (1) | BE833488A (en) |
| BG (1) | BG27049A3 (en) |
| BR (1) | BR7506049A (en) |
| CA (1) | CA1044912A (en) |
| CH (1) | CH619113A5 (en) |
| CS (1) | CS191946B2 (en) |
| DD (1) | DD119700A5 (en) |
| DE (1) | DE2541702A1 (en) |
| DK (2) | DK421775A (en) |
| EG (1) | EG11973A (en) |
| FI (1) | FI752645A (en) |
| FR (1) | FR2285070A1 (en) |
| GB (1) | GB1481389A (en) |
| HU (1) | HU176584B (en) |
| IL (1) | IL48010A (en) |
| IN (1) | IN144613B (en) |
| IT (1) | IT1060068B (en) |
| NL (1) | NL7510946A (en) |
| NZ (1) | NZ178624A (en) |
| OA (1) | OA05112A (en) |
| PL (1) | PL101883B1 (en) |
| RO (1) | RO71395A (en) |
| SE (1) | SE426772B (en) |
| SU (2) | SU628799A3 (en) |
| TR (1) | TR18679A (en) |
| ZA (1) | ZA755662B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3032259A1 (en) * | 1980-08-27 | 1982-04-08 | Basf Ag, 6700 Ludwigshafen | HERBICIDES BASED ON CYCLOHEXANE-1,3-DION DERIVATIVES AND 3,6-DICHLOR-2-PICOLINE ACID DERIVATIVES |
| DE3047924A1 (en) * | 1980-12-19 | 1982-07-15 | Basf Ag, 6700 Ludwigshafen | 5-ARYL-CYCLOHEXAN-1,3-DION DERIVATIVES, HERBICIDES THAT CONTAIN THESE COMPOUNDS, AND METHOD FOR THE PRODUCTION THEREOF |
| DE3121355A1 (en) * | 1981-05-29 | 1982-12-16 | Basf Ag, 6700 Ludwigshafen | CYCLOHEXANDION DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND HERBICIDES CONTAINING THEM |
| NZ204160A (en) * | 1982-05-24 | 1985-07-31 | Imp Chemical Ind Australia Ltd | Heterocyclic compounds and herbicidal compositions |
| GB8313774D0 (en) * | 1983-05-18 | 1983-06-22 | Ici Plc | Herbicidal compositions |
| US4511391A (en) * | 1983-05-24 | 1985-04-16 | Ici Australia Limited | Cyclohexane-1,3-dione derivatives and their herbicidal compositions and methods |
| ES2038592T3 (en) * | 1985-12-30 | 1993-08-01 | Stauffer Chemical Company | PROCEDURE FOR PREPARING A SYNERGIC HERBICIDE COMPOSITION. |
| US9073969B2 (en) | 2009-11-16 | 2015-07-07 | Centre National de la Recherche Scientifique—CNRS | Compounds and methods for purifying peptides produced by solid phase peptide synthesis |
-
1974
- 1974-09-20 JP JP49107654A patent/JPS5931481B2/en not_active Expired
-
1975
- 1975-08-28 IL IL48010A patent/IL48010A/en unknown
- 1975-09-02 AU AU84475/75A patent/AU477150B2/en not_active Expired
- 1975-09-04 SE SE7509840A patent/SE426772B/en not_active IP Right Cessation
- 1975-09-04 CA CA234,775A patent/CA1044912A/en not_active Expired
- 1975-09-04 ZA ZA00755662A patent/ZA755662B/en unknown
- 1975-09-08 FR FR7527459A patent/FR2285070A1/en active Granted
- 1975-09-08 NZ NZ178624A patent/NZ178624A/en unknown
- 1975-09-09 CH CH1167575A patent/CH619113A5/en not_active IP Right Cessation
- 1975-09-15 IN IN1765/CAL/1975A patent/IN144613B/en unknown
- 1975-09-16 TR TR18679A patent/TR18679A/en unknown
- 1975-09-16 HU HU75NI192A patent/HU176584B/en unknown
- 1975-09-17 BG BG7531005A patent/BG27049A3/xx unknown
- 1975-09-17 NL NL7510946A patent/NL7510946A/en not_active Application Discontinuation
- 1975-09-17 BE BE160097A patent/BE833488A/en not_active IP Right Cessation
- 1975-09-18 OA OA55612A patent/OA05112A/en unknown
- 1975-09-18 DE DE19752541702 patent/DE2541702A1/en active Pending
- 1975-09-18 DD DD188421A patent/DD119700A5/xx unknown
- 1975-09-18 PL PL1975183476A patent/PL101883B1/en unknown
- 1975-09-18 GB GB38348/75A patent/GB1481389A/en not_active Expired
- 1975-09-19 CS CS756364A patent/CS191946B2/en unknown
- 1975-09-19 DK DK421775A patent/DK421775A/en unknown
- 1975-09-19 BR BR7506049*A patent/BR7506049A/en unknown
- 1975-09-19 AR AR260460A patent/AR218213A1/en active
- 1975-09-19 RO RO7583429A patent/RO71395A/en unknown
- 1975-09-19 IT IT51405/75A patent/IT1060068B/en active
- 1975-09-19 SU SU752173209A patent/SU628799A3/en active
- 1975-09-19 AT AT719475A patent/AT347174B/en active
- 1975-09-20 EG EG562/75A patent/EG11973A/en active
- 1975-09-22 FI FI752645A patent/FI752645A/fi not_active Application Discontinuation
-
1976
- 1976-08-10 SU SU762392645A patent/SU651640A3/en active
- 1976-08-19 DK DK374276AA patent/DK141642B/en not_active IP Right Cessation
Also Published As
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE3884076T2 (en) | Herbicidal compositions of acylated 1,3-dicarbonyl herbicides and antidots therefor. | |
| CA1044912A (en) | Herbicidal compositions | |
| HU180094B (en) | Synergetic composition for controlling growth of plants first of all for defoliation | |
| CA1158257A (en) | Cyclohexane derivatives | |
| CA1200250A (en) | S-benzyl thiolcarbamates and their use in controlling weeds in rice fields | |
| US5108488A (en) | Synergistic herbicidal composition | |
| DE1695989B2 (en) | 2- (3 ', 4'-DICHLOROPHENYL) -4-METHYL-1,2,4-OXYDIAZOLIDINE-3,5-Dione, METHOD FOR ITS PREPARATION AND ITS USE AS A HERBICIDAL AGENT | |
| US3999974A (en) | Barbituric acid derivatives | |
| US4531966A (en) | Herbicide compositions | |
| EP0053699A1 (en) | 2'-Phenyl-hydrazino-2-cyanacrylic-acid esters and herbicides containing them | |
| US4264777A (en) | Herbicidal diphenyl ether compound | |
| US3681406A (en) | N-alkoxyalkylidenesulfonamide compounds | |
| US3973945A (en) | Pyran-2,4-dione derivatives | |
| CA1111062A (en) | Diphenyl ether derivatives, process for preparing the same and herbicidal compositions containing the same | |
| CA1293620C (en) | Herbicidal composition | |
| CA1308928C (en) | Herbicidal composition | |
| KR790001602B1 (en) | Herbicidal composition | |
| JPS62185003A (en) | Herbicidal composition | |
| BR9914709B1 (en) | 3- (substituted phenyl) -5- (substituted cyclopropyl) -1,2,4-triazole compounds, their preparation process, composition and non-therapeutic process for controlling insects or mites. | |
| US3966452A (en) | Herbicide mixtures of 3-lower alkyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxides or salts thereof and lower alkyl N-(4-aminobenzenesulfonyl)-carbamates | |
| PL103048B1 (en) | A WORMHOUSE FOR COTTON CULTIVATION | |
| CA1146766A (en) | Herbicidal compositions with a base of diamino-2,4-chloro-6-methylthio-5-pyrimidine and of herbicidal derivatives of urea and treatment process for crops with the said compositions | |
| US4078913A (en) | Herbicidal 3-(2-phenylisopropyl)urea derivatives | |
| DE2915406A1 (en) | ACTIVE SUBSTANCES AND PROCESS FOR THEIR PRODUCTION | |
| JPS5993007A (en) | Herbicidal composition |