CA1117122A - Herbicidal compositions - Google Patents
Herbicidal compositionsInfo
- Publication number
- CA1117122A CA1117122A CA000274314A CA274314A CA1117122A CA 1117122 A CA1117122 A CA 1117122A CA 000274314 A CA000274314 A CA 000274314A CA 274314 A CA274314 A CA 274314A CA 1117122 A CA1117122 A CA 1117122A
- Authority
- CA
- Canada
- Prior art keywords
- alkyl
- halogen
- formula
- phenoxy
- phenyl
- 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
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
- C07C205/57—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C305/00—Esters of sulfuric acids
- C07C305/02—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton
- C07C305/04—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton being acyclic and saturated
- C07C305/10—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton being acyclic and saturated being further substituted by singly-bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/63—Esters of sulfonic acids
- C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
- C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
- C07C309/66—Methanesulfonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
- C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Herbicidal preparations containing compounds of the formula wherein (R)n is one or more halogen atoms, CF3, CH3, C2H5; (R1)n1 is H, halogen or CF3; R2 is H or alkyl; X and Y are O or S; Z is, among others, OH, SH,
Herbicidal preparations containing compounds of the formula wherein (R)n is one or more halogen atoms, CF3, CH3, C2H5; (R1)n1 is H, halogen or CF3; R2 is H or alkyl; X and Y are O or S; Z is, among others, OH, SH,
Description
The subject of the invention is herbicidal preparations, and in particular relates to novel compounds of yeneral formula I
and to a method of controlling the growth of monocatyledonous weeds which comprises applying to th.e monocatyledenous weeds or a track of land a herbicidally effective amount of a compound of the general formula ( ~ X ~ Y-CHCH2-Z
(R)n (Rl)nl in which R represents the same or different substituents from the group halogen, CF3, CH3 or C2H5, Rl = the same or different substituents from the group consisting of halogen and CF3, n = the numbers 1 or 2, _1 = , 1, 2;
X and Y = O
Z = -OH, ~ R4 , \ R5,' -Cl, ~Br, -OCO-OR3 -O-CO-N R~
\ R-~
.
O CO R6 ' ~2 R6 ~ SO 3 R7 or the raclical of the ~ormula II
-O-CO--CH-Y ~ X ~> II
(Rl)nl (R)n R3 = (Cl-C12) alkyl, (C3 C8) cycloalkyl, (C2-C10) alkenyl, (C5-C6) cycloalkenyl, (C3-C8) alkinyl, phenyl or benzyl, where such radicals may be substituted by halogen, CF3, N02, CN, (Cl-C4) alkyl, (Cl-C4) alkylthio, (Cl-C4)-alkoxy, -OEI, -NH2, (Cl-C6) alkylamino, Di-(Cl-C6) alkylamino and/or (Cl-C6) alkoxycarbonyl, R4 = H, (Cl-C4) alkyl, (C2-C4) alkenyl, cyclopentyl, cyclohexyl, (Cl-C4) alkoxy or phenyl, which is optionally substituted by halogen, CF3, N02, CN, (Cl-C4) alkyl, (Cl-C4) alkylthio, (Cl-C4) alkoxy, OH, NH2, (Cl-C6)-alkylamino, Di-(Cl-C6) alkylamino and/or (Cl-C6) alkoxycarbonyl, R5 = H or (C1-C4) alkyl, or R4 and R5 together with the nitrogen atom are piperidine and pyrrollidine.
R6 a radical of the formula R3 or phenoxy-(C2-C3) alkyl, which is optionally substituted in the phenyl ring 1 to 3 times by F. Cl, Br and/or -CH3;
R7 = H, (Cl-C4) alkyl or cat and . , ', :, ~, .
.
cat+ represents the cation of an inorganic or organic base, with the proviso that, when Z = OH or -OCOR6 in which R6 = (Cl-C3) alkyl and X and Y = , (R)n canno-t be 4-haloyen.
The alkyl, alkenyl and alkinyl radicals mentioned under R3 to R7 may be straiyht-chained or branched.
Among the aforesaid radicals the following preferably mean:
(R)n = one to two identical or different -Cl, -Br and CF3, especially 4-Cl, 2,4-Cl, 2-Cl-4-Br, 4-CF3 and 2--C1-4-CF3i -1 = or (Rl)n = Cl or Br in the 2-position relatively to Y, R2 = CH3, X, Y = O, Z = -OH, -Cl, -Br; the radical of the formula II, in which (R)n and nl have the meaning given above; also the groups " ~ R4 ~
-O-C-N \ I R4 = H, (Cl-C4) alkyl, phenyl, halogen-R5 phenyl, methylphenyl or trifluoro-methylphenyl., and R5 as given above;
-0-S02 R6 in which R6 = CH3, phenyl, methylphenyl or chlorophenyl;
-O-S03~R7 in which R7 = (Cl-C4) alkyl or cat ~;
. .
:
Z
-O-C-R6 in which R6 = (Cl-Cg)alkyl, (Cl-C~)chloroalky:l, phenoxy-(Cl-C4)alkyl, which is optionally substituted in the phenyl radical by 1-2 halogen atoms and/or methyl groups, (C2-C5)alkenyl or phenyl, which is oplionally substituted once or twice by -Cl, -Br, -N02, -CH3, -CF3 or -OCH3, and cat~3 = Nà+ K+, N~14~, l/2 Ca , H~N C2~15, H3N CH2CH20H, 3 3, 2 5 3 NH~_ 0, }~ ~C~12CH20~1)3.
lOEspecially preferred owing to their biological properties are tbose compounds in which Z~= -OH, -O-CO-NH2 or -0-CO-R6 The compounds of the formula I o the invention can be prepared, starting from phenoxyphenols of the formula -X ~ ~ ~ Y- H III
n (Rl) nl , or corresponding phenolates by many methods known to the expert~ Thus, com-pounds o the formula III are reacted in a manner in itself known witb compou~ds of the formula R
:~ 20 B-C-CH2-Z IV
H
~:~in which B represents halogen or a sulpho-ester group, for example, 2-bromopro-~:pane, 2-bromo-l-chloropropane or 2-bromopropanol, optionally in the presence of acid-binding agents, and are then converted into further compounds of the form-:, ' ' : ' ' `, ~ ~ ' " , ~ ' " ' ' , zz ~lla I by reactions customary in organic chemistry, especially by esterification of the propanols so obtained.
~ or preparing the compounds of the invention various methods may be used, of which a few are described as fol:Lows and in the examples.
1.) Alcohols of the formula I ~Z = 0}1) can be obtained, as described above, by the reaction of compounds of the formuLa III with halogen-alcohols of the formula IV, by hydrolysis of the corresponding halogenalkyl-compounds (Z = hal-ogen) or by reduction of the corresponding esters of carboxylic acids of the formula II preferably with metal hydrides such, for example, as lithium aluminum hydride. For the case in which R2 = Z alcohols of the formula I can also be ob-tained by reacting a compound of the formula III, preferably an alkali salt thereof, with ethylene oxide.
and to a method of controlling the growth of monocatyledonous weeds which comprises applying to th.e monocatyledenous weeds or a track of land a herbicidally effective amount of a compound of the general formula ( ~ X ~ Y-CHCH2-Z
(R)n (Rl)nl in which R represents the same or different substituents from the group halogen, CF3, CH3 or C2H5, Rl = the same or different substituents from the group consisting of halogen and CF3, n = the numbers 1 or 2, _1 = , 1, 2;
X and Y = O
Z = -OH, ~ R4 , \ R5,' -Cl, ~Br, -OCO-OR3 -O-CO-N R~
\ R-~
.
O CO R6 ' ~2 R6 ~ SO 3 R7 or the raclical of the ~ormula II
-O-CO--CH-Y ~ X ~> II
(Rl)nl (R)n R3 = (Cl-C12) alkyl, (C3 C8) cycloalkyl, (C2-C10) alkenyl, (C5-C6) cycloalkenyl, (C3-C8) alkinyl, phenyl or benzyl, where such radicals may be substituted by halogen, CF3, N02, CN, (Cl-C4) alkyl, (Cl-C4) alkylthio, (Cl-C4)-alkoxy, -OEI, -NH2, (Cl-C6) alkylamino, Di-(Cl-C6) alkylamino and/or (Cl-C6) alkoxycarbonyl, R4 = H, (Cl-C4) alkyl, (C2-C4) alkenyl, cyclopentyl, cyclohexyl, (Cl-C4) alkoxy or phenyl, which is optionally substituted by halogen, CF3, N02, CN, (Cl-C4) alkyl, (Cl-C4) alkylthio, (Cl-C4) alkoxy, OH, NH2, (Cl-C6)-alkylamino, Di-(Cl-C6) alkylamino and/or (Cl-C6) alkoxycarbonyl, R5 = H or (C1-C4) alkyl, or R4 and R5 together with the nitrogen atom are piperidine and pyrrollidine.
R6 a radical of the formula R3 or phenoxy-(C2-C3) alkyl, which is optionally substituted in the phenyl ring 1 to 3 times by F. Cl, Br and/or -CH3;
R7 = H, (Cl-C4) alkyl or cat and . , ', :, ~, .
.
cat+ represents the cation of an inorganic or organic base, with the proviso that, when Z = OH or -OCOR6 in which R6 = (Cl-C3) alkyl and X and Y = , (R)n canno-t be 4-haloyen.
The alkyl, alkenyl and alkinyl radicals mentioned under R3 to R7 may be straiyht-chained or branched.
Among the aforesaid radicals the following preferably mean:
(R)n = one to two identical or different -Cl, -Br and CF3, especially 4-Cl, 2,4-Cl, 2-Cl-4-Br, 4-CF3 and 2--C1-4-CF3i -1 = or (Rl)n = Cl or Br in the 2-position relatively to Y, R2 = CH3, X, Y = O, Z = -OH, -Cl, -Br; the radical of the formula II, in which (R)n and nl have the meaning given above; also the groups " ~ R4 ~
-O-C-N \ I R4 = H, (Cl-C4) alkyl, phenyl, halogen-R5 phenyl, methylphenyl or trifluoro-methylphenyl., and R5 as given above;
-0-S02 R6 in which R6 = CH3, phenyl, methylphenyl or chlorophenyl;
-O-S03~R7 in which R7 = (Cl-C4) alkyl or cat ~;
. .
:
Z
-O-C-R6 in which R6 = (Cl-Cg)alkyl, (Cl-C~)chloroalky:l, phenoxy-(Cl-C4)alkyl, which is optionally substituted in the phenyl radical by 1-2 halogen atoms and/or methyl groups, (C2-C5)alkenyl or phenyl, which is oplionally substituted once or twice by -Cl, -Br, -N02, -CH3, -CF3 or -OCH3, and cat~3 = Nà+ K+, N~14~, l/2 Ca , H~N C2~15, H3N CH2CH20H, 3 3, 2 5 3 NH~_ 0, }~ ~C~12CH20~1)3.
lOEspecially preferred owing to their biological properties are tbose compounds in which Z~= -OH, -O-CO-NH2 or -0-CO-R6 The compounds of the formula I o the invention can be prepared, starting from phenoxyphenols of the formula -X ~ ~ ~ Y- H III
n (Rl) nl , or corresponding phenolates by many methods known to the expert~ Thus, com-pounds o the formula III are reacted in a manner in itself known witb compou~ds of the formula R
:~ 20 B-C-CH2-Z IV
H
~:~in which B represents halogen or a sulpho-ester group, for example, 2-bromopro-~:pane, 2-bromo-l-chloropropane or 2-bromopropanol, optionally in the presence of acid-binding agents, and are then converted into further compounds of the form-:, ' ' : ' ' `, ~ ~ ' " , ~ ' " ' ' , zz ~lla I by reactions customary in organic chemistry, especially by esterification of the propanols so obtained.
~ or preparing the compounds of the invention various methods may be used, of which a few are described as fol:Lows and in the examples.
1.) Alcohols of the formula I ~Z = 0}1) can be obtained, as described above, by the reaction of compounds of the formuLa III with halogen-alcohols of the formula IV, by hydrolysis of the corresponding halogenalkyl-compounds (Z = hal-ogen) or by reduction of the corresponding esters of carboxylic acids of the formula II preferably with metal hydrides such, for example, as lithium aluminum hydride. For the case in which R2 = Z alcohols of the formula I can also be ob-tained by reacting a compound of the formula III, preferably an alkali salt thereof, with ethylene oxide.
2.) Halogen-compounds of the formula I (Z = Hal) can be prepared by reacting the corresponding alcohols with halogenating agents such as thionyl chloride.
3.) Mercaptans of the formula I ~Z = SH) are obtained, for example, from the corresponding halogen-compounds of the formula I (Z = Hal) by reaction with metal hydrogen sulphides, preferably alkali hydrogen sulphides or xanthates or by reaction with thiourea and subsequent alkaline splitting of the resulting isothiouronium salts.
4.) Esters are prepared, for example, by the reaction of alcohols of the form-ula I ~Z = OH) in the presence of acid-binding agents ~bases) by reaction with the corresponding acid halides, preferably acid chlorides or acid anhydrides, preferably in inert organic solvents, or also by the direct esterification of the components in the presence of acid catalysts and the use of suitable sol-vents forming azeotropes with water or in the presence of water-binding agents.
As acid halides ~chlorides) there may be used those of mono-basic acids such as alkane carboxylic acids, benæoic acids, benzenesulphonic acids and others, but also those of poly-basic acids such as carbonic acid, sulphuric acid, dicarboxy-~'7~ Z
lic acids, in which then the other acid group or groups are, for example, ester-fied or amidated, for example, by ester radicals OR6 or amide residues /
As acid halides ~chlorides) there may be used those of mono-basic acids such as alkane carboxylic acids, benæoic acids, benzenesulphonic acids and others, but also those of poly-basic acids such as carbonic acid, sulphuric acid, dicarboxy-~'7~ Z
lic acids, in which then the other acid group or groups are, for example, ester-fied or amidated, for example, by ester radicals OR6 or amide residues /
5~
Especially carbonic acid amides can be obtained by reacting compounds of the formula I (Z =OH) with corresponding carbamic acid halides in the pres-ence of acid-binding agents or by reaction with isocyanates of the formula R~NCO.
5.) Amines of the formula I ~Z = NR4R5~ are obtained by reaction of the corres-ponding halides (chlorides) of the formula I (Z = Hal (Cl)) with amines HNR~R5 in a manner in itself known.
The primary compounds of the formula III can be prepared by methods in themselves known, for example, in a manner analogous to the processes of German Offenlegungsschriften 1,668,896 and 2,~33,067.
The compounds of the formula I have a wide spectrum of action again-st weed grasses, but are well tolerated by dicotyledonous crop plants and by various types of cereals, and can therefore be used for combating weed grasses in crop plants selectively.
The preparations of the invention generally contain 2 to 95% by weight of the active substances of the formula I. They may be used in the form of wettable powders~ emulsifiable concentrates, solutions capable of being sprayed, dusting preparations or granulates in the usual preparations.
We~table powders are preparations capable of being dispersed uni-formly in water, which contain in addition to the active substance, besides a diluent or inert substance, also wetting agents, for example, polyoxethylated alkyl-phenols, polyoxethylated oleyl- or stearyl-amines, alkylsulphonates or alkylphenylsulphonates and dispersing agents, for example, sodium lignin sul-phonate, sodium 2,2'-dinaphthylmethane-6,6'-disulphonate, sodium dinaphthyl-methane disulphonate or also sodium oleylmethyl-taurinate.
~ -7_ ~17~%Z
Eimulsifiable concentrates are obtained by dissolving the ackive sub-stance in cm organic solvent, for example, butanol, cyclohexanone, dimethylform-amide, xylene or also high boiling aromatics and the addition of a non-ionic wetting agent, for e~ampleJ a polyoxethylated alkylphenol or a polyoxethylated oleyl- or stearyl-amine.
Dusting preparations are obtained by grinding the active substance with finely divided solid substances, for example, talcum, natural clays, such as kaolin, bentonite, pyrophyllite or diatomaceous earths.
Solutions capable of being sprayed, such as are often marketed in spraying cans, contain the active substance dissolved in an organic solventJ as well asJ for exampleJ a mixture of 1uorochloro-hydrocarbons as a propellant.
Granulates can be prepared either by directing the active substance in the form of a jet onto granulated inert material capable of adsorption or by applying concentrates of the active substance by means of adhesives, for exam-ple, polyvinyl alcohol, sodium polyacrylate or also mineral oils, onto the sur-face of carrier substancesJ such as sand, kaolinikes~ or of granulated inert material. Also, suitable active substances may be prepared in the manner usual for producing fertiliser granules, if desired in admixture with fertili~ers.
In the herbicidal preparations the concentrations of the active substances in the ordinary commercial formulations may vary. In wettable pow-ders the concentration of active substance varies, for example, between about 10% and 95%, the remainder consisting of the formulation additions mentioned above. In the case of emulsifiable concentrates the concentration of active substance is about 10% to 80%. Dust-like formulations contain generally 5 to 20% of active substance, and solutions capable of being sprayed contain about 2 to 20%. In the case of granulates the content of active substance depends in part on whether the active compound is present in liquid or solid form and on ~ -8-~7~2 what granulatin~ assistants~ i1Lers etc. are used.
For use, the ordinary commercial concentrates are optionally dilu~ed in the usual manner, for example, with water in the case of wettable powders and emulsifiable concentrates. Dust-like and granulated preparations and also solutions capable of being sprayed are not diluted with further inert substances before usa. The quantities required for use vary with the external condltions such as temperature, humidity, etcO They may vary within wide limits, for ex-ample, between 0.1 and lOoO kg per hectare of active substance, but preferably between 0.5 and 5 kg per hectare.
The active substances o the invention may be combined with other herbicides and soil insecticides.
The following Examples illustrate the invention.
FORMULATION EXAMPLES
Example A:
An emulsifiable concentrate is obtained from 15 parts by weight of active substance 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxethylated nonyl-phenyl(10 EO) as emulsifier.
Example B:
A wettable powde~ easily dispersible in wa~er is obtained by mixing together 25 parts by weight of active substance 64 parts by weight of kaolin-containing quart~ as inert substance 10 parts by weight of potassium lignin sulphonate and l part by weight of sodium oleylmethyl-taurinate as wetting and dispersing agent and ground in a rod mill.
~ _9_ '' :, ' , .
~1~7~ZZ
~e~
A dus~ing preparation is obtained by mixing to~ether 10 parts by weight of active substance and 90 parts by weight of talcum as inort substance and pulverised in a hammer mill.
Example D:
A granulate consists, for example, of about 2-15 parts by weight of active substance 98-85 parts by weight of inert granulate materials such, for example, as atapulgite, pumice and quartz sand.
PROCEDURAL EXAMPLES
Example 1:
2-~4'-~',4''-Dichlorophenoxy~-phenoxy~-propanol.
28.6 grams ~0.75 mol) of lithium aluminium hydride are introduced into 2 litres of absolute ether. 354.3 grams ~1 mol) of 2-~4'-~2",4"-dichloro-phenoxy)-phenoxy~-propionic acid ethyl ester dissolved in 500 ml of absolute ether are added dropwise while stirring, in a manner such that the reaction mix-ture is maintained at the boil. After the addi~ion, the mixture is further stirred for 1 hour at the boiling temperature. After the addition of one litre of water and one litre of sulphuric acid of 10% strength, the ether phase is separated and the aqueous phase is extracted by agitation twice with 300 ml of ether each time. The combined ether phases are washed neutral with water and dried. After remo~ing the ether, the residue that remains behind is distilled in vacuo. By distillation there are obtained 303 grams ~96.7% of theory) of 2-C4'-(2'',4''-dichlorophenoxy)-phenoxy~-propanol of Bp~o 1 181C.
Cl-~C)~ -<~--~ C~'2- ~' In an analogous mamler there were prepared:
Example _ mpound of the formula I _ Bp ~ C) 2 r ~ C~13 168-172/0,05 Torr C~O~- ~0~''' ~'-' C~12-' 011 < Cl ICH3164/0,02 Torr Br- ~ O ~ -- ~ -O- C-CH2- OH
C~13 4 F3C - ~C ~ ~ ~ O- C- CH2- OH140/0,05 Torr H3C ~O } - ~ O ~ CH2- OH156/0,07 Torr ~ 6 ~l3C ~ O - C -CH2- OH165/0,02 Torr :~ 20 /Cl ~H3 7 F3C ~ O ~ O-- C- CH2 -OH133/0~02 Torr H
:: _ Example 8.
2-~4'-~4"-Trifluoromethylphenoxy)-phenoxy]-l-chloro-pro~ane.
31.2 grams ~0.1 mol) of the alcohol obtained in Example ~4) are , , . ' :
., -: :
: .
: :
introduced in~o 150 nll of toluenc together with 7.9 grams ~0.1 mol) of pyridine, and the mixture is cooled to -5~C. lo the mixture are added dropwise 13.1 grams (0.11 mol) of thionyl chlorid~ in a manner such that the temperature does no-t exceecl lO~C. After the addition, the mixture is further stirred for ~ an hour, and the temperature is slowly raised to llO~C, and maintained at that tempera-ture for 2 hours. The mixture is cooled, about 150 ml of hydrochloric acid o 20% strength are added and the mixture is stirred for ~ an hour. The toluene phase is separated off and the aqueous phase is 0xtracted by agitation twice with 100 ml of toluene each time. The combined toluene extracts are washed neutral with water and dried. The toluene is distilled off and the residue that remains is distilled. By the distillation there are obtained 31.3 grams ~94.6% of theory) of 2-~4',4"-trifluoromethylphenoxy)-phenoxy~-1-chloro-propane Bp.l 2 182C., which solidifies after 4 days and has an Mp. of 38-39~C.
Cl l3 F3C ~ 0 ~ - o - C - CH2 Cl In an analogous manner there were prepared:
20Example No. ~ Bp.( C) 9 ICH3 159/0,05 Torr C ~ 0 ~ 0 - C - CH2 ~ Cl Cl H CH3 170/0,08 Torr Cl ~ 0 - ~ ~ O - C - CH2 - Cl ~1~7~2~
Example No. Col~ound of the formula I Bp. ~ C~ _ _ _ _ 11 ~ C~)~ O-- C--Ctl2~- Cl _ -Cl 11 -~12:
Benzoic acid_2~4'-(4"-chloroPhenoxy)-phenoxy3-prop-1-yl) ester.
23 grams (0.083 mol) of the alcohol obtained in ~xample (2) are dissolved together with 9.3 grams (0.092 mol) of triethylamine in 50 ml of tol-uene, and is added dropwise in the course of lS minutes to a prepared solution at room temperature of 11.7 grams (0.083 mol) of benzoyl chloride in 150 ml of toluene. After the addition, during which the solution heats up to about 40 C, it is stirred for 2 hours, and washed twice with 200 ml of water each time to remove the triethylamine hydrochloride. The toluene phase is dried, and the toluene is distilled off. Drying the residue yields 31.4 grams (99% of theory) of benzoic acid-<2-[4'-(4"-chlorophenoxy)-phenoxy~-prop-1-yl> esterj which be-comes solid a~ter 3 days and has a Bp. of 68.5 C.
C~13 ~ I O
Cl ~ 0 ~ 0 - C - CH2 - 0 - C ~
H
'~ ~
:, . ; : :
- .
. .
- .:
a~ - .
:~ ., ., . ~, ~ ~ a~ a ~aa _ .
. . ..
o I o- I c, o-v o~ I O ~ I
~\~ ~1 ~5 u~ ~C.)--u ~$u _r~ _~ u ~u ~~
a ~
h~ ~3 U . ~
. , , ,~ ' C> O~
~ . , r^l r ' a) ~J ~ ~ r-l r~ r~ r-l ..
, ~' , ' , ' .',' ~, .
` C~ ~
o ~ ~ ~ ~ ~ ~ o L~
'' S~ t~ . " u :. `~ Q
. ' ' . . . . '.
.. . ' ' ', . .' ', ' ,.', " ' .' ' .
.
H ~ . V ' . O W r1 ¦ ~ ~5~' V ~ Z V V
O C~ :V O -C> O -U O - O -V O =C~ O -o C>--V--~ V--V--~' V--V--~ V--C~ V--~ C~--V ~ ~ r ~--V - ~.
;'. ~
' '' '' . I , I I ~ l ~V
r~
_ a~
O ri . C~J rt C~l .
~ . ' .' '. , ' ' .. ..
.' .
"' ;, ~i' . ''' ' ,f.S~ . ' ' ~7 u' , ' ' ' .
.
~7~L:22 ..
~ . , ' ' ','' t~~o ~ Ln ~ 0~
~1r~ L-- rl ~i r i r~ r~ ~
ra: ra :~ . ra ra ra ra r~a , , "
; ~ rl rl 3 ~
a~ \ \ I, I V .~V-~ U - I -~
41 O cc~ ~ ) O -V C) O - X O - U O =V O '-~>
æ ~
r-l o r~l o r~ o r~ o r-l o r-l c rl o D ~I U ~ r1 : . ~ i . . . .
~ . . . .. . . .
:
11~7~
L`O ~ct t~ O ~ G~
V ~ ' C\J 1~ ~ d' `;t o Lr\Lr~
Q '' ~ i ., ri ~ ~, ~?
_ . ~_~ , , , , ,: , ' '.
. ~ . . ~ .
.~ ' . '' ,''' : ,' ' . , . " ' .
~3 D ~ ~ D
= I o-_ I o_ I -~~ ,- - O-~ O~-cj Fi ¦ U ~ ? D ~ .-,r ¦ ~1 o r rl ' . ~ '~ ~ ' ~
I I I U ~`~1^ V ~
u ~ ~ r2.~ r~' Q) . ' !~ .
.. . . .
- l 7 ~ -. ~
7~ZZ
. . .. .. . . ...... . .... ... ...
~ ~ ~ o ~ o (~
r~ ! - r~
~Q NQ~Q : ~ ~ Nb~ ~ Q
, ..
~ ~ ~ ~ ~ Q ~ D
Cll-C~ ~-V~ CI~
41 0-~~) O =C>O .-~) O -~ O-C) O-C) O ~.V
, OO
. C~ -~C~-V-~ V-V-~ C~V-X V~
S~ OO O O O C~ O
3 ~ ~
'' ' ' ~ i ', ' ' ' ' " ~ _.
' /g .
, ' , ~7~ZZ
, ' ' '. . ' .''. ~ .
.. ' ~ ' ' ~5 ' ' ' v al ( ) "~ ~
t~ ~; ~t~ O
~,Q ~Q ~ ~ ~
. . ~
., :, , . . . -. ~ ,.'' , ' .
~ ~
,~, ~rl,P g~
r3 - v o- o~~
O ~ ~V ~ ~
~ .~ O $ o - ~, ~
o . o 1- o o o .
5P ~5P
: , . . . ..
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~xample 51:
2,2-Dichloropropionic acid <2~ 2'',4"-clichlorophenox~ 3C_~
ester.
31.3 grams ~0.1 mol) of the aLcohol obtained in Example ~1~ are boiled under reflux for 6 hours with 21.5 grarns ~0.15 mol) of dichloropropionic acid, 50 ml of chloroform and 1 ml of concentrated sulphuric acid. The water of reaction ~ormed is distilled off azeot-ropically. The mixture is cooled and washed three times with 60 ml of water each time, neutralised with bicarbonate solution, washed with lO0 ml of water, dried and dis~illed to dryness. The oily residue that remains behind is distilled m vacuo. By tho distillation there are obtained 39.1 grams ~1% of theory) of 2,2-dichloropropionic acid <2-C4'-(2",4"-dichlorophenoxy)-phenoxy~-prop-1-yl~ ester Bp. : 204 to 206 &.;
nD23: 1.5602.
Cl CI~O~O--C--CH2--~3-- C--( --CH3 In an analogous manner there were obtained Example Compound of the formula I nD/Bp (C) 52 ~(~ -C--CH2--O - C--C-CH3 nD 3: 1.5525 53 B~ O} -- C CH2 -- 0 --C - C--CH3 .., .
~' 7~
Example No. ____Compoun _o the folmula L ~ _ ,~ _ . ____ 54 (tl 0 Cl Bp.193-97/0.1 Torr ~l Cl ~ Cl ~H3 Cl nD : 1~522s _ ~3C _ ~ ~ ~ ~ ~ -C - C~l2- o - ~-- C -C~3~
_ _ ~ ~, .. .....
Example 56:
l-Methylaminocarbonyloxy-2-C4'-(2''-chloro-4''-trifluoromethylphenoxy)-phenoxy]-propane.
15 grams ~0.043 mol) of the alcohol obtained in Example (7) are maintained for 7 hours at 100C. with 6.3 grams (0.11 mol) of methyl isocyanate and 1 ml of triethylamine in 150 ml of toluene. The mixture is cooled, washed with lO0 ml of water, dried and the toluene is distilled off in vacuo. The residue that remains behind is dried at 100C. in vacuo. By drying there are obtained 17.1 grams ~98.5~ of theory) of 1-methylaminocarbonyloxy-2-C~'-~2"-chloro-4"-trifluoromethyIphenoxy)-phenoxy~-propane Mp. 64~-65&.
F3C ~ 0 ~ o - C-CH2 - O G~-N~I CH3 H
:
In an analogous manner there were obtained (see the Table):
,~ ' .
: ~ ' :: ' , , :
' :
: , :' :
, oo ~ o t~ r. ~ o) O o~
0, ~D ~ CO
. .~
. ~, . . ~ ~ ~, ~:: ~ R~
. _,.
~ ~ 0~
4~ ~ ~; O ;~ o, _ O ~
a~ a ~ a~ x ~
a R 1 ,~
o o o o o o _ . ...... ~
o a~
e4 '` ' ~ ~ ~
~ In In In ~ D
U~
~`i.`~ - - 22 ~ ' .
:
o U~ , ~ t , ~
~- ~ "
.. . . ..
. '" ''. ' ~' ', ' ' .
~-~ I , ~,, . C ) ~ n ~ 0=~) 0~1, 0=1, 0 1 O=CI =C~ =C~, ¦ C)~ V-~C CI'_C _~ ~-V~ Cl ~' C -C~ c''-r~
O ~-1 O r l O r~l O I i I C C) . . ' ' ' , '' . ' . . '' ' , '.' ~--¦ A
~;~ d-, ~ D
~3 ~'' ~, , ' '`' ' ` ' .
~ 3 .~ . . . .. , .. ., . , , ~
. . :
,. . .:
',,~ Z
rl ~_I O ' ' ~ ' '' ' V , 1~ 1 ~' ' ' ' ., o rl .
":
~ ¦ O=c~ O=c~ 0=1~ O~
~1 V V~ r, L
q~ C~ ~ O O ' O
Ln .~ . . ' ' ' ., ' ', ...
. ' a~
,, ,,,r~ "
, .
7~;ZZ
e 75:
l-Dimethylaminocarbonyloxy-2-~4'-(2'',4''-dichloro~henoxy)-phenoxy3-propane~
25 grams ~0.08 mol) of the alcohol obtained in Example ~1) are heated under reflux with 21.5 grams (0.2 mol) of dimethylcarbamic acid chloride and 20 grams (0.198 mol) of triethylamin~ in 150 ml of toluene, until no start-ing ma~erial can be detected in the thin layer chromatogram. The mixture is filtered off while hot, and after cooling washed with 150 ml of water and dried.
The toluene is distilled of in vacuo. The residue remaining behind is purified by column chromatography over aluminium oxide neutral with ethyl acetate as eluting agent. By distilling off the ethyl acetate there are obtained 26.6 grams (86.4% o theory) o 1-dimethylaminocarbonyloxy-2C4'-(2",4"-dichlorophen-oxy)-phenoxy~-propane having an nD 4: 1.5609.
Cl ~ 0 ~ _ o - C -Cl2 - 0 - C - N(CH3~2 In an analogous manner were prepared:
Example No. Compound of the formula I nD
76 ¦ Cl ~ 0 ~ 0- -CH2 0 -C -N(CH ) 0 ~ o-C -CH2 - 0--C -N~CH ) :
. ' ';~ . ~ ~ , ' , ~71%Z
~xample No. Cornpound of the formula f nD
. , .. . ~__ _____ C~3 0 78 r \ / \ _ Analysis 3 ~ o ~ ~ ~ 0-C~CII2- O C N(C~I3)2 C H N
_ I Calc 59,5 5,3 3,7 _ _ _~ ~ ~ Fnd. 59,4 5,2 3,4 Example 79:
l-Ethoxycarbonyloxy 2-c4'-~2~4''-dichlorophenoxy)-phenoxy~-propane~
31.3 grams ~0.1 mol) of the alcohol obtained in P.xample ~1~ are heated at the boil with 15O9 grams ~0.105 mol~ of C<-chlorocarbonic acid ethyl ester and 16.6 grams (0.12 mol~ of potassium carbonate in 100 ml of acetone. A
slight splitting off of carbon dioxide takes place. After 18 hours, the salt constituent is filtered off and the acetone is distilled off. The residue is purified by column chromatography with aluminium oxide and ethyl acetate as eluting agent The eluting agent is split off and the residue is dried in vacuo.
After drying, 1805 grams ~48% of theory) of 1-ethoxycarbonyloxy-2-~4'-~2",4"-di-chlorophenoxy)-phenoxy~-propane having an nD24: 1.5516 is obtained.
~Cl ICH3 Cl- ~ 0 ~ O~~C -CH2 - 0 ~ C-- 0 C2H5 H
Example 80:
Methanesulphoni_ acid ~2~C4'-(4''-trifluoromethylphenoxy)-phenoxy3-prop-l-yl>
ester :: :
25 grams ~0.08 mol) of the alcohol obtained in Example (4) are dis-solved with 10.1 grams (0.1 mol~ of triethylamine in 50 ml of toluene, and the solution is introduced dropwise in the course of 10 minutes into a solution of :
~ - ~26 -`
;:
1~7~
9.2 grams (0.08 mol) of rnc~hane sulphonyl chloride in 140 ml o~ toluene. After the addition, the mixture is further stirred for 2 hours and washed three times with 150 ml of water each time. Drying is carried out7 and the toluene is dis-tilled off _ vacuo. Drying in vacuo of the residue remaining behind yi~lds 29_ grams ~92.7% of theory) of methane sulphonic acid ~2-C4'(4"-trifluoromethylphen-oxy)-phenoxy~-prop-l-yl> ester.
c~l3 ~ ~ 0 --C- C~l2 - 0 -S02--C~l3 Analysis:
Calculated: C 52.3%; H 4.4%; S 8.2%
Found: C 52.0%; H 4.3%; S 8.0%
In an analogous manner were prepared:
Example No. Compound of the formula I nD/Mp. (C) . -81 F3C ~ 0 ~ -0~ C -C~l2- -52- ~ nD23 5 1.5412 82 ~ CH3 ~ _ ~ Mp.: 56-58 ~-- ~ Cl CH2 O--so2~Q
83 Cl ~ ~ 0 -C -CH -0 -S0 ~ - 27 -.
' ~ '` ' :. .
.
zz example No. Compound of t.he formula I nD/Mp. tC) . . , . ,, . ... . ~ ..
84 C~13 ~l3C ~ O } O - C ~ 2--50 Example 85:
l-N-Piperidino-? {4~-~2~',4"-dichlorophenoxx2-phenoxy~-propane.
27.5 grams ~0.083 mol) of the chloride obtained in Bxample (10) are maintained at 140 C. in an autoclave with lS0 ml of piperidine for 10 hours.
After cooling, the product is taken up in 400 ml of methylene chloride and washed neutral with water. Methylene chloride is distilled off and the residue remaining behind is dried in vacuo. After the drying, 28.5 grams (90.4% of theory) of l-N-piperidino-2i~4'-(2"~4"-dichlorophenoxy)-phenoxy~-propane~ are obtained: nD22: 1.5688.
Cl CH3 Cl ~ 0 ~ O- C - CH2-- N
In an analogous manner were prepared:
Example No. Compound of the formula I nD
~: . ....... ... ~ _ ,, .. , 86 CH3 ~D : 1.5597 Cl ~ o~ ~ o -I -CH
H
:
; ~ - 2~ -. :
~7~2 Exa7~lo No. Compo7~d of the formula I nD
~__ __ A
87 Ctl3 C tl F3C ~ O~ ~ 0 ~ -0-C -Ctl2 - N ~calc.66,5 6,4 15,0 - tl nd. 66,0 6,2 15,0 88 Ctl3 nD23 5: 1.5208 ~ ~0, ~
89 /Cl CH3 Cl- ~ - C ~ -O-C- Ctl2- N
Cl ~ ~ ~ - 0-C -CH2 N
H
Example 91:
l-Aminocarbonyloxy-2-~4'-~47'-trifluoromethylphenoxy)~e~_nox~3-propane.
31.2 gra~s (0.1 mol) of the alcohol obtained in Example (4) were in-troduced with 13 grams ~0.2 mol) of sodium cyanate into 200 ml of methylene chloride, and 24 grams of trifluoracetic acid were added dropwise, while stir-ring, in the course of one hour. After the addition, the mixture is heated at the boil ~about 2 days) until no starting material is detected by thin layer chromatography. lhe mixture is cooled and stirred into 400 ml of water, the - 2~9 -r ~ : ~
' ~L~17~ZZ
or~anic phasc is separated and washed neutral with water. The methylene chlor-ide is distilled off, an~ the residue remaining behind is recrystallised from ethanol/water. A:Eter recrystallisation there are obtained 27.2 grams (80.4% of theory) of l-aminocarbonyloxy-2-C4'-~4"-trifluoromethylphenoxy~-phenoxy3-propane melting at 80~-82C.
C~13 F3C ~ ~ ~ 0 C CH2- 0 ~ C -N~1z In an analogous manner are prepared:
Example Cl~o-~o--C--CH2--O--C--NH2 93 l CH3 C l~o ~ ~_ o - c--C~12--O - c ~2 Br ~ - ~ _0 - C -GM2 - 0 - C-- NH2 ~ ~ U ~ ~0--C--CH2--O--C--I~H2 Example '96:
Sodium 2-C4'-(4''-trifluoronlethylphenoxy)-phenoxy3-propyl sulphate.
13.4 grams (0.115 mol) of chlorosulphonic acid are cautiously mixed with about 15 ml of diethyl ether, the mixture is cooled to -10C. and 31,2 grams tO.l mol) of 2{4'-(4"-trifluoromethyl-phenoxy)-phenoxy~-propanol-(1) are added dropwise. After the addition, the temperature is maintained for 2 hours and then the mixture is warmed up to room temperature. The ether is removod _ vacuo, and to the free acid so obtained is added dropwise a solution of 9 grams (0.225 mol) of sodium hydroxide in 50 ml of water. Immediately on the addition bhe salt precipitates out, it is filtered off with suction, washed well with water and then dried. 36.6 grams (95.7% of theory) of sodium 2-~4'-(4"-trifluoromethylphenoxy)-phenoxy]-propyl sulphate melting at 235.50 & (with de-composition), are obtained.
F3C ~ o ~ 0 - CH - CH2 0 S03Na In an analogous manner the following compounds can be prepared:
~ - 31 -~ 7~ 2 Exa1n pl e l Mp ( c 7 C ~ ) o{O~o C CII;~ -O-SO~ T,l 9B ¦ Cl~(g~-O-~-O C CH2-O-DO H
F5 C~ O-~-O-C-CI~2 -O-SO;, H
1 0 0 Br-~- 0~ O - C ~C~!e - O- 9 0 ~ rl tO1Cl~~~O~ O-C~CH2-O-SOsNa 226 - 7 (a~com, ) 102 Cl~ O-~-O-C~CH2-O-SCaNa 1 0 3~/ 0~ ~1s F3C-~-O~ C-(:H,~ SOs I~ 20~ - 209(d e coi.1p. ) 105~ o~(~-O-C-CHe SH .
~: 106¦ Cl- (<~ o--~ o- -C- e~9~
~' . , .' ', , ' ' ~ ' ' .
.
. ~ .. , .. ~ ...... ... ... . ~ . ., , , -~17~Z
ample ~ Mp (C3 07 r~< CE13 ~_......... _ Br-~-U-~-0-C-C~,2-SH .
.108 ~" C~ o-@3~û-C-(~H2 -S~I
109 r3C-~-O~_O llclb,~rl ~
110 Cl-~-0 ~-O~C-~ O-So~ ~O 136--137~ (d.
1 1 1 ~ (~ 0-C-CH2 - o-so3 I~\0 127 -123 (~L . ) ¦ Cl ~-~--o- CH o s 3 r 113 ¦~3C ~-G-~-O- -Crr2-~o-9o3 N~O ¦ 112-113~ (d.) 1 14 ~ 3 7 ~ ~( d ~; ~; . ' . ' ' ' ' ' :'~ ~ ' ' , .
.~ ~ . . . .
- .7 ~
.
In a mann~r analogous to that in E~ample .12 the fo]lo~:rin~, ~u r-th er co mpound ~ ~/ere p r~p Lred: -~k~npl~ . . nD. bz~,l. Bp (~c) _~Cl CH3 / CEI2 115 Cl- ~ -0- ~ -O~C;-CH2-~0-r-C~ ¦ nD : 1.5645 Cl 116 <Cl CH5 0 ~ ~p 220/0,05 mm ~3r--~) ~ W) ~ C--C--C T-~2--O C a~)~
F5C-~-O-~ C-C~2--O-C-CH-CH Bp. 170/0,003 mm 118 F C-~-O~~-O-C-CM2-O-C-CII~a~ ~ Blj.170/olo2 mm and -CT-I, -C
. ~ `C~13 F3C-~-o-~ o c cH2 o-C-CH f n25: 1.5142 ~ ~ CH~ O CI~cl ~ -C~ 12l4 5: 1.5452 ~3~ ~ -C~ ~ ~ -CH2-^-r-CH-CI~ nU :1.5202 ' , ' , . ' . .
3 Y .
~71;:~
. .
~he :ollo~.n~ fu:rther compound~ oen be pre~ared by the pro ce~~ det3cribed a~ under ~ample Cl~ ~-O-CH-CH2 OH
~Cl-~-O-~-O-C Ci~2-OI~ 1 O C, C~12-ON
~-~-O-~-O-C Ciz-Or ~ 1 Cl--~-O-~-O C Cri2-O}i -cl~_o ~- -c c~ o l 1 Cl-(~-O-~-O-C CH2~OH
' ¦ ~Cl ~ C I
~3 C~ .
," . . . : . '.
- .
.. . . .
.
' .
~ . . . .
~1~7~Z
.
.... ..
. . . . . a~ u nd~r .. . . ~Y,~Ipl~
C~ O-~o_C-~,l13-ol~ . .
E`,C~ O~-O- -C~I.~OH
~ O-~-O-~ -CI12 -OI ' I 1 , 1~ C-~-O-~)-O- -C~12 OH
Br-~- G-~- O-C-CT~;~ - O~I
¦ Br-~- ~~~ O_ -CH2-OH ~ ~ 1 B -~)-O-~ C~.2-0 . Br~) -~~ O -C-CH2 - OH
- ~3 C . .
~) ~ H - .
. .,~ ' . - . .,, - .
.. ---.. . .... . ... .. .
12'~
''''''': ''': . - : ............. .. . . . .
a~ unrl~^r . ' . EY~ J 113 ¦ Cl-C~--~o ( -~H2-Cl ¦ 8 C~ -O~C-CH2 -Cl .
. ,,. .. . .
~1-~ o-~2- o-c-c~2 -Cl , . Cl~ O~ O-CH-CEI2 -CI 8 H;~ C . . - . -~Cll 8 Cl~ 0-~ o--c_c~I2- cl 8 '~ ~3 C .
:: - . . . .
: . - F3 C-~-o-Q-o-c~cH2 -Cl 8 . . . . .
.
F2 C~- O-~O-C-CH2 -Cl .
, , ~: " , -.. `.. ~.. ,.... ......... ' ' ' .li~qlZZ
as under ____ ~ }i-`
C~)~~~~-O~C -CH~ -Cl 8 ~13C .
¦ Br-~--~-O-C-CII~-Cl ¦ B
r,~ CH~,, .
. Br-~- O-~- O-~CH2 -Cl .
Br-~-O~-O-C-CH2 ~' I ' S
Br-~ O~-O-C CH2-Cl ~ 8 ~ C~.13 ~0 1~
Cl-~)-O~)_o CH_ H2~o-c-ch2-c~3 12 . c~ - o ~)-o- c c~ ~ O-C-C-H 12 Cl ~_o r~-O-C-CHa-O-C-CH=CH2 12 or 51 .: . , .
.~,_.. .,.. ~.... ........... . . .
~17~Z~
a~ under . . , ,, . l~.pl~3 Cl-~_o~~O-C CH2 ~-(C-CH=C~1-CH;, :12 ox 51 C 1-~ - o-~ ~ O C-CH2 - O-C-CH-C~ 12 Cl-~-O-~ O-C-CH2 -O-C- ICH~CH~ 12 C .-~-O-~) O-C 5Hz-O-C-CH ¦ ~ 12 Cl~ O~ O-C-C~H2 - O-c-cHa ~ o-~o3~cl 1.2 Cl-~ - 0~ ~ ~-C-CHz - G~ -O-~-C 1 ¦ lZ
Cl-~-0--~3- -C-CHz - O-C-CHz - 0~ -C 1 ¦ 12 C 1~ 0~ - 0~ C~CH2 ~ ~ C-CH~ O- ~-C 1 :L2 Cl-~-o-~)- -C-CHz-O-C--CH-O-~-C1 ~ 12 - .
.
a~ u~cl c~r ¦ Ex~r.p:L~
Cl-~-O-~-O-C-C~12-O-C-C~I-O-~-C~ 12 CHs o Cl~ -~3~0-C-~H2 -O C (CI-72 )3~0~ Cl 12 ~ ~ C~3 o Cl~ 12 Ci~ -o-~)-o-c-c~2 ~ (C~i2 )s- O~~--Cl ~1.2 Cl~ 0-~)-0-C--CI-I2-O-C C-0-~)-0~ 3r 1 Cl-~;Cl -C-C-C.-. -(` C Cl~ C~ 12 C] -~-o~3-G~C~CH2 ~ C/l 12 ~) , 2 C CH C~12 . 12 o:r 51 C.l-~Cl -0-C-CI-12~0-C-CH=CH-CH;~ . 12 o c 51:
CH~; '' CH ¦ 12 :- ' '"' ~ , , :
.
, . ,~, .. ............................. ... . ... .... . .... . . .
~17~
- a~ under . , . Exa:m pl g ___ ____~_ ~... ~
. . ~ ~ CJl,s i2 Cl-~$~o-~- -CH-~I-I2 -O C~Cl-la ~ Cl 12 ~_~Cl C~13 0 ~1~>
¦~l-C~--~-o~ a-~e-CHa-o~-Cl ¦ 12 Cl- ~-O~ 3-0-C-C~-O-C-CJ.l?-O~ Cl 12 Cl-~-O (g~ O_c-C~;a-O-e-C~-O-~ Cl Cl-~- 0-~)- O- ,-CH~ - O-C-C J- O-~-C~ 12 Cl c~3 CH., Hs C~ .
CI~ O-~-O-C-CH2-O-C-CH-O-~-Cl ~12 ¦' 1 ~ 0~ 0 '-CH2-O-C-CH O-~-CE~
¦Cl-~-0~ 0 cHa O e(Cl,, 3~ o-~)-CI¦ 12 ' . ' ' . ' ~ , -' ' ~- - ' - .
- . , -- . . .
, .. ~ .
2~Z
... . . . . . . . .
a~ .und er .
Es~ampl~3 CIJ3 C~-Cl 1 Cl-~~ o ~ o-C-C~I2 -O-C ( CHa )s - ~~)~C 1 12 Cl-~_ o_~-O-C-CII2 - O-C-CH- 0~~-0~ - BI 12 Br~~Cl }CE~3 0 12 _~Cl C~'3 . .
Br- ~(~ - 0~ O~C~CH~ - G~~-C~2 -C~s 1 Br-~Q-~-O-c-cHe-c-c-cu3-c~3-~tu~ ~ 12 Cl Crl O ~ l7 c~ l o /c~l3 ~¦ 12 ~$ ~) u ~ 1, o r 51 CH3 O . : :
Br~ )-O-~-O-C-CH2-~C-CH=CH-CH3 - : 12 or: 51~
, . , : , . . ;
- , . . . .
.
,; ' , ' ~ . ' :, ' " ' ~' , , :
~1~7~Z2 ... .. .. ..... ...... . .
as u.nd er Br-~Cl O-C -C]ie ~ O-C-Cl l=C~ . . :L2 ~ O ~g~-O-C~CH2 O-C~CB~-CH3 :L2 Br~ 0~ 0-C CH,-O-C-CilC12 . :L2 .
Br-(~ o_~-O-C-CII,~-O-C~ 12 Br-~$-O-~)-O-C-C~ ~O-C-(g~-Cl ~ 12 Br-~-O-~)~O-~C-cH2-o-c-~) Cl ¦ 12 Br-(~-O ~ O-CH C~ ~) 12 Br-~ O-~)-O-C-CHz-O-C-~-Cll ~ 12 ~< ~) CHH~ ~
. .
111'7~Z
af~ v-nder I ~xam~
Br'~<S- o~ V~ C~~IJ2 - O~ T~)2 , :I.Z
Br-~_o_~C~-o ~C~CIJ2 -O C- CH2 --~) Cl 12 H
r-~ O- ~ - O-C-Cliz - O -C-CHz - O- (~ -C l ¦ 12 Cl ~r-~)-o_~ -o-c-CT12 ~G-C CI-I2 O- ~Cl 1~
B ~Cl -O-C CH2~0-' ~CH~O-~Cl ~ 2 ~Cl CH3 CH~ C-Br~~))~ 'v'~) ~ O-C C~2 - O~e-C'H- -~-C' 1 12 B~Cl O C CH o , ~-Cl 12 r-~-O-~)-O- C-CHz-O-C-CH-O-~-CH5 ~ 12 r-Cc~- o-~ -O-C-CII2 -O-C ( CrI2 )z - ~~ -Cl~ 12 Br-e$0~ O-C-CH -O-e(CH2 ) -1 ~ 3~
.
.. .... . .... . . . . . . ................... ..
.
a~ und er ~Cl C~; 0 ~3C
~ o~ o-c- cIlLl ~o~c (c~I2 )s ~~ Zl 12 Br-~-O~ O-C-C~-~2-O C-C -O~ O~ Cl I.
Br ~; ~ O C CI~ O C ~ 3 ~ ~0~ 12 Bl~-O~ ~CH2-G-c-c~l-o-~ o-~-cl . . ,~
Dr-~- o--~- O-C- Cl12 - G- C-CII- O-~- O-~, -~ h's 12 I~3 C--~)-O-~_ O- ~-CH~ ~~ O-v--C~12 ~-CH3 :L2 ... , ~ .
- - - - . . ' ' . . .
F3C-~)-C-~3-o-c-c~l2-o-c-c~ 12 F~,C-~-O~-O-C~CIi2-O-C~-CH-- CII-CH~ ; ¦ 12 Qr 51:
.
:~ , . - :
~ . . .
: . ' .. - . , .
S ~, . . .
' . .
1~71~
.
.. . . . .
- . ..
.
a~ und ~r .~,ple . . ..
s C ~~)-O-~-O-C -CII~ -O-C-CHCl2 12 ~i'S C~)~ -C-C~2 O~C-C~Iz~ CI 1~?
FbC-~-o_~-O- C-CI~-O-C-_~la-O ~-Cl ~ 12 Fs C-~)-O-~-O-C-C'5 -O-C-CH,~ 0~ ~-Cl ¦ 3 2 C o~ C- CH2 -O-C-CH-t) ~-Cl 12 .. . . .. .. ., .- ......... .....
- - CH3 O CH3 H3 ~
C~)-O~ O~C-CH~-O-C~CH-O~ Cl . CH3 o CH H3 C~
F3 C-~ O- C-CH2~0-C~CH-O-~-CH3 12 : - : . . ' ' . - . .
- : : - . . ~
.. , , :, .
. .
.. . . .
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' , ' ':
':, . ' ' ' :
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. . a~ r F5C~ o~ o~rl~H2-~-C(C'H2 )~~~)-C~ 12 F3C~ O~ O-C CrI2 C)-C,(C~12 )8 C~ C]. 12 ~3C-~) o~ O-Cr-C~2~0~C (C~ 2 ) ~-O-~ -Cl 12 ~35-~-0-~ 0-r'-Cli3-0-C-C-0-~)~ 0 ~(~-Br ~ 12 C .~)-O-(~-O-C-C~12-O- -Cr'3 ~ lZ
C l~ - O- C-Ch3 - O-C-C ~ 2 ~C~ie ~' ~1~ 12 Cl~-O~-O-C-Cr~,-O-C-CH=C~ ¦ 12 Cl H
Cl-~ o~-o_C_c~ _c~ 2 - . . CH3 Cl-~-o-~-o-c-cH3-o-c-cHecl ~ 12 .. . . .
.. ' - :- .... ..
)~ 7, "
~l171Z~
a~. una~r L~ J e_ C] ~ - O-~-O-C ~CH2 - O-C ~CIb ~ -C I .12 o--~-o-C-c~2~ o-c-cHcl2 ¦ 12 Cl-0-0_(~ O-C-CHz-O-C-CI~-O-~-Cl ¦ ].2 C l -~- o Q- O-C~(~E2 - O-C -CH- O -~ - O-~-CF3 ¦ 12 ~ ~ - C - C- C;''2--O--C--CE~; 12 Cl-~ ~ CH3 0 ~ :12 Cl-~_o_~-O-C-CI O " C- . ¦ 12 c:~--C~C~I2--C-~ ~1 ~ 12 ; ~; F3C~~C ~O-C~CN2~0~C-CH5 ~ ~
- . .
. ., " .
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.
, ... ,.. ,.~.. ~, ............. ... .. .. . . .
. :
:' a~ u~de li ~ C~ O~ O-C-C~-12 -~ -C- C~I 12 ~C-~)-O-~-O-C-C 2-O-~-CH=C~ I~5 :12 - 0-~- C-CHz O-C~CH2 -CEI8 -CH~, 12 -O-~;O-C-CH2-O- G~) C~3 12 F~ C-(~ O C-CH2 -O~ CH8 ~ 12 3 ~0~ O-C-~,H2--O-C~-CH3 . 12 .
F C-~)H;~c~)-o-c-cE~2-o-c cE~2-cll2-cl~
-O-C-CH2-O-C -CH- C~ a ¦ 12 F3 C~ 3-o-c-cH2 ~O- C-~HCl2 12 , ~ C ' . . ' .
:~ ' . ''' '. .
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. ' 7:1Z2 . . . . . . . .. .
. .
t~ un(ler.
~C-~C~)-O~-O-C-CI12-O-C-C-CH~ 12 Pi5C~<g~-~-O-C-C~12-O-C-~-Cl ¦ 12 F,~C--~-O~ O-C-C-tl2-O-C-CH- ~ Cl 12 D~ O-~-O-C-CH2-O-C-Cllj 12 ~ ~ C~l3 0 ~C~ 12 , , . ' ' . ' ' .
, .
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Z
BIOLOGIC~L EY~MPL~S
~xample I:
Ihe seeds of grasses were sown in pots and the preparations of the invention formulated as scatterable powders were sprinkled at various dosages onto the surface of the soil. The pots were then placed in a gree~ for 4 weeks. The result o the treatment (as also in the case of the following ~xam-ples) was assessed by the method of evaluation according to the system of Bolle ~Nachrichtenblatt des Deutschen Pflanzenschutzdienstes 16, 1964, 92 - 94):
.. ~ .. .. ~
ValuePercentage degree of damage number Weeds Crop plants 2 97.5 to <100 ~0 to 2.5 3 95 to cg7.s >2.5 to 5 4 90 to <95 >5 to 10 85 to <90 >10 to 15
Especially carbonic acid amides can be obtained by reacting compounds of the formula I (Z =OH) with corresponding carbamic acid halides in the pres-ence of acid-binding agents or by reaction with isocyanates of the formula R~NCO.
5.) Amines of the formula I ~Z = NR4R5~ are obtained by reaction of the corres-ponding halides (chlorides) of the formula I (Z = Hal (Cl)) with amines HNR~R5 in a manner in itself known.
The primary compounds of the formula III can be prepared by methods in themselves known, for example, in a manner analogous to the processes of German Offenlegungsschriften 1,668,896 and 2,~33,067.
The compounds of the formula I have a wide spectrum of action again-st weed grasses, but are well tolerated by dicotyledonous crop plants and by various types of cereals, and can therefore be used for combating weed grasses in crop plants selectively.
The preparations of the invention generally contain 2 to 95% by weight of the active substances of the formula I. They may be used in the form of wettable powders~ emulsifiable concentrates, solutions capable of being sprayed, dusting preparations or granulates in the usual preparations.
We~table powders are preparations capable of being dispersed uni-formly in water, which contain in addition to the active substance, besides a diluent or inert substance, also wetting agents, for example, polyoxethylated alkyl-phenols, polyoxethylated oleyl- or stearyl-amines, alkylsulphonates or alkylphenylsulphonates and dispersing agents, for example, sodium lignin sul-phonate, sodium 2,2'-dinaphthylmethane-6,6'-disulphonate, sodium dinaphthyl-methane disulphonate or also sodium oleylmethyl-taurinate.
~ -7_ ~17~%Z
Eimulsifiable concentrates are obtained by dissolving the ackive sub-stance in cm organic solvent, for example, butanol, cyclohexanone, dimethylform-amide, xylene or also high boiling aromatics and the addition of a non-ionic wetting agent, for e~ampleJ a polyoxethylated alkylphenol or a polyoxethylated oleyl- or stearyl-amine.
Dusting preparations are obtained by grinding the active substance with finely divided solid substances, for example, talcum, natural clays, such as kaolin, bentonite, pyrophyllite or diatomaceous earths.
Solutions capable of being sprayed, such as are often marketed in spraying cans, contain the active substance dissolved in an organic solventJ as well asJ for exampleJ a mixture of 1uorochloro-hydrocarbons as a propellant.
Granulates can be prepared either by directing the active substance in the form of a jet onto granulated inert material capable of adsorption or by applying concentrates of the active substance by means of adhesives, for exam-ple, polyvinyl alcohol, sodium polyacrylate or also mineral oils, onto the sur-face of carrier substancesJ such as sand, kaolinikes~ or of granulated inert material. Also, suitable active substances may be prepared in the manner usual for producing fertiliser granules, if desired in admixture with fertili~ers.
In the herbicidal preparations the concentrations of the active substances in the ordinary commercial formulations may vary. In wettable pow-ders the concentration of active substance varies, for example, between about 10% and 95%, the remainder consisting of the formulation additions mentioned above. In the case of emulsifiable concentrates the concentration of active substance is about 10% to 80%. Dust-like formulations contain generally 5 to 20% of active substance, and solutions capable of being sprayed contain about 2 to 20%. In the case of granulates the content of active substance depends in part on whether the active compound is present in liquid or solid form and on ~ -8-~7~2 what granulatin~ assistants~ i1Lers etc. are used.
For use, the ordinary commercial concentrates are optionally dilu~ed in the usual manner, for example, with water in the case of wettable powders and emulsifiable concentrates. Dust-like and granulated preparations and also solutions capable of being sprayed are not diluted with further inert substances before usa. The quantities required for use vary with the external condltions such as temperature, humidity, etcO They may vary within wide limits, for ex-ample, between 0.1 and lOoO kg per hectare of active substance, but preferably between 0.5 and 5 kg per hectare.
The active substances o the invention may be combined with other herbicides and soil insecticides.
The following Examples illustrate the invention.
FORMULATION EXAMPLES
Example A:
An emulsifiable concentrate is obtained from 15 parts by weight of active substance 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxethylated nonyl-phenyl(10 EO) as emulsifier.
Example B:
A wettable powde~ easily dispersible in wa~er is obtained by mixing together 25 parts by weight of active substance 64 parts by weight of kaolin-containing quart~ as inert substance 10 parts by weight of potassium lignin sulphonate and l part by weight of sodium oleylmethyl-taurinate as wetting and dispersing agent and ground in a rod mill.
~ _9_ '' :, ' , .
~1~7~ZZ
~e~
A dus~ing preparation is obtained by mixing to~ether 10 parts by weight of active substance and 90 parts by weight of talcum as inort substance and pulverised in a hammer mill.
Example D:
A granulate consists, for example, of about 2-15 parts by weight of active substance 98-85 parts by weight of inert granulate materials such, for example, as atapulgite, pumice and quartz sand.
PROCEDURAL EXAMPLES
Example 1:
2-~4'-~',4''-Dichlorophenoxy~-phenoxy~-propanol.
28.6 grams ~0.75 mol) of lithium aluminium hydride are introduced into 2 litres of absolute ether. 354.3 grams ~1 mol) of 2-~4'-~2",4"-dichloro-phenoxy)-phenoxy~-propionic acid ethyl ester dissolved in 500 ml of absolute ether are added dropwise while stirring, in a manner such that the reaction mix-ture is maintained at the boil. After the addi~ion, the mixture is further stirred for 1 hour at the boiling temperature. After the addition of one litre of water and one litre of sulphuric acid of 10% strength, the ether phase is separated and the aqueous phase is extracted by agitation twice with 300 ml of ether each time. The combined ether phases are washed neutral with water and dried. After remo~ing the ether, the residue that remains behind is distilled in vacuo. By distillation there are obtained 303 grams ~96.7% of theory) of 2-C4'-(2'',4''-dichlorophenoxy)-phenoxy~-propanol of Bp~o 1 181C.
Cl-~C)~ -<~--~ C~'2- ~' In an analogous mamler there were prepared:
Example _ mpound of the formula I _ Bp ~ C) 2 r ~ C~13 168-172/0,05 Torr C~O~- ~0~''' ~'-' C~12-' 011 < Cl ICH3164/0,02 Torr Br- ~ O ~ -- ~ -O- C-CH2- OH
C~13 4 F3C - ~C ~ ~ ~ O- C- CH2- OH140/0,05 Torr H3C ~O } - ~ O ~ CH2- OH156/0,07 Torr ~ 6 ~l3C ~ O - C -CH2- OH165/0,02 Torr :~ 20 /Cl ~H3 7 F3C ~ O ~ O-- C- CH2 -OH133/0~02 Torr H
:: _ Example 8.
2-~4'-~4"-Trifluoromethylphenoxy)-phenoxy]-l-chloro-pro~ane.
31.2 grams ~0.1 mol) of the alcohol obtained in Example ~4) are , , . ' :
., -: :
: .
: :
introduced in~o 150 nll of toluenc together with 7.9 grams ~0.1 mol) of pyridine, and the mixture is cooled to -5~C. lo the mixture are added dropwise 13.1 grams (0.11 mol) of thionyl chlorid~ in a manner such that the temperature does no-t exceecl lO~C. After the addition, the mixture is further stirred for ~ an hour, and the temperature is slowly raised to llO~C, and maintained at that tempera-ture for 2 hours. The mixture is cooled, about 150 ml of hydrochloric acid o 20% strength are added and the mixture is stirred for ~ an hour. The toluene phase is separated off and the aqueous phase is 0xtracted by agitation twice with 100 ml of toluene each time. The combined toluene extracts are washed neutral with water and dried. The toluene is distilled off and the residue that remains is distilled. By the distillation there are obtained 31.3 grams ~94.6% of theory) of 2-~4',4"-trifluoromethylphenoxy)-phenoxy~-1-chloro-propane Bp.l 2 182C., which solidifies after 4 days and has an Mp. of 38-39~C.
Cl l3 F3C ~ 0 ~ - o - C - CH2 Cl In an analogous manner there were prepared:
20Example No. ~ Bp.( C) 9 ICH3 159/0,05 Torr C ~ 0 ~ 0 - C - CH2 ~ Cl Cl H CH3 170/0,08 Torr Cl ~ 0 - ~ ~ O - C - CH2 - Cl ~1~7~2~
Example No. Col~ound of the formula I Bp. ~ C~ _ _ _ _ 11 ~ C~)~ O-- C--Ctl2~- Cl _ -Cl 11 -~12:
Benzoic acid_2~4'-(4"-chloroPhenoxy)-phenoxy3-prop-1-yl) ester.
23 grams (0.083 mol) of the alcohol obtained in ~xample (2) are dissolved together with 9.3 grams (0.092 mol) of triethylamine in 50 ml of tol-uene, and is added dropwise in the course of lS minutes to a prepared solution at room temperature of 11.7 grams (0.083 mol) of benzoyl chloride in 150 ml of toluene. After the addition, during which the solution heats up to about 40 C, it is stirred for 2 hours, and washed twice with 200 ml of water each time to remove the triethylamine hydrochloride. The toluene phase is dried, and the toluene is distilled off. Drying the residue yields 31.4 grams (99% of theory) of benzoic acid-<2-[4'-(4"-chlorophenoxy)-phenoxy~-prop-1-yl> esterj which be-comes solid a~ter 3 days and has a Bp. of 68.5 C.
C~13 ~ I O
Cl ~ 0 ~ 0 - C - CH2 - 0 - C ~
H
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~xample 51:
2,2-Dichloropropionic acid <2~ 2'',4"-clichlorophenox~ 3C_~
ester.
31.3 grams ~0.1 mol) of the aLcohol obtained in Example ~1~ are boiled under reflux for 6 hours with 21.5 grarns ~0.15 mol) of dichloropropionic acid, 50 ml of chloroform and 1 ml of concentrated sulphuric acid. The water of reaction ~ormed is distilled off azeot-ropically. The mixture is cooled and washed three times with 60 ml of water each time, neutralised with bicarbonate solution, washed with lO0 ml of water, dried and dis~illed to dryness. The oily residue that remains behind is distilled m vacuo. By tho distillation there are obtained 39.1 grams ~1% of theory) of 2,2-dichloropropionic acid <2-C4'-(2",4"-dichlorophenoxy)-phenoxy~-prop-1-yl~ ester Bp. : 204 to 206 &.;
nD23: 1.5602.
Cl CI~O~O--C--CH2--~3-- C--( --CH3 In an analogous manner there were obtained Example Compound of the formula I nD/Bp (C) 52 ~(~ -C--CH2--O - C--C-CH3 nD 3: 1.5525 53 B~ O} -- C CH2 -- 0 --C - C--CH3 .., .
~' 7~
Example No. ____Compoun _o the folmula L ~ _ ,~ _ . ____ 54 (tl 0 Cl Bp.193-97/0.1 Torr ~l Cl ~ Cl ~H3 Cl nD : 1~522s _ ~3C _ ~ ~ ~ ~ ~ -C - C~l2- o - ~-- C -C~3~
_ _ ~ ~, .. .....
Example 56:
l-Methylaminocarbonyloxy-2-C4'-(2''-chloro-4''-trifluoromethylphenoxy)-phenoxy]-propane.
15 grams ~0.043 mol) of the alcohol obtained in Example (7) are maintained for 7 hours at 100C. with 6.3 grams (0.11 mol) of methyl isocyanate and 1 ml of triethylamine in 150 ml of toluene. The mixture is cooled, washed with lO0 ml of water, dried and the toluene is distilled off in vacuo. The residue that remains behind is dried at 100C. in vacuo. By drying there are obtained 17.1 grams ~98.5~ of theory) of 1-methylaminocarbonyloxy-2-C~'-~2"-chloro-4"-trifluoromethyIphenoxy)-phenoxy~-propane Mp. 64~-65&.
F3C ~ 0 ~ o - C-CH2 - O G~-N~I CH3 H
:
In an analogous manner there were obtained (see the Table):
,~ ' .
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O ~-1 O r l O r~l O I i I C C) . . ' ' ' , '' . ' . . '' ' , '.' ~--¦ A
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e 75:
l-Dimethylaminocarbonyloxy-2-~4'-(2'',4''-dichloro~henoxy)-phenoxy3-propane~
25 grams ~0.08 mol) of the alcohol obtained in Example ~1) are heated under reflux with 21.5 grams (0.2 mol) of dimethylcarbamic acid chloride and 20 grams (0.198 mol) of triethylamin~ in 150 ml of toluene, until no start-ing ma~erial can be detected in the thin layer chromatogram. The mixture is filtered off while hot, and after cooling washed with 150 ml of water and dried.
The toluene is distilled of in vacuo. The residue remaining behind is purified by column chromatography over aluminium oxide neutral with ethyl acetate as eluting agent. By distilling off the ethyl acetate there are obtained 26.6 grams (86.4% o theory) o 1-dimethylaminocarbonyloxy-2C4'-(2",4"-dichlorophen-oxy)-phenoxy~-propane having an nD 4: 1.5609.
Cl ~ 0 ~ _ o - C -Cl2 - 0 - C - N(CH3~2 In an analogous manner were prepared:
Example No. Compound of the formula I nD
76 ¦ Cl ~ 0 ~ 0- -CH2 0 -C -N(CH ) 0 ~ o-C -CH2 - 0--C -N~CH ) :
. ' ';~ . ~ ~ , ' , ~71%Z
~xample No. Cornpound of the formula f nD
. , .. . ~__ _____ C~3 0 78 r \ / \ _ Analysis 3 ~ o ~ ~ ~ 0-C~CII2- O C N(C~I3)2 C H N
_ I Calc 59,5 5,3 3,7 _ _ _~ ~ ~ Fnd. 59,4 5,2 3,4 Example 79:
l-Ethoxycarbonyloxy 2-c4'-~2~4''-dichlorophenoxy)-phenoxy~-propane~
31.3 grams ~0.1 mol) of the alcohol obtained in P.xample ~1~ are heated at the boil with 15O9 grams ~0.105 mol~ of C<-chlorocarbonic acid ethyl ester and 16.6 grams (0.12 mol~ of potassium carbonate in 100 ml of acetone. A
slight splitting off of carbon dioxide takes place. After 18 hours, the salt constituent is filtered off and the acetone is distilled off. The residue is purified by column chromatography with aluminium oxide and ethyl acetate as eluting agent The eluting agent is split off and the residue is dried in vacuo.
After drying, 1805 grams ~48% of theory) of 1-ethoxycarbonyloxy-2-~4'-~2",4"-di-chlorophenoxy)-phenoxy~-propane having an nD24: 1.5516 is obtained.
~Cl ICH3 Cl- ~ 0 ~ O~~C -CH2 - 0 ~ C-- 0 C2H5 H
Example 80:
Methanesulphoni_ acid ~2~C4'-(4''-trifluoromethylphenoxy)-phenoxy3-prop-l-yl>
ester :: :
25 grams ~0.08 mol) of the alcohol obtained in Example (4) are dis-solved with 10.1 grams (0.1 mol~ of triethylamine in 50 ml of toluene, and the solution is introduced dropwise in the course of 10 minutes into a solution of :
~ - ~26 -`
;:
1~7~
9.2 grams (0.08 mol) of rnc~hane sulphonyl chloride in 140 ml o~ toluene. After the addition, the mixture is further stirred for 2 hours and washed three times with 150 ml of water each time. Drying is carried out7 and the toluene is dis-tilled off _ vacuo. Drying in vacuo of the residue remaining behind yi~lds 29_ grams ~92.7% of theory) of methane sulphonic acid ~2-C4'(4"-trifluoromethylphen-oxy)-phenoxy~-prop-l-yl> ester.
c~l3 ~ ~ 0 --C- C~l2 - 0 -S02--C~l3 Analysis:
Calculated: C 52.3%; H 4.4%; S 8.2%
Found: C 52.0%; H 4.3%; S 8.0%
In an analogous manner were prepared:
Example No. Compound of the formula I nD/Mp. (C) . -81 F3C ~ 0 ~ -0~ C -C~l2- -52- ~ nD23 5 1.5412 82 ~ CH3 ~ _ ~ Mp.: 56-58 ~-- ~ Cl CH2 O--so2~Q
83 Cl ~ ~ 0 -C -CH -0 -S0 ~ - 27 -.
' ~ '` ' :. .
.
zz example No. Compound of t.he formula I nD/Mp. tC) . . , . ,, . ... . ~ ..
84 C~13 ~l3C ~ O } O - C ~ 2--50 Example 85:
l-N-Piperidino-? {4~-~2~',4"-dichlorophenoxx2-phenoxy~-propane.
27.5 grams ~0.083 mol) of the chloride obtained in Bxample (10) are maintained at 140 C. in an autoclave with lS0 ml of piperidine for 10 hours.
After cooling, the product is taken up in 400 ml of methylene chloride and washed neutral with water. Methylene chloride is distilled off and the residue remaining behind is dried in vacuo. After the drying, 28.5 grams (90.4% of theory) of l-N-piperidino-2i~4'-(2"~4"-dichlorophenoxy)-phenoxy~-propane~ are obtained: nD22: 1.5688.
Cl CH3 Cl ~ 0 ~ O- C - CH2-- N
In an analogous manner were prepared:
Example No. Compound of the formula I nD
~: . ....... ... ~ _ ,, .. , 86 CH3 ~D : 1.5597 Cl ~ o~ ~ o -I -CH
H
:
; ~ - 2~ -. :
~7~2 Exa7~lo No. Compo7~d of the formula I nD
~__ __ A
87 Ctl3 C tl F3C ~ O~ ~ 0 ~ -0-C -Ctl2 - N ~calc.66,5 6,4 15,0 - tl nd. 66,0 6,2 15,0 88 Ctl3 nD23 5: 1.5208 ~ ~0, ~
89 /Cl CH3 Cl- ~ - C ~ -O-C- Ctl2- N
Cl ~ ~ ~ - 0-C -CH2 N
H
Example 91:
l-Aminocarbonyloxy-2-~4'-~47'-trifluoromethylphenoxy)~e~_nox~3-propane.
31.2 gra~s (0.1 mol) of the alcohol obtained in Example (4) were in-troduced with 13 grams ~0.2 mol) of sodium cyanate into 200 ml of methylene chloride, and 24 grams of trifluoracetic acid were added dropwise, while stir-ring, in the course of one hour. After the addition, the mixture is heated at the boil ~about 2 days) until no starting material is detected by thin layer chromatography. lhe mixture is cooled and stirred into 400 ml of water, the - 2~9 -r ~ : ~
' ~L~17~ZZ
or~anic phasc is separated and washed neutral with water. The methylene chlor-ide is distilled off, an~ the residue remaining behind is recrystallised from ethanol/water. A:Eter recrystallisation there are obtained 27.2 grams (80.4% of theory) of l-aminocarbonyloxy-2-C4'-~4"-trifluoromethylphenoxy~-phenoxy3-propane melting at 80~-82C.
C~13 F3C ~ ~ ~ 0 C CH2- 0 ~ C -N~1z In an analogous manner are prepared:
Example Cl~o-~o--C--CH2--O--C--NH2 93 l CH3 C l~o ~ ~_ o - c--C~12--O - c ~2 Br ~ - ~ _0 - C -GM2 - 0 - C-- NH2 ~ ~ U ~ ~0--C--CH2--O--C--I~H2 Example '96:
Sodium 2-C4'-(4''-trifluoronlethylphenoxy)-phenoxy3-propyl sulphate.
13.4 grams (0.115 mol) of chlorosulphonic acid are cautiously mixed with about 15 ml of diethyl ether, the mixture is cooled to -10C. and 31,2 grams tO.l mol) of 2{4'-(4"-trifluoromethyl-phenoxy)-phenoxy~-propanol-(1) are added dropwise. After the addition, the temperature is maintained for 2 hours and then the mixture is warmed up to room temperature. The ether is removod _ vacuo, and to the free acid so obtained is added dropwise a solution of 9 grams (0.225 mol) of sodium hydroxide in 50 ml of water. Immediately on the addition bhe salt precipitates out, it is filtered off with suction, washed well with water and then dried. 36.6 grams (95.7% of theory) of sodium 2-~4'-(4"-trifluoromethylphenoxy)-phenoxy]-propyl sulphate melting at 235.50 & (with de-composition), are obtained.
F3C ~ o ~ 0 - CH - CH2 0 S03Na In an analogous manner the following compounds can be prepared:
~ - 31 -~ 7~ 2 Exa1n pl e l Mp ( c 7 C ~ ) o{O~o C CII;~ -O-SO~ T,l 9B ¦ Cl~(g~-O-~-O C CH2-O-DO H
F5 C~ O-~-O-C-CI~2 -O-SO;, H
1 0 0 Br-~- 0~ O - C ~C~!e - O- 9 0 ~ rl tO1Cl~~~O~ O-C~CH2-O-SOsNa 226 - 7 (a~com, ) 102 Cl~ O-~-O-C~CH2-O-SCaNa 1 0 3~/ 0~ ~1s F3C-~-O~ C-(:H,~ SOs I~ 20~ - 209(d e coi.1p. ) 105~ o~(~-O-C-CHe SH .
~: 106¦ Cl- (<~ o--~ o- -C- e~9~
~' . , .' ', , ' ' ~ ' ' .
.
. ~ .. , .. ~ ...... ... ... . ~ . ., , , -~17~Z
ample ~ Mp (C3 07 r~< CE13 ~_......... _ Br-~-U-~-0-C-C~,2-SH .
.108 ~" C~ o-@3~û-C-(~H2 -S~I
109 r3C-~-O~_O llclb,~rl ~
110 Cl-~-0 ~-O~C-~ O-So~ ~O 136--137~ (d.
1 1 1 ~ (~ 0-C-CH2 - o-so3 I~\0 127 -123 (~L . ) ¦ Cl ~-~--o- CH o s 3 r 113 ¦~3C ~-G-~-O- -Crr2-~o-9o3 N~O ¦ 112-113~ (d.) 1 14 ~ 3 7 ~ ~( d ~; ~; . ' . ' ' ' ' ' :'~ ~ ' ' , .
.~ ~ . . . .
- .7 ~
.
In a mann~r analogous to that in E~ample .12 the fo]lo~:rin~, ~u r-th er co mpound ~ ~/ere p r~p Lred: -~k~npl~ . . nD. bz~,l. Bp (~c) _~Cl CH3 / CEI2 115 Cl- ~ -0- ~ -O~C;-CH2-~0-r-C~ ¦ nD : 1.5645 Cl 116 <Cl CH5 0 ~ ~p 220/0,05 mm ~3r--~) ~ W) ~ C--C--C T-~2--O C a~)~
F5C-~-O-~ C-C~2--O-C-CH-CH Bp. 170/0,003 mm 118 F C-~-O~~-O-C-CM2-O-C-CII~a~ ~ Blj.170/olo2 mm and -CT-I, -C
. ~ `C~13 F3C-~-o-~ o c cH2 o-C-CH f n25: 1.5142 ~ ~ CH~ O CI~cl ~ -C~ 12l4 5: 1.5452 ~3~ ~ -C~ ~ ~ -CH2-^-r-CH-CI~ nU :1.5202 ' , ' , . ' . .
3 Y .
~71;:~
. .
~he :ollo~.n~ fu:rther compound~ oen be pre~ared by the pro ce~~ det3cribed a~ under ~ample Cl~ ~-O-CH-CH2 OH
~Cl-~-O-~-O-C Ci~2-OI~ 1 O C, C~12-ON
~-~-O-~-O-C Ciz-Or ~ 1 Cl--~-O-~-O C Cri2-O}i -cl~_o ~- -c c~ o l 1 Cl-(~-O-~-O-C CH2~OH
' ¦ ~Cl ~ C I
~3 C~ .
," . . . : . '.
- .
.. . . .
.
' .
~ . . . .
~1~7~Z
.
.... ..
. . . . . a~ u nd~r .. . . ~Y,~Ipl~
C~ O-~o_C-~,l13-ol~ . .
E`,C~ O~-O- -C~I.~OH
~ O-~-O-~ -CI12 -OI ' I 1 , 1~ C-~-O-~)-O- -C~12 OH
Br-~- G-~- O-C-CT~;~ - O~I
¦ Br-~- ~~~ O_ -CH2-OH ~ ~ 1 B -~)-O-~ C~.2-0 . Br~) -~~ O -C-CH2 - OH
- ~3 C . .
~) ~ H - .
. .,~ ' . - . .,, - .
.. ---.. . .... . ... .. .
12'~
''''''': ''': . - : ............. .. . . . .
a~ unrl~^r . ' . EY~ J 113 ¦ Cl-C~--~o ( -~H2-Cl ¦ 8 C~ -O~C-CH2 -Cl .
. ,,. .. . .
~1-~ o-~2- o-c-c~2 -Cl , . Cl~ O~ O-CH-CEI2 -CI 8 H;~ C . . - . -~Cll 8 Cl~ 0-~ o--c_c~I2- cl 8 '~ ~3 C .
:: - . . . .
: . - F3 C-~-o-Q-o-c~cH2 -Cl 8 . . . . .
.
F2 C~- O-~O-C-CH2 -Cl .
, , ~: " , -.. `.. ~.. ,.... ......... ' ' ' .li~qlZZ
as under ____ ~ }i-`
C~)~~~~-O~C -CH~ -Cl 8 ~13C .
¦ Br-~--~-O-C-CII~-Cl ¦ B
r,~ CH~,, .
. Br-~- O-~- O-~CH2 -Cl .
Br-~-O~-O-C-CH2 ~' I ' S
Br-~ O~-O-C CH2-Cl ~ 8 ~ C~.13 ~0 1~
Cl-~)-O~)_o CH_ H2~o-c-ch2-c~3 12 . c~ - o ~)-o- c c~ ~ O-C-C-H 12 Cl ~_o r~-O-C-CHa-O-C-CH=CH2 12 or 51 .: . , .
.~,_.. .,.. ~.... ........... . . .
~17~Z~
a~ under . . , ,, . l~.pl~3 Cl-~_o~~O-C CH2 ~-(C-CH=C~1-CH;, :12 ox 51 C 1-~ - o-~ ~ O C-CH2 - O-C-CH-C~ 12 Cl-~-O-~ O-C-CH2 -O-C- ICH~CH~ 12 C .-~-O-~) O-C 5Hz-O-C-CH ¦ ~ 12 Cl~ O~ O-C-C~H2 - O-c-cHa ~ o-~o3~cl 1.2 Cl-~ - 0~ ~ ~-C-CHz - G~ -O-~-C 1 ¦ lZ
Cl-~-0--~3- -C-CHz - O-C-CHz - 0~ -C 1 ¦ 12 C 1~ 0~ - 0~ C~CH2 ~ ~ C-CH~ O- ~-C 1 :L2 Cl-~-o-~)- -C-CHz-O-C--CH-O-~-C1 ~ 12 - .
.
a~ u~cl c~r ¦ Ex~r.p:L~
Cl-~-O-~-O-C-C~12-O-C-C~I-O-~-C~ 12 CHs o Cl~ -~3~0-C-~H2 -O C (CI-72 )3~0~ Cl 12 ~ ~ C~3 o Cl~ 12 Ci~ -o-~)-o-c-c~2 ~ (C~i2 )s- O~~--Cl ~1.2 Cl~ 0-~)-0-C--CI-I2-O-C C-0-~)-0~ 3r 1 Cl-~;Cl -C-C-C.-. -(` C Cl~ C~ 12 C] -~-o~3-G~C~CH2 ~ C/l 12 ~) , 2 C CH C~12 . 12 o:r 51 C.l-~Cl -0-C-CI-12~0-C-CH=CH-CH;~ . 12 o c 51:
CH~; '' CH ¦ 12 :- ' '"' ~ , , :
.
, . ,~, .. ............................. ... . ... .... . .... . . .
~17~
- a~ under . , . Exa:m pl g ___ ____~_ ~... ~
. . ~ ~ CJl,s i2 Cl-~$~o-~- -CH-~I-I2 -O C~Cl-la ~ Cl 12 ~_~Cl C~13 0 ~1~>
¦~l-C~--~-o~ a-~e-CHa-o~-Cl ¦ 12 Cl- ~-O~ 3-0-C-C~-O-C-CJ.l?-O~ Cl 12 Cl-~-O (g~ O_c-C~;a-O-e-C~-O-~ Cl Cl-~- 0-~)- O- ,-CH~ - O-C-C J- O-~-C~ 12 Cl c~3 CH., Hs C~ .
CI~ O-~-O-C-CH2-O-C-CH-O-~-Cl ~12 ¦' 1 ~ 0~ 0 '-CH2-O-C-CH O-~-CE~
¦Cl-~-0~ 0 cHa O e(Cl,, 3~ o-~)-CI¦ 12 ' . ' ' . ' ~ , -' ' ~- - ' - .
- . , -- . . .
, .. ~ .
2~Z
... . . . . . . . .
a~ .und er .
Es~ampl~3 CIJ3 C~-Cl 1 Cl-~~ o ~ o-C-C~I2 -O-C ( CHa )s - ~~)~C 1 12 Cl-~_ o_~-O-C-CII2 - O-C-CH- 0~~-0~ - BI 12 Br~~Cl }CE~3 0 12 _~Cl C~'3 . .
Br- ~(~ - 0~ O~C~CH~ - G~~-C~2 -C~s 1 Br-~Q-~-O-c-cHe-c-c-cu3-c~3-~tu~ ~ 12 Cl Crl O ~ l7 c~ l o /c~l3 ~¦ 12 ~$ ~) u ~ 1, o r 51 CH3 O . : :
Br~ )-O-~-O-C-CH2-~C-CH=CH-CH3 - : 12 or: 51~
, . , : , . . ;
- , . . . .
.
,; ' , ' ~ . ' :, ' " ' ~' , , :
~1~7~Z2 ... .. .. ..... ...... . .
as u.nd er Br-~Cl O-C -C]ie ~ O-C-Cl l=C~ . . :L2 ~ O ~g~-O-C~CH2 O-C~CB~-CH3 :L2 Br~ 0~ 0-C CH,-O-C-CilC12 . :L2 .
Br-(~ o_~-O-C-CII,~-O-C~ 12 Br-~$-O-~)-O-C-C~ ~O-C-(g~-Cl ~ 12 Br-~-O-~)~O-~C-cH2-o-c-~) Cl ¦ 12 Br-(~-O ~ O-CH C~ ~) 12 Br-~ O-~)-O-C-CHz-O-C-~-Cll ~ 12 ~< ~) CHH~ ~
. .
111'7~Z
af~ v-nder I ~xam~
Br'~<S- o~ V~ C~~IJ2 - O~ T~)2 , :I.Z
Br-~_o_~C~-o ~C~CIJ2 -O C- CH2 --~) Cl 12 H
r-~ O- ~ - O-C-Cliz - O -C-CHz - O- (~ -C l ¦ 12 Cl ~r-~)-o_~ -o-c-CT12 ~G-C CI-I2 O- ~Cl 1~
B ~Cl -O-C CH2~0-' ~CH~O-~Cl ~ 2 ~Cl CH3 CH~ C-Br~~))~ 'v'~) ~ O-C C~2 - O~e-C'H- -~-C' 1 12 B~Cl O C CH o , ~-Cl 12 r-~-O-~)-O- C-CHz-O-C-CH-O-~-CH5 ~ 12 r-Cc~- o-~ -O-C-CII2 -O-C ( CrI2 )z - ~~ -Cl~ 12 Br-e$0~ O-C-CH -O-e(CH2 ) -1 ~ 3~
.
.. .... . .... . . . . . . ................... ..
.
a~ und er ~Cl C~; 0 ~3C
~ o~ o-c- cIlLl ~o~c (c~I2 )s ~~ Zl 12 Br-~-O~ O-C-C~-~2-O C-C -O~ O~ Cl I.
Br ~; ~ O C CI~ O C ~ 3 ~ ~0~ 12 Bl~-O~ ~CH2-G-c-c~l-o-~ o-~-cl . . ,~
Dr-~- o--~- O-C- Cl12 - G- C-CII- O-~- O-~, -~ h's 12 I~3 C--~)-O-~_ O- ~-CH~ ~~ O-v--C~12 ~-CH3 :L2 ... , ~ .
- - - - . . ' ' . . .
F3C-~)-C-~3-o-c-c~l2-o-c-c~ 12 F~,C-~-O~-O-C~CIi2-O-C~-CH-- CII-CH~ ; ¦ 12 Qr 51:
.
:~ , . - :
~ . . .
: . ' .. - . , .
S ~, . . .
' . .
1~71~
.
.. . . . .
- . ..
.
a~ und ~r .~,ple . . ..
s C ~~)-O-~-O-C -CII~ -O-C-CHCl2 12 ~i'S C~)~ -C-C~2 O~C-C~Iz~ CI 1~?
FbC-~-o_~-O- C-CI~-O-C-_~la-O ~-Cl ~ 12 Fs C-~)-O-~-O-C-C'5 -O-C-CH,~ 0~ ~-Cl ¦ 3 2 C o~ C- CH2 -O-C-CH-t) ~-Cl 12 .. . . .. .. ., .- ......... .....
- - CH3 O CH3 H3 ~
C~)-O~ O~C-CH~-O-C~CH-O~ Cl . CH3 o CH H3 C~
F3 C-~ O- C-CH2~0-C~CH-O-~-CH3 12 : - : . . ' ' . - . .
- : : - . . ~
.. , , :, .
. .
.. . . .
' , ' ' :
' , ' ':
':, . ' ' ' :
7~L22 .
. . a~ r F5C~ o~ o~rl~H2-~-C(C'H2 )~~~)-C~ 12 F3C~ O~ O-C CrI2 C)-C,(C~12 )8 C~ C]. 12 ~3C-~) o~ O-Cr-C~2~0~C (C~ 2 ) ~-O-~ -Cl 12 ~35-~-0-~ 0-r'-Cli3-0-C-C-0-~)~ 0 ~(~-Br ~ 12 C .~)-O-(~-O-C-C~12-O- -Cr'3 ~ lZ
C l~ - O- C-Ch3 - O-C-C ~ 2 ~C~ie ~' ~1~ 12 Cl~-O~-O-C-Cr~,-O-C-CH=C~ ¦ 12 Cl H
Cl-~ o~-o_C_c~ _c~ 2 - . . CH3 Cl-~-o-~-o-c-cH3-o-c-cHecl ~ 12 .. . . .
.. ' - :- .... ..
)~ 7, "
~l171Z~
a~. una~r L~ J e_ C] ~ - O-~-O-C ~CH2 - O-C ~CIb ~ -C I .12 o--~-o-C-c~2~ o-c-cHcl2 ¦ 12 Cl-0-0_(~ O-C-CHz-O-C-CI~-O-~-Cl ¦ ].2 C l -~- o Q- O-C~(~E2 - O-C -CH- O -~ - O-~-CF3 ¦ 12 ~ ~ - C - C- C;''2--O--C--CE~; 12 Cl-~ ~ CH3 0 ~ :12 Cl-~_o_~-O-C-CI O " C- . ¦ 12 c:~--C~C~I2--C-~ ~1 ~ 12 ; ~; F3C~~C ~O-C~CN2~0~C-CH5 ~ ~
- . .
. ., " .
4~ , .
.
, ... ,.. ,.~.. ~, ............. ... .. .. . . .
. :
:' a~ u~de li ~ C~ O~ O-C-C~-12 -~ -C- C~I 12 ~C-~)-O-~-O-C-C 2-O-~-CH=C~ I~5 :12 - 0-~- C-CHz O-C~CH2 -CEI8 -CH~, 12 -O-~;O-C-CH2-O- G~) C~3 12 F~ C-(~ O C-CH2 -O~ CH8 ~ 12 3 ~0~ O-C-~,H2--O-C~-CH3 . 12 .
F C-~)H;~c~)-o-c-cE~2-o-c cE~2-cll2-cl~
-O-C-CH2-O-C -CH- C~ a ¦ 12 F3 C~ 3-o-c-cH2 ~O- C-~HCl2 12 , ~ C ' . . ' .
:~ ' . ''' '. .
" .
' ..
. ' 7:1Z2 . . . . . . . .. .
. .
t~ un(ler.
~C-~C~)-O~-O-C-CI12-O-C-C-CH~ 12 Pi5C~<g~-~-O-C-C~12-O-C-~-Cl ¦ 12 F,~C--~-O~ O-C-C-tl2-O-C-CH- ~ Cl 12 D~ O-~-O-C-CH2-O-C-Cllj 12 ~ ~ C~l3 0 ~C~ 12 , , . ' ' . ' ' .
, .
' ,' ~; ' ' ~, :. .
Z
BIOLOGIC~L EY~MPL~S
~xample I:
Ihe seeds of grasses were sown in pots and the preparations of the invention formulated as scatterable powders were sprinkled at various dosages onto the surface of the soil. The pots were then placed in a gree~ for 4 weeks. The result o the treatment (as also in the case of the following ~xam-ples) was assessed by the method of evaluation according to the system of Bolle ~Nachrichtenblatt des Deutschen Pflanzenschutzdienstes 16, 1964, 92 - 94):
.. ~ .. .. ~
ValuePercentage degree of damage number Weeds Crop plants 2 97.5 to <100 ~0 to 2.5 3 95 to cg7.s >2.5 to 5 4 90 to <95 >5 to 10 85 to <90 >10 to 15
6 75 to <85 >15 to 25
7 65 to <75 >25 to 35
8 32.5 to <65 >35 to 37.5
9 O to c3205 >67.5 to 100 .. _. _ . .. ., . . . ~
The procedure was the same with the herbicidal agents used for com-parison, fluorodifen (4-nitrophenyl-~2'-nitro-4'-trifluoromethylphenyl) ether) and mecoprop (2-~4'-chloro-2'-methylphenoxy)-propionic acid). The results col-lated in Table 1 show that the claimed compounds are on the average more active ~ - 51 -~171~
against grasses thall the two herbicicles for comp~Lrison. A similar action against grasses is shown also by the claimecl compounds according to Examples 2, 9, 10, 12, 13, 14, 15, 21, 26, 27, 28, 36, 37, 38, 39, 40, 41, 42, 58, 60, 61, 62, 64, 69, 70, 72, 75 and 81.
Table I
___ Evaluation numbers against weeds treated in pre-e~ergence.
ExampleDosage Type of plants No k ha A S AL SAL0 ~C
t g/ ~ _ _ ~
1 2.5 2 1 1 2 0.6 3 2 1 2 4 2.5 1 1 1 0.6 1 1 1 8 ~.5 1 1 2 0.6 2 2 2 2 22 2.5 3 l 1 0.6 4 2 2 2 2,5 1 l 1 0.6 3 2 1 29 2.5 2 1 1 0.6 3 1 1 24 2.5 ~ 2 2 2 0.6 5 4 3 2 63 2.5 4 3 1 3 0.6 4 5 ~ 5 71 2.5 l l 1 0.6 2 1 1 ``~2.5 2 2 1 0.6 5 3 3 3 Fluoro- 2.5 7 1 l 4 difen 0.6 8 5 8 8 Mecoprop O 6 4 6 B 3 ~ 52 -:
.
', ' ;
AL = Alopecurus myosuroides, SA = Setaria lutescens, L0 = Lolium multiflorum, EC = Echino~hloa crus-galli.
Example II:
The seeds of grasses were sown ln pots and grown in a greenhouse.
3 weeks after sowing the preparations of the invention formulated as scatterable powders were sprinkled at different dosages on the plants and th~ effect of the preparations was evaluated after a period of 4 weeks in the greenhouse. Also in this case fluorodifen and mecoprop served as herbicidal agents for comparison.
The claimed compounds in this method of application did indeed have a somewhat weaker action than in the pre-emergence method describPd in Example 1, but had a better action against grasses than the two agents for comparison ~Table II). A
similar action against grasses was exhibited by the claimed compounds according to Examples 2, 10, 24, 36, 37, 39 and 41.
Table II
Evaluation numbers against weeds in post-emergence.
~xample Dosage Type of plants No. ~k~ha A.S ) AL SA L0 EC
1 2.5 5 1 1 0.6 8 2 1 4 2.5 1 1 1 0.6 2 1 2 8 2~5 1 1 2 0.6 2 2 2 2 2.5 3 2 2 0.6 9 4 3 ' example l)osage 'I'ype of plants No. fk~/ha A S.l AL SA L0 EC
.~. . ... _~ .... ,- ___ , _ 29 2.5 2 1 1 71 2.5 4 1 1 0.~ 6 2 6 Fluoro- 2.5 8 2 6 4 difen 0.6 8 3 8 6 Mecoprop 2.5 8 7 8 8 0.6 _ 8 9 9 Example III:
The seeds for a large number of crop plants were inserted in pots.
Some of the pots were placed in a greenhouse for 2 to 3 weeks for germination and sprouting, and treated with the substances of the invention after the plantshad developed 2 to 3 true leaves. The outer pots were sprinkled immediately after being sown in the same manner as is given in Example 21. The result was ascertained 4 to 4~ weeks after the treatment, and is given in Table III. In particular, the results show that almost all dicotyledonous crop plants at the highest dosage ~2.5 kg per hectare) tolerate very well the preparations of the invention both in pre-emergence and post-emergence. As the effective dosage is about 0.6 kg per hectare, the active substances of the invention have a good selectivity in these crops.
, :
.
~1171~Z
o ~ U7 O . ~ ';t N r~ `1 t~N ~`1 ~I r-l _I t~l ~1 ~`J ~t _1 P,,~
_ _ .
~O
¢ ~_ nd h Ln p, . I I t~ ~,1 ~~ ~ ~ t-~ t,) ,I t~ ~ ,~ ,-1 ,_1 ,1 ,_1 ,1 ,_1 o . ... __ _ _____ o ~o ~4~ ,~ t~ I In ~I t~ t~~1 ~I t~ t ~
_ o _ "
U) ~ r1 ~ _ 1--1 O ~i I I t~ t~r~ 1 t~ N r1 _I N tt~ N r~ r-l N r l ~I r-l r l h .:
~ ~ _ _, f l13 0 r~ r~ r~ r~r ~ 1 r~ r l rl ri r l rl ~I r-( r1 r l r~ r~ ~I rt r1 Q~ ~
J~ N N N ~I r I _1 t~r~ r l 1--l rt r~ r l r l r l N r~l N r1 _I
O
~i Q~
Q~
X
~r-- -- ~_ ~_ ~H~
Q ~ h Q~ ~3 0 h ~3 Q~
O ~ 3 Q~ O r l Q~Q~ Q~ ,a O
~ o ~ O ~ ,D R C~
Q~ ~ h ~ ~ Q 'r~ d h ~ ~ ~ ~d ~ h h h O a)~ o ~ ~ I h ~ ~ o ~a~ h ~ O o o a> t~
, ~7~L22 ~xample IV
Seeds of n~aize and rice and of a few weed grasses that occur in these crops were sown in poks and al]owed to germina-te in a greenhouse Eor 3 weeks.
The preparations formulated in accordance with the invention as scattering pow-ders and the agents for comparison were then sprinkled on the plants in vari.ous dosages, and after ~ weeks the eEfect of the preparations was ascertained.
As agents for comparison the following compounds were used:
A = 2 { 4'(2",4"-dichlorophenoxy)-phenoxy]-propion:ic acid methyl ester tDT-OS 22 23 894) B = 2~4'~4"-chlorophenoxy)-phenox ~ propionic acid isobutyl ester (DT-OS 22 23 894) C = 2 ~4'-(4"-trifluoromethylphenoxy)-phenoxy~propionic acid methyl ester (DT-OS 24 33 067) The claimed compounds showed, as compared with the herbicides used for comparison, 8 distinctly better tolerability by maize and/or rice. At the dosages which did not, or only very slightly, damage the crop plants, they were outstandingly effective against the weed grasses tested. On the other hand, the compounds for comparison were not selective in mai~e and rice.
~71~
rra~ Q~:v Evalu~l;i.on nl~mb~rs i.n Po~:t~ r~encc -tr~ltrn~nt.
l~o~3e Crop plan t~ Weed g:ra~e.s Colnpoulld (kc~/h~) Ma;lze Ri~e . . ~3v. . . I . . s2 ? 5 6 ~ _ _~
2 ¦ 0 6 ~ 2 ¦ 3 ¦ 2 ¦
~ ¦ 2 s ¦ 1 1 2 1 6 22 . 5 _ 1 1 ¦
0.15 ¦ 6 ¦ 6 ~ 3 0.1S 8 ~ 2 . 7 c ¦ 2. 5 9 .
, :
" ~: . ' ''' ' ' ' ' '' .' ' '' " -_ ,' ' ~ ~i _a~ le V
In a further tes~ the cormpourld~ 8, ~6, 117 and 162 were used together with the comparison compound C at post-emergence .in a manner corresporldillg to that in Example I.
S The results gi.ven in rl'abl~ V show that the claimed compoun(~s are super:i.or to the agents :~or cornparison with regard to tolerability by crop plr~nts (compound ~), and, coupled w.ith the same good to]erability by the .50ya bean, they exhihit advantageous act:i.ons ac:Ja:i.n.r3t the we~d CJrarsseS
tested.
5~
~.
- ~ :
.~
~1~7~
~ . ............................... . .
- . TQble V
-- _.
I~valu~t:Lon number,ei in pre-emergcnce treatment.
. . . ' .
. Do ~ C~ro p plE3~ts Wee(l -~ra ,e~s~
. Co mpound . ( k ~ /ha ) ~3 arl ey Wh e a t ~o ya b ean AI, l~I SA I l,C
~_ __ __~_ ~ ____~_ __...... _ _~ ._~ __.
8 2 . 5 1 l 1 2 _ 1 . 0.6 1 1 1 ,~ . 2 4 0 . 1 5 1 l 1 7 ~ 5 5 . ~6 2.5 _ . 1 1 1 1 1 0.6 ~ . _ 1 2 1 1 . 2 . . 0 . 1 5 _ _ 1 . 3 1 2 2 - 1G2 2.5 _ ~ 1 1 1 1 0 . 6 _ 1 1 1 1 1~.
0 . 1 5 . _ 1 . 3 1 1 2 117 0 65 _ _ 1 1 1 1 1 0.15 _ _ . 1 3 I 2 3 C 2 . 5 9 9 1 1 1 1 'I
O . 6 9 ~ 1 1 2 1 2 5 1 8 Is I I !s;6 DI ~ Di6i taria ~nguin~l is ' -.
.
.
:
.
.. . .
:' - . - ' . ', ` .
.
:
7~:~2 example VI
'I'he efficiency of fur-ther compounds of the in-vention in pre-emergence is shown in the following Table.
Table VI
Evaluation results in pre-emergence treatment against important weed grasses.
Compound Dose Action against weed grasses .~ ~ ~ ~
12 0 56 1 1 _ _ 1 ,~ 4 ~' .-, ' 11~712:2 !` no~npou~ld ¦ DOJe Actlon a~;ai.nf~t weed gra~b~.
. ... . ... . ~}~J/]1a) .. ... AL . ... ~:C . ~;A . DI
_____ ~ .. ~ ___ __.__ .. ____. _~
2/ 1~ ~ 4 1 23 26 ~ _ ~ 3 1 31 31 0 6 4 . 3 3 3 2 2 . 5 2 1 1 3~ 25 _ 1 2 I .
0.~ _ 3 _ _ 0 65 . .~ 43 _ ~: 3 6 0 6 1 1 . 1 1 3 7 2 . 5 _ 1 ~ 1 1 .
0 . 6 1 . 1 ¦ 3 3 D 6 ¦ _ ¦ 2 7~3 Compound Do .c.e ~ot;i on aga:inst weecl grà~ s.
. .. .... .. (JccJ/ha) .. ... ~L................................................. EC. ... SA.... J~I.
91 2.5 2 0.6 3 1 ?
43 2.5 1 ... 1 0.6 2 2 ~5 2.5 . 2 0.6 3 ~ 3 ~3 2.5 ~ 2 2 0 . 6 47 2.5 1 1 ~ 1 ~
0.6 3 2 46 2.5 1 1 1.
0.6 2 2 52 2.5 3 3 ~ -0 ~
54 2.5 0.6 1 . 2 56 2.5 - 3 - -0. 6 - 5 - -58 2.5. - 1 3 --0.6 - ~ ~
61 2.5 ~ 2 2 0- 6 - 3 ~ _ 62 2.5 . - 4 0. 6 - 5 2 - .
6 3 2 . 5 ~ 3 3 - . . 0.6 4 5 5 64 ~ 2~5 - 2 2 -0.6 : - - 3 ~ -~ . . . ..
69 2. 5 - 3 - 2 -. 0 . 6 - 4 3 , ~ .
: ~ G~
.
..... ..... ;. ... ~.. ;.. . .. , :.. ,.. . .:
: . . , aompound :I)o 30 ~c t:L on ~ain~3t weod ~,ra~ F~, ... .. (ky/~a) I~ 'C... , S~ .. DI.
7 0 2 . 5 o.~ . - 2 2 72 2.5 0.6 ~ - 1 . 2 2.5 - 2 2 -0.6 - 3 3 78 2.5 - 2 0.6 - 3 3 79 2.5 ~ 2 2 - O . G
2.5 - 1 2 0.6 ~ 3 3 ~
81 2.5 - 2 0.6 -- 2 ~ --82 2.5 - .
- 0.~ - 2 6 162 ~5 1 . 1 1.
0.6 1 1 1 ~ 1 - 117 2.5 0. 6 1 1 ~ 1 1 -118 . 2.5 1 1 1 -~
0.6 2 1 2 121 2. 5 1 1 0.6 2 2 119 2.5 0. 6 3 2 116 2 . S 3 3 0.6 4 4 3 115 2.5 . 3 . 0.6 4 2 ,: . , , ' : 3 . ' - .
Compound DO~e l~o-t~on a~;sj.n~t we~d ~raE~:3e~, . .( k~ /}~ . . AIJ . . . E~ .. . ~A . . D:l~
96 . 2.5 7. 2 0.6 3 ~ 7. .
101 2.5 . 1 .1 ~ ~
0.6 . . 3 - 2 5 113 2.5 ~2 0.6 3 2 2 114 2.5 0.6 . 3 7 2 104 2.5 7.
0.6 3 2 2 110 2.5 ~ 1 ~ 2 0.6 3 2 3 -~
111 2.5 3 3 2 0.6 4 4 3 . -112 2.5 4 3 2 ~ :
0.6 ~ 4 3 - 17 2.5. 3 1 2 --0.6 5 ~ 3 .
- , ' .
~, .:
' '~ . . ' . ' .
;
~ . ' . - : - ' ;
,' ' ~ - ~ ~ ,' . ~
. .
' , : .
The procedure was the same with the herbicidal agents used for com-parison, fluorodifen (4-nitrophenyl-~2'-nitro-4'-trifluoromethylphenyl) ether) and mecoprop (2-~4'-chloro-2'-methylphenoxy)-propionic acid). The results col-lated in Table 1 show that the claimed compounds are on the average more active ~ - 51 -~171~
against grasses thall the two herbicicles for comp~Lrison. A similar action against grasses is shown also by the claimecl compounds according to Examples 2, 9, 10, 12, 13, 14, 15, 21, 26, 27, 28, 36, 37, 38, 39, 40, 41, 42, 58, 60, 61, 62, 64, 69, 70, 72, 75 and 81.
Table I
___ Evaluation numbers against weeds treated in pre-e~ergence.
ExampleDosage Type of plants No k ha A S AL SAL0 ~C
t g/ ~ _ _ ~
1 2.5 2 1 1 2 0.6 3 2 1 2 4 2.5 1 1 1 0.6 1 1 1 8 ~.5 1 1 2 0.6 2 2 2 2 22 2.5 3 l 1 0.6 4 2 2 2 2,5 1 l 1 0.6 3 2 1 29 2.5 2 1 1 0.6 3 1 1 24 2.5 ~ 2 2 2 0.6 5 4 3 2 63 2.5 4 3 1 3 0.6 4 5 ~ 5 71 2.5 l l 1 0.6 2 1 1 ``~2.5 2 2 1 0.6 5 3 3 3 Fluoro- 2.5 7 1 l 4 difen 0.6 8 5 8 8 Mecoprop O 6 4 6 B 3 ~ 52 -:
.
', ' ;
AL = Alopecurus myosuroides, SA = Setaria lutescens, L0 = Lolium multiflorum, EC = Echino~hloa crus-galli.
Example II:
The seeds of grasses were sown ln pots and grown in a greenhouse.
3 weeks after sowing the preparations of the invention formulated as scatterable powders were sprinkled at different dosages on the plants and th~ effect of the preparations was evaluated after a period of 4 weeks in the greenhouse. Also in this case fluorodifen and mecoprop served as herbicidal agents for comparison.
The claimed compounds in this method of application did indeed have a somewhat weaker action than in the pre-emergence method describPd in Example 1, but had a better action against grasses than the two agents for comparison ~Table II). A
similar action against grasses was exhibited by the claimed compounds according to Examples 2, 10, 24, 36, 37, 39 and 41.
Table II
Evaluation numbers against weeds in post-emergence.
~xample Dosage Type of plants No. ~k~ha A.S ) AL SA L0 EC
1 2.5 5 1 1 0.6 8 2 1 4 2.5 1 1 1 0.6 2 1 2 8 2~5 1 1 2 0.6 2 2 2 2 2.5 3 2 2 0.6 9 4 3 ' example l)osage 'I'ype of plants No. fk~/ha A S.l AL SA L0 EC
.~. . ... _~ .... ,- ___ , _ 29 2.5 2 1 1 71 2.5 4 1 1 0.~ 6 2 6 Fluoro- 2.5 8 2 6 4 difen 0.6 8 3 8 6 Mecoprop 2.5 8 7 8 8 0.6 _ 8 9 9 Example III:
The seeds for a large number of crop plants were inserted in pots.
Some of the pots were placed in a greenhouse for 2 to 3 weeks for germination and sprouting, and treated with the substances of the invention after the plantshad developed 2 to 3 true leaves. The outer pots were sprinkled immediately after being sown in the same manner as is given in Example 21. The result was ascertained 4 to 4~ weeks after the treatment, and is given in Table III. In particular, the results show that almost all dicotyledonous crop plants at the highest dosage ~2.5 kg per hectare) tolerate very well the preparations of the invention both in pre-emergence and post-emergence. As the effective dosage is about 0.6 kg per hectare, the active substances of the invention have a good selectivity in these crops.
, :
.
~1171~Z
o ~ U7 O . ~ ';t N r~ `1 t~N ~`1 ~I r-l _I t~l ~1 ~`J ~t _1 P,,~
_ _ .
~O
¢ ~_ nd h Ln p, . I I t~ ~,1 ~~ ~ ~ t-~ t,) ,I t~ ~ ,~ ,-1 ,_1 ,1 ,_1 ,1 ,_1 o . ... __ _ _____ o ~o ~4~ ,~ t~ I In ~I t~ t~~1 ~I t~ t ~
_ o _ "
U) ~ r1 ~ _ 1--1 O ~i I I t~ t~r~ 1 t~ N r1 _I N tt~ N r~ r-l N r l ~I r-l r l h .:
~ ~ _ _, f l13 0 r~ r~ r~ r~r ~ 1 r~ r l rl ri r l rl ~I r-( r1 r l r~ r~ ~I rt r1 Q~ ~
J~ N N N ~I r I _1 t~r~ r l 1--l rt r~ r l r l r l N r~l N r1 _I
O
~i Q~
Q~
X
~r-- -- ~_ ~_ ~H~
Q ~ h Q~ ~3 0 h ~3 Q~
O ~ 3 Q~ O r l Q~Q~ Q~ ,a O
~ o ~ O ~ ,D R C~
Q~ ~ h ~ ~ Q 'r~ d h ~ ~ ~ ~d ~ h h h O a)~ o ~ ~ I h ~ ~ o ~a~ h ~ O o o a> t~
, ~7~L22 ~xample IV
Seeds of n~aize and rice and of a few weed grasses that occur in these crops were sown in poks and al]owed to germina-te in a greenhouse Eor 3 weeks.
The preparations formulated in accordance with the invention as scattering pow-ders and the agents for comparison were then sprinkled on the plants in vari.ous dosages, and after ~ weeks the eEfect of the preparations was ascertained.
As agents for comparison the following compounds were used:
A = 2 { 4'(2",4"-dichlorophenoxy)-phenoxy]-propion:ic acid methyl ester tDT-OS 22 23 894) B = 2~4'~4"-chlorophenoxy)-phenox ~ propionic acid isobutyl ester (DT-OS 22 23 894) C = 2 ~4'-(4"-trifluoromethylphenoxy)-phenoxy~propionic acid methyl ester (DT-OS 24 33 067) The claimed compounds showed, as compared with the herbicides used for comparison, 8 distinctly better tolerability by maize and/or rice. At the dosages which did not, or only very slightly, damage the crop plants, they were outstandingly effective against the weed grasses tested. On the other hand, the compounds for comparison were not selective in mai~e and rice.
~71~
rra~ Q~:v Evalu~l;i.on nl~mb~rs i.n Po~:t~ r~encc -tr~ltrn~nt.
l~o~3e Crop plan t~ Weed g:ra~e.s Colnpoulld (kc~/h~) Ma;lze Ri~e . . ~3v. . . I . . s2 ? 5 6 ~ _ _~
2 ¦ 0 6 ~ 2 ¦ 3 ¦ 2 ¦
~ ¦ 2 s ¦ 1 1 2 1 6 22 . 5 _ 1 1 ¦
0.15 ¦ 6 ¦ 6 ~ 3 0.1S 8 ~ 2 . 7 c ¦ 2. 5 9 .
, :
" ~: . ' ''' ' ' ' ' '' .' ' '' " -_ ,' ' ~ ~i _a~ le V
In a further tes~ the cormpourld~ 8, ~6, 117 and 162 were used together with the comparison compound C at post-emergence .in a manner corresporldillg to that in Example I.
S The results gi.ven in rl'abl~ V show that the claimed compoun(~s are super:i.or to the agents :~or cornparison with regard to tolerability by crop plr~nts (compound ~), and, coupled w.ith the same good to]erability by the .50ya bean, they exhihit advantageous act:i.ons ac:Ja:i.n.r3t the we~d CJrarsseS
tested.
5~
~.
- ~ :
.~
~1~7~
~ . ............................... . .
- . TQble V
-- _.
I~valu~t:Lon number,ei in pre-emergcnce treatment.
. . . ' .
. Do ~ C~ro p plE3~ts Wee(l -~ra ,e~s~
. Co mpound . ( k ~ /ha ) ~3 arl ey Wh e a t ~o ya b ean AI, l~I SA I l,C
~_ __ __~_ ~ ____~_ __...... _ _~ ._~ __.
8 2 . 5 1 l 1 2 _ 1 . 0.6 1 1 1 ,~ . 2 4 0 . 1 5 1 l 1 7 ~ 5 5 . ~6 2.5 _ . 1 1 1 1 1 0.6 ~ . _ 1 2 1 1 . 2 . . 0 . 1 5 _ _ 1 . 3 1 2 2 - 1G2 2.5 _ ~ 1 1 1 1 0 . 6 _ 1 1 1 1 1~.
0 . 1 5 . _ 1 . 3 1 1 2 117 0 65 _ _ 1 1 1 1 1 0.15 _ _ . 1 3 I 2 3 C 2 . 5 9 9 1 1 1 1 'I
O . 6 9 ~ 1 1 2 1 2 5 1 8 Is I I !s;6 DI ~ Di6i taria ~nguin~l is ' -.
.
.
:
.
.. . .
:' - . - ' . ', ` .
.
:
7~:~2 example VI
'I'he efficiency of fur-ther compounds of the in-vention in pre-emergence is shown in the following Table.
Table VI
Evaluation results in pre-emergence treatment against important weed grasses.
Compound Dose Action against weed grasses .~ ~ ~ ~
12 0 56 1 1 _ _ 1 ,~ 4 ~' .-, ' 11~712:2 !` no~npou~ld ¦ DOJe Actlon a~;ai.nf~t weed gra~b~.
. ... . ... . ~}~J/]1a) .. ... AL . ... ~:C . ~;A . DI
_____ ~ .. ~ ___ __.__ .. ____. _~
2/ 1~ ~ 4 1 23 26 ~ _ ~ 3 1 31 31 0 6 4 . 3 3 3 2 2 . 5 2 1 1 3~ 25 _ 1 2 I .
0.~ _ 3 _ _ 0 65 . .~ 43 _ ~: 3 6 0 6 1 1 . 1 1 3 7 2 . 5 _ 1 ~ 1 1 .
0 . 6 1 . 1 ¦ 3 3 D 6 ¦ _ ¦ 2 7~3 Compound Do .c.e ~ot;i on aga:inst weecl grà~ s.
. .. .... .. (JccJ/ha) .. ... ~L................................................. EC. ... SA.... J~I.
91 2.5 2 0.6 3 1 ?
43 2.5 1 ... 1 0.6 2 2 ~5 2.5 . 2 0.6 3 ~ 3 ~3 2.5 ~ 2 2 0 . 6 47 2.5 1 1 ~ 1 ~
0.6 3 2 46 2.5 1 1 1.
0.6 2 2 52 2.5 3 3 ~ -0 ~
54 2.5 0.6 1 . 2 56 2.5 - 3 - -0. 6 - 5 - -58 2.5. - 1 3 --0.6 - ~ ~
61 2.5 ~ 2 2 0- 6 - 3 ~ _ 62 2.5 . - 4 0. 6 - 5 2 - .
6 3 2 . 5 ~ 3 3 - . . 0.6 4 5 5 64 ~ 2~5 - 2 2 -0.6 : - - 3 ~ -~ . . . ..
69 2. 5 - 3 - 2 -. 0 . 6 - 4 3 , ~ .
: ~ G~
.
..... ..... ;. ... ~.. ;.. . .. , :.. ,.. . .:
: . . , aompound :I)o 30 ~c t:L on ~ain~3t weod ~,ra~ F~, ... .. (ky/~a) I~ 'C... , S~ .. DI.
7 0 2 . 5 o.~ . - 2 2 72 2.5 0.6 ~ - 1 . 2 2.5 - 2 2 -0.6 - 3 3 78 2.5 - 2 0.6 - 3 3 79 2.5 ~ 2 2 - O . G
2.5 - 1 2 0.6 ~ 3 3 ~
81 2.5 - 2 0.6 -- 2 ~ --82 2.5 - .
- 0.~ - 2 6 162 ~5 1 . 1 1.
0.6 1 1 1 ~ 1 - 117 2.5 0. 6 1 1 ~ 1 1 -118 . 2.5 1 1 1 -~
0.6 2 1 2 121 2. 5 1 1 0.6 2 2 119 2.5 0. 6 3 2 116 2 . S 3 3 0.6 4 4 3 115 2.5 . 3 . 0.6 4 2 ,: . , , ' : 3 . ' - .
Compound DO~e l~o-t~on a~;sj.n~t we~d ~raE~:3e~, . .( k~ /}~ . . AIJ . . . E~ .. . ~A . . D:l~
96 . 2.5 7. 2 0.6 3 ~ 7. .
101 2.5 . 1 .1 ~ ~
0.6 . . 3 - 2 5 113 2.5 ~2 0.6 3 2 2 114 2.5 0.6 . 3 7 2 104 2.5 7.
0.6 3 2 2 110 2.5 ~ 1 ~ 2 0.6 3 2 3 -~
111 2.5 3 3 2 0.6 4 4 3 . -112 2.5 4 3 2 ~ :
0.6 ~ 4 3 - 17 2.5. 3 1 2 --0.6 5 ~ 3 .
- , ' .
~, .:
' '~ . . ' . ' .
;
~ . ' . - : - ' ;
,' ' ~ - ~ ~ ,' . ~
. .
' , : .
Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of controlling the growth of monocatyledonous weeds which comprises applying to the monocatyledenous weeds or a track of land a herbicidally effective amount of a compound of the general formula I
in which R represents the same or different substituents from the group halogen, CF3, CH3 or C2H5, R1 = the same or different substituents from the group consisting of halogen and CF3, n = the numbers 1 or 2, n1 = 0, 1, 2;
X and Y = 0 Z = -OH, , -C1, -Br, -OCO-OR3 -O-CO-R6, -O-SO2-R6, -O-SO3-R7 or the radical of the formula II
II
R3 = (C1-C12) alkyl, (C3-C8) cycloalkyl, (C2-C10) alkenyl, (C5-C6) cyclo-alkenyl, (C3-C8) alkinyl, phenyl or benzyl, where such radicals may be substituted by halogen, CF3, NO2, CN, (C1-C4) alkyl, (C1-C4) alkylthio, (C1-C4)-alkoxy, -OH, -NH2, (C1-C6) alkylamino, Di-(C1-C6) alkylamino and/or (Cl-C6) alkoxycarbonyl, R4 = H, (C1-C4) alkyl, (C2-C4) alkenyl, cyclopentyl, cyclohexyl, (C1-C4) alkoxy or phenyl, which is optionally substituted by halogen, CF3, NO2, CN, (C1-C4) alkyl, (C1-C4) alkylthio, (C1-C4) alkoxy, OH, NH2, (C1-C6)-alkylamino, Di-(C1-C6) alkylamino and/or (C1-C6) alkoxycarbonyl, R5 = H or (C1-C4) alkyl, or R4 and R5 together with the nitrogen atom are piperidine and pyrrollidine.
R6 a radical of the formula R3 or phenoxy-(C2-C3) alkyl, which is optionally substituted in the phenyl ring 1 to 3 times by F. C1, Br and/or -CH3;
R7 = H, (C1-C4) alkyl or cat+ and cat+ represents the cation of an inorganic or organic base, with the proviso that, when Z= OH or -OCOR6 in which R6 = (C1-C3) alkyl and X and Y = 0, (R)n cannot be 4-halogen.
in which R represents the same or different substituents from the group halogen, CF3, CH3 or C2H5, R1 = the same or different substituents from the group consisting of halogen and CF3, n = the numbers 1 or 2, n1 = 0, 1, 2;
X and Y = 0 Z = -OH, , -C1, -Br, -OCO-OR3 -O-CO-R6, -O-SO2-R6, -O-SO3-R7 or the radical of the formula II
II
R3 = (C1-C12) alkyl, (C3-C8) cycloalkyl, (C2-C10) alkenyl, (C5-C6) cyclo-alkenyl, (C3-C8) alkinyl, phenyl or benzyl, where such radicals may be substituted by halogen, CF3, NO2, CN, (C1-C4) alkyl, (C1-C4) alkylthio, (C1-C4)-alkoxy, -OH, -NH2, (C1-C6) alkylamino, Di-(C1-C6) alkylamino and/or (Cl-C6) alkoxycarbonyl, R4 = H, (C1-C4) alkyl, (C2-C4) alkenyl, cyclopentyl, cyclohexyl, (C1-C4) alkoxy or phenyl, which is optionally substituted by halogen, CF3, NO2, CN, (C1-C4) alkyl, (C1-C4) alkylthio, (C1-C4) alkoxy, OH, NH2, (C1-C6)-alkylamino, Di-(C1-C6) alkylamino and/or (C1-C6) alkoxycarbonyl, R5 = H or (C1-C4) alkyl, or R4 and R5 together with the nitrogen atom are piperidine and pyrrollidine.
R6 a radical of the formula R3 or phenoxy-(C2-C3) alkyl, which is optionally substituted in the phenyl ring 1 to 3 times by F. C1, Br and/or -CH3;
R7 = H, (C1-C4) alkyl or cat+ and cat+ represents the cation of an inorganic or organic base, with the proviso that, when Z= OH or -OCOR6 in which R6 = (C1-C3) alkyl and X and Y = 0, (R)n cannot be 4-halogen.
2. A method according to claim 1, characterised by a content of compounds of the formula I, in which (R)n = one to two identical or different, chlorine or bromine atoms or CF3 groups, n1 = 0 or (R1)n1 = C1 or Br in the 2-position relatively to Y, R2 = CH3;
X, Y = oxygen, Z = -OH, -C1, -Br; the radical of the formula II, in which (R)n and n1 have the meanings given above; and also the groups R4 = H, (C1-C4) alkyl, phenyl, halogenphenyl, methylphenyl or trifluoromethylphenyl and R5 as given in claim 1 -O-SO2-R3 in which R3 = CH3, phenyl, methylphenyl or chlorophenyl -O-SO3-R7 in which R7 = (C1-C4) alkyl or cat?;
in which R6 = (C1-C9) alkyl, (C1-C4) chloroalkyl, phenoxy-(C1-C4) alkyl, which is optionally substituted in the phenyl radical by 1-2 halogen atoms and/or methyl groups, (C2-C5) alkenyl or phenyl, which is optionally substituted once or twice by -Cl, -Br, -NO2, -CH3, -CF3 or -OCH3, and cat + = Na+, K=, NH4+, 1/2 Ca++, H2N+ (CH3)2, H2N+(C2H5)2, H3N+CH2CH2OH, HN+ (C2H5)3, or HN(CH2CH2OH)3,
X, Y = oxygen, Z = -OH, -C1, -Br; the radical of the formula II, in which (R)n and n1 have the meanings given above; and also the groups R4 = H, (C1-C4) alkyl, phenyl, halogenphenyl, methylphenyl or trifluoromethylphenyl and R5 as given in claim 1 -O-SO2-R3 in which R3 = CH3, phenyl, methylphenyl or chlorophenyl -O-SO3-R7 in which R7 = (C1-C4) alkyl or cat?;
in which R6 = (C1-C9) alkyl, (C1-C4) chloroalkyl, phenoxy-(C1-C4) alkyl, which is optionally substituted in the phenyl radical by 1-2 halogen atoms and/or methyl groups, (C2-C5) alkenyl or phenyl, which is optionally substituted once or twice by -Cl, -Br, -NO2, -CH3, -CF3 or -OCH3, and cat + = Na+, K=, NH4+, 1/2 Ca++, H2N+ (CH3)2, H2N+(C2H5)2, H3N+CH2CH2OH, HN+ (C2H5)3, or HN(CH2CH2OH)3,
3. A method according to claim 2, characterised in that in the compounds of the formula I (R)n = 4-chloro, 2,4-dichloro, 2-chloro-4-bromo, 4-trifluoro-methyl or 2-chloro-4-trifluoromethyl, n1 = zero, R2 = CH3, and X, Y = oxygen, and Z has the same meanings as in claim 2.
4. A method according to claim 2, characterised in that in the compounds of the formula I Z = - OH, -C1, -Br; the radical of the formula II (in which (R)n and n1 have the meanings given in claim 3); and also the groups , -O-SO3-cat+
and -O-CO-R6;
(R)n, n1, R2, X, Y, R4, R5 and R6 have the same meanings as in claim 3, and cat+ represents Na+, K+ NH? or
and -O-CO-R6;
(R)n, n1, R2, X, Y, R4, R5 and R6 have the same meanings as in claim 3, and cat+ represents Na+, K+ NH? or
5. Compounds of the general formula I
in which R represents the same or different substituents from the group halogen, CF3, CH3 or C2H5, R1 = the same or different substituents from the group consisting of halogen and CF3, n = the numbers 1 or 2, n1 = 0, 1, 2;
X and Y = 0 Z = -OH, , -C1, -Br, -O-CO-R6, -O-SO2-R6, -O-SO3-R7 or the radical of the formula II
II
R3 = (C1-C12) alkyl, (C3-C8) cycloalkyl, (C2-C10) alkenyl, (C5-C6) cyclo-alkenyl, (C3-C8) alkinyl, phenyl or benzyl, where such radicals may be substituted by halogen, CF3, NO2, CN, (C1-C4) alkyl, (C1-C4) alkylthio, (C1-C4)-alkoxy, -OH, -NH2, (C1-C6) alkylamino, Di-(C1-C6) alkylamino and/or (C1-C6) alkoxycarbonyl, R4 = H, (C1-C4) alkyl, (C2-C4) alkenyl, cyclopentyl, cyclohexyl, (C1-C4) alkoxy or phenyl, which is optionally substituted by halogen, CF3, NO2, CN, (C1-C4) alkyl, (C1-C4) alkylthio, (C1-C4) alkoxy, OH, NH2, (C1-C6)-alkylamino, Di-(C1-C6) alkylamino and/or (C1-C6) alkoxycarbonyl, R5- H or (C1-C4) alkyl, or R4 and R5 together with the nitrogen atom are piperidine and pyrrollidine.
R6 a radical of the formula R3 or phenoxy-(C2-C3) alkyl, which is optionally substituted in the phenyl ring 1 to 3 times by F. Cl, Br and/or -CH3;
R7 = H, (C1-C4) alkyl or cat+ and cat+ represents the cation of an inorganic or organic base, with the proviso that, when Z= OH or -OCOR6 in which R6 = (C1-C3) alkyl and X and Y = 0, (R)n cannot be 4-halogen.
in which R represents the same or different substituents from the group halogen, CF3, CH3 or C2H5, R1 = the same or different substituents from the group consisting of halogen and CF3, n = the numbers 1 or 2, n1 = 0, 1, 2;
X and Y = 0 Z = -OH, , -C1, -Br, -O-CO-R6, -O-SO2-R6, -O-SO3-R7 or the radical of the formula II
II
R3 = (C1-C12) alkyl, (C3-C8) cycloalkyl, (C2-C10) alkenyl, (C5-C6) cyclo-alkenyl, (C3-C8) alkinyl, phenyl or benzyl, where such radicals may be substituted by halogen, CF3, NO2, CN, (C1-C4) alkyl, (C1-C4) alkylthio, (C1-C4)-alkoxy, -OH, -NH2, (C1-C6) alkylamino, Di-(C1-C6) alkylamino and/or (C1-C6) alkoxycarbonyl, R4 = H, (C1-C4) alkyl, (C2-C4) alkenyl, cyclopentyl, cyclohexyl, (C1-C4) alkoxy or phenyl, which is optionally substituted by halogen, CF3, NO2, CN, (C1-C4) alkyl, (C1-C4) alkylthio, (C1-C4) alkoxy, OH, NH2, (C1-C6)-alkylamino, Di-(C1-C6) alkylamino and/or (C1-C6) alkoxycarbonyl, R5- H or (C1-C4) alkyl, or R4 and R5 together with the nitrogen atom are piperidine and pyrrollidine.
R6 a radical of the formula R3 or phenoxy-(C2-C3) alkyl, which is optionally substituted in the phenyl ring 1 to 3 times by F. Cl, Br and/or -CH3;
R7 = H, (C1-C4) alkyl or cat+ and cat+ represents the cation of an inorganic or organic base, with the proviso that, when Z= OH or -OCOR6 in which R6 = (C1-C3) alkyl and X and Y = 0, (R)n cannot be 4-halogen.
6. A compound having the general formula A:
A
wherein Q is selected from:
- hydroxy;
- chlorine;
- bromino;
- alkylcarbonyloxy containing 2 to 5 carbon atoms; and - phenylcarbonyloxy wherein the phenyl group may be substituted with halogen;
wherein Q' is selected from:
- hydrogen; and - halogen; and wherein Q" is selected from:
- halogen; and - trifluoromethyl ,
A
wherein Q is selected from:
- hydroxy;
- chlorine;
- bromino;
- alkylcarbonyloxy containing 2 to 5 carbon atoms; and - phenylcarbonyloxy wherein the phenyl group may be substituted with halogen;
wherein Q' is selected from:
- hydrogen; and - halogen; and wherein Q" is selected from:
- halogen; and - trifluoromethyl ,
7. A process of inhibiting the growth of unwanted graminaceous plants which comprises applying to the plants or to a locus thereof a herbicidally effective amount of a compound of formula A as set forth in claim 6.
8. .beta.-[4-(4-Trifluoromethylphenoxy)-phenoxy]-propanol.
9. .beta.-[4-(4-Trifluoromethylphenoxy)-phenoxy]-propyl benzoate.
10. .beta.-[4-(4-Trifluoromethylphenoxy)-phenoxy]-propyl chloride.
11. .beta.[4-(4-chlorophenoxy)-phenoxy]-propanol.
12. .beta.-[4-(2,4-Dichlorophenoxy)-phenoxy]-propanol.
13. .beta.-[4-(2,4-Dichlorophenoxy)-phenoxy]-propyl chloride,
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762611695 DE2611695A1 (en) | 1976-03-19 | 1976-03-19 | HERBICIDAL AGENTS |
| DEP2611695.0 | 1976-03-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1117122A true CA1117122A (en) | 1982-01-26 |
Family
ID=5972943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000274314A Expired CA1117122A (en) | 1976-03-19 | 1977-03-18 | Herbicidal compositions |
Country Status (25)
| Country | Link |
|---|---|
| JP (1) | JPS52114020A (en) |
| AR (1) | AR224331A1 (en) |
| AT (1) | AT354800B (en) |
| AU (1) | AU509124B2 (en) |
| BE (1) | BE852701A (en) |
| BG (1) | BG27714A3 (en) |
| BR (1) | BR7701656A (en) |
| CA (1) | CA1117122A (en) |
| CH (1) | CH627916A5 (en) |
| DD (1) | DD128799A5 (en) |
| DE (1) | DE2611695A1 (en) |
| EG (1) | EG12622A (en) |
| FR (1) | FR2360253A1 (en) |
| GB (1) | GB1577181A (en) |
| GR (1) | GR71448B (en) |
| HU (1) | HU178576B (en) |
| IE (1) | IE44653B1 (en) |
| IL (1) | IL51685A (en) |
| IT (1) | IT1125764B (en) |
| NL (1) | NL7702985A (en) |
| OA (1) | OA05607A (en) |
| PL (1) | PL104153B1 (en) |
| PT (1) | PT66324B (en) |
| SU (1) | SU882403A3 (en) |
| ZA (1) | ZA771606B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1512189A (en) * | 1975-10-29 | 1978-05-24 | Ishihara Mining & Chemical Co | Herbicidal composition and method of use thereof |
| DE2748658A1 (en) * | 1977-10-29 | 1979-05-10 | Hoechst Ag | HERBICIDES BETA-NAPHTHYL-PHENYL ETHER |
| EP0003114B1 (en) | 1978-01-18 | 1982-01-27 | Ciba-Geigy Ag | Herbicidal active unsaturated esters of 4- (3',5'-dihalogenpyridyl-(2')-oxy)-alpha-phenoxy propionic acids, process for their preparation, herbicidal compositions containing them and their use |
| DE2967674D1 (en) * | 1978-02-15 | 1988-03-10 | Ici Plc | Herbicidal derivatives of 2-(4(2-pyridyloxy)phenoxy)propane, processes for preparing them, and herbicidal compositions containing them |
| PH18417A (en) * | 1981-06-25 | 1985-06-24 | Nihon Tokushu Noyaku Seizo Kk | Substituted phenoxypropionates and herbicidal compositions |
| DE3272723D1 (en) * | 1981-08-17 | 1986-09-25 | Hoffmann La Roche | Carbamic esters, preparation thereof, pesticidal compositions on the basis of these compounds and their use in combating pests |
| US4625048A (en) * | 1982-08-13 | 1986-11-25 | Hoffmann-La Roche Inc. | Carbamic acid esters |
| JPS59199673A (en) * | 1983-04-25 | 1984-11-12 | Sumitomo Chem Co Ltd | Nitrogen-containing heterocyclic compound, its preparation and pesticide containing the same |
| US4550192A (en) * | 1983-09-01 | 1985-10-29 | The Dow Chemical Company | Fluorophenoxyphenoxypropionates and derivatives thereof |
| DE3823521A1 (en) * | 1988-07-12 | 1990-02-15 | Basf Ag | CYCLOPROPANCARBOXAMIDES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR CONTROLLING Pests |
| US5012017A (en) * | 1988-08-18 | 1991-04-30 | Dowelanco | Phenoxyphenoxypropionates, intermediates thereof and methods of preparation |
| IL156363A0 (en) * | 2001-01-31 | 2004-01-04 | Warner Lambert Co | Method for carbamoylating alcohols |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2415867A1 (en) * | 1974-04-02 | 1975-10-09 | Merck Patent Gmbh | PHENOXY ALCANOL DERIVATIVES AND THE PROCESS FOR THEIR PRODUCTION |
| FR2285859A1 (en) * | 1974-09-30 | 1976-04-23 | Lafon Labor | PHENYLSULFINYL-AMIDINES AND DERIVATIVES |
-
1976
- 1976-03-19 DE DE19762611695 patent/DE2611695A1/en not_active Withdrawn
-
1977
- 1977-03-15 BG BG7735671A patent/BG27714A3/en unknown
- 1977-03-16 CH CH328077A patent/CH627916A5/en not_active IP Right Cessation
- 1977-03-16 EG EG161/77A patent/EG12622A/en active
- 1977-03-17 AR AR266886A patent/AR224331A1/en active
- 1977-03-17 AT AT181677A patent/AT354800B/en not_active IP Right Cessation
- 1977-03-17 GB GB11375/77A patent/GB1577181A/en not_active Expired
- 1977-03-17 GR GR53011A patent/GR71448B/el unknown
- 1977-03-17 IL IL51685A patent/IL51685A/en unknown
- 1977-03-17 DD DD7700197912A patent/DD128799A5/en unknown
- 1977-03-17 ZA ZA00771606A patent/ZA771606B/en unknown
- 1977-03-17 IT IT7721376A patent/IT1125764B/en active
- 1977-03-17 BR BR7701656A patent/BR7701656A/en unknown
- 1977-03-18 NL NL7702985A patent/NL7702985A/en not_active Application Discontinuation
- 1977-03-18 PL PL1977196753A patent/PL104153B1/en not_active IP Right Cessation
- 1977-03-18 IE IE583/77A patent/IE44653B1/en unknown
- 1977-03-18 SU SU772462914A patent/SU882403A3/en active
- 1977-03-18 HU HU77HO1969A patent/HU178576B/en unknown
- 1977-03-18 CA CA000274314A patent/CA1117122A/en not_active Expired
- 1977-03-18 AU AU23417/77A patent/AU509124B2/en not_active Expired
- 1977-03-18 JP JP2939477A patent/JPS52114020A/en active Pending
- 1977-03-18 PT PT66324A patent/PT66324B/en unknown
- 1977-03-19 OA OA56109A patent/OA05607A/en unknown
- 1977-03-21 FR FR7708352A patent/FR2360253A1/en active Granted
- 1977-03-21 BE BE175972A patent/BE852701A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| AR224331A1 (en) | 1981-11-30 |
| IE44653L (en) | 1977-09-19 |
| BR7701656A (en) | 1978-01-03 |
| PT66324B (en) | 1978-11-07 |
| GB1577181A (en) | 1980-10-22 |
| HU178576B (en) | 1982-05-28 |
| AU2341777A (en) | 1978-09-21 |
| IE44653B1 (en) | 1982-02-10 |
| IT1125764B (en) | 1986-05-14 |
| FR2360253B1 (en) | 1983-10-07 |
| BE852701A (en) | 1977-09-21 |
| FR2360253A1 (en) | 1978-03-03 |
| GR71448B (en) | 1983-05-18 |
| DE2611695A1 (en) | 1977-09-29 |
| PL104153B1 (en) | 1979-08-31 |
| ATA181677A (en) | 1979-06-15 |
| IL51685A0 (en) | 1977-05-31 |
| IL51685A (en) | 1981-11-30 |
| PT66324A (en) | 1977-04-01 |
| EG12622A (en) | 1981-12-31 |
| ZA771606B (en) | 1978-01-25 |
| AU509124B2 (en) | 1980-04-24 |
| DD128799A5 (en) | 1977-12-14 |
| SU882403A3 (en) | 1981-11-15 |
| BG27714A3 (en) | 1979-12-12 |
| CH627916A5 (en) | 1982-02-15 |
| AT354800B (en) | 1979-01-25 |
| OA05607A (en) | 1981-04-30 |
| PL196753A1 (en) | 1978-01-16 |
| JPS52114020A (en) | 1977-09-24 |
| NL7702985A (en) | 1977-09-21 |
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| MKEX | Expiry |