CA1253517A - N-(CARBAMYLMETHYL)-.alpha.-HALOACETANILIDE COMPOUNDS - Google Patents
N-(CARBAMYLMETHYL)-.alpha.-HALOACETANILIDE COMPOUNDSInfo
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- CA1253517A CA1253517A CA000237515A CA237515A CA1253517A CA 1253517 A CA1253517 A CA 1253517A CA 000237515 A CA000237515 A CA 000237515A CA 237515 A CA237515 A CA 237515A CA 1253517 A CA1253517 A CA 1253517A
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Abstract
ABSTRACT OF THE DISCLOSURE
Fungicidal and herbicidal alpha-haloacetanilides of the formula:
wherein R1 is alkyl, R2 is hydrogen or alkyl; R3 is hydrogen or methyl; X
is halo; and Y is -SR4 or NR5R6 wherein R4 is alkyl, alkenyl phenylalkyl, or halophenylalkyl, R5 is hydrogen, alkyl, alkenyl or alkynyl and R6 is hydrogen, alkyl, alkenyl or alkynyl, with the proviso that R5 and R6 may be joined to form a divalent alkylene group.
Fungicidal and herbicidal alpha-haloacetanilides of the formula:
wherein R1 is alkyl, R2 is hydrogen or alkyl; R3 is hydrogen or methyl; X
is halo; and Y is -SR4 or NR5R6 wherein R4 is alkyl, alkenyl phenylalkyl, or halophenylalkyl, R5 is hydrogen, alkyl, alkenyl or alkynyl and R6 is hydrogen, alkyl, alkenyl or alkynyl, with the proviso that R5 and R6 may be joined to form a divalent alkylene group.
Description
~Z~3~
DESCRIPTION OF THE PRIOR ART
United States Patent 3,780,090 of Akiba et al discloses the use of alkyl alpha-(N-haloacetyl-N-2,6-dialkylphenylamino)~-alkanoate esters as herb-icides. German Offenlegungsschrift 2,350,944 of Ciba-Geigy discloses alpha-~-haloacetyl-N-2,6-dialkyl-phenylamino) alkanoate es~ers as antifungal agents.
Belgian Patent 813,469 of Ciba-Geigy discloses the use of phenylamine acet-amides as herbicides.
DESCRIPTION OF THE INVENTION
The alpha-haloacetanilides of the invention are represented by the formula (I):
~ Rl IR3 ll H-C-Y (I)
DESCRIPTION OF THE PRIOR ART
United States Patent 3,780,090 of Akiba et al discloses the use of alkyl alpha-(N-haloacetyl-N-2,6-dialkylphenylamino)~-alkanoate esters as herb-icides. German Offenlegungsschrift 2,350,944 of Ciba-Geigy discloses alpha-~-haloacetyl-N-2,6-dialkyl-phenylamino) alkanoate es~ers as antifungal agents.
Belgian Patent 813,469 of Ciba-Geigy discloses the use of phenylamine acet-amides as herbicides.
DESCRIPTION OF THE INVENTION
The alpha-haloacetanilides of the invention are represented by the formula (I):
~ Rl IR3 ll H-C-Y (I)
2 1lC~l2X
R O
wherein Rl is lower alkyl of 1 to 6 carbon atoms; R2 is hydrogen or lower alkyl of 1 to 6 carbon atoms; R3 is hydrogen or a methyl group; X is fluorine, chlorineJ bromine or iodine; and Y is -SR4 or -NR5R6 wherein R4 is lower alkyl of 1 to 6 carbon atoms, lower alkenyl of 3 to 6 carbon atoms or phenylalkyl of 7 to 10 carbon atoms substituted on the phenyl ring with up to 2 (0 to 2) fluoro, chloro, bromo substituents, R5 is hydrogen, lower alkyl of 1 to 6 carbon atoms, lower alkenyl of 3 to 6 carbon atoms or lower alkynyl o 3 to 6 carbon atoms, and R is hydrogen, lower alkyl of 1 to 6 carbon atoms, lower alkenyl of 3 to 6 carbon atoms or lower alkynyl of 3 to 6 carbon atoms, with the proviso that R5 and R6 may together form a divalent alkylene group of 4 to 6 carbon atoms.
Representative alkyl groups which Rl, R2, R3, R4, R5 and R6 may represent include methyl, ethyl, propyl, isopropyl, ~253~L7 butyl, sec-butyl, t-butyl, pentyl, isohexyl, etc.
Representative alkenyl groups which R4, R5 and R6 may represent include allyl, 2-butenyl, 3-pentenyl, etc.
Representative alkynyl groups which R5 and R6 may represent include propargyl, 2-butynyl, 3-pentynyl, etc.
Representative divalent alkylene groups formed by joining R5 and R6 include tetramethylene, pentamethylene and 3-methylpentamethylene.
Representative phenylalkyl R4 groups include benæyl, 2-fluorobenzyl, 3,4-dichlorobenzyl, 2-phenylethyl, 3-(p-chlorophenyl)propyl, 4-methylbenzyl and 3-(p-tolyl)propyl. Preferred phenylalkyl R4 groups are phenylalkyl of 7 to lO carbon atoms substituted on the phenyl ring with up to 2 fluoro, chloro or bromo.
Repre~entative N-carbamylalkyl-substituted compounds of the invention (Y is -NR5R6) are:
N-(N' methylcarbamylmethyl)-2,6-dimethyl-alpha-chloroacetanilide, N-(N'-propargylcarbamylethyl)-2,6-dimethyl-alpha-chloroacetanilide, N-(N'-propargylcarbamylmethyl)-2,6-diethyl-alpha-chloroacetanilide, N-(N',N'-dipropargylcarbamylm~thyl)-2,6-dimethyl-alphachloroacetanilide, N-(N'-2-butynylcarbamylmethyl)-2,6-diisopropyl-alphabromoacetanilide, N-(N'-3-hexynylcarbamylmethyl)-2,6-dimethyl-alpha-fluoroacetanilide, ~L25;3~;~7 N-(N' allyl-N'-methylcarbamylmethyl-2,6-dimethyl-alphabromoacetanilide, N-(N'-allylcarbamylmethyl)-2,6--dimethyl-alpha-iodoacetanilide, N-(piperidinocarbonylmethyl)-2-methyl-6-ethyl-alphachloroacetanilide, and N-morpholinocarbonylmethyl-2,6-dimethyl-alpha-halo-acetanilide.
; Representative thioate ester-substituted compounds of the invention (Y is -SR4) include:
methyl alpha-(N-fluoroacetyl-N-2,6-dimethylphenylamino)-thioacetate, ethyl alpha-(N-chloroacetyl-N-2,6-diisopropyl-phenylamino)-thioacetate.
propyl alpha-(N-iodoacetyl-N-2-butylphenylamino)-thioacetate, benzyl alpha-(N-chloroacetyl-N-2,6-dimethylphenyl-amino)-thiopropionate, methyl alpha-~N-bromoacetyl-N-2,6-dimethylphenyl-amino)-thiopropionate, and p-bromobenzyl alpha-(N-iodoacetyl-N-2-methyl-6-ethylphenylamino)thiopropionate.
The N-carbamylalkyl-substituted compounds of the invention wherein Y is -NR5R6 may be prepared by alkylating an aniline compound (II) with an alpha-haloamide (III) to produce an N-(carbamylalkyl)aniline (IV) and subsequently acylating the N-(carbamylalkyl)aniline (IV) with an alpha-haloacetyl halide (V) to give the N-carbamylalkyl-alpha-~i3~
4ahaloacetanilide product (VI). This sequence of reactions is depicted by the following equations:
~, .
~35~
, Rl ~ Nll2 + XC~I- -N / basc (II) E~2 (III) Rl N}ICH-C~N
R5 ~l) ~IV) \R2 -NIIC}I-C-N ~ ~ XCC~I2X b~se>
~ R5 (V) (IV) \R2 ~1 R3 o ~6 ~ CII-C-N
</ \) - N \ \ll5 CCH2X (2) ~VI) R2 ~, ~ ~ .
1 wherein ~1, R2,;R3, Rs~ R6 and X have the same significance as 2 previously defined.
R O
wherein Rl is lower alkyl of 1 to 6 carbon atoms; R2 is hydrogen or lower alkyl of 1 to 6 carbon atoms; R3 is hydrogen or a methyl group; X is fluorine, chlorineJ bromine or iodine; and Y is -SR4 or -NR5R6 wherein R4 is lower alkyl of 1 to 6 carbon atoms, lower alkenyl of 3 to 6 carbon atoms or phenylalkyl of 7 to 10 carbon atoms substituted on the phenyl ring with up to 2 (0 to 2) fluoro, chloro, bromo substituents, R5 is hydrogen, lower alkyl of 1 to 6 carbon atoms, lower alkenyl of 3 to 6 carbon atoms or lower alkynyl o 3 to 6 carbon atoms, and R is hydrogen, lower alkyl of 1 to 6 carbon atoms, lower alkenyl of 3 to 6 carbon atoms or lower alkynyl of 3 to 6 carbon atoms, with the proviso that R5 and R6 may together form a divalent alkylene group of 4 to 6 carbon atoms.
Representative alkyl groups which Rl, R2, R3, R4, R5 and R6 may represent include methyl, ethyl, propyl, isopropyl, ~253~L7 butyl, sec-butyl, t-butyl, pentyl, isohexyl, etc.
Representative alkenyl groups which R4, R5 and R6 may represent include allyl, 2-butenyl, 3-pentenyl, etc.
Representative alkynyl groups which R5 and R6 may represent include propargyl, 2-butynyl, 3-pentynyl, etc.
Representative divalent alkylene groups formed by joining R5 and R6 include tetramethylene, pentamethylene and 3-methylpentamethylene.
Representative phenylalkyl R4 groups include benæyl, 2-fluorobenzyl, 3,4-dichlorobenzyl, 2-phenylethyl, 3-(p-chlorophenyl)propyl, 4-methylbenzyl and 3-(p-tolyl)propyl. Preferred phenylalkyl R4 groups are phenylalkyl of 7 to lO carbon atoms substituted on the phenyl ring with up to 2 fluoro, chloro or bromo.
Repre~entative N-carbamylalkyl-substituted compounds of the invention (Y is -NR5R6) are:
N-(N' methylcarbamylmethyl)-2,6-dimethyl-alpha-chloroacetanilide, N-(N'-propargylcarbamylethyl)-2,6-dimethyl-alpha-chloroacetanilide, N-(N'-propargylcarbamylmethyl)-2,6-diethyl-alpha-chloroacetanilide, N-(N',N'-dipropargylcarbamylm~thyl)-2,6-dimethyl-alphachloroacetanilide, N-(N'-2-butynylcarbamylmethyl)-2,6-diisopropyl-alphabromoacetanilide, N-(N'-3-hexynylcarbamylmethyl)-2,6-dimethyl-alpha-fluoroacetanilide, ~L25;3~;~7 N-(N' allyl-N'-methylcarbamylmethyl-2,6-dimethyl-alphabromoacetanilide, N-(N'-allylcarbamylmethyl)-2,6--dimethyl-alpha-iodoacetanilide, N-(piperidinocarbonylmethyl)-2-methyl-6-ethyl-alphachloroacetanilide, and N-morpholinocarbonylmethyl-2,6-dimethyl-alpha-halo-acetanilide.
; Representative thioate ester-substituted compounds of the invention (Y is -SR4) include:
methyl alpha-(N-fluoroacetyl-N-2,6-dimethylphenylamino)-thioacetate, ethyl alpha-(N-chloroacetyl-N-2,6-diisopropyl-phenylamino)-thioacetate.
propyl alpha-(N-iodoacetyl-N-2-butylphenylamino)-thioacetate, benzyl alpha-(N-chloroacetyl-N-2,6-dimethylphenyl-amino)-thiopropionate, methyl alpha-~N-bromoacetyl-N-2,6-dimethylphenyl-amino)-thiopropionate, and p-bromobenzyl alpha-(N-iodoacetyl-N-2-methyl-6-ethylphenylamino)thiopropionate.
The N-carbamylalkyl-substituted compounds of the invention wherein Y is -NR5R6 may be prepared by alkylating an aniline compound (II) with an alpha-haloamide (III) to produce an N-(carbamylalkyl)aniline (IV) and subsequently acylating the N-(carbamylalkyl)aniline (IV) with an alpha-haloacetyl halide (V) to give the N-carbamylalkyl-alpha-~i3~
4ahaloacetanilide product (VI). This sequence of reactions is depicted by the following equations:
~, .
~35~
, Rl ~ Nll2 + XC~I- -N / basc (II) E~2 (III) Rl N}ICH-C~N
R5 ~l) ~IV) \R2 -NIIC}I-C-N ~ ~ XCC~I2X b~se>
~ R5 (V) (IV) \R2 ~1 R3 o ~6 ~ CII-C-N
</ \) - N \ \ll5 CCH2X (2) ~VI) R2 ~, ~ ~ .
1 wherein ~1, R2,;R3, Rs~ R6 and X have the same significance as 2 previously defined.
3 The alk~lation reaction (1~ is pLefera~ly co~ducted in
4~ the presence of an acid acceptor. Suitable acid acceptors are inorganic alkali ~etal carbonates such as sodium carbonate or 6 potassium carbonateO Generally, substantially eguimolar amounts 7 of reactants (II) and lIII) and the acid acceptor are employed.
8 The reaction is conducted in lnert polar inorganic sol~ents, 9 e.g. t apolar aiprotic solvents such as dimethylformamide and ; 10 acetonitrile, at ~eacticn temperatures varying from 0C to 90C, 11 preferably from 20C to 50C~ The ~eac*ion pressure may be 12 atmospheric, subatmospheric or superatmospheric. Ho~ever, for 13 convenience o~ conducting the reaction, the pressure is generally 14 atmospheric. The reaction time will, of course, vary dependlng ~ S ~
~;35~L7 upon the reactants and the reaction temperature.
Generally the reaction time is from 0.25 to 24 hours.
The product (IV) is generally purified by conventional procedures, e.g., extraction, distillation or crystallization, before use in the acylation reaction (2).
The acylation reaction (2) is conducted by conventional procedures, preferably in the presence of an acid acceptor such as a trialkyl amine or pyridine.
The reactants ~IV) and (V) and the acid acceptor are generally contacted in substantially equimolar amounts in the liquid phase in an inert organic solvent at a temperature of 0 to 100C. Suitable inert organic solvents include ethyl acetate, methylene dichloride, dimethoxyethane, benzene, etc. The product is isolated , and purified by conventional procedures such as extraction, distillation, chromatography, crystal-lization, etc.
The thioate ester compounds of the invention wherein Y is -SR4 may be prepared by alkylating an aniline compound (II) with an alpha-halothioate ester (VII) to produce alpha-(N-phenylamino)thioate ester (VIII) and subsequently acylating the thioate ester (VIII~ with an alpha-haloacetyl halide (V) to give the alpha-(N-haloaceatyl-N-phenylamino)thioate ester (IX).
This sequence of reactions is depicted by the following equations:
~2S:3 S~
Rl R3 O
~ NH2 + XCH-C-S-R4 (II) R2 (VII) R R3 o ~ NHlH-c-s-~4 (VIII) ~ R2 (3) ~ NHCH-C-S-R4 ~ XCCH2X base \ 2 (V) (VIII) R
~ N
( IX ) R2 CCH2X (4) O
:' ~wherein Rl, R2, R3, R4 and X have the same ~ignificance :~20 as previously defined.
~:The alkylation reaction~(3) i5 conducted in the presence of an acid acceptor by a procedure essentially , identical to that described for reaction (1), and the acylation reaction (4~ is conducted by a procedure ~25 essentially identical to that described for reaction :~ (2).
The N-(carbamylalkyl)aniline intermediate (IV) employed in reaction (2) may also be prepared by 7a reacting the alpha-(N-phenylamino)thioate ester (VIII) with an amine in the presence of a base such as pyridine in the liquid phase at a temperature of O to 100C, as depicted by the following reaction (5):
~Læs3~
ICH 5 R4 + ~IN~
(VIII) R2 Rl ~\~ N HC 11 C- N / ~ H S R 4 \=/ R 6 (IV) R2 (5) 1 ExAMELEc 2 The preparation of the compounds of the invention by 3 the above reactions is illustrated by the followi~g examples.
4 Example 1 -- Preparatian of N-(N',N'-diallyl-carb__Xlm__h~lL-2,6-di-thyl-a-~la-~hlo--oa-e--nilide C2ll5 0 CiI2-(:H=C~12 --N / Cl12 - Cil = C~l 2 CCII 2 Cl ` C2~15 o 6 A 78-g lO-8 mol) sample of diallylamine was added drop-7 wise to a stirred and ccoled (dry ice/acetone bath) solution oF
8 ao g (o. 4 mol) brcmoacetylbromide in 200 ml methylene 9 dichloride. The reaction mixture was allowed to ~arm to about 25C and stirred cvernight. The reaction mixture was the~ washed 11 with waterr aqueous sodium bicar~onate, again with water, dried 12 over magnaslum sulfate and evaporated under reduced pressure to 13 gi~e 38 g of N,~-diallyl-alpha-~romoacetamide.
14 A mixture of 19 g ~0.088 mol) N,N-diallyl-alpha-bromoacetamide ~preFared above), 13.1 g (0.088 mol3 2y6~
16 diethylaniline and 12.2 g (0.088 mol) potassium carbonate in 150 17 ml dimethylformamide was heated at 50-65C for 24 hours~ The 18 reaction mixture was filtered and the filtrate was diluted with 19 300 ml water. Tbe aguecus filtrate mixtur~ was extracted ~ith ~ _ ~S3S~7 1 hexane. The hexane extracts were dried over magnesium slllfate 2 and e~aporated under reduced pressure to give a viscous oil. rrhe 3 oil ~as chromatograFhed Cll a silica-gel column.
4 N-(N',Ns-diallylcarba~ylmethyl)-2,6-diethylaniline ~12~3 g) was eluted from the cclumn ~ith 5~ ether/hexane~
6 ~ solution of 2.48 g (0.0313 mol) pyridine in 25 ml 7 ethyl acetate was added dropwise to a stirred and cooled (ice r~ 8 bath) solution of 8.93 9 (0.0313 mol) M-(N',N'-diallyl-9 carbamylmethyl)-2,6-diethylaniline ~prepared ahove) and 3.54 g (0.0313 mol) chloroacetyl chloride in 150 ml of ethyl 11 acetate. The reaction mixture was then stirred at about 25C
12 overnight. The reaction mixture was diluted ~ith 100 ml water.
13 The aqueous layer ~as separated and e~tracted with diethyl ether.
14 The ether extract and the organic lay~r were comhined and washed ~ith aqueous sodium bicarbonate and t~en water, dried over 16 magnesium sulfate, and evaporated under reduced press~re to give 17 a viscous oil. The oil was chromatographed OD silica gel.
18 Elution ~ith 40~ etheL/hexane gave the product, N~ diallyl-19 car~amylmethyl)-'2~,~-diethyl-alpha-chloroacetanilide, as a yellow oil. Elemental analysis on the product tCzH27clN2~) 21 showed: ~C1, calculated 9.77, found 10.2.
22 _xam~le_2~aL~2lqL
23 ~y a proc~dure similar to that o~ Example 1:
24 (a3 alpha-chlcroacetyl chloride and N-tN',N'-diallylcarkamylmethyl)-2,6-dimethylanili~e uere 26 reacted to produce N-IN'jN'-diallylcarhamylmethyl)-2~6-27 dimethyl-alpha-chloroacetanilide. Elemental analysis for 28 Cl8H23Cl~2O2) sho~ed: ~Cl, calculated 10.59, found 10.9.
29 (b~ alE~a-chloroacetyl chloride and N-(N'-methyl-N'-allylcarbamylmethyl)-2,6-di~ethylaniline were reacted to 31 produce N-(N~-methyl-N'-allylcar~amylmethyl)-2,6-dimethyl-32 alpha-chloroacetanilide as a white solid, m.p. 82-84~C.
_ g _ ~253~7 Elemental analysis for ClH21ClN202) showed: %Cl, calculated 11.4, found 10.5.
(c) alpha-chloroacetyl chloride and N-(N'-methyl-N'-allylcarbamyl-methyl)-2,6-diethylaniline were reacted to produce N-(N'-methyl-N'-allyl-carbamylmethyl)-2,6-diethylalpha-chloroacetanilide, as a yellow solid, m.p.
85-86.5 C. Elemental analysis for C18H25ClN202 showed: %Cl, calculated 10.5, found 10Ø
(d) alpha-chloroacetyl chloride and N-(piperidino-carbonylmethyl)-2,6-dimethylaniline were reacted ~o produce N-(piperidinocarbonylmethyl)-2,6-dimethyl-alpha-chloroacetanilide, m.p. 109-111C. Elemental analysis for C16H21ClN202 showed: %Cl, calculated 11.48, found 11.5. The structural formula of this product is:
C~1 CH2CN~
/
CCH2Cl (e) alpha-chloroacetyl chloride and N-(piperidinocarbonylmethyl)-2,6-diethylaniline were reacted to produce N-(piperidinocarbonylmethyl)-2,6-die~hyl-alpha-chloroacetanilide, m.p. 123-124C. Elemental analysis for C18H25ClN202 showed: %Cl, calculated 10.52, found 10.2.
(f) alpha-chloroacetyl chloride and N-(N',N'-dimethylcarbamyl-methyl)-2,6-diethylaniline were reacted to produce N-(N',N'-dimethylcarbamyl-I methyl)-2,6-diethyl-alpha-chloroacetanilide as a white solid, m.p. 81-82 C.
Elemental analysis for C16H23ClN2O2 showed: %Cl, calculated 11.41, found 11.8.
~g) alpha-chloroacetyl chloride and N-(N',N'-dimethylcarbamyl-methyl)-2,6-dimethylaniline were ~25i3~i~L7 1 reacted to prod~ce N-(N~,N~-dimethylcarbamylmethyl~ h-2 dimethyl-alpha-chloroacetanilide, as a white solid, m.p. 85-3 86.5C~ Elemental analysis for Cl~Hl~ClN202 sho~ed: ~Cl, 4 calculated 12.54, fcund 12.1~
,~ 5 (h) alp~a-chloroacetyl chloride and N-(N'-t-6 butylcarbamylmethyl)-2,6-dimethylaniline were reacted to 7 produce N-~N'-t-butylcarbamylmethyl)-2,6-dimethyl-alpha-8 chloroacetanilide, as a white sclid, m.p. 110-112C. Elemental 9 analysis for C16H23ClN202 showed: %Cl, calculated 11.41, fou~d 11.1.
11 (i) alFha-chloroacetyl chloride and N-(~'-t-12 bu~ylcarbamylmethyl)-2,6-diethylaniline were reacted ~o 13 produce N ~N'-t-butylcar~amylmethyl)-2,6-diethyl-alpha-14 chloroacetanilide~ as a white sclid, m.p. 118-120C. Elemental analysis for C18H27ClN2C2 showed: %Cl, calculated 10~46~ fou~d j 16 10.2.
17 ~j) alpha-chloroacetyl chloride and 18 N-(N',N'-diethylcarbamylmethyl)-2,6-dimethylaniline were 19 reacted ~o prod~c~ (N',N' diethylcarbamylmethyl)-2,6-dimethyl-alpha-chloroacetanilide, as a yellow oil~ Elemental 21 analysis for C,6H23ClN202 sho~ed: ~Cl, calculated 11.41, found .1 ~ 2? 11.9.
23 (k) alEha-chloroacetyl chloride and 24 N-~N',N'-diethylcarba~ylmethyl)-2,6-diethylaniline ~ere reacted to produce N-(N',N'-diethylcarba~ylmethyl)-2,6-26 diethyl-alpha-chlcroacetanilide, a yellow oil. Eleme~tal 27 analysis for Cl8H27ClN202 showed: %Cl, calculated 10~46, found 28 10.4.
29 (1) alp~a-chloroacetyl chloride and N-~N' sec-butylcarba~yl~ethyl)-2,6-diethylanilille were reacted to 31 produce N-~N'-sec-butylcarbamylmethyl)-2,6-diethyl 32 alpha-chloroacetanilide as a white solid, m~p~ 120--122C.
` ~.25i35~7 Elemental analysiS for C18H27ClN22 showed %Cl, calculated 10~46, found 10.3.
(m) alpha-chloroacetyl chloricle and N-(N'-sec-butylcarbamylmethyl)-2 t 6-dimethylaniline were reacted to produce N-(N'-sec-butylcarbamylmethyl)-2,6-dimethyl-alpha-chloroacetanilide as a white solid, m.p. 97-99C.
Elemental analy5is for C18H23ClN22 showed %cl, calculated 10.41, ~ound 10.4C.
(n) alpha-chloroacetyl chloride and N-(carbamyl-2,6-dimethylaniline were reacted to produce N-(carbamyl-methyl)-2,6-dimethyl-alpha-chloroacetanilide, as a white solid, m.p. 139-141C. Elemental analysis for C12H15ClN202 showed: %Cl, calculated 13.92, found 13.70.
(o) alpha-chloroacetyl chloride and N-(carbamyl-2,6-diethylaniline were reacted to produce N-(carbamyl)-2,6-diethyl-alpha-chloroacetanilide, m.p. 150-152C.
Elemental analysis for C14H19ClN22 showed %Cl, calculated 12.54, found 12.6. The structural formula of this product is ~ N ,,CH2-CNH2 ~ ~ CCH2Cl ~p) alpha-chloroacetyl chloride and N-[l-(N,N-dimethylcarbamyl)ethyl]-2,6-dimethylaniline were reacted to produce N-[1-(N,N-dimethylcarbamyl)-ethyl]-2,6-dimethyl-alpha-chloroacetanilide, m.p. 112-~Z~3~;~7 12a114C. Elemental analysis for C15H21ClN22 showed-%Cl, calculatad 11. 95, found 11. 7 . The structural formula for this product is , :~2~;~S~7 N o \ CH
CCH2Cl 1 (q~ alpha-chloroacetyl chloride and 2 N-[1-(N',N'-dimethylcar~amyl)ethyl]-2,6-diethylanili~e were 3 reacted to produce ~ N'jN'-dimethylcar~amyl)ethrl~-4 2,6-dimethyl-alpha-chloroacetanilide, m.p. 100-102C.
Elemental analysic for Cl7Hz5ClNzO~ showed: %Cl, calculated 6 10.9, found 10.7.
7 Example 3 -- Preparation of N ~N'-proparg~l-N~-8 ~ ~ethYlcarbamylmethylL-2~6-dlm-t-Ql-al~ha-chlQroacetanil-d-e Cll3O /C~ 3 ll ~C~12CI`I
)--L~jC~12-C-CH
:~ ~ CCH2Cl ~ ;
C~13 o ~` 9 A solutic~ of 13.8 g ~0.2 mol) of N--methylp~opargyl-.- ,;
amine in 20 ml methylene chloride was added dropwise to a stirred 11 and cooled (below 15C) solution of 40.2 9 (0.2 mol) bromoacetyl 12 bromide and 16 g (0.2 mol) sodium bicarbonate in 250 mL methyle~e 13 chloride. The reaction mixture was allowed to warm to about 25C
14 and stirred or 2 hcurs. The reaction mi~ture was then filtered and evaporated undr reduced pressure to give an oily residue.
16 The residue was diluted with 150 ml ether to form a two-phase ; 17 mixture consis~ing of an ether phase and a dark oil~ The ether 18 phase was sep~rated, dried over magnesium sulfate, a~d ~aporated 19 to give 32.3 g o~ ~-methyl-N-propargyl-alpha-bromoacetamide.
21 A mixtuLe o 16.2 g (0.085 mol) N-methyl-N-22 propargyl-alpha-bromoacetamidA (Erepared above), 10.2 g .
~Z~;35~
1 (0.085 mol~ 2~6-dimethylaniline and 8.9 g (0~085 mol) sodium 2 carbonate in 200 ~l dimethylformamide was heated at 140C ~or 1 3 hours. The reacticn mixture ~as diluted ~ith 300 ml water a~d 4 extracted with beDzeDe. The benzene extracts were ~ashed with ~ater, dried over magn~sium sulfate and evaporated under reduced 6 pressure to gi~e a viscous oil. The oil was chrcmatographed on a ; 7 silica gel column. N-(N'-methyl-N'-propargyl-8 carbamylmethyl~-2,6-dimethylaniline was eluted from the 9 column with 50:50 h~ane-ethyl ethern ~ sampl~ of 3.2 g (0.029 mol) chloroacetyl chloride ~as 11 added dropwise to a stirred and warmed (45-50C) solution of 12 6.6 g ~0.029 mol~ N-tN'-methyl-13 N'-propargylcarbamylmethyl)-2,6-dimethylaniline (~repared 14 above) and 2.3 g ~0~029 mol) pyridine in 250 ml of methyle~e chloride. The reaction mixture was stirred at a~out 25C for 1 16 hour. The reacticn mixture was washed with 250 ml ~ater, with 17 aqueous sodium bicar~cnate and then water, dried o~er magnesium 18 sulfate and evaporated unde~ red~ced prescure to ~ive a viscous 19 oil. The oil was crystallized from ether to yiYe the product, N-(N'-methyl-N'-propargylcarbamylmethyl~-2,6-dimethyl-21 alpha-chloroacetanilide, as a colorless sclid, m.p. 72-22 74C. Elemental analysis for C~6H~gClN202 showed: ~Cl, 23 calculated 11.6, found 11.8.
24 Exa_~ 4l_L~4leL
By a procedure similar to that above:
26 (a) alpha-chloroacetyl chloride and N-(N'-methyl-27 N~-propargylcarbamylmethyl)-2,6~diethylaniline were reacted 28 in the presence of pyridine to produce N-(N~ methyl-29 N'~propargylcarha~ylmethyl~-2,6-diethyl-alpha-chloroacetanilide as a cclorless solid, m.p. 69-70C.
31 Elemental analy~ic for C~aH23ClN202 showed: %Cl, calc~ 10.6 32 found 10.5.
~Z~3~7 1 (b) alEba-chloroacetyl chloride and N-(N '~
2 dimethyl-2-propynylcarbamylmethyl)-2,6-diethylaniline were 3 reacted in the prese~ce of pyridine in ethyl aceta~e to produce 4 N-tN'~ dimethyl-2-propynylcarbamylmethyl)-2,6-diethyl-alpha-chloroacetanilide as a ~hite solid~ m.p. 114-6 115C. Elemental analysis for Cl9H25ClN2O2 sho~ed: ~Cl, 7 calculated 10. 2r f~und 10.1. The structural for~ula of this 8 product is:
s O C1-13 ~\ ~C~12C~`IIIC-C-C~
- N Cll3 CC~12C
9 (c) alEha-chloroacetyl ch~oride and N-~'-1,1-dimethyl-2-propynylcarbamylmethyl)-2,6-dimethylanili~e ~ere 11 reacted in the pr~s~nce of pyridine in ethyl acetate to produce 12 N-~N~-1,1-dimethyl-2-prcpynylcar~amylmethyl)-2,6-13 dimethyl-alpha-chloroacetanilide as a white solid, m.p. 100-14 102C. Elementài~analysis for C17~1Cl~zO2 sho~ed: ~Cl, calc.
11.0; found 11.1.
16 (d) alpha-chloroacetyl chloride and N-(~'-prop~rgyl-17 carbamylmethyl)-2,6-dimethylaniline were reacted i~ the 18 presence of pyridine to ~rod~ce 19 N-~N'-propargylcarbamylmethyl)-2,6-dimethyl-alpha-chloroacetanilide as a white solid, m.p. 89-94~C. Elemental 21 analysis for C1sHI7ClN202 showed: ~Cl~ calculated 12.1, found 22 11Ø
23 (e) Alpha-chloroacetyl chloride and N-IN~-propargyl-24 carbamylmethyl)-2,k-diethylanili~e were reacted in the presence 2S of pyridine to prcd~ce N-(N'-FroEargylcarbamylmethyl)-~,6-di-26 ethyl-alpha chlorcacetanilide as a white solid, m.p. 97-27 99C. Elemental analysis for C~lH2lClN202 sho~ed: ~Cl~
i35~
1 calculated 11.1~ found 10.4.
2 Example 5 -- Prepara~ion of isoFropyl alpha-3 IN-chlor-ac~tyl-N-2~6-dime-hyl~hen~l3m}n-L-hioace--ate 4 Isopropyl mercaptan (7r6 gr 0~1 mol) was added drop-wise to a stirred and cooled (ice bath) soluticn of 2~.2 g (0.1 6 mol) ~romoacetyl brc~ide in 250 ml methylene chloride. The 7 reaction ~as allowed to ~arm tc about 25C and stirred for 48 8 hours. Nitrogen gac was then bubbled into the reaction mixture 9 to remove dissol~ed hydrogen bromide. The reactio~ mi~ture was evaporated under reduced pressure to give 21 9 of crude isopropyl 11 alpha-bromothioac6tate (contaminated by a little CH2Cl23.
12 A slurry of 10.6 g ~0.05 mol) isopropyl alpha-bro~o-1~ thioacetate ~prepared above), 6.1 g (0.05 mol) 2,6-dimethyl-14 aniline, and 5.3 g ~0.05 mol) sodium carbonate in ~50 ml dimethylforma~ide ~as stirred at 25C for 24 hours. The 16 reaction mixture ~ac then diluted ~ith 1 liter water and 17 extracted with benzene. The benzene extracts were ~ashed with 10 water, dried over mag~esium sulfate and evaporated under reduced 19 pressure to give an oil. The oil was chro~atographed on 200 g silica gel. Isopropyl alpha-(N-2,~-dimethylphenylamino)-21 thioacetate (9 g) was eluted from the silica gel ~ith 97.5/2.5 22 hexane/ether.
23 A soluticn of 4.3 g (0.038 mol) chloroacetyl chloride 24 in 75 ml ethyl ac~tate was added dropwise to a stirred and cooled tice bath) solutlcn of ~ g (0.038 mol) isopropyl alpha-~N-2,6-26 dimethylphenylamino)thioacetate ~prepared above) and 3 g (0.03~
27 mol) pyridine in 150 ml ethyl acetate. After stirring at about 28 25C for 1-1/2 hoursO an additional 1 g pyridine and 1.4 g 29 chloroacetyl chloride were added. The reacticn mixture was stirred another 1/2 hcul at a~out 25C. ~hin-layer 31 chromatography shcwed ~he absence of isopropyL alpha-tN-2,6-32 dimethylphenylaminothioacetate in the reaction mixture~ WateL
~æ535~7 (100 ml) was added to the reaction mixture. The organic layer was separated, washed with 10% aqueous sodium bicarbonate solution, washed with water, dried over magnesium sulfate and evaporated under reduced pressure to give an oil which solidified on standing. Recrystal-lization of the solid form from hexane gave 7.7 g of isopropyl alpha-(N-chloroacetyl-N-2,6-dimethylphenyl-phenylamino)thiocyanate, as a colorless solid, m.p. 92-96OC. The elemental analysis on the product is tabulated in Table I, under Compound No. 5(a).
The other compounds tabulated in Table I were prepared by a procedure similar to that of this example.
Example 6 -- Preparation of N-(N'-propargylcarbamyl-methyl)-2-methyl-6-ethyl-alpha-chlQroacetanilide A slurry of 24.2 g (0.2 mol) ethyl alpha-bromo-thioacetate, 36~8 g (0.2 mol) 2 methyl~6-ethylaniline and 2.2 g (0.2 mol) sodium carbonate in 200 ml dimethylformamide was stirred at 25C for 5 days. The reaction mixture was diluted with about 250 ml water and extracted with benzene. The benzene extracts were washed with water, dried over magnesium sulfate and evaporated under reduced pressure to give 48.2 g of crude ethyl alpha-(N-2-methyl-6-ethylphenylamino)-thioacetate.
A solution of 24.2 g (0.096 mol) ethyl alpha-(N-2-methyl-6-ethylphenylamino)thioacetate, 5.5 g tO.l mol) propargyl amine and 0.5 g pyridine in 250 ml aceto-nitrile was stirred at 25C ~or about 16 hours. An ..~, v- ~ æ53~
additional 3 g of propargylamine was then added and the reaction mixture was heated under reflux for 16 hours.
The reaction mixture was then evaporated under reduced pressure and the residue was chromatographed on 250 g silica gel (50% ether/hexane eluent) to give 15.8 g o~
N-(N'-propargylcarbamylmethyl)-2-methyl-6-ethylaniline.
A sample of 2.5 g ~0.022 mol~ chloroacetyl chloride was added dropwise to a solution of 5 g (0.22 mol) N-(N'-propargylcarbamylmethyl)-2-methyl-6-ethylaniline and 1.9 g (0.022 mol~ pyridine in 150 ml methylene chloride. The reaction mixture was stirred at about 25C for 2 hours. The reaction mixture was then washed with water, dried over magnesium sulfate and evaporated to give a viscous oil. The oil was crystallized from ether to give the product, N-(N'-propargylcarbamylmethyl)-2-methyl-6-ethyl-alpha-chloro-acetanilide, as a colorless solid, m.p. 83-85C.
Elemental analysis for C16HlgClN22 showed %Cl, calculated 11.6, found 12Ø
Example 7 ~- Preparation of N-(N'-propargyl-! N'-methylcarbamylmethyl)-2,6-dimethylaniline A solution of 543 g (2.6 mol) methyl alpha-N-2,6-dimethylphenylamino)thioacetate, 179 g (2.6 mol) N methyl-propargylamine and 205 g pyridine was heated under reflux for 5 hours and then at 25C for 16 hours.
The reaction mixture was diluted with methylene chloride, washed with water, dried over magnesium sulfate and evaporated to give a solid residue.
Crystallization from 50% hexane/isopropyl alcohol gave , :1 ~ ~i3S~L7 the product, m.p. 54-55C (68% yield).
The compounds of the present invention are herbicidal in both pre- and post-~mergent applications.
For pre-emergent control of undesirable vegetation, the herbicidal compounds will be applied in herbicidally effective amounts to the locus or growth medium o~ the vegetation, e.g., soil infested with seeds and/or seedlings of such vegetation. Such application will inhibit the growth of or kill the seeds, germinating seeds and seedlings. For post-emergent applications, the herbicidal compounds will be applied directly to the foliage and other plant parts. Generally, th~
herbicidal compounds of the invention are effective against weed grasses as well as broadleaved weeds. Some may be selective with respect to the type of application and/or type of weed~
The herbicidal compounds of the present invention can be used alone as herbicides. However, it is generally desirable to apply the compounds in herbicidal compositions comprisiny one or more of the herbicidal compounds intimately admixed with a biologically inert carrier. The carrier may be a liquid diluent or a solid, e.g~, in the form of dust powder or granules. In the herbicidal composition, the active herbicidal compounds can be from about ~.01 to 95% by weight of the entire composition.
Suitable liquid diluent carriers include water and organic solvents, e.g., hydrocarbons such as benzene, toluene, kerosene, diesel oil, fuel oil, and petroleum e ~S,.
~ 2~i3~
naphtha. Suitable solid carriers are natural clays such as kaolinite, atalpulgite and montmorillonite. In addition, talcs, pyrophillite, diatomaceous silica, synthetic fine silicas, calcium alumino-silicate and tricalcium phosphate are suitable carriers. Organic materials such as walnut-shell flour, cottonseed hulls, wheat flour, wood flour or redwood-bark flour may also be used as solid carriers.
The herbicidal composition will also usually contain a minor amount of a surface-active agent. Such surface agents ælre those commonly known as wetting agents, dispersing agents and emulsifying agents, and can be anionic, cationic or nonionic in character. The herhicidal compositions may also contain other pesticides, adjuvants, stabilizers, conditioners, fillers, and the like.
The amount of herbicidal compound or composition administered will vary with the particular plant part or plant growth medium which is to be contacted, the general location of application -- i.e., sheltered areas such as greenhouses, as compared to exposed areas such as fields -~ as well as the desired type of control.
Generally, for both pre- and post-emergent control, the herbicidal compounds of the invention are applied at rates of 0.2 to ~0 kg/ha, and the preferred rate is in the range 0.5 to 40 kg/ha.
The thioate esters of the invention wherein Y is -SR4 (Formula IX) are also useful for controlling fungi, particularly plant funqal infections caused by Botrytis , ~253~57 cinera, leaf blights caused by organisms such as Septoria a , Alternaria solani con _ia and Phytophthora infestans conidia, powdery mildew caused by organisms such as Erysiphe ~olyqoni and E. chicoraciarum and leaf rust caused by organisms such as Uromyces Phaseoli ty~ica. However, some fungicidal compounds of the invention may be more fungicidally active than others against particular fungi.
When used as fungicides, the thioate esters are applied in fungicidally effective amounts to fungi and/or their habitats, such as vegetative hosts and non-vegetative hosts, e.g., animal products. The amount used will, of course, depend on several factors such as the host, the type of fungus and the particular compound of the invention. As with most pesticidal compounds, the fungicides of the invention are not usually applied full stre~gth, but are generally incorporated with conventional, biologically inert extenders or carriers normally employed for facilitating dispersion of active fungicidal compounds, recognizing that the formulation and mode of application may affect the activity of the fungicide. Thus, the fungicides of the invention may be formulated and applied as granules, as powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions, or as any of several other known types of formulations, depending on the desired mode of application.
Wettable powders are in the form of finely divided particles which disperse readily in water or other 1 .:
3~7 dispersant. These compositions normally contain from about 5-80% fungicide, and the rest inert material, which includes dispersing agents, emulsifying agents and wetting agents. The powder may be applied to the soil as a dry dust, or preferably as a suspension in water. Typical carriers include fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wettable, inorganic diluents. Typical wetting, dispersing or emulsifying agents include, for example:
the aryl and alkylaryl sulfonates and their sodium salts; alkylamide sulfonates, including fatty methyl taurides; alkylaryl polyether alcohols, sulfated higher alcohols, and polyvinyl alcohols; polyethylene oxides, sulfonated animal and vegetable oils; sulfonated petroleum oils, fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters;
and the addition products of long-chain mercaptans and ethylene oxide. Many other types o~ useful surface-active agents are available in commerce. The surface-active agent, when used, normally comprises from 1% to15% by weight of the fungicidal composition.
Dusts are freely flowing admixtures of the active fungicide with fin~ly divided solids such as talc, natural clays, kieselguhr, pyrophyllite, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sul~ur, lime, flours, and other organic and inorganic solids which act as dispersants and carriers for the toxicant. These finely divided solids have an average particle size of less than about ~253~7 50 microns. A typical dust formulation useful herein contains 75% silica and 25% of the t:oxicant.
Use~ul liquid concentrates include the emulsifiable concentrates, which are homogeneous li~uid or paste compositions which are reaclily dispersed in water or other dispersant, and may consist entirely of the fungicide with a liquid or solid emulsifying agent, or may also contain a liquid carrier such as xylene, heavy aromatic naphthas, isopAorone, and other nonvolatile organic solvents. For application, these concentratas ar~ dispersed in water or other liquid carrier, and are normally applied as a spray to the area to be treated.
Other useful formulations for fungicidal applications include simple solutions of the active fungicide in a dispersant in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene, or other organic solvents. Granular formulations, wherein the fungicide is carried on relatively coarse particles, are of particular utility for aerial distribution or for penetration of cover-crop canopy. Pressurized sprays, typically aerosols wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low-boiling dispersant solvent carrier, such as the Freons, may also ~e used. All of those techniques for formulating and applying fungicides are well known in the art.
The percentages by weight of the fungicide may vary according to the manner in which the composition is ~2~35 5L~
23a to be applied and the particular type of formulation, but in general comprise 0.5 to 95% of the toxicant by weight of the fungicidal composition.
The fungicidal compositions may be formulated and applied with other active ingredients, including other fungicides, insecticides, nematocides, bactericides, plant growth regulators, fertilizers, etc.
Exdmple 9 -~ Herbicidal Tests Pre-emergent herbicidal tests with representative compounds of the invention were made using the following method:
An acetone solution o~ the test compound was prepared by mixing 750 mg of the compound, 220 mg of a nonionic surfactant and 25 ml of acetone. This solution was added to approximately 125 ml of water containing 156 mg of surfactant.
Seeds of the test vegetation were planted in a pot of soil and the test solution was sprayed uniformly onto the soil surface at a dose of 33 micrograms/cm~.
The pot was watered and placed in a greenhouse. The pot was watered intermittently and was observed for seedling emergence, health of emerging seedlings, etc., for a 3-week period. At the end of this period, the herbicidal effectiveness of the compound was rated based on the physiological observations. A 0-to-100 scale was used, 0 repressnting no phytotoxicity, 100 representing Fomplete kill. The results of these tests i ' /
~253S~'7 23b appear in the last two columns of Table I and in Table II.
Example 10 -- Tomato Late Bliqht Compounds of the invention werle tested for th~
control of the Tomato Late ~light o:rganism Phytophthora infestans conidia. Five- to six-week-old tomato (variety Bonny Best) seedlings were used. The tomato plants were sprayed with a 250-ppm solution of the test compound in acetone, water and a small amount o~ a nonionic emulsifier. The sprayed plants were then inoculated one day later with the organism, placed in an environmental chamber and incubated at 66-68F and 100%
relative humidity ~or at least 16 hours. Following the incubation, the plants were allowed to dry and then were maintained at 60-80~ relative humidity for approximately 7 days. The percent disease control provided by a given test compound was based on the percent disease reduction relative to untreated check plants. Representative compounds tabulated in Table I
were tested, and compound Nos. 5(a)-5(b), 5(f)-5(h) and
8 The reaction is conducted in lnert polar inorganic sol~ents, 9 e.g. t apolar aiprotic solvents such as dimethylformamide and ; 10 acetonitrile, at ~eacticn temperatures varying from 0C to 90C, 11 preferably from 20C to 50C~ The ~eac*ion pressure may be 12 atmospheric, subatmospheric or superatmospheric. Ho~ever, for 13 convenience o~ conducting the reaction, the pressure is generally 14 atmospheric. The reaction time will, of course, vary dependlng ~ S ~
~;35~L7 upon the reactants and the reaction temperature.
Generally the reaction time is from 0.25 to 24 hours.
The product (IV) is generally purified by conventional procedures, e.g., extraction, distillation or crystallization, before use in the acylation reaction (2).
The acylation reaction (2) is conducted by conventional procedures, preferably in the presence of an acid acceptor such as a trialkyl amine or pyridine.
The reactants ~IV) and (V) and the acid acceptor are generally contacted in substantially equimolar amounts in the liquid phase in an inert organic solvent at a temperature of 0 to 100C. Suitable inert organic solvents include ethyl acetate, methylene dichloride, dimethoxyethane, benzene, etc. The product is isolated , and purified by conventional procedures such as extraction, distillation, chromatography, crystal-lization, etc.
The thioate ester compounds of the invention wherein Y is -SR4 may be prepared by alkylating an aniline compound (II) with an alpha-halothioate ester (VII) to produce alpha-(N-phenylamino)thioate ester (VIII) and subsequently acylating the thioate ester (VIII~ with an alpha-haloacetyl halide (V) to give the alpha-(N-haloaceatyl-N-phenylamino)thioate ester (IX).
This sequence of reactions is depicted by the following equations:
~2S:3 S~
Rl R3 O
~ NH2 + XCH-C-S-R4 (II) R2 (VII) R R3 o ~ NHlH-c-s-~4 (VIII) ~ R2 (3) ~ NHCH-C-S-R4 ~ XCCH2X base \ 2 (V) (VIII) R
~ N
( IX ) R2 CCH2X (4) O
:' ~wherein Rl, R2, R3, R4 and X have the same ~ignificance :~20 as previously defined.
~:The alkylation reaction~(3) i5 conducted in the presence of an acid acceptor by a procedure essentially , identical to that described for reaction (1), and the acylation reaction (4~ is conducted by a procedure ~25 essentially identical to that described for reaction :~ (2).
The N-(carbamylalkyl)aniline intermediate (IV) employed in reaction (2) may also be prepared by 7a reacting the alpha-(N-phenylamino)thioate ester (VIII) with an amine in the presence of a base such as pyridine in the liquid phase at a temperature of O to 100C, as depicted by the following reaction (5):
~Læs3~
ICH 5 R4 + ~IN~
(VIII) R2 Rl ~\~ N HC 11 C- N / ~ H S R 4 \=/ R 6 (IV) R2 (5) 1 ExAMELEc 2 The preparation of the compounds of the invention by 3 the above reactions is illustrated by the followi~g examples.
4 Example 1 -- Preparatian of N-(N',N'-diallyl-carb__Xlm__h~lL-2,6-di-thyl-a-~la-~hlo--oa-e--nilide C2ll5 0 CiI2-(:H=C~12 --N / Cl12 - Cil = C~l 2 CCII 2 Cl ` C2~15 o 6 A 78-g lO-8 mol) sample of diallylamine was added drop-7 wise to a stirred and ccoled (dry ice/acetone bath) solution oF
8 ao g (o. 4 mol) brcmoacetylbromide in 200 ml methylene 9 dichloride. The reaction mixture was allowed to ~arm to about 25C and stirred cvernight. The reaction mixture was the~ washed 11 with waterr aqueous sodium bicar~onate, again with water, dried 12 over magnaslum sulfate and evaporated under reduced pressure to 13 gi~e 38 g of N,~-diallyl-alpha-~romoacetamide.
14 A mixture of 19 g ~0.088 mol) N,N-diallyl-alpha-bromoacetamide ~preFared above), 13.1 g (0.088 mol3 2y6~
16 diethylaniline and 12.2 g (0.088 mol) potassium carbonate in 150 17 ml dimethylformamide was heated at 50-65C for 24 hours~ The 18 reaction mixture was filtered and the filtrate was diluted with 19 300 ml water. Tbe aguecus filtrate mixtur~ was extracted ~ith ~ _ ~S3S~7 1 hexane. The hexane extracts were dried over magnesium slllfate 2 and e~aporated under reduced pressure to give a viscous oil. rrhe 3 oil ~as chromatograFhed Cll a silica-gel column.
4 N-(N',Ns-diallylcarba~ylmethyl)-2,6-diethylaniline ~12~3 g) was eluted from the cclumn ~ith 5~ ether/hexane~
6 ~ solution of 2.48 g (0.0313 mol) pyridine in 25 ml 7 ethyl acetate was added dropwise to a stirred and cooled (ice r~ 8 bath) solution of 8.93 9 (0.0313 mol) M-(N',N'-diallyl-9 carbamylmethyl)-2,6-diethylaniline ~prepared ahove) and 3.54 g (0.0313 mol) chloroacetyl chloride in 150 ml of ethyl 11 acetate. The reaction mixture was then stirred at about 25C
12 overnight. The reaction mixture was diluted ~ith 100 ml water.
13 The aqueous layer ~as separated and e~tracted with diethyl ether.
14 The ether extract and the organic lay~r were comhined and washed ~ith aqueous sodium bicarbonate and t~en water, dried over 16 magnesium sulfate, and evaporated under reduced press~re to give 17 a viscous oil. The oil was chromatographed OD silica gel.
18 Elution ~ith 40~ etheL/hexane gave the product, N~ diallyl-19 car~amylmethyl)-'2~,~-diethyl-alpha-chloroacetanilide, as a yellow oil. Elemental analysis on the product tCzH27clN2~) 21 showed: ~C1, calculated 9.77, found 10.2.
22 _xam~le_2~aL~2lqL
23 ~y a proc~dure similar to that o~ Example 1:
24 (a3 alpha-chlcroacetyl chloride and N-tN',N'-diallylcarkamylmethyl)-2,6-dimethylanili~e uere 26 reacted to produce N-IN'jN'-diallylcarhamylmethyl)-2~6-27 dimethyl-alpha-chloroacetanilide. Elemental analysis for 28 Cl8H23Cl~2O2) sho~ed: ~Cl, calculated 10.59, found 10.9.
29 (b~ alE~a-chloroacetyl chloride and N-(N'-methyl-N'-allylcarbamylmethyl)-2,6-di~ethylaniline were reacted to 31 produce N-(N~-methyl-N'-allylcar~amylmethyl)-2,6-dimethyl-32 alpha-chloroacetanilide as a white solid, m.p. 82-84~C.
_ g _ ~253~7 Elemental analysis for ClH21ClN202) showed: %Cl, calculated 11.4, found 10.5.
(c) alpha-chloroacetyl chloride and N-(N'-methyl-N'-allylcarbamyl-methyl)-2,6-diethylaniline were reacted to produce N-(N'-methyl-N'-allyl-carbamylmethyl)-2,6-diethylalpha-chloroacetanilide, as a yellow solid, m.p.
85-86.5 C. Elemental analysis for C18H25ClN202 showed: %Cl, calculated 10.5, found 10Ø
(d) alpha-chloroacetyl chloride and N-(piperidino-carbonylmethyl)-2,6-dimethylaniline were reacted ~o produce N-(piperidinocarbonylmethyl)-2,6-dimethyl-alpha-chloroacetanilide, m.p. 109-111C. Elemental analysis for C16H21ClN202 showed: %Cl, calculated 11.48, found 11.5. The structural formula of this product is:
C~1 CH2CN~
/
CCH2Cl (e) alpha-chloroacetyl chloride and N-(piperidinocarbonylmethyl)-2,6-diethylaniline were reacted to produce N-(piperidinocarbonylmethyl)-2,6-die~hyl-alpha-chloroacetanilide, m.p. 123-124C. Elemental analysis for C18H25ClN202 showed: %Cl, calculated 10.52, found 10.2.
(f) alpha-chloroacetyl chloride and N-(N',N'-dimethylcarbamyl-methyl)-2,6-diethylaniline were reacted to produce N-(N',N'-dimethylcarbamyl-I methyl)-2,6-diethyl-alpha-chloroacetanilide as a white solid, m.p. 81-82 C.
Elemental analysis for C16H23ClN2O2 showed: %Cl, calculated 11.41, found 11.8.
~g) alpha-chloroacetyl chloride and N-(N',N'-dimethylcarbamyl-methyl)-2,6-dimethylaniline were ~25i3~i~L7 1 reacted to prod~ce N-(N~,N~-dimethylcarbamylmethyl~ h-2 dimethyl-alpha-chloroacetanilide, as a white solid, m.p. 85-3 86.5C~ Elemental analysis for Cl~Hl~ClN202 sho~ed: ~Cl, 4 calculated 12.54, fcund 12.1~
,~ 5 (h) alp~a-chloroacetyl chloride and N-(N'-t-6 butylcarbamylmethyl)-2,6-dimethylaniline were reacted to 7 produce N-~N'-t-butylcarbamylmethyl)-2,6-dimethyl-alpha-8 chloroacetanilide, as a white sclid, m.p. 110-112C. Elemental 9 analysis for C16H23ClN202 showed: %Cl, calculated 11.41, fou~d 11.1.
11 (i) alFha-chloroacetyl chloride and N-(~'-t-12 bu~ylcarbamylmethyl)-2,6-diethylaniline were reacted ~o 13 produce N ~N'-t-butylcar~amylmethyl)-2,6-diethyl-alpha-14 chloroacetanilide~ as a white sclid, m.p. 118-120C. Elemental analysis for C18H27ClN2C2 showed: %Cl, calculated 10~46~ fou~d j 16 10.2.
17 ~j) alpha-chloroacetyl chloride and 18 N-(N',N'-diethylcarbamylmethyl)-2,6-dimethylaniline were 19 reacted ~o prod~c~ (N',N' diethylcarbamylmethyl)-2,6-dimethyl-alpha-chloroacetanilide, as a yellow oil~ Elemental 21 analysis for C,6H23ClN202 sho~ed: ~Cl, calculated 11.41, found .1 ~ 2? 11.9.
23 (k) alEha-chloroacetyl chloride and 24 N-~N',N'-diethylcarba~ylmethyl)-2,6-diethylaniline ~ere reacted to produce N-(N',N'-diethylcarba~ylmethyl)-2,6-26 diethyl-alpha-chlcroacetanilide, a yellow oil. Eleme~tal 27 analysis for Cl8H27ClN202 showed: %Cl, calculated 10~46, found 28 10.4.
29 (1) alp~a-chloroacetyl chloride and N-~N' sec-butylcarba~yl~ethyl)-2,6-diethylanilille were reacted to 31 produce N-~N'-sec-butylcarbamylmethyl)-2,6-diethyl 32 alpha-chloroacetanilide as a white solid, m~p~ 120--122C.
` ~.25i35~7 Elemental analysiS for C18H27ClN22 showed %Cl, calculated 10~46, found 10.3.
(m) alpha-chloroacetyl chloricle and N-(N'-sec-butylcarbamylmethyl)-2 t 6-dimethylaniline were reacted to produce N-(N'-sec-butylcarbamylmethyl)-2,6-dimethyl-alpha-chloroacetanilide as a white solid, m.p. 97-99C.
Elemental analy5is for C18H23ClN22 showed %cl, calculated 10.41, ~ound 10.4C.
(n) alpha-chloroacetyl chloride and N-(carbamyl-2,6-dimethylaniline were reacted to produce N-(carbamyl-methyl)-2,6-dimethyl-alpha-chloroacetanilide, as a white solid, m.p. 139-141C. Elemental analysis for C12H15ClN202 showed: %Cl, calculated 13.92, found 13.70.
(o) alpha-chloroacetyl chloride and N-(carbamyl-2,6-diethylaniline were reacted to produce N-(carbamyl)-2,6-diethyl-alpha-chloroacetanilide, m.p. 150-152C.
Elemental analysis for C14H19ClN22 showed %Cl, calculated 12.54, found 12.6. The structural formula of this product is ~ N ,,CH2-CNH2 ~ ~ CCH2Cl ~p) alpha-chloroacetyl chloride and N-[l-(N,N-dimethylcarbamyl)ethyl]-2,6-dimethylaniline were reacted to produce N-[1-(N,N-dimethylcarbamyl)-ethyl]-2,6-dimethyl-alpha-chloroacetanilide, m.p. 112-~Z~3~;~7 12a114C. Elemental analysis for C15H21ClN22 showed-%Cl, calculatad 11. 95, found 11. 7 . The structural formula for this product is , :~2~;~S~7 N o \ CH
CCH2Cl 1 (q~ alpha-chloroacetyl chloride and 2 N-[1-(N',N'-dimethylcar~amyl)ethyl]-2,6-diethylanili~e were 3 reacted to produce ~ N'jN'-dimethylcar~amyl)ethrl~-4 2,6-dimethyl-alpha-chloroacetanilide, m.p. 100-102C.
Elemental analysic for Cl7Hz5ClNzO~ showed: %Cl, calculated 6 10.9, found 10.7.
7 Example 3 -- Preparation of N ~N'-proparg~l-N~-8 ~ ~ethYlcarbamylmethylL-2~6-dlm-t-Ql-al~ha-chlQroacetanil-d-e Cll3O /C~ 3 ll ~C~12CI`I
)--L~jC~12-C-CH
:~ ~ CCH2Cl ~ ;
C~13 o ~` 9 A solutic~ of 13.8 g ~0.2 mol) of N--methylp~opargyl-.- ,;
amine in 20 ml methylene chloride was added dropwise to a stirred 11 and cooled (below 15C) solution of 40.2 9 (0.2 mol) bromoacetyl 12 bromide and 16 g (0.2 mol) sodium bicarbonate in 250 mL methyle~e 13 chloride. The reaction mixture was allowed to warm to about 25C
14 and stirred or 2 hcurs. The reaction mi~ture was then filtered and evaporated undr reduced pressure to give an oily residue.
16 The residue was diluted with 150 ml ether to form a two-phase ; 17 mixture consis~ing of an ether phase and a dark oil~ The ether 18 phase was sep~rated, dried over magnesium sulfate, a~d ~aporated 19 to give 32.3 g o~ ~-methyl-N-propargyl-alpha-bromoacetamide.
21 A mixtuLe o 16.2 g (0.085 mol) N-methyl-N-22 propargyl-alpha-bromoacetamidA (Erepared above), 10.2 g .
~Z~;35~
1 (0.085 mol~ 2~6-dimethylaniline and 8.9 g (0~085 mol) sodium 2 carbonate in 200 ~l dimethylformamide was heated at 140C ~or 1 3 hours. The reacticn mixture ~as diluted ~ith 300 ml water a~d 4 extracted with beDzeDe. The benzene extracts were ~ashed with ~ater, dried over magn~sium sulfate and evaporated under reduced 6 pressure to gi~e a viscous oil. The oil was chrcmatographed on a ; 7 silica gel column. N-(N'-methyl-N'-propargyl-8 carbamylmethyl~-2,6-dimethylaniline was eluted from the 9 column with 50:50 h~ane-ethyl ethern ~ sampl~ of 3.2 g (0.029 mol) chloroacetyl chloride ~as 11 added dropwise to a stirred and warmed (45-50C) solution of 12 6.6 g ~0.029 mol~ N-tN'-methyl-13 N'-propargylcarbamylmethyl)-2,6-dimethylaniline (~repared 14 above) and 2.3 g ~0~029 mol) pyridine in 250 ml of methyle~e chloride. The reaction mixture was stirred at a~out 25C for 1 16 hour. The reacticn mixture was washed with 250 ml ~ater, with 17 aqueous sodium bicar~cnate and then water, dried o~er magnesium 18 sulfate and evaporated unde~ red~ced prescure to ~ive a viscous 19 oil. The oil was crystallized from ether to yiYe the product, N-(N'-methyl-N'-propargylcarbamylmethyl~-2,6-dimethyl-21 alpha-chloroacetanilide, as a colorless sclid, m.p. 72-22 74C. Elemental analysis for C~6H~gClN202 showed: ~Cl, 23 calculated 11.6, found 11.8.
24 Exa_~ 4l_L~4leL
By a procedure similar to that above:
26 (a) alpha-chloroacetyl chloride and N-(N'-methyl-27 N~-propargylcarbamylmethyl)-2,6~diethylaniline were reacted 28 in the presence of pyridine to produce N-(N~ methyl-29 N'~propargylcarha~ylmethyl~-2,6-diethyl-alpha-chloroacetanilide as a cclorless solid, m.p. 69-70C.
31 Elemental analy~ic for C~aH23ClN202 showed: %Cl, calc~ 10.6 32 found 10.5.
~Z~3~7 1 (b) alEba-chloroacetyl chloride and N-(N '~
2 dimethyl-2-propynylcarbamylmethyl)-2,6-diethylaniline were 3 reacted in the prese~ce of pyridine in ethyl aceta~e to produce 4 N-tN'~ dimethyl-2-propynylcarbamylmethyl)-2,6-diethyl-alpha-chloroacetanilide as a ~hite solid~ m.p. 114-6 115C. Elemental analysis for Cl9H25ClN2O2 sho~ed: ~Cl, 7 calculated 10. 2r f~und 10.1. The structural for~ula of this 8 product is:
s O C1-13 ~\ ~C~12C~`IIIC-C-C~
- N Cll3 CC~12C
9 (c) alEha-chloroacetyl ch~oride and N-~'-1,1-dimethyl-2-propynylcarbamylmethyl)-2,6-dimethylanili~e ~ere 11 reacted in the pr~s~nce of pyridine in ethyl acetate to produce 12 N-~N~-1,1-dimethyl-2-prcpynylcar~amylmethyl)-2,6-13 dimethyl-alpha-chloroacetanilide as a white solid, m.p. 100-14 102C. Elementài~analysis for C17~1Cl~zO2 sho~ed: ~Cl, calc.
11.0; found 11.1.
16 (d) alpha-chloroacetyl chloride and N-(~'-prop~rgyl-17 carbamylmethyl)-2,6-dimethylaniline were reacted i~ the 18 presence of pyridine to ~rod~ce 19 N-~N'-propargylcarbamylmethyl)-2,6-dimethyl-alpha-chloroacetanilide as a white solid, m.p. 89-94~C. Elemental 21 analysis for C1sHI7ClN202 showed: ~Cl~ calculated 12.1, found 22 11Ø
23 (e) Alpha-chloroacetyl chloride and N-IN~-propargyl-24 carbamylmethyl)-2,k-diethylanili~e were reacted in the presence 2S of pyridine to prcd~ce N-(N'-FroEargylcarbamylmethyl)-~,6-di-26 ethyl-alpha chlorcacetanilide as a white solid, m.p. 97-27 99C. Elemental analysis for C~lH2lClN202 sho~ed: ~Cl~
i35~
1 calculated 11.1~ found 10.4.
2 Example 5 -- Prepara~ion of isoFropyl alpha-3 IN-chlor-ac~tyl-N-2~6-dime-hyl~hen~l3m}n-L-hioace--ate 4 Isopropyl mercaptan (7r6 gr 0~1 mol) was added drop-wise to a stirred and cooled (ice bath) soluticn of 2~.2 g (0.1 6 mol) ~romoacetyl brc~ide in 250 ml methylene chloride. The 7 reaction ~as allowed to ~arm tc about 25C and stirred for 48 8 hours. Nitrogen gac was then bubbled into the reaction mixture 9 to remove dissol~ed hydrogen bromide. The reactio~ mi~ture was evaporated under reduced pressure to give 21 9 of crude isopropyl 11 alpha-bromothioac6tate (contaminated by a little CH2Cl23.
12 A slurry of 10.6 g ~0.05 mol) isopropyl alpha-bro~o-1~ thioacetate ~prepared above), 6.1 g (0.05 mol) 2,6-dimethyl-14 aniline, and 5.3 g ~0.05 mol) sodium carbonate in ~50 ml dimethylforma~ide ~as stirred at 25C for 24 hours. The 16 reaction mixture ~ac then diluted ~ith 1 liter water and 17 extracted with benzene. The benzene extracts were ~ashed with 10 water, dried over mag~esium sulfate and evaporated under reduced 19 pressure to give an oil. The oil was chro~atographed on 200 g silica gel. Isopropyl alpha-(N-2,~-dimethylphenylamino)-21 thioacetate (9 g) was eluted from the silica gel ~ith 97.5/2.5 22 hexane/ether.
23 A soluticn of 4.3 g (0.038 mol) chloroacetyl chloride 24 in 75 ml ethyl ac~tate was added dropwise to a stirred and cooled tice bath) solutlcn of ~ g (0.038 mol) isopropyl alpha-~N-2,6-26 dimethylphenylamino)thioacetate ~prepared above) and 3 g (0.03~
27 mol) pyridine in 150 ml ethyl acetate. After stirring at about 28 25C for 1-1/2 hoursO an additional 1 g pyridine and 1.4 g 29 chloroacetyl chloride were added. The reacticn mixture was stirred another 1/2 hcul at a~out 25C. ~hin-layer 31 chromatography shcwed ~he absence of isopropyL alpha-tN-2,6-32 dimethylphenylaminothioacetate in the reaction mixture~ WateL
~æ535~7 (100 ml) was added to the reaction mixture. The organic layer was separated, washed with 10% aqueous sodium bicarbonate solution, washed with water, dried over magnesium sulfate and evaporated under reduced pressure to give an oil which solidified on standing. Recrystal-lization of the solid form from hexane gave 7.7 g of isopropyl alpha-(N-chloroacetyl-N-2,6-dimethylphenyl-phenylamino)thiocyanate, as a colorless solid, m.p. 92-96OC. The elemental analysis on the product is tabulated in Table I, under Compound No. 5(a).
The other compounds tabulated in Table I were prepared by a procedure similar to that of this example.
Example 6 -- Preparation of N-(N'-propargylcarbamyl-methyl)-2-methyl-6-ethyl-alpha-chlQroacetanilide A slurry of 24.2 g (0.2 mol) ethyl alpha-bromo-thioacetate, 36~8 g (0.2 mol) 2 methyl~6-ethylaniline and 2.2 g (0.2 mol) sodium carbonate in 200 ml dimethylformamide was stirred at 25C for 5 days. The reaction mixture was diluted with about 250 ml water and extracted with benzene. The benzene extracts were washed with water, dried over magnesium sulfate and evaporated under reduced pressure to give 48.2 g of crude ethyl alpha-(N-2-methyl-6-ethylphenylamino)-thioacetate.
A solution of 24.2 g (0.096 mol) ethyl alpha-(N-2-methyl-6-ethylphenylamino)thioacetate, 5.5 g tO.l mol) propargyl amine and 0.5 g pyridine in 250 ml aceto-nitrile was stirred at 25C ~or about 16 hours. An ..~, v- ~ æ53~
additional 3 g of propargylamine was then added and the reaction mixture was heated under reflux for 16 hours.
The reaction mixture was then evaporated under reduced pressure and the residue was chromatographed on 250 g silica gel (50% ether/hexane eluent) to give 15.8 g o~
N-(N'-propargylcarbamylmethyl)-2-methyl-6-ethylaniline.
A sample of 2.5 g ~0.022 mol~ chloroacetyl chloride was added dropwise to a solution of 5 g (0.22 mol) N-(N'-propargylcarbamylmethyl)-2-methyl-6-ethylaniline and 1.9 g (0.022 mol~ pyridine in 150 ml methylene chloride. The reaction mixture was stirred at about 25C for 2 hours. The reaction mixture was then washed with water, dried over magnesium sulfate and evaporated to give a viscous oil. The oil was crystallized from ether to give the product, N-(N'-propargylcarbamylmethyl)-2-methyl-6-ethyl-alpha-chloro-acetanilide, as a colorless solid, m.p. 83-85C.
Elemental analysis for C16HlgClN22 showed %Cl, calculated 11.6, found 12Ø
Example 7 ~- Preparation of N-(N'-propargyl-! N'-methylcarbamylmethyl)-2,6-dimethylaniline A solution of 543 g (2.6 mol) methyl alpha-N-2,6-dimethylphenylamino)thioacetate, 179 g (2.6 mol) N methyl-propargylamine and 205 g pyridine was heated under reflux for 5 hours and then at 25C for 16 hours.
The reaction mixture was diluted with methylene chloride, washed with water, dried over magnesium sulfate and evaporated to give a solid residue.
Crystallization from 50% hexane/isopropyl alcohol gave , :1 ~ ~i3S~L7 the product, m.p. 54-55C (68% yield).
The compounds of the present invention are herbicidal in both pre- and post-~mergent applications.
For pre-emergent control of undesirable vegetation, the herbicidal compounds will be applied in herbicidally effective amounts to the locus or growth medium o~ the vegetation, e.g., soil infested with seeds and/or seedlings of such vegetation. Such application will inhibit the growth of or kill the seeds, germinating seeds and seedlings. For post-emergent applications, the herbicidal compounds will be applied directly to the foliage and other plant parts. Generally, th~
herbicidal compounds of the invention are effective against weed grasses as well as broadleaved weeds. Some may be selective with respect to the type of application and/or type of weed~
The herbicidal compounds of the present invention can be used alone as herbicides. However, it is generally desirable to apply the compounds in herbicidal compositions comprisiny one or more of the herbicidal compounds intimately admixed with a biologically inert carrier. The carrier may be a liquid diluent or a solid, e.g~, in the form of dust powder or granules. In the herbicidal composition, the active herbicidal compounds can be from about ~.01 to 95% by weight of the entire composition.
Suitable liquid diluent carriers include water and organic solvents, e.g., hydrocarbons such as benzene, toluene, kerosene, diesel oil, fuel oil, and petroleum e ~S,.
~ 2~i3~
naphtha. Suitable solid carriers are natural clays such as kaolinite, atalpulgite and montmorillonite. In addition, talcs, pyrophillite, diatomaceous silica, synthetic fine silicas, calcium alumino-silicate and tricalcium phosphate are suitable carriers. Organic materials such as walnut-shell flour, cottonseed hulls, wheat flour, wood flour or redwood-bark flour may also be used as solid carriers.
The herbicidal composition will also usually contain a minor amount of a surface-active agent. Such surface agents ælre those commonly known as wetting agents, dispersing agents and emulsifying agents, and can be anionic, cationic or nonionic in character. The herhicidal compositions may also contain other pesticides, adjuvants, stabilizers, conditioners, fillers, and the like.
The amount of herbicidal compound or composition administered will vary with the particular plant part or plant growth medium which is to be contacted, the general location of application -- i.e., sheltered areas such as greenhouses, as compared to exposed areas such as fields -~ as well as the desired type of control.
Generally, for both pre- and post-emergent control, the herbicidal compounds of the invention are applied at rates of 0.2 to ~0 kg/ha, and the preferred rate is in the range 0.5 to 40 kg/ha.
The thioate esters of the invention wherein Y is -SR4 (Formula IX) are also useful for controlling fungi, particularly plant funqal infections caused by Botrytis , ~253~57 cinera, leaf blights caused by organisms such as Septoria a , Alternaria solani con _ia and Phytophthora infestans conidia, powdery mildew caused by organisms such as Erysiphe ~olyqoni and E. chicoraciarum and leaf rust caused by organisms such as Uromyces Phaseoli ty~ica. However, some fungicidal compounds of the invention may be more fungicidally active than others against particular fungi.
When used as fungicides, the thioate esters are applied in fungicidally effective amounts to fungi and/or their habitats, such as vegetative hosts and non-vegetative hosts, e.g., animal products. The amount used will, of course, depend on several factors such as the host, the type of fungus and the particular compound of the invention. As with most pesticidal compounds, the fungicides of the invention are not usually applied full stre~gth, but are generally incorporated with conventional, biologically inert extenders or carriers normally employed for facilitating dispersion of active fungicidal compounds, recognizing that the formulation and mode of application may affect the activity of the fungicide. Thus, the fungicides of the invention may be formulated and applied as granules, as powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions, or as any of several other known types of formulations, depending on the desired mode of application.
Wettable powders are in the form of finely divided particles which disperse readily in water or other 1 .:
3~7 dispersant. These compositions normally contain from about 5-80% fungicide, and the rest inert material, which includes dispersing agents, emulsifying agents and wetting agents. The powder may be applied to the soil as a dry dust, or preferably as a suspension in water. Typical carriers include fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wettable, inorganic diluents. Typical wetting, dispersing or emulsifying agents include, for example:
the aryl and alkylaryl sulfonates and their sodium salts; alkylamide sulfonates, including fatty methyl taurides; alkylaryl polyether alcohols, sulfated higher alcohols, and polyvinyl alcohols; polyethylene oxides, sulfonated animal and vegetable oils; sulfonated petroleum oils, fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters;
and the addition products of long-chain mercaptans and ethylene oxide. Many other types o~ useful surface-active agents are available in commerce. The surface-active agent, when used, normally comprises from 1% to15% by weight of the fungicidal composition.
Dusts are freely flowing admixtures of the active fungicide with fin~ly divided solids such as talc, natural clays, kieselguhr, pyrophyllite, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sul~ur, lime, flours, and other organic and inorganic solids which act as dispersants and carriers for the toxicant. These finely divided solids have an average particle size of less than about ~253~7 50 microns. A typical dust formulation useful herein contains 75% silica and 25% of the t:oxicant.
Use~ul liquid concentrates include the emulsifiable concentrates, which are homogeneous li~uid or paste compositions which are reaclily dispersed in water or other dispersant, and may consist entirely of the fungicide with a liquid or solid emulsifying agent, or may also contain a liquid carrier such as xylene, heavy aromatic naphthas, isopAorone, and other nonvolatile organic solvents. For application, these concentratas ar~ dispersed in water or other liquid carrier, and are normally applied as a spray to the area to be treated.
Other useful formulations for fungicidal applications include simple solutions of the active fungicide in a dispersant in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene, or other organic solvents. Granular formulations, wherein the fungicide is carried on relatively coarse particles, are of particular utility for aerial distribution or for penetration of cover-crop canopy. Pressurized sprays, typically aerosols wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low-boiling dispersant solvent carrier, such as the Freons, may also ~e used. All of those techniques for formulating and applying fungicides are well known in the art.
The percentages by weight of the fungicide may vary according to the manner in which the composition is ~2~35 5L~
23a to be applied and the particular type of formulation, but in general comprise 0.5 to 95% of the toxicant by weight of the fungicidal composition.
The fungicidal compositions may be formulated and applied with other active ingredients, including other fungicides, insecticides, nematocides, bactericides, plant growth regulators, fertilizers, etc.
Exdmple 9 -~ Herbicidal Tests Pre-emergent herbicidal tests with representative compounds of the invention were made using the following method:
An acetone solution o~ the test compound was prepared by mixing 750 mg of the compound, 220 mg of a nonionic surfactant and 25 ml of acetone. This solution was added to approximately 125 ml of water containing 156 mg of surfactant.
Seeds of the test vegetation were planted in a pot of soil and the test solution was sprayed uniformly onto the soil surface at a dose of 33 micrograms/cm~.
The pot was watered and placed in a greenhouse. The pot was watered intermittently and was observed for seedling emergence, health of emerging seedlings, etc., for a 3-week period. At the end of this period, the herbicidal effectiveness of the compound was rated based on the physiological observations. A 0-to-100 scale was used, 0 repressnting no phytotoxicity, 100 representing Fomplete kill. The results of these tests i ' /
~253S~'7 23b appear in the last two columns of Table I and in Table II.
Example 10 -- Tomato Late Bliqht Compounds of the invention werle tested for th~
control of the Tomato Late ~light o:rganism Phytophthora infestans conidia. Five- to six-week-old tomato (variety Bonny Best) seedlings were used. The tomato plants were sprayed with a 250-ppm solution of the test compound in acetone, water and a small amount o~ a nonionic emulsifier. The sprayed plants were then inoculated one day later with the organism, placed in an environmental chamber and incubated at 66-68F and 100%
relative humidity ~or at least 16 hours. Following the incubation, the plants were allowed to dry and then were maintained at 60-80~ relative humidity for approximately 7 days. The percent disease control provided by a given test compound was based on the percent disease reduction relative to untreated check plants. Representative compounds tabulated in Table I
were tested, and compound Nos. 5(a)-5(b), 5(f)-5(h) and
5(j)-5(n) were found to give 18 to 63% control.
, .
,~,.
~ii3~ii3L~7 1 ~xa~ple~ T-o0ato-Ea-lx ~ ht 2 Compou~ds of the invention were tested for the control 3 of the Tomato Early Blight organism, Alt_Enarl3 SQ1an~ dla-4 Tomato (variety Bcnny Best) seedlings of 6 to 7 weeks old ~ere used. The tomatc plantc were s~rayed ~ith a 250-ppm solution
, .
,~,.
~ii3~ii3L~7 1 ~xa~ple~ T-o0ato-Ea-lx ~ ht 2 Compou~ds of the invention were tested for the control 3 of the Tomato Early Blight organism, Alt_Enarl3 SQ1an~ dla-4 Tomato (variety Bcnny Best) seedlings of 6 to 7 weeks old ~ere used. The tomatc plantc were s~rayed ~ith a 250-ppm solution
6 of the compound in an aceto~e-and-~ater solution containing a
7 small amount of a ncn-ionic emulsifier. The sprayed plants
8 ~ere inoculated one day later with the orga~lsm, dried and main-
9 tained at 60-80% relative humidity for about 12 days. Percent disease control was ~ased on the percent disease development on 11 un~reated check Elants. The comEounds takulated in Table I were 12 tested, and Com~ound Nos~ 5(a)-5(b), 5(d)-5(e), 5(i)-5(;) and 13 5(1n~-5(t) were found to give 21 to 88% control.
.
.
59~'7 ~ ~ oo~oLnmomo~ Lno ~ ~11 ~ ~ oooocoooo ~ O
~ ~ ~ o ~ o ~
o ~ ~r o o ~1 ~ 1` ~1 oo ,1 ~ ~ o ~ ~ f' ~ ~ o r ~ i 0 ~ ~P ~ 1~ N _i ~ , ~i a~ ~i --i t~ Cl~ a) co r ~ o o ~
~ I ~ ~ co o ln o a~
~ 1'ii~ ri O ~i t~ ~ In o ~ ~ ~ o o ~i o c~ r o o ~ d~ x ~ o ~ o ~ co o i~ ~ o~no~ $
H S ~}
~ ~ ~1 u ~ ~ t~ ) O O~
1~ ,,~ o~
1~ 0 cn N ~ ~ ~ tX~ CO cr O t~ ~ a~ Ot\ ~1 ~r r~l 1~ ~1 0 ~9 .g ~ ~ o ~ o N
t~J
.-- z r~
`~ *
Ln L~ In Ln Ln m u~ Ln L~ n ~ Ln Ln In Ln ~
''`
`
.
~;253~;~7 TABLE II
Example Herbicidal Effectiveness No. O W C M P L
l 100 100 100 55 100 50 2(a)100 100 100 10 50 0 2(b) 0 100 60 0 0 0 2(c) 98 100 98 0 0 0 2(d) 95 100 100 30 75 50 2(e) 90 100 100 10 70 50 2(f) 80 100 100 100 100 90 2(y)100 100 100 100 100 100 2(h) 93 100 100 0 65 45 2(i) 15 98 90 0 20 0 2(j)100 100 100 100 100 100 2(k) 75 98 100 0 7S 25 2(1) 88 100 100 0 0 0 2(m) 70 100 100 50 25 60 2(n) 60 100 100 0 10 50 2(o) 55 100 100 0 35 78 2(p) 0 20 0 40 35 0 2(q) 0 20 0 0 0 0 4(a) 25 98 90 15 20 4(b)100 100 100 25 100 98 4(c) 93 100 100 0 95 0 4(d)10G. 100 100 30 80 40 4(e) 93 100 100 0 O = Wild Oats tAvena fatua) W = Watergrass (Echinochloa crusgalli) c = Crabgrass (Digitaria sanguinalis) M = Mustard ~Brassica arvensis) P = Pigweed (Amaranthus retroflexus) L = Lambsquarter (Chenopodium album)
.
.
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~ ~ ~ o ~ o ~
o ~ ~r o o ~1 ~ 1` ~1 oo ,1 ~ ~ o ~ ~ f' ~ ~ o r ~ i 0 ~ ~P ~ 1~ N _i ~ , ~i a~ ~i --i t~ Cl~ a) co r ~ o o ~
~ I ~ ~ co o ln o a~
~ 1'ii~ ri O ~i t~ ~ In o ~ ~ ~ o o ~i o c~ r o o ~ d~ x ~ o ~ o ~ co o i~ ~ o~no~ $
H S ~}
~ ~ ~1 u ~ ~ t~ ) O O~
1~ ,,~ o~
1~ 0 cn N ~ ~ ~ tX~ CO cr O t~ ~ a~ Ot\ ~1 ~r r~l 1~ ~1 0 ~9 .g ~ ~ o ~ o N
t~J
.-- z r~
`~ *
Ln L~ In Ln Ln m u~ Ln L~ n ~ Ln Ln In Ln ~
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.
~;253~;~7 TABLE II
Example Herbicidal Effectiveness No. O W C M P L
l 100 100 100 55 100 50 2(a)100 100 100 10 50 0 2(b) 0 100 60 0 0 0 2(c) 98 100 98 0 0 0 2(d) 95 100 100 30 75 50 2(e) 90 100 100 10 70 50 2(f) 80 100 100 100 100 90 2(y)100 100 100 100 100 100 2(h) 93 100 100 0 65 45 2(i) 15 98 90 0 20 0 2(j)100 100 100 100 100 100 2(k) 75 98 100 0 7S 25 2(1) 88 100 100 0 0 0 2(m) 70 100 100 50 25 60 2(n) 60 100 100 0 10 50 2(o) 55 100 100 0 35 78 2(p) 0 20 0 40 35 0 2(q) 0 20 0 0 0 0 4(a) 25 98 90 15 20 4(b)100 100 100 25 100 98 4(c) 93 100 100 0 95 0 4(d)10G. 100 100 30 80 40 4(e) 93 100 100 0 O = Wild Oats tAvena fatua) W = Watergrass (Echinochloa crusgalli) c = Crabgrass (Digitaria sanguinalis) M = Mustard ~Brassica arvensis) P = Pigweed (Amaranthus retroflexus) L = Lambsquarter (Chenopodium album)
Claims (30)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound of the formula wherein R1 is alkyl of 1 to 6 carbon atoms; R2 is hydrogen or alkyl of 1 to 6 carbon atoms; R is hydrogen or a methyl group; X is fluorine, chlorine, bromine or iodine; and Y is -SR4 or -NR5R6 wherein R4 is alkyl of 1 to 6 carbon atoms, alkenyl of 3 to 6 carbon atoms or phenylalkyl of 7 to 10 carbon atoms substituted on the phenyl ring with up to 2 fluoro, chloro, or bromo substituents, R5 is hydrogen, alkyl of 1 to 6 carbon atoms, alkenyl of 3 to 6 carbon atoms or alkynyl of 3 to 6 carbaon atoms and R6 is hydrogen, alkyl, alkenyl of 3 to 6 carbon atoms or alkynyl of 3 to 6 carbon atoms, with the proviso that R5 ant R6 may together form a divalent alkylene group of 4 to 6 carbon atoms or the group - CH2CH2CH2CH2-,
2. The compound of claim 1 wherein R3 is hydrogen.
3. The compound of claim 2 wherein X is chlorine or bromine.
4. The compound of claim 3 wherein R1 and R2 are alkyl of 1 to 3 carbon atoms.
5. The compound of claim 4 wherein Y is -SR4.
6. The compound of claim 5 wherein R4 is alkyl.
7. The compound of claim 6 wherein R1 and R2 are ethyl, R4 is isopropyl, and X is chlorine.
8. The compound of claim 4 wherein Y is -NR5R6,R5 is hydrogen, alkyl or alkenyl and R6 is alkenyl.
9. The compound of claim 4 wherein R5 and R6 together form a divalent alkylene group or -CH2CH2OCH2CH2-.
10. The compound of claim 4 wherein Y is -NR5R6, R5 is hydrogen or alkyl and R6 is alkynyl.
11. The compound of claim 10 wherein R1, R2 and R5 are methyl, R6 is propargyl and X is chlorine.
12, The compound of claim 4 wherein R5 and R6 are alkyl.
13. The compound of claim 12 wherein R1, R2, R5 and R6 are methyl and X is chlorine.
14. A method for controlling the growth of undesirable vegetation which comprises applying to the vegetation or the growth medium of the vegetation an herbicidally effective amount of the compound of claim 1.
15. A method for controlling fungi which comprises applying to said fungi or their habitat a fungicidally effective amount of the compound of claim 5.
16. A process for preparing a compound of the formula defined in claim l which comprises reacting a compound of the formula with an alpha-haloacetyl halide in the liquid phase at a temperature of 0 to 100°C.
17. The process of claim 16 wherein an acid acceptor is employed.
18. A compound of the formula (VIII) (VIII) wherein:
R6 is methyl R13 is hydrogen or lower alkyl R14 is alkyl of 1 to 6 carbon atoms, alkenyl of 3 to 6 carbon atoms or alkynyl of 3 to 6 carbon atoms Hal is halogen.
R6 is methyl R13 is hydrogen or lower alkyl R14 is alkyl of 1 to 6 carbon atoms, alkenyl of 3 to 6 carbon atoms or alkynyl of 3 to 6 carbon atoms Hal is halogen.
19. A process for the preparation of a compound of the formula (VIII) (VIII) wherein:
R6 is methyl R13 is hydrogen or lower alkyl R14 is alkyl of 1 to 6 carbon atoms, alkenyl of 3 to 6 carbon atoms or alkynyl of 3 to 6 carbon atoms Hal is halogen which comprises reacting a compound of the formula (IX) IX) Wherein R6, R13, R14 are as defined above, with a haloacetylating agent.
R6 is methyl R13 is hydrogen or lower alkyl R14 is alkyl of 1 to 6 carbon atoms, alkenyl of 3 to 6 carbon atoms or alkynyl of 3 to 6 carbon atoms Hal is halogen which comprises reacting a compound of the formula (IX) IX) Wherein R6, R13, R14 are as defined above, with a haloacetylating agent.
20. A compound of the formula (X) wherein:
R15 is lower alkyl R13, R16 and R17 are independently hydrogen or lower alkyl Hal is halogen
R15 is lower alkyl R13, R16 and R17 are independently hydrogen or lower alkyl Hal is halogen
21. A process for the preparation of a compound of the formula (X) wherein:
R15 is lower alkyl R13, R16 and R17 are independently hydrogen or lower alkyl Hal is halogen which comprises reacting a compound of the formula (XI) Wherein R13, R15, R16 and R17 are as defined above, with a haloacetylating agent.
R15 is lower alkyl R13, R16 and R17 are independently hydrogen or lower alkyl Hal is halogen which comprises reacting a compound of the formula (XI) Wherein R13, R15, R16 and R17 are as defined above, with a haloacetylating agent.
22. A method for controlling the growth of undesirable vegetation which comprises applying to the habitat of said vegetation a herbicidally effective amount of a compound of the formula (X) wherein:
R15 is lower alkyl R13, R16 and R17 are independently hydrogen or lower alkyl Hal is halogen,
R15 is lower alkyl R13, R16 and R17 are independently hydrogen or lower alkyl Hal is halogen,
23. A compound of the formula (XIV) wherein:
R6 is methyl R21 is methyl or ethyl R22 is an unbranched unsaturated aliphatic chain containing 3 carbon atoms.
R6 is methyl R21 is methyl or ethyl R22 is an unbranched unsaturated aliphatic chain containing 3 carbon atoms.
24. A process for the preparation of a compound of the formula (XIV) wherein:
R6 is methyl R21 is methyl or ethyl R22 is an unbranched unsaturated aliphatic chain containing 3 carbon atoms which comprises reacting a compound of the formula (XV) wherein R6, R21 and R22 are as defined above, with a chloroacetylating agent.
R6 is methyl R21 is methyl or ethyl R22 is an unbranched unsaturated aliphatic chain containing 3 carbon atoms which comprises reacting a compound of the formula (XV) wherein R6, R21 and R22 are as defined above, with a chloroacetylating agent.
25. A compound of the formula (XVI) wherein:
R21 and R23 are independently methyl or ethyl R24 and R25 are independently hydrogen, methyl or ethyl.
R21 and R23 are independently methyl or ethyl R24 and R25 are independently hydrogen, methyl or ethyl.
26. A process for the preparation of a compound of the formula (XVI) wherein:
R21 and R23 are independently methyl or ethyl R24 and R25 are independently hydrogen, methyl or ethyl which comprises reacting a compound of the formula (XVII) (XVII) wherein R21, R23 R24 and R25 are as defined above with a chloroacetylating agent.
R21 and R23 are independently methyl or ethyl R24 and R25 are independently hydrogen, methyl or ethyl which comprises reacting a compound of the formula (XVII) (XVII) wherein R21, R23 R24 and R25 are as defined above with a chloroacetylating agent.
27. A method for controlling the growth of undesirable vegetation which comprises applying to the habitat of said vegetation a herbicidally effect amount of a compound of the formula (XVI) (XVI) wherein:
R21 and R23 are independently methyl or ethyl R24 and R25 are independently hydrogen, methyl or ethyl
R21 and R23 are independently methyl or ethyl R24 and R25 are independently hydrogen, methyl or ethyl
28, A compound of the formula (XII) ( XII ) wherein:
R2 is alkyl of 1 to 6 carbon atoms R18 is alkyl of 1 to 6 carbon atoms R19 and R20 are independently hydrogen or alkyl of 1 to 6 carbon atoms Hal is halogen,
R2 is alkyl of 1 to 6 carbon atoms R18 is alkyl of 1 to 6 carbon atoms R19 and R20 are independently hydrogen or alkyl of 1 to 6 carbon atoms Hal is halogen,
29, A process for the preparation of a compound of the formula (XII) ( X I I ) wherein:
R2 is alkyl of 1 to 6 carbon atoms R18 is alkyl of 1 to 6 carbon atoms R19 and R20 are independently hydrogen or alkyl of 1 to 6 carbon atoms Hal is halogen which comprises reacting a compound of the formula (XIII) (XIII) wherein R2, R18, R19 and R20 are as defined above, with a haloacetylating agent.
R2 is alkyl of 1 to 6 carbon atoms R18 is alkyl of 1 to 6 carbon atoms R19 and R20 are independently hydrogen or alkyl of 1 to 6 carbon atoms Hal is halogen which comprises reacting a compound of the formula (XIII) (XIII) wherein R2, R18, R19 and R20 are as defined above, with a haloacetylating agent.
30, A method of inhibiting the growth of undesirable plants, which comprises applying to the habitat of said plants a phytotoxic quantity of a compound of the formula (XII) (XII) wherein:
R2 is alkyl of 1 to 6 carbon atoms R18 is alkyl of 1 to 6 carbon atoms R19 and R20 are independently hydrogen or alkyl of 1 to 6 carbon atoms Hal is halogen.
R2 is alkyl of 1 to 6 carbon atoms R18 is alkyl of 1 to 6 carbon atoms R19 and R20 are independently hydrogen or alkyl of 1 to 6 carbon atoms Hal is halogen.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US515,781 | 1974-10-17 | ||
| US05/515,781 US3944607A (en) | 1974-10-17 | 1974-10-17 | Herbicidal N-(N'-alkynylcarbamylmethyl)-2,6-dialkyl-α-haloacetanilides |
| US54181475A | 1975-01-17 | 1975-01-17 | |
| US541,814 | 1975-01-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1253517A true CA1253517A (en) | 1989-05-02 |
Family
ID=27058601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000237515A Expired CA1253517A (en) | 1974-10-17 | 1975-10-14 | N-(CARBAMYLMETHYL)-.alpha.-HALOACETANILIDE COMPOUNDS |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS51125741A (en) |
| CA (1) | CA1253517A (en) |
| DE (1) | DE2545964C2 (en) |
| FR (1) | FR2288084A1 (en) |
| GB (2) | GB1520777A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2915026A1 (en) * | 1979-04-12 | 1980-10-30 | Bayer Ag | N, N-DISUBSTITUTED ETHYLGLYCIN (THIOL) ESTERS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES |
| EP2046739B1 (en) * | 2006-07-24 | 2015-08-26 | UCB Biopharma SPRL | Substituted aniline derivatives |
| US11339153B2 (en) * | 2018-08-08 | 2022-05-24 | Inorbit Therapeutics Ab | Compounds useful in modulating the farnesoid X receptor and methods of making and using the same |
-
1975
- 1975-10-13 JP JP12317775A patent/JPS51125741A/en active Pending
- 1975-10-13 FR FR7531306A patent/FR2288084A1/en active Granted
- 1975-10-14 CA CA000237515A patent/CA1253517A/en not_active Expired
- 1975-10-14 DE DE19752545964 patent/DE2545964C2/en not_active Expired
- 1975-10-17 GB GB4281975A patent/GB1520777A/en not_active Expired
- 1975-10-17 GB GB4281875A patent/GB1520776A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB1520777A (en) | 1978-08-09 |
| DE2545964A1 (en) | 1976-04-29 |
| DE2545964C2 (en) | 1983-09-01 |
| FR2288084B1 (en) | 1979-06-29 |
| FR2288084A1 (en) | 1976-05-14 |
| JPS51125741A (en) | 1976-11-02 |
| GB1520776A (en) | 1978-08-09 |
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| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |