Note: Descriptions are shown in the official language in which they were submitted.
liZ4~5
-2-
~ he pre~en~ invent~on iB concerned with new carbamic
ac~d phenyl e~ters, with proces~e~ ~or the manu~acture o~
these compou~d6 and ~ith their use a~ herbic~dal agent~
Herbicidal 3-(carbamoyloxy)-anilides are already
known (BelgiaR Patent ~pecification No. 686~2~9)o
The problem upon which the pre~ent i~entio~ iB
basea ha~ bean to provide ~ew active ~ub~ta~ce~ havi~g
superior herbicidal prop~rtiesO
Thi~ problem is sol~ed ~n accordance with the
present invent~on by the compound~ of the general ~ormula
I, as dei$ned below.
~ he pre~ent in~ention accordingly provides compounds
oi the general ~ormula I
o_00
(I)
~ CO-R3
in which
repre~ent~ a Cl-C2-alko~y-Cl-C2 alky , 1 2
o~y C i C2 alkyl, cyano-Cl-C2-alkyl, haloge~o-
al-c2- ~ yl, hydro ~ -Cl-C2-al ~ l, phenyl-Cl-C~-
alkyl, 193-d~oxolan-2-yl-~thyl, 2-methy1-1~3-
dio~olan-4-yl-methgl, 4-met~yl-1~3 dlo~olan-2-yl-
... . . . ....
~L~2425~
methyl~ 2,2-dimethyl-1,3-dio~ol~n-4-yl-mothyl or
aminor.arbon;srl-~ a2-al~rl group~ ,. I
R2 repre~ent~ an unsub~tituted phenyl group or a phenyl
group substituted by one or two substituent~
selected from halogen atom~, methyl group~ ~nd
metho~y groups, a~d
repre~ents a cl~Cg~al~Yl~ ~2-a8-aI-~enY ' Y P
or trichloromethyl group, or I.
repre~nts a nethyl or ~thyl group,
represe~ts an a-cyano-benzyl or l-cyano-2-phenyl-
ethyl group, and
represents an ethyl group~
~he compounds oi the pre&ent invention are surpris-
ingly superior in their herbicidal aotion to the kno~n
anilide~ of the ki~d mentioned abo~e and thereiore enrich
the state oi the axt in thi~ iield. I
The herbicidal actio~ o~ these compounds e~tends to
a great number of u~de~irable plant specie~, but not crop
plant~, to~ards which they pos~e~s an e~cellent ~el0ctivity
spectrum.
The ~ollowing are e~ample~ o~ ~pecie~ of plants
that can be co~trolled Yer~ well:
... .. ... .. ... . ... . ... . .. . ..... .. ..
4 _ ~lZ~ZSl
~C~ .
Fe~tuca ~., &2sI~a~EBQ ~, ,AFro~ti~ ~., Echinoch~oa,
Set,aria ~., Sor~hu~ ~., Poa ~., Ioliu~
A~rhenaterum ~., Pbalari~ , Phleum 8P., Eleu~ine ~0
Bromu sP., Hordeum ~. and oth~r~.
a Y P e r a c!Q~
CYPeru~ 8P. and others.
~!1 ' .
~lliu~ ~. and oth~rs.
- m a r a n t h a c e a e
Amaranthu~ ~. and other~.
B o r a ~ i n a c e a ~
Anchusa 8~ msinc~i~ 8~ b~ 51~ ~P. and other~.
a a r ~ o P h ~ 1 a c e a o
~tellaria 8P., S~ la ~ Cerast~um ~. and other~.
¢ h e n o P o d i a c e a e
ohenoPodium sP., Salsola kali, ~trlplex sP., Eochia ~.
and others.
a o n v o 1 v u 1 a c e a e
- IPomea ~P. and other~.
a o m ~ o 9 i t a e
mbrosia sP.~ ~actuca 9P. ~ Senecio ~P-, ganthium pOt
~alinsoRa ~0, Centaurea ~p., M~atricar~a ~., Halianthus
B~., Chrvsanthemum sP., Cichorium inty~u9 and other~.
~ 4Z51
~5- !
~ r u c i r o~r a e
3~QiQ~ P-~ Cheiranthus cheiri, ~ .. Thla~
~P-- ~ia~a~ 8P, and other~
Euphorbia.
a b i a t a e
T~lum 8~ ~ GaleoPs~ . and other~.
e ~ u m i n o 8 a o
Medica~o 8P~ ~ ~ri~olium ~., Vioia sP., Cassia sP. and
- other~. .
a 1 v a o e a e
Abut~o~ theo~hrasti, Sida s~ J~2~ 8Po~ hnoda and
others.
P a ~ a v e r a c e a e
Pa~aver 8P~ ~ scholtzia ~na other~.
P o 1 ~ ~ o n a c e a e
Pol~onum 8P~ and other~.
t u 1 a c a ¢ e a e
Portulaca sPO and other~. ;
R u b i a c e a e
~alium 8P~ ~ Richardia sP. and others~.
a n u n c u 1 a c e a_e
~el~hinium s~., Adonis ~. and others.
- - 6 _ ~lZ42S~
8_c r o P h u 1 a r i a c e a e
~inaria ~ LL~ ~0, Veronica 8P. and other~.
S o 1 a n a c e a e ~
Datura sPOr Sola~um ~., PhYsalis ~. and othersO
_ r t i c a c~e a e
~rt~ca P. and others.
m b e 1 1 i ~ e r a e
Daucu~ carota and othersO
~ or the control o~ ~eed weeds, application quantities
within the range o~ ~rom 1 to 5 kg o~ active substance per
hectare are generally used. ~he active substances can be
used again~t these plant ~pecie~ accordi~g to tha pre-
emergence method and the post-emergence method. ~ parti-
cular advantage 1~ that the compound~ o~ the pre~ent
invention di~play a speci~ically high toleranc~ in agricul-
tural crops, especially in cotton, potato, rice, soya and
~ugar beet orops~ When two or more compounds o~ the
present invention are u~ed the range o~ 1 to 5 kg re~ers
oi course to the ~otal application ~uantities o~ these
compound3 .
The ~re~ent i~ven~ion accordingl~ al~o provide~ a
herbicidal preparat$on which comprises a compound oi the
general iormula I, in admixture or con~unction with a
suitable carrier. 2he preparation may of cour~e contain
one or more compounds o~ the general fo~mula I.
, . . . . . .. . . . . .. .. . .
llZ4Z
_ 7 - ,
.,
~he present ~nventio~ ~urther pro~ide~ a method o~ t
protecting a livi~g plant against weed~ herein the
area in the ~ic1nit~ oi ths li~ing plant i8 treated ~ith
a compound o~ the general iormula I.
The pre~ent ~nvention ~urther pr~ide~ a method oi
protecting a crop ~rea agaln~t weeds, wherein the crop
area-i8 treated with a compound o~ the general formula I.
The present invention further provide~ a pack
~bich comprises a compou~d o~ the general ~ormula I
together with instruct~ons for its use as a herbicide.
The compounds o~ the present invention may be used
either 8in~1y or in t~e form o~ miæture~ with one another
or with other active sub~tance~ de~ired, other de~ol- ¦
iants, plant protecting agents and/or pe~ticides may be
added, depending on the desired purpose.
If a broadening o~ the ~pectrum o~ action i~ intended,
oth~r herbicide~ may also be added. A~ ~uitable herbici-
dally-ac~i~e co-compo~ents there may be mentio~ed, ~or
e~ample, active sub~tance~ ~rom the groups o~ triazi~es,
aminotriazoles, anilides, diazines, uracils, aliphatic
carboxylic acid~ and halocarboxylic acids, ~ubstituted
benzoic acids and ar~loxycarbo~ylic acids, hydrazide~,
am~des, nitriles~ e~ters o~ ~uch carboyglic acids,
carbamic acid esters and thiocarbamic acid esters, ureas~
2,~,6-trichlorobenzyloxyprop~nil, thiocyanogen-containi~g
agent~ and other ~dditives.
.
- 8 _ ~ ~ 2 ~Z S 1
As other additi~es there may be u~ed, ior e~ample,
non-phytotoxic addit~ve~ which, with herbicide~, are capable
o~ producing a ~yner~istic increase in aotion, ~or e.~ample
inter ~ wetting agent~, emul~iYier~, solvent~ and oily
additive~
~ he active compound~ of the pre~ent invention or
mixtures co~taining them are advantageou~lg u~ed in the
iorm oi herb~cidal preparations, ior example powder~,
strewable preparation~, granule~, solutions, emulsion~ or
suspen3ions, with the addition o* liquid and/or solid
~ehicle~ or diluents and, i~ desired, of ~uriace-active
agents, ior e~ample ~etting, adhesive, emui~iiyi~g and/or
diRpersing agent~.
. Suitable liquid carriers are, for example, water,
aliphatic hydrocarbon~, aro~atic hydrocarbons, ~or ex~mple
benzene, toluene and ~ylene, oyclohe~anone, isophorone,
dimethyl sulpho~ide, dimet~yl~ormamide and al~o mineral
oil iractions.
Sultable ~olid oarrier~ are, ior example, mineral
earth~, ior example ton~il, silica gel, talcum~ kaolin,
attaclay, lime~tone and ~ilicic acid, and vegetable
- product~, ~or egample meals~
~ urface-active agent~ there may be mentioned,
~or e~ample, calcium lignin ~ulphonate, polyoxyethylene~
alkylphenol ether~, naphthalenesulphonic acids and ~alt~
,. ~. ~ -- -
~242~1
_ g _
thereoi, phenolsulphonic acid~ and salt~ thereo~9 ~orm-
aldehyde condensate~, ~atty alcohol ~ulphate~ and also
substituted benzenesulphonic acids a~d salt~ thereo~. ~
The proportion o~ the acti~e ~ub~tance or ~ub~tance~ ¦
~n the various herbicidal preparation~ may vary within
~ide limit~. For e~ample, the preparation~ may contain
approx~mat~ly 10 to 80~o by weight o~ active substance(~),
appro~imately 90 to 20% by weight o~ liquid or solid
carrier and also, i~ de~ired, up to 20% by weight o~
~ur~ace-aotiv~ agent(~).
- The active compounds may be applied in the usual
manner, ~or e~ample with water a~ the carrier in ~uantities
o~ sp~ay liquor ranging ~rom appro~imately 100 to 1000
litre~ per hectare. It i~ al~o pos~ible to apply the
active compound~ by the so-called Iow Volume-Method ~nd
~ltra-~o~-Volume-Method a~ well as to apply them ln the - .
form oi ~o-called microgra~ule~.
~ he new compounds o~ the general iormula I ma~ be
prepared, ~or example, b~ the processes oi the pre~ent
in~e~tion, as de~ined belo~. :
The pre3ent in~ention accordingly ~urther provides .
a proce~ ~or the manu~acture oi the compou~d~ of the .
general formula I, ~herein a compound o~ the general ,
ior ~1a II
1.
.
.
' ~- ,
~LlZ4ZSl
- 10 ~
o~ , ~
(II) ,
in ~hich ~ has the meaning gi~en above, is rea~ted i~
the preæence o~ a~ organic base, for egample pyridine,
or i~ reacted in the ~orm oi an alkali ealt thereo~, ~or
e~ample a sodium or potassium salt, with a compou~d o~
the general ~ormula III
~, . .
~-CO-Cl (III)
.' . ~2 .
in which ~ and R2 hava the m~anings given above.
~he present i~v~ntion ~urther provi~e~ a proce~ ~or
the manuiacture of the compou~ds o~ the general ~ormula I, : .
~herein a chloro~ormic acid e~ter o~ the general ~ormula
IV
,.
O-CO-Cl .
(IV) ,
~ CO~
in which ~ ka~ the meaning given abo~e, i~ reacted in the
presence o~ a ba~e, ~or example potassium carbonate, with
- a compound o~ the general ~ormula V
.- ~ . ... . - - .
11~4Z
~' , ',,
~ ,
(V), . . ..
~2
i~ which ~ and X2 have the mean~ngs gi~e~ abo~e.
~ he product~ o~ these pro¢es3e~ o~ the prese~t
invention ma~ be i~olated in a m~nner known E~E ~c.
~ he chloro~ormic acid e~ter o~ the general ~o~mula
IV is advantageou~ly prepared by reacting a compound o~
the general ~o~mula II with phosgene in the pre~ence o~
an inorganio or organic base, ior e~ample ~odium hydro~ide
or dlme~hylaniline, or b~ reacting an alkali ealt oi a
compou~d oi the general io~mula II with pho~gene~
Su~table ~olvent~ ~or ths~e reaction~ are, ~or
e~ample, ethyl acetate, ~cetonitrile, he~ane, benzene,
toluene, methylene chlor~de, carbon tetrachloride,
tetrahydro~ura~3 dimethyl~ormamide and other eub~tance~
that are ~nert towards the reactants.
Al~ the reactio~s are carried out at temperatures . :
of between 0 and the respective boili~g point o~ the !,
~ol~ent. ,
~ he h~dro~yan$1ides which may be u3ed as starting
materials are obtai~ed in a man~er k~ow~ per ~ by -
reacting the correspondi~g acid chlorides with m-
am~Qophenol.
r
, :, - , ~," ~" ,,, ,~r ~ , ~, , ,,_ , ,
.
~124Z5~
The compounds o~ the present invention are colourle~
and odourless, crg~tall~ne or oily ~ub~tances which are
readily ~oluble in acetone, dime~hyl~ormamide, isophorone,
cyclohexanone, tetrahydro~uran and dimeth~l sulpho~ide.
~he ~ollo~ri~g ~xamples illustrate the inYention.
E~amples 1 to 5 illustrate the ma~ufacture o~ the compou~ds
o~ the present invention and E~ample~ 6 and 7 illustrate
the possible way~ o~ using the compounds o~ the present
invention and bheir superior herbicidal action.
Exam~le ~
~-(2,2-Dietho~yeth~ carbanilic acid ~3-(2,2-dimethyl-
valerylamino)-phenyl] eæter
~ solution o~ 2803 g (0.1 mole) o~ chloroiormic
acid ~-~2,2-dimethylvalery1amino)-phenyl e~ter in 100 ml
o~ ethyl acetate and ~imultaneously a solution o~ 1~o8 g
(0.1 mole) o~ potassium carbonate in 70 ml oi l~ater were
added dropwise to a solution o~ 20.9 g (0.1 mole) o~ ~-
(2,2-diethoxyethyl)-aniline in 50 ml o~ ethyl acetate,
while ~tirring 2nd cooling to 10 to 15~o ~tirring wa8
continued ~or 30 minute~ at room temperature, the organic
phase wa8 then separated oi~, diluted with a little ethyl
acetate, washed at 0~ with dilute h~drochloric acid and
a ~odium chloride 901ut~0n, and dried with magnesium -
~ulphate, and the solvent wa~ di~tilled o~i ~nder reduced
pre~ure. ~he re~idue was recr~talliæed from ethyl
. ` ~ ,~ " ` .
' ~
lZ4~51
~ ,r
acetate/pentane.
Yield: 36 g - 79~0 o~ the theoretical yleld. t
M.p.: 88 - 89C.
am~le 2
N-(2-Cyanethyl)-3-methylcarbanilic acid ~3-(trichloro-
methylcarbonylamino)-phenyl] e~ter
.
31~7 g o~ chloro~ormic acid t~-(trichloromethyl-
osrbonylamino)-phenyl] ester, taken up in 100 ml o~ aceto-
nitrile, were added dropwi~e to a solution o~ 1600 g o~
N-(2-cyanethyl)-3-methylaniline ~n 100 ml o~ acetonitrile.
12.1 g o~ N,N-dimethylan~line were then added to the
reaction mi~ture. In ~o doing, the temperature rose to
46C. ~he reaction mixture wa~ heated at the bo~l for a
further 10 minute~, cooled, and stirred into 500 ml of
ice-water, ~nd the precipitated substa~ce was ~iltered
o~f and recry~tallized from isopropanol.
~ield: 3105 g ~ 72% o~ the theoretical yield.
M.p.: 118C.
E~am~le ~
~-Cyanomethylcarbanilic acid ~3-(tert.-butylcarbonylamino)-
phengl] e~ter
25.57 g o~ chloro~ormic acid ~3-(tert.-butylcarbo~yl-
amino)-phenyl] e~ter were introduced into a solution oi i
13.2 e of N-cyanomethglaniline in 150 ml o~ acetonitrile,
!
I1~4Z51
- 14 -
then, while ~urther ~tirri~, 12.1 g o~ N,~-dimethylaniline
~ere added dropwi~e, and the mi~ture wa~ heated at the boil
ior a Iurther 15 minute3. A~ter ha~ing cooled, the mi~ture
~as stirred into 1 litre OI ice-water, the substatlce that
separated out was ~lltered oIf with ~uction and, af ter
drying in vacuo, recrg~tallized from a little acetonitrile.
~ield: 24.0 g = 68% o~ the theoretical yield.
M~po: 173C.
le 4
~1-(2-~yaneth~ carba~l~ c acid ~3-(cyclopropylcar~onyl-
amino)-phenyl] ester
.
2902 g of N-(2-¢yallethyl)-aniline were di~olved irL
200 ml oi acetonitrile~ and 23.97 g of chloro~ormic acid
[3-(cyclopropylcarbonylamino)-phenyl] ester ~rere then added
thereto, while ~tirxing, during whieh the temperature of
the ~olution ro~e to 35~ A~ter leaving the m~ture to
stand overnight, the solvent was distilled o~i in vacuo,
ths oily residue remai~ing behind was treated with water,
the water was decanted o~f a~d the oil ~a~ crystalliæed
by means of a 1 : 1 mi~ture of ~sopropyl ether and
isopropanol. The ory~talli~ate wa~ then recry~tallized
~rom isopropanol.
Yield: 16.59 g = 48% of the theoretical yield.
M.p.: 142O.
- ' .. ~ - `
~Z4ZSl i
r
~ 15 ~ ~
~ ' ,, 1~
N-Cyanomethyl-~-~ethylcarbanilic acid [3-(propionylamino)- . .
phenyl] e~ter ' .
. .
~ he potassium salt prepared from 64.4 g ~0.39 mole)
of propionic acid 3-hydro~yanilide was taken up ~n 300 ml
of acetonitrile. Upon adding dropwise a solutio~ o~
81.4 g (O,39 mole) o~ ~-cyanomethyl-N-(3-methylphenyl)-
carbamoyl chloride in 250 ml o~ acetonitrile, while
stirring, over a period o~ 5 min~tes, the temperature ro~e
from 28 to 44a. ~The mi~ture was then reiluxed ~or 30
minutes. ~fter concentration by evaporation u~der reduced
pressure, the mixture wa~ di~solved in ethyl acetate and
water, ~ashed at oa with a little dilute soaium hydro~ide
solution, dried with magne~ium sulphate and concentrated
by eYaporation u~der reduoed pres~ure. ~he residue,
which was at ~ir~t oily, crystallized ~rom ether. I
Yield: 80.4 g = 61~ o~ the theoretical yield.
M.p.: 97 - 99C.
The iollow~ng compo~unds of the present i~vention
may be ma~u~actuxed in a manner,analogous to that described
i~ ~ one o~ the above :E~campl
llZ4;~51
-16-
.
Name oi the compound Phy~ical constant
N-(2,2-Dimethor~ethyl)-oarbanilic acid
[3-(propionylamino)-phe~l] ester M.p.: 71 - 73C
~-Cyanomethylcarbanilic acid ~3-
tP~PiOnylamino)-phen~l] e~ter M.p.: 130C
N-(2-Cyanethyl)-3-meth~lcarbanllic
acid ~3-(propionylami~o)-phenyl] e~ter Mop~ 149 - 151C
N-(2-Metho~yethyl)-carbanilic acid
~3-(propionylamino)-phenyl] ester M.p.: 71 - 72C
~-(2-Cyaneth~ 4-methylcarbanilic
acid ~3-(propionylamino)-phenyl] ester M.p.: 124 - 126a
N-(2-Cyanethyl)-2-methylcarbanilic
acid [3-(propionglamino)-phenyl~ e~ter M.p.: 120 - 122C
N-(2-Metho~yethyl)-3-methylcarbanili¢
acid [3-(propionylamino)-phenyl] ester M.p.: 82 - 84C
N-(2,2-~imethoxyethYl)-4-meth~l-
carb~nilic acid [3-(propionylamino)- 2
phenyl] e~ter ~D0 : lo 5343
~-(2,2-~imetho~yethyl)-3 methyl-
carbanilic acid ~-(propionylamino)- 20
phe~yl] e~ter ~D : 1. 5405
N-(2-Bromethyl)-carbanilic acid t~-
(propiGnylamino )-phenyl~ e~ter M.p.: 86 - 87C
N-(2-~tho~yethyl~-carbanilic acid [3-
(propionglamino)-phenyl] ester Mop~ 83 - 84C
~-(2-Cyanethyl)-carb~nilic acid ~3-
(propionylamino)~phenyl] eBter M.p.: 126 - 128~
~-(2,2-Dimetho~yethyl)-2-methyl-
carbanilic acid ~3-(propionylamino)-
phenyl] es~er M.p.: 105 - 107C
N-(l-Cyano-2-phengl-ethyl)-N-methyl-
carbamic acid ~-(propionylam~no)-
phengl] eater M~po 104C
~-(a-~yanobenzyl)-~-ethvl-carbamic
acid [~-(propionylamino~-phenyl] e~ter M.p.: 76C
- 17 _ 'ILlZ4Z51
Name o~ the compound Phyaical const~nt
., , . ", . . . . . .
~-(2-Cyaneth~ 3-methylcarbanilic acid
~3-(tert.-butylcarbonylamino)-phenyl] 0
e~ter M.p.: 122 C
~-(2-Cyanethyl)-carbanilic ~cid ~3-
(tert.-butylcarbonylamino)-phe~yl] O
ester N.p.: 118 C
N-(1,3-Dio~olan-2-yl-methyl)- -
carbanilic acid [~-(propionylamino)-
phenyl] e~ter M.p.: 98 - 99C
3-Metho~y-~-(2-methoxyethyl)-
carbanilic acid ~3-(propionylamino)- 20
phenyl] ester nD : 1.5614
N-t4-Methyl-1,3-dio2clan-2-yl-meth~l)-
carbanilic acid [~-(propionylamino)- 20
phenyl] ester nD : 1.5559
~-Cyanomethylcarbanilic acid ~3-
(2,2-dimethy~valer~lamino)-phenyl]
ester . M.p.: 152 - 153C .
N-(2-Cyanethyl)-carbanilic acid ~2-
(2,2-d~ ~thylvalerylamino)-phenylJ
e~ter Nop- 93 - 95C
~-(2-Cyanethyl)-carbanilio acid [3-(~-
methylpropionylamino)-phenyl] ester M.p.: 136 - 137C
N-(2-Chlorethyl)-carbanilic acid [3-
(2,2-dimethylvalerylamino)-phenyl] ~
e~ter M.p.: 101 - 102.5C .
~-(2-Chlorethyl~-oarba~ilic acid ~- .
(propio~ylamino)-phenyl] ester ~p.: 107 - 109C
N-(2-Phenylethyl)-carbanilic acid [3- . ~!
(prop~onylamino)-phenyl] ester Mop.: 93 - 94C
N-t2-Cyanethyl)-carbanilic acid ~3-
(crotonoylamino)-phenyl~ ester Mop~ 117 - 1l9C' t
N-(2-Chlorethyl~-carbanilic acid C3-
(crotonoylami~o)-phe~yl~ ester Mop~ 131 - 1~3C
~ Z ~Z 51 j
Nam~ of the compound Phy~ical con~tant
,
N-~2,2-Dimetho~yethyl)-carbanilic acid li
C3-(2,2-dimethylvalerylam~no)-phenyl~
e~ter M~p.: 77 - 79C
N-t~minocarbonylmethyl)-car.~anil~c
acid ~-(cyclopropylcarbonylamino)-
phe~ylJ ester M~p.: 197C
N-(2-~minocarbonylethyl)-carbanilic
acid t~-(cyclopropylcarbonylami~o)-
phenyl] e~ter M.p.: 166~
N-~2-Cyanethyl)-3-methylcarbanilic
acid [~-(cyclopropylcarbonylamino)- . 'i
phenyl] ester~ Mop~ 175C
N-Cyanomethylcarbanili¢ acid ~3-
(trichloromethylcarbonylamino)-
phenyl] e~ter M.p.: 102C
N-(2-Cyanethyl)-carbanilic acid [3-
(trichloromethylcarbonylamino)-
phenyl] ester Mop~ 137C
~-(2-Methoxyethyl)-carbanilic acid
~-(tert~-butylcarbonylamino)- 20
ph~nyl] e~ter nD : 1.5509
N-(2-Metho~yethyl)-3-metho~ycarbani~ic
acid ~-(ter~.-butylcarbonylamino)- 20
phenylJ e~ter nD : 1.5482
N-(2-Metho~yethyl)-carbanilic acid
~3-(cyclopropylcarbonylamino)-phenyl]
e~ter M.p.: 133C
~-(2 Metho~yeth~ carbanllic acid [3- ~ i
(trichloromethylcarbonylamino)-phenyl] 20
eBter Il~ lo 5804
~-(2-Metho~yethyl)-3-metho~ycarbanilic
acid [~-(triohloromethylcarbonylamino)-
phenylJ e~ter Mopo 135C
N-(2,2-Dimethyl-1,3-dioxolan-4-yl-
methyl)-carbanilic acid [3-(2,2-
dimethylvalerylamino)-ph~nyl] e~ter Mop~ 100 ~ 102a
;
I
- 19 - ~ 2 4Z S~
Name o~ the compound Physi.cal con~tant
~-(2-~thoxyethyl)-carbanilic acid [~-
- (cyclopropylcarbo~ylamino)-phenylJ
ester M.p.: 109C
~ N-C~anomethyl-3-chlorocar.banilic acid
.~ ~3-(trichlorome~hylcarbonylamino)-
. phenyl] e~ter M.p.: 162C
N-(2,2-Dimetho~yethyl)-3-me~hyl-
carba~ilic acid [3-(tert.-butyl-
carbo~lamino)-phenyl~ ester vi~cou~ oil
I N-(2-Hydroxyethyl)-carbanilic acid
.-~ - r3-(cyclopropylcarbonylamino)-
I phenyl] ester Mop~ 116 - 117C
-1 N-(2-Methoxyethyl)-4-fluorocarbanilic
. acid ~-(cyclopropylcarbo~ylami~o)-
phenylJ ester M.p.: 10~ - losa
N-(2-Etho~yethyl)-4-~luorocarba~ilic
acid ~-(cyclopropyloarbonylami~o)-
henylJ ester Mop~ 77 - 79C
.: -,
~ .1 ,
he ma~u~actule o~ a iew starting materlals i6
described in detail below.
a) 2,2 Dimethylvaleric acid 3-hydro~yanilid~
445 g (3 mole~) o~ 2,2-dimethylvaleric acid chloride
were added dropwise, while stirring, and while the tempera-
ture ~a~ maintained at 10 - 20C by cooling> to a ~olution
o~ 327 g (3 mole~) o~ m-aminophenol in appro~imately 1
litre o~ eth~l acetate a~ter the additio~ o~ 400 ml o~
water and 76 g o~ magne~ium o~ide. ~he mi~ture W8~ then
stirred ror one hour at room temperatureO ~hen, at 0 -
5Cp 400 ml of concentrated hydrochloric acid were added
~L1242S~
- 20 -
dropwise and the miæture wa~ ~tirred ior 10 mintlte~. The
orga~ic phase was then separated o~, washed until neutral
with a sodlum chloride,solution and dried with magnesium
sulphateO The ethyl acetate was partially di~tilled o~ !
and pentane ~ras added to the residue, whereupon the
reaction product crystallized outO
~ield: 550 g = 83~ o~ the theoretical yield.
M.p.: 155 - 156C.
The ~ollowing were obtained in an analogou~ manner:
Propionic acid ~-hydro~yanilide M.p.: 18~ - 185C
2-~ethylproplonic acid ~-hydro~yanilide M~po 180a
Crotonic acid 3-hydroæ~anilide I~.p.: 158 - 159C
b) Chloroformic acid ~3-(propionyl~Lino)-phenyl~ ester
~ . . .
292 g (1.77 mole) o~ propionlc acid ~-hydro~yanilide
were added to a ~olution of 177 ml of phosgene in 700 ml
o~ ethyl acetate. ~ solution o~ 225 ml (1.77 mole) o~
N,~-dimethylaniline in 300 ml o~ eth~l acetate was then
added dropwise, while stirring and cooling to lO to 15C.
Stirring was then continued ~or 30 mi~utes at 50C. The
solution, cooled to 10C, was poured onto ice, and stirred
ior appro~imately 10 minute~, a~d the organic pha~e wa~
~eparated o~, wa~hed with a ~odium chloride ~olution,
dried with magnesium ~ulphate and concentrated by evapora-
tion under reduced pres~ure. The re~idue crystallized
upo~ adding 600 ml o~ pe~tane.
~,, .. _ . _.. ., ,, . , .. , . .. , _ .. , . _. ,, . , .. , _ ... . . . . .. . . ..
-,
1124Z51
~ield: ~27 g = 81% o~ the theoretical yield.
M~p.: 72 - 73O.
~he ~ollowing were obtained in an analogou~ manner:
Chloro~ormic acid [3-(2-methyl-
propionylamlno)-phenyl] ester ~pO 69 - 71~
ohloroformic acid t3-(croto~oylamino)-
phenyl] eæter . . ~ : 1.5~27
Chloroio~mic acid t3-(2,~-dimethyl- ,
valeroylamino)-phen~l] ester ~ : 1.5~7~ ¦
c) ~hloro~ormic acid ~3-(cyclopropylcarbonylamino)-
phenyl~ eater
100 ml o~ phosgene were conden~ed at -20C, then
taken up in 1 litre o~ ethyl acetate, and 177.2 g of
cyclopropanecarbo~ylic acid 3-hydro~yanilide melt~ng at
184C were added thereto, while stirring, at 0~. ~hile
continuing to cool the reaction mixture, 121 g of N,N-
dimethylanilin0 were then added dropwi~e thereto. ~he
mixture was then stirred ~or a ~urther hour at 40C, the
cxcess phoægene was driven of~ by a stream o~ nitrogen gaæ,
the m~xture was cooled to room temperature and the ethyl
acetate phase was e~tracted twice with 250 ml o~ ice water.
After separating o~I the organic phase it was dried ~ith
magne~ ulphate, the solvent was di~tilled OII in ~racuo
a~d the result~g re idue wa~ cr;y~tallized by addirlg
pstroleum ether. There wa~ thus obtained 207 g (86~6 OI
" ~ ' _
. _'
1 ~l 2 4 Z 5 ~L t
- 22 - i
the theoretical yield) o~ the above-mentioned æub~tance l
melti~g at 94a. ,
~he following were prepared in an ~nalogou~ manner; i
Chloroformic acid ~3-tterb.-bu~ylcarbonyl-
amino)-phe~yl] e~ter M.p.: 75C
Chloro~ormic acid t3-(trichloromethyl-
carb~nylamino)-phenyl] ester ~ : 1.5786
xQmPle 6
In a series o~ tests carried out in a greenhou~e,
the compounds o~ the present ~nvention~ listed in the
~able below, were each æprayed in accordance with the .
po~t-emergence method at a rate o~ applicatàon o~ 5 kg
o~ active ~ub~ta~lce per hectare~ dissolved in 500 litres
of water per hectare, on to Sola~um and Bra~sica as the
test plant~. .
3 Week~ a~ter the treatment the resultæ ~ere . :
evaluated and eæpressed b~ a numerlcal scale e~tending
from O to 4, the value O representing no action and the
value 4 r~presenting de~truction o~ the plant. .
- As will be æeen ~rom the Table, destruction of the
test pla~ts wa3 generDI y achieved.
!
.
1 1,Z4Z51 ~
23
N-(2,2-Dimethoxyethyl)-carbanilic
acid [~-(propionylaminQ)-phenyl]
ester - . 4 4
N-~yanomethylcarb~nilic acid [3-
(propionylamino)-phenyl] ester 4 4
~-(2-Cyanethyl)-3-methylcarbanilic
acid [3-(propion~lamino)-~henyl]
ester 4 4
N-(2-Methoxyethyl)-carbanilic acid
[~-(propionylamino)-phenyl] ester 4 4
N-(2-Cyanethyl)-~-methylcarbanilic
acid [3-(propionyla~ino)-phenyl]
ester . 4 4
N-(2-~yanethyl)-2-methylcarba~ilic '
acid [3-(propionylamino)-phenyl] e~ter 4 4
N-(2-Methoxyethyl)-~-methylcarbanilic
acid ~3-(propionylamino)-phenyl]
e6ter 4 4
~-(2,2-Dimethoxyeth~1)-4-methyl-
carbanilic acid [3-(prop~onylamino)-
phenyl] e~ter 4 4
N-(2,2-Dimethoxyethy1)-3-methyl-
carbanilic acid ~3 (propiol~lamino)-
phenyl] ester 4 4
~-(2-~romethyl)-carbanilic acid ~3-
(propionylamino) -ph6nyl~ ester 4 4
N-(2-Etho~yethyl)-car~anilic acid
[3-(propionylamino)-phenyl] ester 4 4
N-(2-~yanethyl)-carbanilic acid [3-
(propio~ylamino)~phen~l] ester 4 4
~-(2,2-Dimethoxyethyl)-2-me~hyl-
carbanilic acid [~-(propionylamino)-
phenyl] ester 4 4
, .; i. ,
: ,
~124Z51
_ 24 -
Compound o~ the invention Bra~ica ~olanum
.
N-Cyanomethyl-3-methylcarbanilic
a¢id ~3-(propio~ylamino)-phe~yl]
e~ter 4 4
N-(l-Cyano-2-phenyl-ethyl)-N-methyl-
carbamic acid ~-(propionylamino)-
phenyl] e~ter 4 4
N.-(a-Cyano-benzyl)-N-ethyl-carbamic
acid.[3-(propionylamino)-phenyl]
ester 4 4
N-(1,~-Dio~olan-2-yl-methyl)-car-
banilic acid [3-(propionylamino)-
phenyl] ester - 4 4
~-Metho~y-~-(2-methogyethyl)-car-
banilic acid ~3-(propionylamino)-
phenyl] ester 4 4
~-(4-Methyl-l,~-dioxolan-2-yl-methyl)-
carhanili~ acid [3-(ethylcarbonyl-
amino)-phenyl] ester 4 4
~-Cya~omethylcarbanilic acid ~3;
(2~2-dimethylvalerylamino)-
phenylJ e~ter 4 4
~-(2-Cya~ethyl)-car~anilic acid ~3-
(2,2-dimethylvalerylamino~-phenyl~
e~ter 4 4
N-(2-Cyanethyl)-carbanilic acid C3-
(2-methylpropionylami~o~-phenyl]
e~ter 4
N-(2,2-Dietho~yethyl)-carbanilic
acid ~3-(2,2-dimethylvalerylamino)-
phenyl] e~ter 4 4
N-(2-Chlorethyl)-carbanilic acid ~3-
(2,2-dime~hylvalerylamino)-phenyl~
ester 4 4
N-~2-Chlol~ethyl)-carbanilic acid C3-
(propionylamino)-phe~yl] ester 4 4
N-(2-Phenylethyl)-carbanilic acid ~3-
(propionylamino)-phenyl] ester 4 4
. --
. .
. . .
~lZ~Z51 .
- 25 - ,
Compound o~ the invent~on ~ra~sica ~olanwn !
~- ., ~ .,. - -- _
~-(2-~yaneth~ carbanilie aeid ,r3- -
(erotonoylam.ino)-phenylJ ester 4 4
N-(2-Chlorethyl ? -carbanilie aeid ~3-
(erotonoylamino)-phenyl] eciter 4 4
N-(2,2-Dimetho~yethyl)-carbanilie
acid ~-(2,2-dimet~ylvalerylamino)-
phenylJ ester 4 4
~-(2-Cyanethyl)-carbanilie acid [~-
(eyelopropylearbonylamino)-phenylJ
ester 4 4
~-Cganomethylearbanilie aeid [3-
(tert.-butylearbonylamino)-phenyl~
e3ter 4 4
N-(2-Cya~ethyl)-3-methylearbanilie ,~
aeid C~-(tert.-butylcarbonylamino)- ~.
phenylJ ei~ter 4 4 ,~
~-(2-Cganethyl)-earbanilie aeid [3-
(tert.-butylcarbonylamino)-phengl]
ester 4 4
~-Cyanomethylearbanilic acid ~3-
(trichloromethylcarbonylamino)- r
phenyl~ e~ter 4 4 ¦
N-(2-Methoxyethyl)-carba~ilie acid
C3-(tert.-butylcarbonylamîno)-phenyl~,
ester 4 4
N~ Methoxyethyl)-3-metho~yoarban-
ilic aeid [3-~tert.-butylcarbonyl-
amino)-phenyl] ester 4 4
N-(2-Methoxyethyl)-earbanilie acid
~3-(cyclopropylearbo~ylamino)- '
phenyl] est~r 4 4
N-(2-Metho~yethyl)-carbanilic acid
~3-(~riehloromethylearbonylamino)-
phenyl~ ester 4 4
N-(2~Metho~yethyl)-3-methoxycarban- !
~lie acid ,~3-(trichloromethyl-
carbonylamino)-phe~yl] e~ter 4 4
, -- . ., . ......... . . , .. . . . . ., .... _ .. .. ~ .. ., . i
.
- . - .... :.:
1;
~.Z4Z51 ~
_ 26 - ,
,
Compound of the invention Brassica Solanu~ .
. . ,, ,., . , " , _ , .
N-(2-Etho~yethyl)-carbanilic acid -
[3-(cyclopropylcarbonylamino)-
phenyl] e~ter 4 4 .
N-(2-~ydroxyethyl)-carbanilic acid
~3-(cyclopropylcarbonylamino)-
phenyl] ester 4 4
~-(2-Metho~yethyl)-4-~luorocarban-
il~c acid t~-(cyclopropylcarbonyl-
amino~-phenylJ e~ter 4 4
~-(2-~3thoxyethyl)-4-~luorocarbanilic
acid [3-(cyclopropylcarbonylami~o~-
phenyl~ ester 4 4 F
N-Cyanomethyl-~-chlorocarbanilic
acid ~3-(trichloromethylcarbonyl-
ami~o)-phe~lyl] ester 4 4
N-(2,2-Dimethoxyethyl)-3-methyl-
carbanilic acid ~3-(tert.-butyl-
carbonylamino)-phenyl] ester 4 4
Untreated O f
~!.Z4ZS~
- - 27 -
~1 ' '
In a serie~ o~ te~ts carried out in ~ greenhou~e,
the plants li~ted in the Table below were treated a~ter
their emergence ~th the agent~ listed, using in each ca~e
an application quantity oi ~ kg of active ~ubstance per
hectare. ~or this purpose, the a~ents ~ere in each case
sprayed uni~ormly over the plants in the iorm o~ an
emulsion, usin~ 500 lltres o~ water per hectare~ ~he
results o~ the treatment were asseæsed and e~pressed by
a numerical scale e~tending irom O to lQ, the value O
representing total destruction of the pla~t and the
~alue 10 representing ~o damage. In this case, ~ weeks
after the treatment, the compound~ oi the present
invention exhibited a high degree oi selectivity together
wtth an e~cellent action against the weeds. ~he agent~
used ior compariso~ did not e~hibit thls selectivltyO
.
~.
.
llZ4Z51
- 2~ -
.
.
a~ 80~S61~ 3 O ~ O O O
s o o o o o
~ O O O O O
o~oa e o o o o o
a~ o o o o o
1s o o o o o
- - - - ~-
as ~ aosa~ o o o
~F~ ~ o~
~o~ o ~
r~
uo~o~ ~o1 r~
o~d: o ~ o~ o~
~aaq
c~
o ~ o ~l ;
h~ h ~ ~ ~ ~
h ~ ~ I h h ~ ~ h
o
O P~
p,c) ~a) v ~1
~ ~ h ~, o ~ "
O Q) O O O O O ~ P~ O ~ 0 h ~J O
~ c~ c~ o ~ ~ l p~
h~1 1a) ~rl Io t~ h~rl I ,rl t~ I
~ C~ ~ V ~
o I ~1 o I ~d o -Id h I ~d O I o
Pl ~ h~d a) ~ ~ ~ N ~J 5
f~ --~ h r `~ h r V r1~ ~- h ~ r
O I ~ EI ~ I O M I ~ E~ I C)
~i c) c :zi o :z; c~ o ~
. . . .. . . . . . .
~12425
-- 29 --
ss~l~[ o o
a~ ~ O O
~ o o
a~ ~ao~OdI o o
~ o o
unu~lo~ o o
a~ B~ dO~:~I~) O O
e~ . ~ co
~e~o~
~o~o~ o O
O~B~O~I I~
~eaq ~reS~ o o
h h
.
Q~ ~ a
~ ~ I r_ I '
~ ~D ~
O ~ GO
n ~ ~ o ~ .
O ~o I ~ ~
~ ~ o ~
~ :2;
o o d ~
o ~ o c~ ~ ,9
~1 ,n a5 h
h ~
~rl ~ O :~ O
h~
o ~ ~ P~
a) o c~ ~ h ~ h
H P'
. .... . ... . . . .. . .. . . . . .
- ; .
.
