Note: Descriptions are shown in the official language in which they were submitted.
107~038
This invention relates to herbicidal processes and
compositions utilising pyrimidine compounds as active
ingredients, and to certain novel pyrimidine compounds.
According to the present invention there is provided
a process of inhibiting the growth of ~mwanted plants, which
comprises applying to the plants, or to the growth medium
thereof, a herbicidally effective amount of a pyrimidine
compound of formula (I),
R2
Rl~ OR 3
N ~ N
R
(I)
or an acid addition salt thPreof, wherein R represents
(a) a hydrogen atom; (b) a phenyl radical optionally substituted
by one or more alkyl, alkoxy, fluorine, chlorine, or
bromine atoms; or (c) an alkyl or alkenyl radical optionally
substituted by one or more of the following:
a fluorine, chlorine, or bromine atom;
a cycloalkyl, hydroxy, alkylthio, furyl, pyridyl or mono-
or di-alkylamino radical;
a phenyl radical optionally substituted by one or more alkyl,
fluorine, chlorine, hromine, phenyl, cyano, haloalkyl, or
alkoxy radicals;
or an alkoxy radical optionally substituted by one or more
. 2
.. . ... .
- : ' , , ~ .
. :.~
~077038
phenyl or alkoxy radicals;
Rl represents a lower alkyl radical;
R represents a hydrogen atom or a lower alkyl radical;
and R3 represents an alkyl or alkenyl radical optionally
substituted by one or more of the following:
cycloalkyl; pyridyl; naphthyl; or phenyl optionally
substituted by one or more fluorine, chlorine, bromine,
iodine, haloalkyl, cyano, alkyl, hydroxymethyl, or 4-methyl-
2-propyl-6-pyrimidin-yloxymethyl radicals.
When R is a phenyl radical substituted by an alkyl or
alkoxy radical, the alkyl or alkoxy radicals may each have,
for example, from 1 to 4 carbon atoms. When R is an alkyl
radical, it may contain, for example, from 1 to 12 or more
carbon atoms. Preferably, when R is an alkyl radical it
contains from 1 to 6 carbon atoms; it may be, for example,
a methyl, ethyl, propyl, _ propyl, butyl, isobutyl, amyl,
or hexyl radical.
When R is an alkyl radical substituted by a cycloalkyl,
alkylthio, monoalkylamino, or dialkylamino radical, the
cycloalkyl radical may contain for example from 3 to 6
carbon atoms; the alkylthio radical from 1 to 6 carbon
atoms; and the one or two alkyl groups in the mono- and
dialkylamino radicals may each contain, for example, from
1 to 6 carbon atoms. When R is a phenyl radical substituted
by an alkyl, alkoxy, or haloalkyl group, each of these groups
~07703~
may contain, for example, from 1 to 4 carbon atoms. The
haloalkyl group may be for example a trifluoromethyl group.
When R is an alkyl radical substituted by an alkoxy radical
which is itself substituted by an alkoxy radical, each
alkoxy radical may have for example from 1 to 6 carbon
atoms. When R is an alkenyl radical it may for example
contain up to six or more carbon atoms. Particular examples
of alkenyl radicals within this range include allyl and
crotyl radicals. Examples of substituted alkenyl radicals
include the alpha-trifluorinated propenyl radical (CF3CH=CH-),
the styryl (i.e. phenylvinyl) radical (PhCH=CH-) and the
furylvinyl radical.
Preferably the lower alkyl radical Rl has not more than
three carbon atoms. More preferably Rl is a methyl group.
When R2 is a lower alkyl radical, it preferably has no
more than four carbon atoms.
The group R3 may contain for example up to eight or
more carbon atoms. Examples of alkyl radicals falling
within this range include ethyl, propyl, isopropyl, butyl,
isobutyl, amyl, isoamyl, 2-methylbutyl, and 2-ethylbutyl. A
preferred alkyl radical is lsobutyl. Examples of alkenyl
radicals include allyl and crotyl radicals.
When R3 is an alkyl radical substituted by a cycloalkyl
radical, the cycloalkyl radical may have for example from
: :.
-
. .. . :
:
.
-: .
1077()38
3 to 6 carbon atoms. R3 may be, for example, a cyclohexyl-
methyl radical. When R3 is an alkyl radical substituted
by an alkyl- or haloalkyl- substituted phenyl radical, the
alkyl or haloalkyl substituent may contain from 1 to 4
carbon atoms. R3 may be, for example, a benzyl radical,
the phenyl ring of which may optionally be substituted by
one or more fluorine, chlorine, bromine, iodine, haloalkyl,
or cyano radicals.
Sub-groups of compounds falling within the broad class
of compounds useful in the process of the invention include
those in which R is a propyl or allyl radical, Rl is a methyl
group, R2 is a hydrogen atom and R3 is a cyclohexylmethyl
group or a benzyl group optionally substituted as set forth
above. A further sub-group comprises those compounds in
which ~ is a benzyl radical, optionally substituted as set
forth above, Rl is a methyl group, R2 is a hydrogen atom,
and R is a propyl, iso-butyl, or butyl radical.
The identity of the acid which is used to form the acid
addition salts of the compounds of the invention is not
critical and a wide variety of acid addition salts of any
particular compound may therefore be used. For reasons of
convenience and economy, however, salts derived from the
readily available mineral acids are preferred, although
others may be used ir desired. In considering the choice
of acid, the purpose for which the salt is to be used will
-- 5 --
,
~(~7~7038
be taken into account; salts formed from herbicidal acids
which are highly persistent in soil would obviously not be
suitable for applications in which crops are to be
~ planted shortly after the herbicide is applied. Particular
S examples of acids which may be used to form the acid addition
salts include hydrochloric, hydrobromic, sulphuric, nitric,
and phosphoric acids.
Particular examples of compounds useful in the invention
are listed in Table I below, together with a characterising
physical constant.
-- 6 --
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1077038
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1077038
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1077038
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1~77038
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-- 18 --
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1077038 .
The compounds used in the invention are herbicides
phytotoxic towards a range of grass species and dicotyle-
donous species. They are generally more effective by pre-
emergence application than by post-emergence application.
S That is to say, they are generally more effective when
applied to soil to prevent the growth of plants from seed or
seedlings present in the soil than they are when applied to
the above-ground parts of growing plants. The rate at which
the compounds are applied will depend upon a variety of
factors, such as for example the particular compound chosen
for use and the identity of the plants whose growth is to be
inhibited. As a general guide, however, an application rate
within the range from 1 to 10 kilograms inclusive per
hectare is usually suitable.
The compounds of the invention have been found to be
severely phytotoxic to grass weeds and certain dicotyledonous
weeds at rates of application which do not substantially
damage certain crop plants, notably soya bean, ground nut,
cotton, wheat, barley, and rice. In a further aspect,
therefore, the invention provides a process of selectively
inhibiting the growth of weeds in crops of soya bean, ground
nut, cotton, wheat, barley, and rice, which comprises
applying to the crop area, before the crop emerges, a
compound of formula (I) or an acid addition salt thereof, as
hereinbefore defined, in an amount sufficient to inhibit the
-- 19 --
- ~ .,,
, ,
.. .. .
-
.~, .
~ . ...
` ~077038
growth of the weeds but insufficient substantially to damage
the crop plants.
The rate at which the compound is applied will depend
upon the identity of the crop and upon the particular
compound chosen for use, but in general an amount of from 1
to 4 kilograms per hectare will be suitable.
The compounds used in the process of the invention are
preferably applied in the form of a composition, in which
the active ingredient is mixed with a diluent or carrier.
In another aspect, therefore, the invention provides a
herbicidal composition, comprising as an active ingredient a
pyrimidine compound of the formula:-
R2
R2 ~,~oR3
N ~ N
wherein R, Rl, R2 and R3 are as hereinbefore defined, in
admixture with a solid diluent or a liquid diluent containing
a surface-active agent.
The solid compositions of the invention may be for
example, in the form of dusting powders, or may take the
form of granules. Suitable solid diluents include, for
example, kaolin, bentonite, kieselguhr, dolomite, calcium,
carbonate, talc, powdered magnesia, and Fuller's earth.
- 20 -
.
: .. .. :, .
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., .
1077038
Solid compositions may also be in the form of disper-
sible powders or grains comprising in addition to the active
ingredient, a wetting agent to facilitate the dispersion of
the powder or grains in liquids. Such powders or grains may
include fillers, suspending agents and the li~e.
Liquid compositions include aqueous solutions, dispersions
and emulsions containing the active ingredient preferably in
the presence of one or more surface active agents. Water or
organic liquids may be used to prepare solutions, dispersions,
or emulsions of the active ingredient. The liquid composi-
tions of the invention may also contain one or more corrosion
inhibitors for example lauryl isoquinolinium bromide.
Surface active agents may be of the cationic, anionic
or non-ionic type. Suitable agents of the cationic type
include for example quaternary ammonium compounds, for
example cetyltrimethyl ammonium bromide. Suitable agents of
the anionic type include for example soaps, salts of aliphatic
mono-esters of sulphuric acid, for example sodium lauryl
sulphate; and salts of sulphonated aromatic compounds, for
example dodecylbenzenesulphonate, sodium, calcium and
ammonium lignosulphonate, butylnaphthalene sulphonate, and a
mixture of the sodium salts of diisopropyl- and triisopropyl-
naphthalenesulphonic acid. Suitable agents of the non-ionic
type include, for example, the condensation products of
ethylene oxide with fatty alcohols such as oleyl alcohol and
- 21 -
... . .:
' . : . -: ~
:. .,:
.: :
~: ,
1077038
cetyl alcohol, or with alkyl phenols such as octyl-phenol,
nonylphenol, and octylcresol. Other non-ionic agents are
the partial esters derived from long chain fatty acids and
hexitol anhydrides, for example sorbitol monolaurate; the
condensation products of the said partial esters with
ethylene oxide and the lecithins.
The compositions which are to be used in the form of
aqueous solutions, dispersions or emulsions are generally
supplied in the form of a concentrate containing a high
proportion of the active ingredient, the concentrate being
diluted with water before use. These concentrates are
usually required to withstand storage for prolonged periods
and after such storage to be capable of dilution with water
in order to form aqueous preparations which remain homogeneous
for a sufficient time to enable them to be applied by
conventional spray equipment. In general concentrates may
conveniently contain from 10 to 85% and preferably from 25
to 60% by weight of active ingredient. Dilute preparations
ready for use may contain varying amounts of the active
ingredient, depending upon the purpose for which they are to
be used; however, dilute preparations suitable for many uses
contain between 0.01% and 10.0% and preferably between 0.1%
and 1% by weight of the active ingredient.
In a further aspect the invention provides novel
pyrimidine compounds having herbicidal properties, having
.""' ~ i
. . ~. .
'- : `,
1077038
the formula (I):
R2
R ~ OR
N ~ N
R
(I)
and acid addltion salts thereof, wherein R represents (a)
a hydrogen atom, (b) a phenyl radical optionally substituted
by one or more alkyl, alkoxy, fluorine, chlorine, or bromine
atoms; or (c) an alkyl or alkenyl radical optionally substituted
by one or more of the following:-
a fluorine, chlorine, or bromine atom;
a cycloalkyl, hydroxy, alkylthio, furyl, pyridyl, or mono-
or di-alkylamino radical; a phenyl radical optionally
substituted by one or more alkyl, fluorine, chlorine,
bromine, phenyl, cyano, haloalkyl, or alkoxy radicals;
or an alkoxy radical optionally substituted by one or more
phenyl or alkoxy radicals:
Rl represents a lower alkyl radical;
R2 represents a hydrogen atom or a lower alkyl radical;
and R3 represents an alkyl or alkenyl radical optionally
substituted by one or more of the following:
cycloalkyl; pyridyl; naphthyl; or phenyl optionally
substituted by one or more fluorine, chlorine, bromine,
Lodine, haloalkyl, cyano, alkyl, hydroxymethyl, or 4-
, . . .: .: ~, . .: . : - - -;
.. : . ~ .: -
107703~
methyl-2-propyl-6-pyrimidinyloxymethyl radicals; provided
that when R is hydrogen or methyl, R3 is not an alkyl
radical of 1 to 4 carbon atoms or a benzyl radical.
The compounds used in the invention may be prepared by
processes which are known in themselves. Thus they may be
prepared by the procedure shown in Scheme A below:-
Scheme A
2 R2
RlCCHCoR4 + NH NH2 Rl ~ O
Il ¦l ~ / N~,NH
O O C T
I R
R (I) (II)
Rl ~ C1
(II) + POC13
N ~ N
R2 (III)
Rl l~OR3
(III) + R30M - > I 1¦
R
(IV)
In Scheme A, the symbols R, Rl, R2, and R3 have any of
the meanings previously assigned to them. R4 stands for a
hydrocarbyl group, preferably a lower alkyl group, for
example an alkyl group of 1 to 4 carbon atoms. M stands for
- 24 -
.
- ~ ~ ,. ....
: . .. . :
~)77038
an alkali metal, for example sod:ium or potassium. In Scheme
A, an acyl-acetic ester RCCH2COR is reacted with a amidine
O O
derivative (I). The amidine derivative is normally obtained
as an acid addition salt, for example, the hydrochloride.
For reaction with the acylacetic ester, the amidine base is
liberated from its acid addition salt by mixing a solution
of the latter with an equimolar proportion of a base, for
example sodium ethoxide. The reaction between the acyl-
acetic ester and the amidine is preferably carried out in a
solvent. Preferred solvents include lower alcohols, for
example methanol and ethanol. The pyrimidine derivative
(II) obtained from the reaction of the acylacetic ester and
the amidine may then be converted to the 4-chloro-pyrimidine
(III) by treatment with phosphorus oxychloride. Conveniently,
the pyrimidine derivative (II) is heated under reflux in an
excess of phosphorus oxychloride. The 4-chloro- compound so
obtained may be isolated by conventional methods, for
example by distilling off the excess of phosphorus oxy-
chloride, and adding ice, followed by purifying the remaining
pyrimidine (III) by recrystallisation from an appropriate
solvent or distillation. The 4-chloropyrimidine may then be
converted to the 4-substituted derivative (IV) by reacting
it with an alkali metal derivative of an alcohol, R30M.
- 25 -
, . .,. :. .
- . . . ..
... : . - :
- - :,
.. . . .
- . : - - -
1077038
The reaction is conveniently carried out in a solvent
for the reactants. The solvent may comprise, for example,
the alcohol R30H from which the metal derivative R30M is
prepared. The metal used to prepare the derivative R30M
will be an alkali metal or an alkaline earth metal, for
example sodium, potassium, calcium, or magnesium. Where the
solvent to be used comprises the alcohol R30H, the prepar-
ation of the 4-substituted derivative (IV) may conveniently
be carried out by dissolving the metal, for example sodium,
in an amount which is at least equimolar with respect to the
amount of the 4-chloropyrimidine derivative to be used, in
an excess of the alcohol R30H, then adding the 4-chloro-
pyrimidine derivative, and heating the reaction mixture for
sufficient time to bring about completion of ~he reaction.
lS The temperature of the reaction is not critical but by way
of general guidance, temperatures in the range from 25 to
100C are generally suitable while from 60 to 100C is
generally preferred. The 4-substituted pyrimidine may be
isolated from the reaction mixture by conventional methods,
for example by pouring the mixture into water, extrdcting
the aqueous mixture with an organic solvent, and evaporating
the organic solvent to recover the extracted material. The
latter may then be distilled or recrystallised by conventional
methods.
- 26 -
,
. . .
.
,
.. .. . :
.
: ~......
107703~
Where it is preferred not to use an excess of the
alcohol R30H as the solvent for the preparation of the 4-
substituted derivatives (IV), the reaction may be carried
out in an aprotic solvent for example a hydrocarbon solvent,
for example toluene or light petroleum. Other solvents
include for example dipolar aprotic solvents, for example
dimethyl sulphoxide, and ethers, for example dioxan.
The following Examples illustrate the invention.
EXAMPLE 1
This Example illustrates the preparation of Compound no
15 of Table I.
4-Chloro-2,6-dimethylpyrimidine (4.28 g) was added to a
solution of sodium (0.92 g) in isobutanol. The mixture was
heated under reflux for 30 minutes, concentrated, and water
added to the residue. The mixture was extracted with
chloroform and the extracts dried and evaporated. The pale
yellow oil was distilled at an oven temperature of 90C and
a pressure of 0.1 Torr to yield a clear, colourless mobile
oil having a refractive index n25 = 1.4757, identified as
compound no 15 of Table I.
Most of the compounds listed in Table I were prepared
by the procedure described above for compound no 15, that
is to say by reaction of the appropriately substituted
.. . . . .
; . . . ~
-, , . ... : ,
.
1077038
4-chloropyrimidine with a metal derivative of the appropriate
hydroxy compound R30H. The bulk of the substituted 4-
chloropyrimidines required as intermediates are known compounds.
Physical constants are tabulated below for those 4-chloro-
pyrimidine derivatives which appear to be new:-
R2
Rl~
N ~ N
R
(III)
:: : ....
-
.
, .. ~:
;
~077038
_ ~E~ U
~ ~ ~, ~, o
E~ O O C~ O C~
u~ ~ ~ o u- o o o a~ o o ~ o
Z o ~ r ~ O ~9 _I O
O ~
I u~ I i~ I I I u~ I I n I
X o I 9 ~O o . a~
O ~1 ~ O
~; _, ~, I~ 1~
~ . . . . ~ . . ,, .
H P~ l C~
u~ Ql Ql Ql ~:
:~ ~ c ~
~ C
.
HH c~ m :: m m m m m m m m m m
~¢ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
E~ _, m m m m m m m m 3: m m m
. P~ ~
. ~ Z
y C~
~ 1~ >1 N ~~ r
1: ~ N N N 1: N ~ ` I
a~ N,~: ~ ~ ~\
~ m o
P~ ~1 r4 Q ~ ~ ~ O I m o
O; O X ~1 0 ~ X ~ Q m ~o u --/
o ~ s o c~ 1 ' ) I m
m m o
U C~ C~ 11 11
U ~ ~c U ~4 ,C~ ~C., ~ I 1I m 5:
I I I I I I I ~ ~ ~ e~
_ Y
-- 29 --
~ , : ... .. : .
.. ` .:. :. :: : : - . . . ~,
. : . .; - - . :. . -
:. . . . .. ~ ~
. ,, , . ~ :
. , ~ i . .. .: ... .
107703~
~ , ~
Z I
U ~ ~ U~
~ ~ ,,
~~ _, ,, ~
c ~C ~i~a ~c
H ~`I
O ~
H ~'7 ~ r~7 ')
H _I
E~1~ ~ C )
l ~
y
tr: o ~
11 ~ ~ r~
~ ~ ~ o
I I I ~
-- 30 --
` ' ' '
., .:
,
. .
~, ..
.~
.
~ 107~7038
The above 4-chloropyrimidines were prepared by heating
the corresponding 4-pyrimidones (II) with phosphorus
oxychloride according to standard procedures. Physical
constants are tabulated below for those 4-pyrimidone derivatives
which appear to be new.
R2
Rl~
N ~ N
R
(II)
- 31 -
: :. . .. ., ... ~., :
, - .. : . . .~, : . i ,
.,
: ,
.. ~........ . . . .
:- . ;
J. 1077038
_
o
E~ u~ LO
H ~ ~1 ~ ~ D
O ~ o ~ x ~D ~`I
P~ _I o~ ~ ~1 ~ _I _I ~1
I I I I ~1 1 1 1 1 ~ I ~
~ co u~ I O
Z ~
H ~ I ~ er O
E~ r~ ~ Ln
.
_ ....... __
H ~I
HH ~ ~ ~ C
Ii3 . . _
a _l $ 3 ~ ~
~ Z
O
:>~ ~ N ~ I el' I
^ N N N ~ N ~ ` ~r
N
~~I rC
C~ ~ R ~ .4 a) I 5: 5:
-- 5~ ~ ~1 0 --I X ~1 ~ ~ ~ ~O
O ~ U ~ . ...
O ~ O ~ .C ~ 11 1 1 ....
t~ I I ~ _I ~ ~ ~ E4 5 ~ ~
5~ ~ S ~ ~ O
_
~ ' ' '' , ' ~ ,
'' ~ ' '' ' '' . ' ' '
, ~ I
~077038
oC~
H
O
Pl t'~
t~ O
Z
H ~ O ~1
E~ _~ ~
a
H ~`J~ ~ ~ ~ 3
z
O
C~
1.1 _ C~ :S
~1 ~
~ ~ r~
~ ~ ,Y ~
O C)
~ )
~ O
, ~ .
Y Y r
~ 33 ~
:: , :- ~
: ' 1 ' ,: ,
.: . , ; .: .
: :. : . .: ` -
- .; ;~ , : - .
1077038
A small number of the compounds in Table I were
prepared using procedures which are additional to those
described for Scheme A above. The preparation of these
compounds and of some intermediates is described below.
Compound no. 115
A mixture of 2-benzyl-4-isobutoxy-5-benzylpy~imidine
(Compound 102 of Table I) (5.0 g) and N-bromosuccinimide
(3.48 g) in dry chloroform (15 ml) was refluxed ror 5 hours,
cooled, and diluted wi~h more chloroform. The diluted
reaction mixture was washed with dilute sodium carbonate
solution, then with water, dried, and evaporated. The
residual orange-red oil was distilled at an oven temperature
of 158-160C and 0.05 Torr to give a colourless viscous oil,
which slowly solidified (m.p. 43-45C).
Compound no. 116
Propylamine (5 ml) was added to a solution of compound
no. 115 (1.43 g) in acetonitrile (15 ml). The solution was
warmed to 60C for 2.5 hours, cooled and poured into water.
The product was extracted with chloroform and the extract
washed with brine, dried, and evaporated to leave a yellow
oil. Distillation at an oven temperature of 140-145C and
a pressure of 0.15 Torr gave compound 116.
- 34 -
" ': -, .
, ~ ,
~077038
Preparation of 6-methyl-2-styryl-4-pyrimidone
2,3-Dimethyl-6-hydroxypyrimidine (30 g) and benzaldehyde
(25.65 g) in acetic anhydride (70 ml) were heated at 150C
for 8 hours. The mixture was concentrated, cooled, and
stirred with dilute aqueous sodium bicarbonate solution.
The precipitated solid was collected, washed, dried, and
recrystallised from chloroform/petroleum (b.p. 30-40C) to
give the required 6-methyl-2-styryl-4-pyrimidone. This was
converted into the corresponding 4-chloro compound in the
usual way with phosphorus oxychloride which was then used as
an intermediate for compounds 117 and 118.
Preparation of 6-methYl-4(2-methylbutoxy)-2-2(4-cyanophenyl)
ethylpyrimidine (Compound no. 96)
2-(4-Cyanostyryl)-6-methyl-4-(2-methylbutoxy)-pyrimidine
(1.87 g) and p-toluenesulphonyl hydrazide (2.28 g) were
heated under reflux in 2-methoxyethanol (25 ml) containing
ethanolamine (0.19 g) for 2 hours. The mixture was cooled,
poured into water, and extracted with dichloromethane. The
extracts were washed with brine, dried, and evaporated. The
remaining oil was purified by passage through a silica gel
column in dichloromethane. Evaporation of the dichloro-
methane solution gave the product (compound no. 96) as an
oil.
- 35 -
-.
: :
. : . .
::, ; / I` ~ '
, .. :: . . , , ~-
..
: ~ . . : ,
: :
-:. : . .
~07703~
Preparation of 2-(3!3,3-trlfluoropropenyl)-6-methyl-4-
pyrimidone
A mixture of 2,4-dimethyl-6-hydroxypyrimidine (22.02 g),
trifluoroacetaldehyde hydrate (20.6 g) and acetic anhydride
(90 ml) was stirred at 150C for 13 hours. Moxt of the
excess of acetic anhydride was removed lmder reduced pressure
and the cooled residue stirred with dilute sodium bicarbonate
solution. The solid which separated was collected, dried,
and washed with ether and then with petroleum to give the
white crystalline product. This was converted into the
corresponding 4-chloropyrimidine and then into compounds 91
and 92 by the method described in Scheme A.
Preparation of 2-(3 t 3,3-trifluoroPropYl)-6-methyl-4-pyrimidone
A solution of 2(3,3,3-trifluoropropenyl)-6-methyl-4-
pyrimidone (5 g), prepared as described above, in ethanol
(80 ml) was shaken in a hydrogen atmosphere with a 5%
palladium on charcoal catalyst (0.2 g) until the calculated
amount of hydrogen was absorbed. The catalyst was removed
and the filtrate evaporated to give the product, having a
melting point of 172-173C. This was converted into the
corresponding 4-chloropyrimidine and then into compound no.
90 by the method described in Scheme A.
- 36 -
1077038
EXAMPLE 2
This Example illustrates the preparation of 4-benzyloxy-
2-~-chlorobenzyl-6-methylpyrimidine (Compound no. 108 of
Table 1).
(a) Preparation of 4-chlorophenylacetamidine.
Dry hydrogen chloride was passed through a mixture of
4-chlorobenzyl cyanide (50 g), ethanol (25.1 g) and cyclo-
hexane (45 ml) maintained at 20-30C until saturated (3 hours).
Dry air was then passed through the mixture for 1 hour to
remove excess of hydrogen chloride. This mixture was added
slowly to isopropanol (250 ml) saturated with ammonia and
maintained at 20-30C. When the addition was complete more
ammonia was passed in to saturation. The mixture was then
left at room temperature overnight. The ammonium chloride
was filtered off, and the filtrate evaporated to dryness.
The residue was washed with ice-cold acetone to give 4-
chlorophenylacetamidine hydrochloride, m.p. 184C.
(b) Preparation of 2-p-chlorobenzyl-6-methylpyrimid-4-one.
The amidine hydrochloride from (a) above (50.0 g) was
added to a solution of sodium (12.35 g) in ethanol (300 ml)
followed by ethyl acetoacetate (34.89 g). The mixture was
stirred at room temperature overnight and then heated under
reflux for 2% hours. The mixture was concentrated to a
small volume and the residue dissolved in water, cooled, and
;,
, : .: . . . : :
:: .. : . .. ..
. : ~: .... : . ,: . -
: . . . ., . . .: ,,: .
.~
.... .
1(~77038
brought to pH 5-6 with acetic acid. The precipitated solid
was washed with acetone and dried, giving the pyrimidone,
with a melting point of 212-215C.
(c) Preparation of 4-chloro-2-~-chlorobenzyl-6-methyl
pyrimidine.
A mixture of the pyrimidone from ~b) above (37.04 g)
and phosphorus oxychloride (130 ml) was heated under reflux
for 1 hour. The mixture was concentrated to a small volume
and the residue cooled and added carefully to ice and water.
The mixture was made alkaline with concentrated ammonia.
The product was extracted with chloroform and the extracts
washed with brine and dried. The extracts yielded a crude
product which was dissolved in a mixture of ether and
petroleum (b.p. 30-40C). The solution was filtered and
the filtrate evaporated to yield the 4-chloropyrimidine,
with a melting point of 70-71.5C.
(d) Preparation of 4-benzyloxy-2-~-chloroben~yl-6-methyl-
pyrimidine.
Benzyl alcohol (2.03 g) was added to a suspension of
sodium hydride (0.522 g) in acetonitrile (25 ml). After
cessation of hydrogen evolution, the chloropyrimidine (5.0 g)
from (c) was added The mixture was stirred at room
temperature overnight and poured into water. The product was
extracted with chloroform and the extract washed with brine,
dried, and concentrated to an oil. Distillation at 176-180C,
- 38 -
1077038
0.15 Torr gave the product as a pale yellow oil, with a
refractive index nD 1.5876.
EXAMPLE 3
This Example ill~lstrates the herbicidal properties of
compounds used in the process of the invention. Each
compound (0.12g) was formulated for test by mixing it with 5
ml of an emulsion prepared by diluting 100 ml of a solution
containing 21.8 grams per litre of Span 80 and 78.2 grams
per litre of Tween 20 in methyl cyclohexanone to 500 ml with
water. Span 80 is a Trade Mark for a surface-active agent
comprising sorbitan monolaurate. Tween 20 is a Trade Mark
for a surface-active agent comprising a condensate of twenty
molar proportions of ethylene oxide with sorbitan mono-
oleate. The mixture of the compound and the emulsion was
shaken with glass beads and diluted to 12 ml with water.
The spray composition so prepared was sprayed on to
young pot plants (post-emergence test) of the species named
in Table II below, at a rate equivalent to 1000 litres per
hectare (lO kilograms of pyrimidine compound per hectare).
Damage to plants was assessed 14 days after spraying by
comparison with untreated plants, on a scale of 0 to 3 where
0 is no effect to 25% damage and 3 represents 75 to 100%
kill. In a test for pre-emergence herbicidal activity,
- 39 -
.-
. .
- . . .:
~07703~
seeds of the test species were placed on the surface of
fibre trays of soil and were sprayed with the compositions
at the rate of 1000 litres per hectare. The seeds were then
covered with further soil. Fourteen days after spraying,
the seedlings in the sprayed fibre trays were compared with
the seedlings in unsprayed control tray~s, the damage being
assessed on the same scale of O to 3. The results are
given in Table II below:-
- 40 -
.
. .~ . .
.
~077038
TABLE IV
*PRE- OR POST- TEST PLANTS
COMPOUND EMERGENCE
NO APPLICATION Lt To Wo/O Ll Cn St
.
l B - 1 O
A 3 O O O O 3
2 B 1 O O O O O
A O O - O O 3 .
3 B 2 1 O O O 1
A 1 2 O ~ O O 3
4 B O O O O O O
A 3 1 O l O 3
B O O O O O O
A O O O 3 O -
6 B O O O O O O
A 1 1 O O O 3
7 B O O O O O O
A 1 O O O O 1
8 B 3 3 2 2 O
A 3 2 O O O 3
9 B 1 2 O O O -
A O O 1 O O
B 3 3 3 3 O 3
O O O O O
- 41 -
.
. -: . .
.. .
.: . .~
107703~
TABLE IV CONTINUED...
~.
PRE- OR POST-TEST PLANTS
COMPOUND EMERGENCE
NO APPLICATIONLt To Wo/O Ll Cn St
11 B 3 3 2 2 0 2
A O O O O O O
12 B 3 3 3 3 0 2
A O O O O 0 3
13 B - 3 3 3 0 3
A 1 0 0 0 0 0
14 B - 3 3 3 0 3
A O O - O O O
3 3 3 3 3 0 3
A 1 2 1 0 0 -
16 B 3 3 3 3 0 3
A 1 1 1 1 0 2
17 B 1 0 0 3 0 0
A 1 0 0 0 0 2
B 3 3 2 3 0 3
A O O O O 0 3
22 B 3 3 2 3 0 3
A O O O O O O
27 B 2 3 3 3 0 3
. OO OOOO
107703~
TABLE IV CONTINUED...
PRE- OR POST-TEST PLANTS
COMPOUND EMERGENCE
NO APPLICATIONLt To Wo/O Ll Cn St
33 B O O O O O O
A 3 2 O O - 2
34 B 3 3 2 3 O 1
A 3 2 O 2 1 2
36 B 3 3 3 3 O 2
A 3 2 1 2 O 3
37 B _ _ _ _ _ _
A 1 O 2 O O 3
39 B 3 1 O 1 O 2
A 3 3 2 2 O 3
B O O O O O O
A 1 2 O O O 2
42 B 3 2 O 3 O 3
A 3 3 2 2 O 3
43 B O O O O O O
A 3 1 O O O 1
44 B 1 3 O O O 1
A O - O O O 3
46 B 1 2 O O O O
O O O O O 3
1077038
TABLE IV CONTINUED...
PRE- OR POST- TEST PLANTS
COMPOUND EMERGENCE
NO APPLICATION Lt To Wo/O Ll Cn St .
47 B O O 2 3 O O
A 3 2 O 1 O 3
48 B O O O 3 O -
A 3 1 1 1 O 3
49 B 3 3 3 3 O 3
A O O O 2 O 3
64 B 1 3 2 3 O 3
A 1 2 1 3 O 3
B O 3 O 1 O O
A O O O O O
66 B _ o -
A O 1 O O O 1
67 B - 3 - 1 O 2
A 1 1 O 1 O
68 B 3 3 3 3 O 3
A O O O O O 2
B 3 3 3 3 O 3
A O 1 1 1 1 2
71 B 2 3 2 3 O 2
1 3 1 2 1 2
- 44 -
~0770'~
TABLE IV CONTINUED...
PRE- OR POST-TEST PLANTS
COMPOUND EMERGENCE
NO APPLICATIONLt To Wo/O Ll Cn St
74 B 2 3 0 2 0 2
A 0 2 0 1 0 1
B 3 3 2 2 0 3
A 2 2 0 0 0 2
76 B 2 3 3 2 0 1
A 2 1 0 1 0 2
77 B O O O 1 0 0
A O 1 1 1 0 2
78 B 1 1 1 3 -O 1
A 2 2 0 2 0 2
79 B 3 3 3 3 0 2
. A 1 2 0 1 0 3
B 3 3 2 3 0 3
A 3 3 2 3 1 3
81 B 1 3 0 1 0 3
A 1 2 1 0 0 2
82 B 3 3 3 3 0 3
A 1 0 0 2 0 3
83 B 3 3 2 2 0 3
; 1 1 1 2 0 3
. .
~077038
TABLE IV CONTINUED...
. PRE- OR POST- TEST PLANTS
COMPOUND EMERGENCE
NO APPLICATION Lt To ~o/O Ll Cn St
84 B O O O 1 O O
A O O O O O 1
B O O O O O O
A 2 O O O o
86 B 2 3 2 3 O 3
. A 3 O O O O O
87 B - 1 3 3 O 1
A 2 O O O O 1
88 B O O 3 3 O 3
A 2 O O O O
89 B O 2 O 1 O O
. 3 O O O O 2
91 B 2 O O O O O
A 1 2 1 1 O 1
92 B O O O O O O
A O~ 1 O O O 1
93 B 1 1 0 1 0 1
. A O 2 O 2 O 2
94 B 2 3 33 O 3
. 2 2 13 G 3
- 46 -
,
,
' . ' ' :
: .
1077~)38
TABLE IV CONTINUED...
PRE- OR POST-TEST PLANTS
COMPOUND EMERGENCE
NO APPLICATIONLt To '~o/O Ll Cn St
B O O O O O O
A O 1 0 0 o
96 B O O O O O O
A 1 1 0 1 0
97 B O O O O O O
A 0 1 1 0 0
98 B O O O O O O
A O 1 0 0 0 1
99 B O O O O O O
A 1 1 0 0 0 3
100 B 3 1 2 2 0 2
A 3 3 1 2 0 3
101 B 3 3 3 3 0 2
A 1 1 0 1 0 2
107 B 3 3 3 3 0 3
A 3 3 2 3 2 3
108 B O O 0 3 0 0
A 1 2 2 3 2 3
109 B 3 0 0 3 0 0
3 2 0 2 - 2
- 47 -
- , :. ,
1077038
TABLE IV CONTINUED...
PRE- OR POST-TEST PLANTS
COMPOUND EMERGENCE
NO APPLICATIONLt To Wo/O Ll Cn St
llO B 3 3 1 2 O
A 2 2 O O 3
111 B 3 3 3 3 O 3
A 3 3 l 3 1 3
112 B 1 2 O 2 - 1
113 r 3 3 3 3 O 2
. A 1 2 O 2 1 3
114 B 3 1 1 3 3 0
A O O O 2 O O
115 B 3 3 3 3 3 3
A 2 2 1 2 O 2
116 B 3 3 3 3 O 3
2 2 O 1 - 2
* In the table, B means pre-emergence application and A means
post-emergence application.
- 48 -
.- ,. ,
"" .. ..... . . . ...
:, ,
~077~)3&~
The names of the test plants were as follows:-
Lt Lettuce
To Tomato
W0/0 Wild oats and cultivated oats~ Wild oats
(Avena fatua) are used in the post-emergence test
and cultivated oats in the pre-emergence test.
Ll Lolium perenne (perennial rye grass)
Cn Cyperus rotundus
St Setaria viridis
EXAMPLE 4
This Example illustrates the herbicidal properties of
compounds used in the invention. Each compound was formulated
for test by mixing an appropriate amount with 5 ml of an
emulsion prepared by diluting 160 ml of a solution containing
21.8 g per litre of Span 80 and 78.2 g per litre of Tween
20 in methylcyclohexanone to 500 ml with water. The 5 ml
of emulsion containing the test compound was then dlluted
to 40 ml with water and sprayed on to the range of test
plants named in Table V.
A pre-emergence test was also carried out as described
in Example 3. The plants were observed for 2 weeks after
treatment in the post-emergence test and for 3 weeks in the
pre-emergence test. Damage to plants was assessed on a
scale of 0 to 5 where 0 is 0 to 20% damage and 5 is complete
kill. The results are given in Table V below:-
- 49 -
:~: , :
10770;~8
_ ~ o o o o o o I o o o o
~ o o o o o ~ o o o ~ o
O O ~r er O O O ~r O
o u~ o ,, er ~ ~r I u~ u~ O
u~ ~1 n O O ~ Lr~ _~ ~1 ~ u~ O
~ I ~1 O O ~ ~ 0~ U~ n~
a ~1 n o o
O O ~1 O O ~r ~r ~ ~1 er
~ I o l l ~ l I o l I o
u~ ~ O ~r O O ~ ~r ~ O u~ n o
~ X oo o o o o o o o o o
~ ~ O ~ ~ O ~ u~ ~ _l n u~ ,~
E~ O ~ ~ ~1 ~ O ~7 O -I ~ ~ ~
E~ P~ O O O O O O O O l O -I
~ 0 ~1 _I . O N ~ O ~`1 n 1~7 ~
H O _I _I O t~l O ~ _I O ~r O
~ 00 O O O ~ 00 U') 00
~ O O O O u7 ~r -I O ~'1 ~ O
N O _i ~ O ~ ~r ~ O ~ ~ O
. ~ O O O O ~ er O -I O ~ O
O ~ ~ O O t~ ~ ~`J ') ~ _l
t,) O O ~ O O O O O _l O O
~ _l _l ~ t~l _l ~r ~r _l ~r u~ O
u~ O ~1 O O ~1 O ~ ,~ O ,~ _l
~ u~ LO u~ u~ u~ ~n u~ Ln
~ m ~ ~ m m m m ~ m m ~
~, ~ o _, _, ~ ~7 ~ _,
-- 50 --
1,. ' .
~77038
U o o o o o o o o o l o o
.C ~ O O O O ~r ~ O ~r ~1 er O
cn ~ ~ O ~ ~r L~ u~ ~r In ~r u~ O
~ ~ ~r ~ ~ ~r ~ u~ ~r ~r ~ ~ O
u~ u~ ,1 ~ O ~ ~r In ~r In ~ Ln
~ ~r ~ ~1 O ~ ~r ul ~r ~ ~
a u~ ~ ~ o ~r ~r ~n er u~ ~r ~
O ~ ~ O O ~r er u~ ~ er ~ ~ ~
~ l I _l l l l l l I ~1 I O .'
u~ ~: ~r O -~ ~1 ~ er ~r ~ er ~ ~r _1
.' ~ X o o o o o o o o o o o o
a ~ 0 n ~r ,1 o ~r u~ ~ ~ Ln ~ ~ ~
H E~ ~.) et~ el~ I O O ~\ ~ O ~r r'l ~ ~
O E-~ P. _1 I O O O ~ O O O ~1 O O
~ el~ ~ O O ~I ~I ~r _l et~-~ ~r o
~ H O ~ O ') O 1~ 1~ ~ ~ t~l ~ O
1~ u~ r~) O O t~l _l ~ ~I ~'t ~r ~ O O
3 ~`I ~ O O ~ ~r ~r ~ ~ el' O
N O ~ --1 ~r ~r ~ ~ _I ~ O
3 O O ~ O O ~r ~1 ~ ~1 ~r ~ O
U~ O O -I ~ _~ ~ ~ er ~ ~ ~ O
C~ O O-I ,~ O ~ ~ _l ~ OO
~r: er O -I ~ ~ ~ ~r ~r ~r _l In _~
R ~ ~r _I O ~:r ~ ~r ~r ~r
~ _ _ _ ___
m m ~ m m m m m m ~ m
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107'7038
The names of the test species are as follows:-
Sb Sugar beet
Rp Rape
Ct Cotton
Sy Soya bean
Mz Maize
Ww Winter wheat
Rc Rice
Sn Senecio vulgaris
Ip Ipomoea purPurea
Am Amaranthus retroflexus
Pi Polygonum aviculare- .
Ca Chenopodium album
Po Portulaca oleracea
Ab Abutilon theoPhrastii
Cv Convolvulus arvensis
Ot/Av As in Example 3
Dg Digitaria sanguinalis
Pu Poa annua
St Setaria viridis
Ec Echinochloa crus-galli
Sh Sorghum halepense
Ag Agropyron repens
Cn Cyperus rotundus
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~077038
ExAMæLE 5
This Example illustrates the selective herbicidal
effects of compounds used in the process of the invention.
The compounds were formulated for test as described in
Example 4. Tests were carried out on gxeenhouse plants as
described in Example 4, except that the procedure in the
pre-emergence test was somewhat different. In this test,
the seeds were sown in a shallow slit in the soil, and the
surface then levelled and sprayed. Fresh soil was then
spread thinly over the sprayed surface. The results of
the post-emergence test were assessed after two weeks and
of the pre-emergence test after four weeks, on a scale of
0 to 9 where 0 is 0 to 10~ damage and 9 is 90 to iO0~
damage to the plant. The results are given in Tables VI,
VII and VIII below.
- 60 -
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Names of test plants:- .
Ww Wheat
Br Barley
Pe Pea
Rp Rape
Sb Sugar beet
Lt Lettuce
Av Avena fatua
Al Alopecurus myosuroides
Bt Bromus tectorum
Ag Agropyron repens
Sm Stellaria media
Ca Chenopodium album
Pi Polygonum aviculare
Ma Matricaria inodora
Sp Sinapis alba
- 62 -
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Names of test plants:-
Mz Maize
Sy Soyabean
Gn Ground-nut
Ct Cotton
To Tomato
Po Portulaca oleracea
Am Amaranthus retroflexus
Ip Ipomoea purpurea
Dt Desmodium tortuosum
Ab Abutilon theoPhrasti
Se Sesbania exaltata
Co Cassia obtusifolia
Si Sida sPinosa
Ds Digitara sanguinalis
Xa Xanthium ~ensylvanicum
- 64 -
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i~7~7038
The names of test plants not previously mentioned are as
follows:-
Rc Rice
Sg Sorghum
Ei Eleusine indica
Ec Echinochloa crus-galli
Dg Digitaria sanguinalis
St Setaria viridis
Sf Setaria faberii
Sh Sorghum halepense
Pm Panicum maximum
Cn Cvperus rotundus
- 66 -
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1077038
EXAMPLE 6
This Example illustrates the selective herbicidal
effect of compounds used in the invention in rice. A test
was carried out in which the compounds were applied to
greenhouse rice plants and weeds grown under simulated flooded
paddy conditions. Twentysix days after treatment, the
damage to the plants was assessed on the O to 9 scale used
in previous Examples. The results are given in Table IX
below. It will be seen that while rice was substantially
undamaged, the weeds were severely damaged at the rates of
application used.
- 67 -
107 7038
~i
U N ~.1 N
-- 68 --
:
~07~7~38
Names of test plants:-
Ec Echinochloa crus-galli
Lp Leptochloa dubia
Cd Cyperus difformis
Mv Monochoria vaginalis
Sv Salvinia auriculata
- 69 -
-
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