Note: Descriptions are shown in the official language in which they were submitted.
5~
~693-3301D
This invention relates to certain novel pyridine
compounds useful in the preparation of pyridyl(oxy/thio)phenoxy
compounds.
This application is divided from applicant's copending
application Serial No. 430,592 filed June 17, 1983 and relating
(a) to navel pyridyl(oxy/thio)phenoxy compounds, (b) to herbicidal
compositions of such novel compounds and (c) to methodsof using
such compounds for the preemergent and postemergent control of
grassy weeds in non-crop areas as well as in the presence of
certain valuable crops such as soybeans, cotton and wheat.
Belgian Patent No. 834,495, issued February 2, 1976
as well as the published German patent application equivalent
-thereto, viz., No.2,546,251, published April 29, 1976, describe
2-((4-pyridinyl-2-oxy)phenoxy)-alkanoic acids, salts and esters
having halo substitution in the 3- and/or 5-ring positions in the
pyridine ring. Later references, e.g. published Brltish Patent
application 2,026,865 disclose such compounds having trifluoro-
methyl substitution on thepyridine ring and European Patent Applica-
tion 0002800 describes the enhanced effect of the D-steroisomers
of such compounds.
The pyridyl(oxy/thio)phenoxy compounds of aforementioned
application Serial No. 430,592 have herbicidal activity and corres-
pond to the ~ormula
-~ T~ O-Z
- 1 -
.,
g
wherein X is CF3, CHF2 or CClF2; T is 0 or S; and z is an organic
moiety containing N, O or S atoms or a metallic, ammonium or
organic amine cation and is or can be hydrolyzed and/or oxidized
in plants or soil to a carboxyl moiety that is in undissociated
and/or dissociated form. The invention is also directed to the
novel stereoisomers of such compounds, the R-isomers having
exceptional activity.
The aforementioned application Serial No. 430,592 is
also directed to a process for making a compound having the
formula: F
X--~T {~ O- Z
wherein X is CF3, CHF2 or CClF2; T is 0 or S; and Z is an organic
moiety containing N, 0 or S atoms or metallic or ammonium ions
which comprises (A) reacting a compound having the formula
~ ~ F
X~O~W'
wherein W' is F, Cl or Br and X is as above defined with a compound
having the formula
MT ~ o-z
wherein M is hydrogen or a metallic cation, and T and Z are as
above defined, in the presence of a base or (B) reacting a
compound having the formula
`3
X ~ O ~ - - T- - ~ OM
wherein 1~ is H or a metallic cation and T and X are as above
defined with a compound having the formula WIZ wherein W' is Cl
or Br and Z is as above defined, :Ln the presence o~ a base.
In accordance with the present invention, there is now
provided a compound having the general formula:
F
lQ ~
X~O,,~W'
wherein W' is F, Br or -O ~ OH, and X is CF3, Cl or Br and its
alkali metal salts, except that when W' is F, ~ is not CF3.
The novel pyridine compounds of the present invention
are listed specifically as follows: 2-bromo-3-fluoro-5-(tri-
fluoromethyl)pyridine, 5-chloro-2,3-difluoropyridine or 5-bromo-
2,3-difluoro-pyridine, 4-((3-fluoro-5-(trifluoromethyl)-2-pyri-
dinyl)oxy)phenol and its alkali metal salts, 4-(5-chloro-3-fluoro-
2-pyridinyloxy)phenol and its alkali metal salts~
The present invention, together with that of applicant's
aforementioned application Serial No. 430,592, will now be
described in more detail.
A variety of herbicidal compounds containing substituted
pyridyl and phenoxy moieties joined via a bivalent -O- and -S-
are described in the art. For example, United States Patent Nos.
4,046,553; 4,317,913, 4,267,336; 4,213,774; 4,324,627 and 4,309,547
- 2a -
and European Patent 483 all describe such compounds, methods ofmaking them, compositions containi:ng them and methods of u-tilizing
said compositions. In general, thle moieties bonded -to the pendant
-O- group of the phenoxy in the herbicidal com~ounds described in
these references will also be suitable as the monovalent organic
radical represented by Z in the formula for the aforementioned
novel compounds and, given the appropriate pyridine starting
material, the compounds of this invention can be prepared by
methods described in the above-mentioned prior art, and can be
utilized in compositions as described in said prior art.
- 2b -
~ I
-3~
Z moieties include, but are not limited to
Rl
-C- (Y )nR2
H
wherein Y is a saturated or unsaturated alkyl group
containing an even number of carbon atoms, preferably
from 2 to 18 carbon atoms, n is 0 or 1, R1 is H or a
Cl-C3 alkyl group and R2 is a group corresponding to
one of the following formulae:
-CN,
N~
//
NH~
/ N
~N~
-C-X, wherein X is halogen, or CN,
o
-C O M , wherein M is a me-tallic cation,
ammonium or an organic amine cation typically, but not
exclusively, containing alkyl (saturated or unsaturated),
alicyclic, heterocyclic or aromatic groups, all unsub-
stituted or substi-tuted with various other groups not
limited to, but including, halo, cyano, ni-tro and
unsubstituted or substituted -thiol, hydxoxy, amino or
: 30,864-F -3~
-4- ~ 5~
carboxyl groups and, additionally, alicyclic, hetero-
cyclic and aromatic groups substituted with unsubsti-
tuted or substituted satural_ed or unsaturated alkyl
groups, for example, trifluoromethyl, chloromethyl,
cyanomethyl and vinyl,
-CH20R3,
C-R3,
~CH20-C-R
- C -oR3,
--C - S~
O/S / R4
-C-N
\ R3
" /
-CH20-C-N
R3
O/S .R5
C-N
~02R6
'' /
-C-N \
CN
30,864-F 4-
_5_
O~S /R3
-CH20-C-N ~
CN
W
- C=N- R3,
R4\ /R3
-C=N-R3,
O ~I~alkyl
-C-NOR
O/S R4 R4
Il , / .
-C - N --- N\
R3
O/S R4 R3
11 /
15-C--N - - N\
CN
O/S R4 / R5
~C--N--N
\ S02R6
2 0 O/S R3 O
" ' " 3
-C--N--C R,
o~6
C~OR6
oR6
30, 864-F -5-
-6- `~
-C(SR6)3
-C(OR6)2
H
-C(SR6)2
(R~
.
-C-H
fR~
~) ~
-C-~
~R~
~S O
o/ N(R )2
-C N-C
~R7~N(R )2
: 25 X N-R3 where X is S or 0,
-CH~
where W is halogen; R3 is H or R6; R4 is H, alkoxy or
R6; R5 is H, a metallic cation or R~; and R6 is an alkyl
(saturated or unsaturated), alicyclic, heterocycl.ic or
aromatic group, unsubstituted or substituted with various
other groups not limited to, but including, halo, cyano,
nitro and unsubstituted or substituted thiol, hydroxy,
30,864-F -6-
amino or carbo~yl groups and, additionally, alicyclic,
heterocyclic and aromatic groups substituted with
unsubstituted or substituted saturated or unsaturated
alkyl groups, for example, trifluoromethyl, chloro-
methyl, cyanomethyl and vinvl,
O/S
" f--~ 7
-C-N R ,
~ .
O/S
" ~ 7
-CH2-O-C-N R ,
(R)
N
-C=N-R3,
~ 7
A R
-C = N where A is O, S or N, or
,, , '~~` 7
-C - N - N R ,
where R7 completes an unsubstituted or substituted
saturated heterocyclic ring system.
The above derivatives can be made by processes
generally known -to those skilled in the art and as des
cribed in the-above-mentioned patents. For example, the
corresponding acid chlorides can be reacted with a
Grignard reager.t to make the desired aldehyde or ketone
derivative. Similarly, reaction of an acid chloride
with KSH will provide the desired thiol acid. Thio-
amides may be prepared from the corresponding amide by
reaction with P2S5 or, if hydrogen is presen-t on the
nitroyen atom, the carbonyl may be converted to, e.g.,
30,864-F -7-
chloride, with removal of HCl, followed by reaction
with hydrogen sulfide. Carbamoyl chlorides are avail-
able in the art or they may be prepared from-the desired
amine and phosgene or thiophosgene for use in making
compounds containing the
0/S R
-C - N \ group.
- The reaction of an amine with a sulfonyl
chloride, e.g., R5NH~ + R6S02Cl provides the group
HN
S02R6
for use in reacting with an appropriate acid chloride.
The reaction of an amine with BrCN provides,
e.g., R3
NH
NC
which reacts with the appropriate acid chloride to
provide compounds con~aining the
O ~3
C - N
CN
moiety. P~S5 is employed to make the corresponding
S-containing compound.
30,864-F -8-
g ~ 3
Reaction of the above cyanoamine with phosgene
or thiophosgene provides
R O~S
N - C - Cl
CN
for use in making the correspondin~ derivatives.
The reaction of the compounds having the
moiety
o
Il 3
-C-~HR
with PCl5 will provide compounds havlng the moiety
Cl
' 3
-C=NR
The reaction of the corresponding acid chloride
with RONH2 will provide compounds having the group
O H
ll l
-C - N - OR
Various hydrazine derivatives can be made,
e.g.~ from trimethyl hydrazine by reaction with the acid
chlorides. The reaction of the amides, e.g.,
~ C-NHR3
with dicarboxylic anhydrides will provide compounds
having the group
30,864-F -9-
.
-10
o o
1, " 3
-C-N-C-R
R is preferably a carboxylic acid group, an
alkali or alkaline earth metal salt thereof, an ammonium
or organic amine salt thereof or a lower alkyl ester
thereof, wherein "lower alkyl" includes straight, brancned
or cyclic saturated or unsaturated alkyl groups containing
no more than 6 carbon atoms. Preferably, n is 0.
In the above formulae the aliphatic groups
preferably contain 1 to 6 carbon atoms, the alkenyl
and alkynyl groups preferably contain 2 to 6 carbon
atoms, the alicyclic groups preferably contain 3 to 6
carbon atoms and the aromatic moiety is preferably
phenyl, although other ring systems, including hetero-
cyclic ring systems, may be employed if desired.
In the formula for the aforementioned novel
compounds, T is preferably O and X is preferably CF3,
Cl or Br. Most preferred are the compounds in which X
is CF3 or Cl, T is O, and Z is
CH3 o
- CH - C - O - R"
wherein R" is methyl, ethyl, propyl, isopropyl, iso-
butyl or n-butyl.
The compounds of the above formula, herein-
after referred to for convenience as "active ingredients",
have been found to be especially active as herbicides
~or the control of und~sired vegetation, for example,
30,864-F -10
grassy or graminaceous weeds and are unexpectedly more
r effective than the compounds of the known art.
Especially surprising is the finding that the
unexpected activity of the presently claimed compounds
5 is specifically related to fluorine substituted in
the 3-position of the pyridine ring; fluorine sub-
stitution in other positions on the pyridine ring, e.g.,
the 5-position, does not cause unusually beneficial
acti~ity to result. With the compounds of this
10 invention, it is possible to employ lower dosage rates
and still obt~in effective control, thus reducing plant
residues and any potential environmental contamination
and/or toxicological effect on fish and warm blooded
animals. Accordingly, the present invention also
15 encompasses herbicidal compositions containing one or
more of these active ingredients as well as preemergent
and postemergent methods of controlling undesired plant
growth, especially in the presence of valuable crops.
Such methods comprise applying a herbicidally-effective
20 amount of one or more of said active ingredients to the
locus of the undesired plants, that is, the seeds,
foliage, rhizomes, stems and roots or other parts of
the growing plants or soil in which the plants are
growing or may be found.
The term "herbicide" is used herein to mean
an active ingredient which controls or adversely
modifies the g~owth of plants because of phytotoxic
or other effects substantial enough to seriously
retard the growth of -the plant or further to damage
the plant sufficiently to kill the plant.
By "growth controlling" or "herbicidally-
-effective" amount is meant an amount of active ingre-
dient which causes a modifying effect and includes
30,864-F -11-
12~
deviations from natural development, killing, regu-
lation, desiccation, retardation, and the like.
The term "plants" is meant to include germinant
seeds, emerging seedlings, rhizomes, stolons and other
underground propagules, and established vegetation.
The active ingredients, i.e., new compounds,
of the present invention are readily prepared by
processes described in the above cited prior art by
choosing the appropriate starting materials. The
stereoisomers are readily ~eparated as described in
European 0002800 referred to above.
Certain of the pyridine reactants employed to
make the novel pyridinyloxyphenoxy compounds of this
invention are themselves novel compounds and such
reactants may be made as generally described hereafter
and as specifically set forth in the following examples
or by methods analagous .hereto, starting with known
compounds.
We have unexpectedly found that the fluorine
atom in 3-chloro-2-fluoro-5-(trifluoromethyl)pyridine
can be readily replaced with a 2-cyano group by reacting
said pyridine compound wlth an alkali metal cyanide,
preferably potassium cyanide, in a polar aprotic solvent,
preferably dimethylsulfoxide, at a temperature of
10-50C., preferably 20-30C. We have further found
that the chlorine atom in the resulting product, ie.,
3-chloro-2-cyano 5-~trifluoromethyl)pyridine is readily
selectively replaced with fluorine by reaction with,
e.g., cesium or potassium fluoride in a polar aprotic
solvent, preferably dimethyl sulfoxide, at a temperature
of 80-140C., preferably 90-100C. The cyano group in
30,~64-F -12-
.,
-13~
the resulting 2 cyano-3-fluoro-5-(trifluoromethyl)pyridine
can be readily converted, by known procedures, to the
corresponding acid or amide, as desired. The resulting
acid may be readily converted to the corresponding
bromine derivative by the Hunsdiecker reaction, as
shown in the following Example 4, or the amide may be
converted to the corresponding amine and then hydroxy
compound by the Hoffmann hypobromite reaction followed
by diazotization and replacement by hydroxide as known
in the art. The latter is then treated with POC13
plus PC15, as known in the art, to prepare, for example,
2-chloro-3-fluoro-5-(tri1uoromethyl)pyridine.
Alternatively, ~,3-difluoro-5-(trifluoro-
methyl)pyridine may be prepared by contacting
2,3-dichloro-5-(trifluoromethyl~pyridine or 3-chloro-
- -2-fluoro-5-(trifluoromethyl)pyridine with a
fluorinating agent and the 2,3-difluoro-5-(tri-
fluoromethyl)pyridine may be used directly to make
2-~4-((3-fluoro-5-(trifluoromethyl)-2-pyridinyl)oxy)-
phenoxy)alkanoic acids and derivatives.
The following examples further illustrate thepresent invention.
Example 1 - PREPARATION OF 3-CHLOR0~2-CYAMO-5-(TRI-
FLUOROMETHYL)PYRIDINE
F3C ~Cl
'l
N CN
30,864-F 13-
/
3-Chloro-2-fluoro-5-(trifluoromethyl)pyridine
(obtained as a by-product from the fluorine exchange
reaction when converting 2,3-dichloro-5-trichloromethyl
pyridine to 2,3-dichloro-5-(trifluoromethyl)pyridine)
(40.0 g, 0.2 mole) was put into 270 ml of dimethyl
sulfoxide and stirred while potassium cyanide ~14.4 g,
0.221 mole) was spooned in over a 20-minute period.
The mixture was then stirred for another 20 minutes.
The temperature was held between 23 and 28C -throughout
the reaction. The mixture was poured into 600 ml of
ice water and the product was extracted into hexane.
The hexane was removed on a rotary evaporator. The
product was treated with activa-ted charcoal and distilled
on a Vigreaux-Claisen still at 198-110C at 30 mm Hg to
yield 31.45 g of colorless oil with an analysis of, in
percent by weight:
Calculated: C=40.70; H=0.98; N=13.56.
Found: C=40.42; H=0.99; N=13.66.
Example 2 - PREPARATION OF 3-FLUORO-2-CYANO--5 (TRI-
FLUOROMETHYL)PYRIDINE
3 ~ F
'l
N CN
A flask fitted with an air s-tirrer and a takeoff
head was set up. Cesium fluoride ~45.6 g, 0.3 mole),
potassium carbonate (1.2 g) and 350 ml of dimethyl
sulfoxide were put into the flask and heated and stirred
under vacuum (30 mm). 120 Ml of dimethyl sulfoxide
was distilled off to dry the system. The reaction
mix-ture was cooled to 80C, the vacuum was released
and 3-chloro-2~cyano-5-~trifluoromethyl)pyridine
30,864 F 14-
-15~ 5~
(41.6 g - 0.201 mole) was aclded over a 7-minute period.
The reaction mixture was then warmed to 93C and held
at 93-111C for about 20 minutes. The mixture was
then cooled to 54C, poured over ice and extracted
twice with hexane and once with methylene chloride.
The solvents were removed and the product was distilled
at about 30 mm Hg at 90-94C to yield 29.6 g of
colorless oil which had an a:nalysis of, in percent by
weight:
Calculated: C=44.22; H=].06; N=14.74.
Found: C=43.53; H=1.11; N=14.44.
Example 3 - PREPARATION QF 3-FLUORO-5-(TRIFLUORO-
METHYL)PICOLINIC ACID
F3C ~ F
COOH
2-Cyano-3-1uoro-5-(trifluoromethyl)-pyridine
(11.1 g, 0.0584 mole) was put into 87 ml of 90% sulfuric
acid in a beaker. The mixture was stirred and heated
~t 100-112C for 1-1/4 hours. The reaction mixture
was then cooled, poured over ice and the solids that
came down were filtered off. The solids were dissolved
in a dilute solu-tion of NaOH. Any material that didn't
go into solution was filtered out and the filtrate was
acidified with aqueous HCl and the precipitate was
filtered off and dried. This yielded 6.47 g of solid
product with an analysis of, in percent by weight:
Calculated. C=40.20; H=1.45i N-6.70.
Found: C=39.29; H=1.35; N=6.98.
30,864-F -15-
-16-
1.05 g of a second crop of solids was obtained
on standing which exhibited the same IR spectrum as the
first solids out. These were combined and used to make
the following bromo compouncl.
Example 4 - PRE~ARATION OF 2-BROMO-3-FLUORO-S-(TRI-
FLUOROMETHYL)PYRIDINE
F3C ~ F
~O l
N Br
The 3-fluoro-5-(trifluoromethyl~-picolinic
acid ~7.35 g, 0.035 mole) starting material was put
into 150 ml of dry carbon tetrachloride and then red
mercuric oxide ~9.1 g, 0.042 mole) was added and the
mixture was stirred and refluxed 1 hour and 25 minutes.
A solution of bromine (6.7 g, 0.042 mole) in 20 ml of
dry carbon tetrachloride was added slowly with the
mixture at reflux over the next 2-1/3 hours. Light from
a W lamp was directed on the reaction mixture during
the addition and the reaction mixture was refluxed for
another hour. 25 Ml more of dry carbon tetrachloride
was added and the refluxing was continued for about 16
hours more while UV radiation was applied. The reaction
was then filtered throu~h CELITE diatomaceous earth to
remove the mercury salt. The carbon tetrachloride was
removed on a still and the product was distilled over to
yield 2.45 g of yellow oil with an analysis of, in per-
cent by weight:
Calculated: C=29.53; H=0.83; ~-5O74.
Found: C=29.36; H=0.77; N-5.82.
30,864-F -16-
~ -17~ 5~
The gas chromatograph shQwed the oil to be a
r 99~% pure compound.
Example 5 - PREPARA~ION OF ~'-(4-((3-FLUORO-5-(TRIFLUORO-
METHYL)-2-PYRID]:NYL)OXY)PHENOXY)PROPANOIC ACID
F3C ~ F oCCHCo2H
2-~4~Hydroxyphenoxy) propanoic acid (1.80 g,
0.00988 mole) was dissolved in 15 ml of dimethyl
sulfoxide. A solution of sodium hydroxide (0.8 g, 0.02
mole in 1 ml of water) was added and the reaction
mixture was heated under nitrogen to 48C over a
27 minu~e period. 2-Bromo-3-fluoro-5-(trifluoromethyl)-
pyridine (2.40 g, 0.00984 mole) dissolved in 5 ml of
dimethyl sulfoxide was added and the reaction mixture
was heated at 75-78C for 40 minutes. The mixture was
poured into 150 ml o cold water and acidified with
aqueous HCl. A gum came down. Upon work-up and puri-
fication, a fraction (0.45 g) was obtained which had an
elemental analysis of, in percent by weight:
Calculated: C-52.18; ~=3.21; N=4.06.
Found- C=51.89; H=3.19; N-4.02.
This material had a melting point of 130-132C.
~ PREPARATION OF 2-(4-((3-FLUORO-5-TRI-
- ~5 FLUOROMETHYL) -2-PYRIDINYL)OXY)PHENOXY)-
PROPIONAMIDE
A~ A fresh sample of 2-(4-(~3-fluoro-5-(trifluoro-
methyl)-2-pyridinyl)oxy)phenoxy propanoic acid was
30,864-F -17-
-18~
prepared by the reaction of 2,3-difluoro-5-(trlfluoro-
methyl~pyridine with 2-(4-hydroxyphenoxy)propanoic
acid in the presence of 2 moles of sodium hydroxide
as above described and 9.0 g (0.026 mole) was refluxed
in excess SOC12 for about 1/2 hour to prepare the
corresponding acid chloride. The excess SOC12 was
removed by heating to 115C under an aspirator
vacuum. The resulting acid rhloride was added to a
mixture of concentrated ammonium hydroxide (30 ml)
lQ and methanol ~60 ml). The flask was rinsed with an
additional 15 ml ammonium hydroxide mixed with about
- 25-ml of methanol and the two fractions were combined.
The acid amide formed as a solid which was filtered
out, rinsed with water, slurried in water, filtered,
dried and analyzed. M.P. 140-141C.
Analysis: %C %H ~oN
Calculated: 52.33 3.51 8.14
Found: 52.54 3.46 8.09
B. Other propionamides of the invention, as set
forth below, were prepared using similar procedures:
CF3 ~ ~ CH3 ,O,
A M. P. C Analysis
~,OC ~ %Cl
-N ~ Cl 142-143.5 Calc... 55.45 3.32 6.16 7.80
Found: 55.88 3.34 6.11 7.70
30,864-F -18~
-19~ 5~
Example 7 - PREPARATION OF 2-(4-((3-FLUORO-5-(TRI-
- FLUOROMETHYL)-2-PYRIDINYL)OXY)PHENOXY)-
PRQPIONITRILE
-A portion of the amide prepared in Example 6A
(5.68 g, 0.0165 mole) was refluxed with an èxcess of
POCl3 for about 2 hours after which the excess POCl3
was removed by dlstillation under an aspirator vacuum.
The reaction mixture was poured over ice and extracted
with methylene chloride. The methylene chloride was
removed on a rotary evaporator and the crude material
was taken up in hexane and decolorized with charcoal.
A gummy material formed which was again placed on
the evaporator leaving an oil which was recovered and
analyzed .
Analysis: %C %H /~
Calculated: 55.22 3.09 8.59
Found: 55.64 3.00 8.81
Refractive Index = 1.5067 at 25C.
Example 8 - PREPA~ATION OF 2-~4-((3-FLUORO-5-(TRI-
FLUOROMETHYL)-2-PYRIDINYL)OXY)PHENOXY)-
METHYL PROPANOATE
Following the procedure of Example 6A the
acid chloride was prepared by refluxing a portion of
the acid from Example 6A with thionyl chloride. The
resulting acid chloride (3.45 g, 0.01 mole) was then
reacted with methanol (l.0 g, 0.0312 mole) in the
presence of triethylamine (2.0 g, 0.02 mole) in 20 ml
of toluene at 80 88C. The salt was removed by
filtration, then rinsed with hexane, the filtrate
combined and solvent removed by evaporation. The
crude product was taken up in hexane, some solids
30,864-F -19~
-20~ 5~
removed by filtration and the solution decolorized
with charcoal after which solvents were removed under
vacuum. The product gradually solidified and was
recovered and analy2ed. M.P. 50-52C.
Analysis: %C %H %N
Calculated: 53.49 3.63 3.90
Found: 53.82 3.68 3.87
Following the above procedure except to
. employ other alcohols or thioalcohols as the
esterifying agent the following compounds were
prepared having the general formula:
F
~ ~ ,CH3 ,O,
30,864-F -20-
-2
U~ I 0
~ ~ Lr)
O U~
.~ I" ~
~1
ta a~ ~1 ~ ~ ~D CS~
O ~ L') ~ ~ ~) ~'1
Q ~Z;
O ;~
r~ r~
m~ t~ L" ~ L') Lr)
~ d' ~
0 c~ ~ r~ ~ OD
~ V .. .. ..
aJ ~ ~D
P I~) Lr) L~') L') Ll-) Ll')
.. .. .. .. .. ..
. ~ . ~ ' ~
(d O ~ O ~ O
V ~4 C,3 kl C) ~4
L')
lR ~ ~
~ ~ ~ O
.,1 ~ ~ ~
~ ~ L')
~ . .
a~ ~ ,~
O 11 11 ~
~LI . . ~1
r--lH ~ I C)h
. ,,1 . O O O
Q, OP:~ Il-) ~; Lrl ~.)
~I) t~
X
~@1
.,1 .
. O O
-~
~ r~
C~ ~
~ h
O
N t~
~ c~
o o u~ -
30, 864-F -21-
-2~ S ~
Example 9 - PREPARATION OF 2-(4-((3-FLUORO-5-(TRI-
FLUOROMETHYL)-2-PYRIDINYL)OXY)PHENOXY-
-1-PROPANOL
The methyl ester of Example 8 ~5.7 g,
0.0159 mole) was dissolved in methanol (75 ml) and a
solution of sodium borohydride (3.5 g, 0.0954 mole)
was added dropwise to the cooled ~19C) solution,
maintaining the temperature at about 25C. The mixture
was stirred for about 1~ hours after which the temperature
was down to 18C. On standing 30 minutes, the temperature
increased to 23.5C after which the reaction mixture was
warmed to 42C ~30 minutes), continued stirring without
heat for 30 minutes, poured into a beaker and added ice
water (200 ml). Extracted with hexane and then twice
-with methylene chloride. Combined extracts, removed
solvents and ob-tained 4.94 g of the above indicated
product as a light yellow oil. R.I. = 1.5144 @ 25C.
Analysis: ~C y~ %N
Calculated: 54.38 3.96 4.23
Found: 54.25 3.98 4.44
Example 10 - PREPARATION OF THE R-ENANTIOMER OF
2-(4-((3-FLUORO-5-(TRIFLUOROMETHYL)-2-
-PYRIDINYL)OXY)PHENOXY)PROP I ON I C AC I D-,
METHYL ESTER
A mixture of 2.11 g (7.72 mmol) of 4-(3-fluoro-
S [trifluoromethyl)~-2-pyridyloxyphenol ~prepared as in
Example 12) 1.07 g (7.72 mmol) of anhydrous K2CO3 and
14.1 g (77.2 mmol) of the methane sulfonate of the methyl
ester of L-(+)-lactic acid in 16 ml of dry dlmethylsul-
foxide (DMSO) was stirred at room temperature for 43
hours. The reaction mix-ture was paxtitioned between
30,864-F -22-
S~
diethylether and water. The organic phase was separated,
dried (Na2SO4) and evaporated at reduced pressure to
give a colorless liquid. Pu:rification by high
pressure liquid chromatography on silica gel eluting
S with ethyl acetate-hexane (3:22, v/v) gave 2.15 g
~78%) of the R-enantiomer of the desired product as
a colorless oil: [N ] 25 ~ 31.4 (CHC13, C 0.0110 g/ml)i
IR (CC14) 1766 and 1741 cm 1; lH NMR (CDC13) ~ 8.0-8.2
(lH, m), 7.5-7.8 (lH, m), 6.7-7.2 (4H, m), 4.71
(lH, q), 3.73 ~3H, s) and 1.59 (3~, d); 19F NMR
(CDC13, ppm upfield from C6F6) 102.1 (s) and 26.3 (d)
Anal. Calculated for C16H13F4NO4: C, 53.49; H, 3.65;
N, 3.90. Found: C, 53.61; ~, 3.53; N, 3.86. The
optical purity of the ~ample was determined to be
15 > 90% ee by lH NMR analysis in the presence of Eu(tfc)3.
Example 11 - PREPARATION OF TEE R-ENANTIOMER OF
2-(4-((3-FLUORO-5-CHLORO-2 PYRIDINYL)-
OXY)PHENOXY)PROPIONIC ACID-, MET~YL ESTER
A mixture of 1.80 g (7.50 mmol) of 4-(3-
-fluoro-5-chloro~-2-pyridyloxyphenol, 1.04 g (7.50 mmol3
of anhydrous K2CO3 and 13.7 g (75.0 mmol) of the
methane sulfonate of the methyl ester of L-(~)-lactic
acid in 16 ml of dry DMSO was stirred at room temperature
for 4~ hours. The reaction mixture was partitioned
between diethylether and water. The organic phase was
separated, dried (Na2SO4) and evaporated at reduced
pressure to give a colorless liquid. Purification by
high pressure liquid chromatography on silica gel
eluting with ethyl acetate-hexane (1-9, v/v) gave
1.82 g (75%) of the R-enantiomer of the desired product
as a colorless oil: [a]25 + 34,4o (CHC13, 0.0112 g/ml);
IR (CC14~ 1762 and 1740 cm 1; lH NMR (CDC13) ~ 7.82
30, 864-F -23-
-24-
(lH, d), 7.43 (lH, d of d), 6.7-7.3 (4H, m), 4.69
(lH, q), 3.72 (3H, s) and 1.58 (3H, d); 19F NMR (CDC13,
ppm upfield from C6F6) 27.2 (d). Analysis: Calculated
for C15H13ClFNO4: C, 55.31; H, 4.02; N, 4.30. Found:
C, 55.04; H, 3.85; N, 4.24. The optical purity of the
sample was determined to be > 76% ee by 1H NMR analysis
in the presence of Eu(tfc)3.
Example 12 - PREPARATION OF 4-((3-FLUORO-5-(TRI-
FLUOROMETHYL)-2-PYRIDINYL)OXY)PHENOL
19 Xydroquinone (4.4 g, 0.04 mole) was
dissolved in 65 ml of dimethylsulfoxide and powdered
sodium hydroxide (1.4 g, 0.035 mole) was added in one
portion and the mixture stirred under nitrogen atmos-
phere fox 10 minutes to convert to the sodium salt.
2,3-Difluoro-5-(trifluoromethyl)pyridine (6.0 g,
0.033 mole) was then added and the mixture stirred
at 50C for 1.5 hours then warmed to 60C for a moment,
let cool for 15 minutes and then poured into 500 ml of
cold water. Additional sodium hydroxide (~3 g in water)
was added to convert the desired product to its sodium
salt. The insoluble bis-derivative was then removed by
extraction with hexane. The clear aqueous phase was
separated, cooled and acidified with concentrated hydro-
chloric acid. The solid which separated was collected on
a filter, washed, dried on a vacuum furmel and taken up
in hot hexane. After treating with decolorizing carbon,
filtering, concentrating and cooling the white crystal-
line product separated. Yield: 2.6 g. M.P. 97.5-98.5.
Analysis: ~OC ~H ~
Calculated: 52.76 2.58 S.12
Founcl: 52.71 2.57 5.12
30,864-F -24-
25-
Example 13 - PREPARATION OF 5-CHLORO-2,3-DIFLUORO-
r PYRIDINE
Cesium fluoride (125 g, 0.82 mol) and DMSO
(300 ml~ were placed in a fluorination flask equipped
with a mechanical stirrer, a thermometer, and a
distilling head. About 50 ml DMSO were distilled off,
under vacuum, to dry the system. 2,3,5-Trichloro-
pyridine (50 g, 0.27 mol) and potassium carbonate
~2.5 g, 0.018 mol) were added and the mixture was
heated at 130-140C for 7 hours, with vigorous
stirring. The product was distilled directly out
of the reaction mixture, under vacuum. The DMSO was
watèred out and the product was xedistilled to give
a clear, colorless li~uid (11.9 g, 29% of theoretical,
b.p. 70-73C @ 85 mmHg).
Analysis: %C ~ Cl
Calculated: 40.16 1.35 9.37 23.71
Found: 39.54 1.36 9.44 23.92
Exam~le 14 - PREPARATION OF 5-BROMO-2,3-DIFLUORO-
PYRIDINE
Cesium fluoride (28.8 g, 0.19 mol), potas-
sium carbonate (1.0 g, 0.007 mol) and sulfolane
(190 ml) were placed in a fluorination flask equipped
with a mechanical stirrer, a thermometer, and a
distilling head. About 20 ml sulfolane were distilled
off, under vacuum, to dry the system. 2,3,5-Tri-
bromopyridine (20 g, 0.063 mol) was added and the
mixture was heated at 180C for 2l-2 days. The product
was dis-tilled directly out of the reaction mixture to
30,864-F -25-
-26~ f~ 5~
yield a clear, colorless liquid (3.94 g, 32%) that was
80% 5-bromo-2,3-difluoropyri,ine and 20% 3-bromo-2,5-
-difluoropyridine isomer.
Analysis: %C /~I /~
Calculated: 30.95 1.04 7.22
Found: 31.36 1.14 7.32
Example 15 - PREPARATION OF 4-(5-CHLORO-3-FLUORO-
-2-PYRIDINYLOXY)PHENOL
A solution of NaOH (1.76 g, 0.044 mol) in
a few ml of water was added to hydroquinone (4.86 g,
0.040 mol) in 250 ml DMSO. The mixture was stirred
under nitrogen for 20 minutes. 5-Chloro-2,3-difluoro-
pyridine (6.0 g, 0.040 mol) was added. The reaction
mixture was heated at 60-70C for 3 hours, then poured
over ice. Aqueous NaOH was added to pH 1~ and the
solid diether side-product was filtered off. The
filtrate was acidified, extrac-ted with ether, treated
with Norite adsorbent, and the solvent was removed by
rotary eVapQration to give a yellow oil which solidified
on s-tanding and was purified by high pressure liquid
chromatosraphy ~HPLC) (80% hexane/20% ethyl acetate) to
give a white solid (2.5 g, 26% yield, m.p. 90-92C).
nalysis: %C
Calculated: 55.14 2.94 5.85
Found: 55.05 2.93 5.65
30,864-F -26-
, ,
-27~ 5~
Example 16 - PREPARATION OF 2-(4-( 3- FLUORO-5-CHLORO-
-2-PYRIDINYLOXY)PHENOXY)PROPIONIC ACID,
METHYL ESTER
A solution of NaOFI (2.7 g, 0.068 mol) in a
few ml of water was added to 2-(4-hydroxyphenoxy)pro-
pionic acid (6.09 g, Q.033 mol) in 55 ml DMSO and the
mixture was stirred for 20 minutes under nitrogen.
5-Chloro-2,3-difluoropyridine (5.0 g, 0.033 mol) was
added and the mixture was heated at 70~C for 5 hours.
The reaction was then poured over ice and extracted
with CH2Cl2. The organic layer was washed with water,
dried over Na2SO4 and the solvent removed ~y rotary
evaporation. The residual oil was dissolved in 130 ml
dry methanol, p-toluene sulfonic acid (0.5 g, 0.003 mmol)
was added and the mixture was stirred at room tempera-
ture for 24 hours. The methanol was removed by rotary
evaporation. The residue was taken up in ether, washed
with dilute aqueous NaOH, and dried over Na2SO~. The
ether was removed by rotary evaporation to yield a tan
oil which solidified on trituration with methylcyclohexane
to give a white solid ~6.4 g, 59%, m.p. 53-56C).
Analysis: %C /~ /~
._
Calculated: 55.31 4.02 4.30
Found: 54.91 4.05 4.21
Example 17 - PREPARATION OF 2-(4-(5-BROMO-3-~LUORO-
-2-PYRIDINYLOXY)PHENOXY)PROPIONIC ACID
A solution of NaOH (0.54 ~, 0.013 mol~ in a
few ml o~ water was added to 2-(4-hydroxyphe~oxy)pro-
pionic acid (1.22 g, 0.0067 mol) in 20 ml DMSO and the
mixture was stirred for 20 minutes under N2. 5-Bromo-
-2,3-difluoropyridine (1.3 g, 0.0067 mol) ~Jas added
30,864-F -27-
. ,
28~ 5~
and the mixture was stirred for 51-2 hours at 80-90C.
The reaction mix-ture was poured into water, acidified
with concentrated HCl to pH 1 and extracted into
CH2C12. The solution was dried over Na2SO4 and the
solvent was removed by rotary evaporation to yield a
gum which became an off-white solid (0.78 g, 33%,
m.p. 94-97C) upon standing.
Anal~ysis: %C /~ y~ ~OBr
Calculated: 47.21 3.11 3.93 22.43
Found: ~6.88 3.12 3.94 22.34
The compounds of the present invention have
been found to be suitable for use in methods for the
selective pre- and postemergent control of annual and
perennial grassy weeds. These compounds, -the active
ingredients of the present invention, have been found
to have advantage over prior art compounds in the
control of annual and perennial grassy weeds in that
the present compounds control such weeds at substan-
tially lower dosage rates. In addition, the present
compounds are sufficiently tolerant towards most broad
leafed crops to contemplate control of grassy weeds
therein at substantially commercially practicable
levels, particularly so with the preferred compounds.
In addition, certain of the compounds have sufficient
tolerance towards cereal crops such as wheat to enable
selective grassy weed control in these crops as well.
For such uses, unmodified active ingredients
of the present invention can be employed. However, the
present invention embraces the use of the compounds in
composition form with an inert material, known in the
30,864-F -28-
-29~
art as an agricultural adjuvant or carrier, in solid or
liquid form. Thus, for exam'ple, an active ingredient
can be dispersed on a finely-divided solid and employed
therein as a dust or granule. Also, the active
ingredients, as liquid concentrates or solid compositions
comprising one or more of thle active ingredients can be
dispersed in water, typically with aid of a wetting
agent, and the resulting aqueous dispersion employed as
a spray. In other procedures, the active ingredients
can be employed as a constituen-t of organic liquid
compositions, oil-in-water and water-in-oil emulsions
or water dispersions, with or without the addition of
wetting, dispersing, or emulsifying agents. Suitable
adjuvants of the foregoing type are well known to those
skilled in the art.
- The herbicidally effective concentration of
the active ingredients in solid or liquid compositions
generally is from 0.0003 to 95 percent by weight or
more. Concentrations from 0.05 to 50 percent by weight
are often employed. In compositions to be employed as
concentrates, the active ingredient can be present in
a concentration from 5 to 98 weight percent. The
active ingredient compositions can also con-tain other
compatible additaments, for example, phytotoxicants,
plant growth regulants and other biologically active
compounds used in agriculture.
In further embodiments, the compounds of the
present invention or compositions containing the same,
can be advantageously employed in combination with one
or more additional pesticidal compounds. Such additional
pesticidal compounds may be insecticides, nematocides,
miticides, arthropodicides, herbisides, fungicides or
30,864-F -29
_30_ ~ 5~
.
bactericldes that are compatible with the compounds of
the present invention in the medium selected for
application and not antagonistic to the activity of the
present compounds. Accordingly, in such embodiments,
the pesticidal compound is employed as a supplemental
toxicant for the same or for a different pesticidal
use or as an additament. The compounds in combination
can generally be present in a ratio of from 1 to 100
parts o the compound of the present invention with
from lO0 to 1 parts of the additional compound(s).
The active ingredients of the present invention
have been found to possess desirable herbicidal activity
in general against grassy weeds such as foxtail, barnyard-
grass, wild oats, seedling johnsongrass and crabgrass in
preemergent operations and also against the same
grasses in postemergent operations while being tolerant
to important broadleaf crops such as cotton, soybeans,
sugarbeets and rape and in the case of certain cf the
compounds, certain cereal crops such as wheat. These
compounds are also uni~uely effective in selectively
controlling perennial grassy weeds such as johnsongrass,
quackgrass, bermudagrass and dallisgrass.
The active ingredients of the present invention
have been found to possess particularly desirable
herbicidal activity against wild oats, ~oxtail, barnyard-
grass, crabgrass and seedling johnsongrass in postemergent
operations as well as desirable broad spectrum activity
against the perennial grassy weeds listed above and at
lower dosage rates than the substituted propanoates and
propanols of the prior art while showing high selectivity
to broadleaf crops and, in the case of certain of the
compounds, wheat.
30,86~-F -30-
-31~ S~
The present compounds which are substituted
propanols or propyl et~ers are more effective in pre-
emergent operations than in postemergent applications.
l'he exact rate to be applied is dependent not
only on a specific active ingredient being applied, but
also on a particular action desired, the plant species
to be modified and the stage of g owth thereof as well
as the part of the plant to be contacted with the toxic
active ingredient. Thus, all of the active ingrediencs
of the present invention and compositions containing
the same may not be equally e~fective at similar concen-
~xa-tions or against the same plant species.
In postemergent operations a dosage of
about 0.05 to about 20 pounds/acre (0.056-22.4 kg/-
15- hectare) is generally applicable, although not all
compounds are equally effective and some ~eeds are more
difficult to control. Thus, a dosage rate in the range
of about 0.01 to about 1.0 pound/acre (0.01-1.12 kg/-
hectare) is preferred in postemergent control o~ annual
grassy weeds, while about 0.05 to about 5 pounds/acre
(0.056-5.6 kg/hectare) is a preferred dosage range for
the postemergent control of perennial grassy weeds. In
applications to tolerant crops a ~eed controlling bu~
less than crop damaglng amount of from about .005 to
about 1.0 lb/acre (0.0056 to 1.12 kgs/hectare~ is
generally employed.
In preemergent operations a dosage rate of
0.01 to 10 lbs/acre (0.011 to 11.2 kgs/hectare), pre-
~erably 0.05 to 2.0 lbs/acre ~0.056 to 2.25 kgs/hectare)
and most pre~erably 0.1 to 1 lb/acre (0.11 -to 1.12 kgs/-
hectare) is generally employed.
30,864-F 31-
-32~ 59
The following examples illustrate effects of
the compounds of this invention.
Exam~le 18
In representative operations, each compound
to be utilized in a series of tests is dissolved in
acetone to one-half of ~he final volume (twice the
final concentration~ to be used and the acetone solution
in each case is admixed with an equal volume of water
containing 0.1 percent by weight of the non-ionic
surfactant TWEEN~ 20 (a polyoxyethylene sorbitan
monolaurate). The compositions, generally in the nature
of an emulsion, were employed to spray separate respective
plant species which had been grown to a height of 2-6
inches in soil of good nutrient content in a greenhouse.
Sufficient amounts were employed to provide various
application rates as listed in the table. The various
beds were positioned side by side and exposed to sub-
stantially identical conditions of temperature and
light. Each bed was maintained so as to prevent any
interaction with test compounds in different seed beds.
Other portions of the plants were left untxeated to
serve as controls~ After treatment, the plants were
maintained for about two weeks under greenhouse condi-
tions conducive for good plant growth and watered as
necessary. The specific plant species, test compound
and dosage and the percen-t postemergent control obtained
are set forth in the table below. Control refers to
the reduction in growth compared to the observed results
of the same untreated species. Note the "NT" means "not
tested".
30,864-F -32-
:
. ,,
-33~ f~ 3
Plant species in these tests were the following:
Common Name Scientific Name
Barnyardgrass
(Watergrass) Echinochloa crusgalli
Crabgrass Di~__aria sanquinalis
Yellow foxtail Setaria lutescens
Johnson grass Sor~hum halepense
Wild Oats Avena fatua
Cotton Gossypium hirsu-tum
Rape Brassica ~
. _
Soybeans Gl~cine max
Sugarbeet B _ vulgarls
Wheat Triticum aestivum
. _
30,864-F -33-
-34
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30, 864-F ~38-
-39
Ex~mDle 19
So as to clearly illustrate -the phytotoxic
properties of the various active ingredients of the
present invention applied preemergently, a controlled
greenhouse experiment is described below.
The seeds of various species of plants were
planted in beds of good agricultural soil in a green-
house. A number of compositions o~ the present
invention, generally in the nature of an aqueous
emulsion, were applied at rates listed in the table so
as to deposit a predetermined amount of active
ingredients uniformly throughout the surface of the bed.
Another seed bed was treated only with water to serve
as a control. After treatment the seed beds were
maintained for two weeks under greenhouse conditions
conducive for good plant growth and watered as necessary.
The specific plant species, test compound, and dosage
and the percent preemergent control are set forth in
the table below. Control refers to the reduction in
growth compared to the observed results of the same
untreated species.
30,864~F -39-
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30, 864-F -40-
-4~ 59
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30, 864-F -45-
-46~
Other compounds within the scope of the
present invention, e.g., the various metal salts,
amine salts and other derivatives of the ahove des~
cribed compounds may also be employed to control
certain plant species with results commensurate to
the above described results~
30,864-F -46- -
