Note: Descriptions are shown in the official language in which they were submitted.
1~8632~
Tetrahydroph~halimide compounds, and their prqduction and
use
The present invention relates to tetrahydro-
phthalimide compounds, and their production and use and,
in particular, to intermediates used in the preparation
of these compounds.
The said tetrahydrophthalimide compounds
(hereinafter referred to as "tetrahydrophthalimide(s)")
are representable by the formula:
O X ~ N
Rl-Z-c-lH-y O
R2
: wherein Rl is hydrogen, alkyl, lower cycloalkyl,
lower alkyl(lower)cycloalkyl, lower cycloalkyl(lower)
alkyl, lower alkoxy(lower)alkyl, lower alkenyl, lower
cycloalkenyl, lower cycloalkenyl(lower)alkyl, phenyl,
cyano(lower)alkyl, lower alkynyl, lower alkylideneamino,
' . .'~
i32~
- la -
lower alkylthio(lower)alkyl, benzyl, halo(lower)alkyl or
lower cycloalkylideneamino, R2 is hydrogen, lower alkyl
or lower alkoxy, X is chlorine or bromine, Y is oxygen or
imino and z is oxygen or sulfur.
This application relates to intermediates used
in the preparation of these compounds. The compounds
themselves, and other aspects of the invention are claimed
in our copending Canadian application serial no. 417,107
filed on December 6, 198~ r of which the present applica-
tion is a division.
Thus, according to one aspect of the invention
there is provided a compound of the formula
F O
X ~ N ~
wherein D represents -NH2 or -NO2 and X represents a
lS chlorine or a bromine atom.
In the above significances, the number of carbon
atoms in the alkyl group is not more than 12. The term
"lower" is generally intended to have not more than 8
carbon atoms, preferably 3 to 7 carbon atoms for a cyclic
moiety and not more than 6 carbon atoms for a non-cyclic
moiety. Preferred numbers of carbon atoms for lower alkyl,
lower cycloalkyl, lower alkenyl, lower cycloalkenyl and
lower
863;20
- . ~
( alkynyl are respectively ~rom 1 to 6, from 3 to 7, from 2 to
6, from 5 to 6 and from 2 to 6. ~referable numbers of
carbon atoms for l.ower alkoxy, lower alkylthio, lower
alkylideneamino and lower cycloalkylideneamino are respec-
tivelv from 1 to 6, from 1 to 6, from 1 to 6 and from-3 t 7.
More preferably, lower cycloalk~l, lower alkyltlower)cyclo-
alkyl, lower cycloalkyl(lower)alkyl, lower alkoxy(lower~-
alkvl, lower alkenyl, lower cycloalkenyl, lower cyclo-
alkenyl(lower)alkyl, cyano(lower)alkyl, lower alkynyl, lower
alkylideneamino, lower alkylthio(lower)alkyl, halo(lower)
alkyl and lower cycloalkylideneamino represented by Rl may
be respectively C3-C7 cycloalkyl, Cl-C2 alkyl(C3-C6)cyclo-
~lkyl, C3-C6 cycloalk~l(Cl-C2)alkyl, Cl-C4 alko~y(Cl-C~)-
alkyl, C2-C4 alkenyl, C5-C6 cycloalkenyl, C5-C6 cyclo-
alkenyl(Cl-C2)alkyl-, cyano(Cl-C3)alkyl, C3-C4 alkynyl, Cl-C4
alkylideneamino, Cl-C~ alkylthio(Cl-C4)alkyl, halo(Cl-C43-
alkyl and C4-C6 c~cloalk~lideneamino; and lower alkyl and
lower alkoxy represented by R2 may be respectively Cl-C3
alkyl and Cl-C2 alkoxy.
It is known that some tetrahydrophthalimide
compounds exhibit a herbicidal activity. For instance, U.S.
patent 3,984,435, EP 0049508A, U~S. patent 4,032,326, etc.
disclose that 2-~4-chlorophenyl)-4,5,6,7-tetrahydro-
2H-isoindole-1,3-dione, 2-[4-chloro-3-(1-propylthiocarbonyl-
butoxy)phenyl]-4,5,6,7-tetrahydro-2~-isoindole-1,3-dione,
2-(4-chloro-2-fluoro)-4,5,6,7-tetrahydro-2H-isoindole-1,3-
dione, etc~ are use~ul as herbicides. However, their
i32 1;)
( herbici~al effect is not alwavs ~tisfactory.
It has now been found that the tetrt~hydrophthal-
imides ~I) show a strong herbicidal actlvity against a wide
variety of ~Jeeds by foliar or soil treatment in plowed
fields. Advantageously, some of them do not produce any
material ~h~totoxicity on agricultural crops le.g. corn,
soybean, cotton). Their herbicidal activity is particularly
notable on post-emergence ~oliar treatment of broad-leaved
weeds such as common purslane (Portulaca oleracea), common
lambs~uarters (ChenoPodium album), redroot pigweed
( maranthus retroflexus~, hemp sesbania (Sesbania exaltata),
velvetleaf (Abtilon theophrasti), prickly sida (Sida
spinosa~, ivyleaf morning~lory (I~omoea hederacea), tall
morningglory (Ipomoea purpurea~, field bindweed (Convolvulus
arvensis), jimsonweed tDatura stramonium), black nightshade
(Solanum n~qrum), cocklebur ~Xanthium pensylvanicum),
sun10wer (EIelianthus annus7, common ragweed (Ambrosia
artemisifolia) in corn or soy~ean fields as they do not
__
afford any toxicity to corn or soybean. Likewise, they
exhibit a good herbicidal activity against Graminaceous
weeds such as barnyardgrass (Echinochloa crus-qalli),
broad-leaved weeds such as false pimpernel (Lindernia
procumbens), toothcup (Rotala indica~ and waterwort (Elatine
triandra) and paddy field weeds such as nutsedge (CYperUs
~5 serotinus), monochoria (Mcnocho_ a va~inalis) and arrowhead
~Sagittaria pyqmaea) in paddy rice fields, while exerting no
significant damage to rice plants. Accordingly, they can be
~863~)
-- 4
I usecl as herbicides applicable to paddy fields as well as
agricultural plowed fields. They are also useful as herbi-
cides to be employed for orchards, pastures, lawns, forests,
- non-agricultural fields, etc.
Among the tetrahydrophthalimi.des (I) of the
invention, favorable are those of the formula (I) wherein R2
is hydrogen or lower alkyl. More favorable are those of the
formula ~I) wherein R2 is hydrogen or methyl. Most favor-
able are those of the formula (I~ wherein R2 is hydrogen as
they show a high selec~ivity to soybean or corn by foliar
treatment~
The tetrahydrophthalimides (I) can be produced by
reacting a EIY-phenyltetrahydrophthalimide of the formula7
X ~ N ~ J (II)
HY
wherein X and Y are each as defined above with an a-halo-
carboxylic acid ester of the formula:
Il .
A-CH-C-Z-Rl (I T I)
R2
wherein A is chlorine or bromine and Rl, R2 and Z are each
as de ined above in a solvent in the presence or absence of
a dehydrohalogenating agent, usuallv at a temperature of 0
to 200C for 1 to 240 hours. The amounts of the ~-halo-
carboxylic acid ester (III~ and the dehydrohalogenating
~` ` 11863Z~
agent may be respectively 1.0 to 10 equivalents and 0.5 to
1.5 eauivalents to the HY-phenyltetrahydrophthalimide (II).
~Ihen desired, a phase transfer catalyst such as tetrabutyl-
ammonium bromide or benzyltributylammonium chloride may be
S employed.
As the solvent, there mav be used an aliphatic
hydrocarbon (e.g. hexane, heptane, ligroin, petroleum
ether), an aromatic hydrocarbon (e.g. benzene, toluene,
xylene), a halogenated hydrocarbon (e.g. chloroform, carbon
tetrachloride, dichloroethane, chlorobenzene, dichloro-
benzene), an ether (e.g. di~thyl ether, diisopropyl ether,
dioxane, tetrahydrofuran, diethylene glycol dimethyl ether),
a ketone ~e.g. acetone, methylethylketone, methylisohutyl-
ketone, isophorone, cyclohexanone), an alcohol (e.g.
L5 methanol, ethanol, isopropanol, ~-butanol, octanol, cyclo
hexanol, methylcelosolve, diethylene glycol, glycerol), a
nitrile (e.g. acetonitrile, isobutyronitrile), an acid amide
(e.g. formamide, N,N-dimethylformamide, acetamide), a sulfur
compound (e.g. dimethylsulfoxide, sulfolane), water, etc.
They may be employed alone or in combination.
Examples of the dehydrohalogenating agent are an
organic base (e.g. pyridine, triethylamine, N,N-diethyl-
aniline), an inorganic base (e.g. sodium hydroxide,
potassium hs~droxide, sodium carbonate, potassium carbonate,
sodium hydride), an alkali metal alko~:ide (e.g. sodium
methoYide, sodium ethoxide), etc.
The produced tetrahydrophthalimide (I) is, ~hen
1~8632~)
( des.ired, puri ied hv a per se conventional procedure such as chromatography or recrystallization.
The s~arting HY-phenyltetrahydrophthalimide (II:
Y = M~) can be produced by treating a nitrophenyltetra-
hydrophthalimide of the formula:
o
X ~ N ~ ~ (TV)
02N~ ~
wherein X is as defined above with 2.0 to 10 eauivalents of
an iron in the presence of an acid in a solvent (e.g. acetic
acid, wat~r, methanol, ethanol, tetrahydrofuran) at a
temperature of 20 to 100C.
The production of the nitrophenyltetrahydrophtal-
imide ~IV~ is summariæed in the following scheme:
X~NH2 , X~NH2 ~ ~
o~ 2
(~) (VI) (IV)
wherein X i~ as defined above~
Name]y, the haloaniline (V) is treated with 1.0 to
1.5 equivalents of conc. nitric acid in conc. sulfuric acid
at a temperature of 10 to -10C to give the nitroaniline
(VI), which is then reacted with 3,4,5,6-tetrahvdrophthalic
anhydride in a solvent (e.g. toluene, xylene, acetic acid,
propionic acid, water, dioxane) at a temperture of 0 to
1~3632~
( 200C, whereby ~he nitrophenyltetrahvdrophthalimide (IV) is
obtained.
The thus obtained compound (IV) may be sub~e~ted
to usal work-up or, if necessasry, to purification by
chromato~r~phy or recrystallization.
The startinq ~Y-phenyltetrahydrophthalimide (II:
Y = O~ can be produced as well by reacting a phenol of the
formula:
F
X ~ (VII)
HO
wherein X is as defined above according to the following
scheme:
~ ~ 2 ~ X ~ NH2 > X ~ N
H H HO HO
(VII) (VIII) (IX) ( I')
wherein X is as defined above.
Namely, the hydroxyphenyltetrahydrophthalimide
(III) can be manufactured ~rom the phenol (VII) by nitrating
the same, redu~ing the resultant nitrophenol (VIII) and
reacting the resulting aminophenol (IX) with 3,4,5,6-
tetrahydrophthalic anhydride.
Conversion of the phenol (VII) into the nitro-
~henol (VIII) may be accomplished by application of a per se
conventional nitration procedure to the former. Usually,
~L~863;~0
-- 8 --
. ., ~ . ~
I however, the indirect nitration which consists of the
following three steps is favorable in achievement of the
selective nitration at the desired position:
F /F
X~ - -, X~ ~,
HO H3COC~
O
(VII) (X)
F F
X~N02 _ 3 X;~No2
H3COICO I~
(XI~ ~VIII)
wherein X is as de~ined above. Thus, the phenol (VII) is
converted into iks alkali metal salt by treatment with an
aqueous solution of an alkali metal hydroxide (e.g. sodium
hydroxide, potassium h~droxide), and the resulting salt is
reacted with an alkyl haloformate such as methyl chloro-
formate in water at a temperature of Q to 10C~ The thus
prepared carbonic ester (X) is nitrated with a mixture of
conc. sulfuric acid and conc. nitric acid at room temper-
ature. Then, the nitrobenzene (XI) thus obtained is hydro-
lyzed with an aqueous alkaline solution such as an aqueous
sodium hydroxide solution at a temperature of 20 to 120C to
give the nitrophenol (VIII).
Conversion of the nitrophenol ~VIII) into the
i321~
g
f aminophenol (IX) may be accomp]ished by any per se conven-
tional reduction procedure for changin~ a nitro group to an
amino group. Examples of such reduction procedure are
catalytic reduction, reduction with iron powder, red~ction
with sodium sulfide, reduction with sulfurated sodium
borohydride, etc. For instance, treatment of one molar
amount of the nitrophenol (VIII) with a 3 molar amount of
hydrogen in the presence of a 1/10 to 1/100 molar amount of
platinum dioxide in an inert solvent ~e.g. ethanol, ethyl
acetate) at room temperatuxe under atmospheric pressure
affords the aminophenol (IX). Further, for instance,
treatment of one molar amount of the nitrophenol (VIII) with
a 2 to 5 molar amount o iron powder such as reductive iron
or electrolytic iron in a 5 % acetic acid solution or a
dil~te hydrochloric acid solution at a temperature of 80 to
100C for a period of 1 to 5 hours produces the aminophenol
(IX).
For production of the hydroxyphenyltetra~ydro-
phthalimide (II') from th~ aminophenol (IX), the latter is
reacted with 3~4,5,6-tetrahydrophthalic anhydride in an
inert solvent (e.g. acetic acid) while refluxing for a
period of 1 to 6 hours, preferably of 2 to 4 hours.
Still, the phenol (VI) is known ~cf. Finger et
al.: J.Am.Chem.SocO, 81, 94 (1959)).
Practical and presently preferred embodiments for
production of the tetrahydrophthalimides (I) as well as the
intermediary compounds are illustratively shown in the
following Examples.
~863;~
-- 10 --
t
Exam~le 1
2-(4-Chloro-2-fluoro-5-hydroxyphenyl)-4,5,6,7-
tetrahydro-2H-isoindole-1,3-dione (3 g) was dissolved in
dimethylformamide (100 ml), and anhydrous potassium carbonae
(0.8 g) was added tereto. To the resultant mixture was
added methyl bromoacetate (1.8 g), and the mixture was
heated at 70 - 80C for 3 hours. After allowed to coo],
water was added to the mixture, which was then extracted
with ether, and the extract was washed with water, dried and
concentrated. The residue was purified by silica gel column
chromatograph~ to ~ive 1.3 g of 2-(4-chloro-2-fluoro-5-
methoxycarbonylmethoxyphenyl)-4,5,6,7-tetrahydro-2H-iso-
indole-1,3-dione (Compound No. 1). M.P., 98 - 99.5C.
Exam~le 2
2-(3-Amino-4-bromo-6-fluorophenyl)-4,5,6,7-
tetrahydro-2H-indole-1,3-dione tO.85 g~ was dissolved in
1,4-dioxane l5 ml), and ethyl bromoacetate (3.3 g) was added
thereto. The resultant mixture was refluxed for 6 hours.
Triethylamine (0.2 g) was added thereto, and the mixture was
refluxed for 1 hour. After allowed to cool, water and
toluene were added to the mixture, which was then extracted
with toluene. The toulene layer was dried and concentrated.
The residue was purified by silica gel column chromatography
to give 1.0 g of 2-(4-bromo-2-fluoro-5-ethoxycarbonyl-
methyliminophenyl)-4,5,6,7-tetrahydro-2H-indole-1,3-dione
(Compound No. 89). nD 1.5281.
Examples of the tetrahydrophthalimides ~I)
il8~32~
. . .
( produced by the same procedure as above are shown in Table
1.
11~632~
-- 12 --
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~3632~
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1~863ZO
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1186320
-- 16 --
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8632~
-- 18 --
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-- 19 -
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~186320
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~8~i320
- 22 -
( Exam~le 3
Production of the HY-phenyltetrahydrophthalimide
(II: X = Cl; Y = NH~:-
A solution of N-(4-chloro-2-fluoro-5-nitrophenyl3-
S 3,4,5,6-tetrahydrophthalimide (16.2 q) in acetic acid (200
ml) was dropwise added to a suspension of iron powder (14 g)
in a 5 % aaueous acetic acid (30 ml) at 90 - 100C and
refluxed for 1 hourO After allowed to cool, chloroform was
added to the resultant mixture, followed by filtration. The
organic layer was separated from the filtrate, washed with a
saturated sodium hydrogen carbonate solution, dried and
concentrated. The residue was recrystallized from a mixture
o~ ether and petleum ether to give 7.5 g o~ N-~3-amino-4
chloro-6-fluorophenyl)-3,4,5,6-tetrahydrophthalimide. M.P.,
144.5 - 146.5C.
Production of the HY-phenyltetrahydrophthalimide
X - Br; Y = NH~:-
In the same manner as in Example 3 but using
N-(4-bromo-2-fluoro-5-nitrophenyl)-3,4,5,6-tetrahydrophthal-
imide in place of N-(4-chloro-2 fluoro-S-nitrophenyl)-
3,4,5,6-tetrahydrophthalimide, there was produced N-(3-
amino-4-bromo-6-fluorophenyl)-3,4,5,6-tetrahydrophthalimide.
M.P., 163 - 164.5C.
ExamPle 5
Production of the HY-phenyltetrahydrophthalimide
(II: X = Cl; Y = O):-
863~
- 23 -
i 2-Chloro-4 fluoro-s-aminophenol ~6.6 g) and
3,4,5,6-tetrahydrophthalic anhydride (6 g) were dissolved in
acetic acid (20 ml) and refluxed for 2 hours. Th~ resultant
mixture was allowed to cool to room temperature and poured
into ice-water, followed by extraction with ether. The
ether extract was washed with a saturated sodium hydrogen
carbonate solution and water in order, dried over anhydrous
magnesium suLfate and concentrated. The residue was
purified by silica gel chromatography to give 4.0 g of
N-(4-chloro 2-fluoro-S-hydroxyphenyl)-3,4,5,6-tetrahy~ro-
phthalimide. M~P., 151C.
NMR ~CDC13, D6-DMSO) ~ (ppm): 1.5 - 2.0 (4H, m),
2.1 - 206 (4H, m), 6.8 (lH, d, J=6Hz), 7.15 (lH, d, J=lOHz).
IR vma~ (cm ~: 3380, 1680.
Example 6
Production of the HY-phenyltetrahydrophthalimide
III: X = Br; Y = 0):-
In the same manner as in Example 5 but using
2-bromo-4-fluoro-5-aminophenol in place of 2-chloro-4-
fluoro-5-aminophenolj there was produced N-(4-bromo-2-
fluoro-5 hydroxvphenyl)-3,4,5,6-tetrahydrophthalimide.
M.P., 167 - 168C.
NMR (CDC13, D6-DMSO) ~ (ppm): 1.5 - 2.0 (4H, m),
2.1 - 2.7 (4H, m), 6.8 (lH, d, J=6Hz), 7.25 (lH, d, J=lOHz).
IR nu~ol (cm-l) 3380, 1690.
ExamPle 7
Production of the nitrophenyltetrahydrophthalimide
36320
- 24 -
( , ~ . .
(IV: X = Cl):-
4-Chloro 2-fluoro-5-nitroaniline (19 g) and
3,4,5,6-tetrahydrophthalic anhydride (15.2 g) were dissolved
in acetic acid (50 ml) and refluxed for 6 hours. After
allowed to cool, the resultant mixture was poured into water
and extracted with toluene. The toluene layer was washed
with water, an aqueous sodium hydrogen carbonate solution
and water in order, dried and concentrated. The residue was
crystallized from ethanol to give 20 g of N-~4-chloro-2-
fluoro-5-nitrophenyl)-3,4,5,6-tetrahydrophthalimide. M.P.,
157 - 157.5C.
Example 8
Production of the nitrophenyltetrahydrophthalimide
~IV: X = ~r)~-
In the same manner as in Example 7 but using
4-bromo-2-1uoro-5-nitroaniline in place of 4-chloro-2-
fluoro-5-nitroaniline, there was produced N-~4-bromo-2-
fluoro-5-nitrophenyl)-,3,4,5,6-tetrahydrophthalimide~ M.P.,
155 - 155C.
Example 9
Production of the nitroaniline (VI: X = Br):-
To a solution of 4-bromo-2-fluoroaniline ~58~ g)
in conc. sulfuric acid (100 ml), there was dropwise added a
mixture of conc. nitric acid ~25.3 g) and conc. sulfuric
acid (15 ml) at a temperature of 0 to -10C. The resultant
mixture was stirred at 0 - 5C for 1 hour, poured into
ice-water and extracted with toluene. The toluene layer was
~863~0
- 25 -
i washed with water and an aqueous sodium hydrogen carbonate
solution and concentrated. The residue was purified by
silica gel chroma~ography to gi~e 16.4 g of 4-bromo-2-
fluoro-5-nitroanilineO M.P., 90 - 92C.
Example 10
Production of the ni~roaniline (VI: X = Cl):-
In the same manner as in Example 9 but using
4-chloro-2-fluoroaniline in place o~ 4-bromo-2-~luoro-
aniline, there was produced 4-chloro-2 fluoro-5-nitro-
aniline. M.P., 83 - 84.5~C~
Example 11
Production of the nitrophenol (VII: X = Cl):-
2-Chloro~4-fluorophenol (83.4 g) was added to a
solution of sodum hydroxide ~27~7 g) in water (450 ml), and
methyl chloro~ormate (69.2 g) was dropwise added thereto at
a temperature below 10C. Precipitated crystals were
collected by filtration and washed with water to give methyl
(2-chloro-4-fluorophenyl)formate (134.8 g). M.P., 69 -
71C.
Methyl (2-chloro-4-fluorophenyl)formate (134.8 g)
obtained ahove was suspended in conc. sulfuric acid (50 ml).
To the suspension, a mixture of conc. sulfuric acid (50 ml)
and conc. nitric acid (50 ml) was added at about 30C, and
the mixture was stirred ~or 1 hour at this temperature. The
reaction mixture was poured into ice-water, and precipitated
crystals were collected and washed with water. Methyl
(2~chloro~4-fluoro-5-nitrophenyl)formate (143 g) was thus
L186320
obtained. ~I.P., 53 - 55C.
The product obtained as above was combined with
sodium hydroxide (27 g) and water (300 ml), and the
resultant mixture was refluxed for 4 hours. Precipitated
insoluble materials were filtered using a celite, and the
filtrate was acidified with conc. hydrochloric acid.
Precipitated crystals were collected by filteration and
washed Wit}l water to obtain 76.3 g of 2-chloro-4-fluoro-5-
nitrophenol. M.P. 106 ~ 107C.
N~IR (CDC13, D6-DMSO) ~ (ppm): 7.25 ~lHr d~
J~lOHz~, 7.64 (lH, d, J~6Hz).
IR vnU~l (cm~l): 3370
Example 12
Production of the nitrophenol (VII: X - Br~:-
2-Bromo-4-fluorophenol (28 g) was added to a
solution of sodium hydroxide (7 g) in water ~100 ml), and
methyl chloroformate was dropwise added thereto at a temper-
ature below 10C. Precipitated crystals were collected by
filtration and washed with water to give methyl (2-bromo-
4-fluorophenyl)formate ~41 g). M.P., 80.7C.
The thus obtained methyl (2-bromo-4-fluorophenyl)-
formate was suspended in conc. sulfuric acid (13 ml). To
the suspension, a mixture of conc. sulfuric acid (13 ml) and
conc. nitric acid (13 ml) was added at about 30C. The
mixture was stirred for 30 minutes and poured onto ice.
Precipitated crystals were thoroughly washed with water,
whereby yellow crystals of methyl (2-bromo-4-fluoro-5-
118632~
~ 27 -
nitrophenyl)ormate (38.3 g) were obtained. M.P., 63.5 -
64.5C.
The product thus obtained was refluxed together
with sodium hydroxide 16.2 g) and water (100 ml) for 3
hours. Insoluble materials were filtered, and the filtrate
was acidified with hydrochloric acid. Precipitated crystals
were collected by filtration and washed with water to obtain
25 g of 2-bromo-4-fluoro-5-nitrophenol. M.P., 126 - 127C.
NMR (CDC13, D6-DMSO) ~ (ppm): 7~42 (lH, d,
J=lOHz), 7.65 (lH, d, J=6Hz).
IR vma~ (cm ): 3450.
Example 13
Production of the aminophenol (IX: X - C1):-
A suspension of 2 chloro-4-fluoro-5-nitrophenol
(9.17 g) and platinum dioxide (500 mg) in ethanol tl20 ml)
was subjected to catalytic reduction with hydrogen under
room temperature and atmospheric pressure until a designed
amount of hydrogen was absorbed. The catalyst was removed
by filtration, and the filtrate was concentrated. The
residue was extracted with ether, and the ether layer was
concentrated to obtain 6.6 g of 3-amino-6-chloro-4-fluoro-
phenol. M.P., 145 - 146C (decompO).
NMR (CDC13, D6-DMSo) ~ Ippm): 6.4 tlH, d, J=8Hz),
6.85 (lH, d, J=llIIz).
IR vmaU~l tcm ): 3400, 3320.
Example 14
Production of the aminophenol (IX: X = Br):-
,
6320
- 28 -
( In the same m~nner as above but using 2-~romo-4-
fluoro-5-nitrophenol in place of 2-chloro-4-1uoro-5-
nitrophenol, ~here was produced 3-amino-6-bromo-4-fluoro-
phenol. M.P., 129 - 130.5C (decomp.).
S NMR (cncl3~ D6-D~VIS0~ ~ (ppm): 6.57 !lH~ d,
~=8H,.), 7.1 (lH, d, J=llHz).
IR vma~ (cm ): 3400, 33~0.
In the practical usage of the tetrahydrophthal-
imides ~I), they may he applied in any composition such as
emulsifiable concentrates, wettable powders, suspensions,
granules or dusts.
The concentration of the active ingredient in such
composi~ion is usually within a ran~e of 0.1 to 9S % by
weight, preferably of 1 to 80 % by weight.
lS In formulation o~ those compositions, a solid or
liquid carrier or diluent may be used. As the solid carrier
or diluent, there may be employed fine dust or granules of
kaolin clay, attapulgite clay, bentonite, terra abla,
pyrophyllite, talc, diatomaceous earth, calcite, walnut
powder, urea, ammonium sulfate, synthetic hydrated silicon
dio~ide, e~. As the liquid carrier or diluent, there may
be employed aromatic hydrocarbons (e.g. xylene, methyl-
naphthalene), alcohols (e.g. isopropanol, ethylene glycol,
celosolve), ketones (e.g. zcetone, cyclohexanone, iso-
phorone), plant oils (e.g. soybean oil, cotton seed oil),
dimethylsulfoxide, acetonitriler water, etc.
A surface active agent used for emulsification,
~1~363~
- 29 -
dispersion or spreading may be any of the non-ionic, .
anionic, cationic and amphoteric ~ype of agents. Examples
of the surface active agent include alkylsulfates, alkylaryl
sulfonates, dialkylsuccinates, polyoxyethylene alkylaryl
phosphates, polyoxvethylene alkyl ethers, polyoxyethylene
alkylaryl ethers, polyoxyethylene-polyoxypropylene blocked
polymers, sorbitan fatty acid esters, polyoxyethylene
sorbitan fatty acid esters, polyoxyethylene resin acid
esters, abietic acid, dinaphthylmethanedisulfonates,
paraffin and the like. If necessary, ligninsulfonates,
alginates, polyvinyl alcohol, gum arabic, CMC (carboxy-
methylcellulose), PAP (isopropyl acid phosphate~ or the like
may be used as an auxiliary agent.
Practical embodiments of the hexbicidal composi-
tion according to the invention are illustratively shown in
the following examples wherein part(s) and % are by weight.
The co~pound number of the active ingredient corresponds to
the one in Table 1.
Formulation Example 1
Eighty parts of Com.pound No. 1, 12, 26, 35 or 47,
5 parts of polyoxyethylene alkylaryl ether and 15 parts of
synthetic hydrated silicon dioxide are well mixed while
being powdered to obtain a wettable powder.
Formulat_on Example 2
Ten parts of Compound No. 2, 8, 14, 22, 32 or 45,
7 parts of pol~oxyethylene alkylaryl ether, 3 parts of
alkylarylsulfonate and 80 parts of cyclohexanone are well
~632~
- 30 -
mixed while being pow~ered to obtain an emulsifiable
concentrate.
Formul~tion Example 3
One part of Compound No. 1, 12, 23, 26, 35 or 44,
1 part of syn~hetic hydrated silicon dioxide, 5 parts of
ligninsul~onate and 93 parts of kaolin clay are well mixed
while being powdered. The mixture is then kneaded with
water, granulated and dried to obtain a granule.
Formulation Example 4
Three parts of Compound No. 1, 30, 31, 44 or 63,
0.5 part of isopropyl acid phospha~e, 66.5 parts of kaolin
clay and 30 parts of talc are well mixed while being
powdered to obtain a dust.
Formulation ExamPle 5
Twenty parts of Compound NOr 2, 13, 17, 2S, 33 or
47 i5 mixed with 50 parts of an aqueous solution containing
3 ~ of polyoxyethylene sorbitan monooleate and pulverized
until the particle size of the active ingredien~ ~e~comes
less than 3 microns. Twenty parts of an aqueous solution
containing 3 % of sodium alginate as a dispersing agent are
incorporated therein to obtain a suspension.
Formulation Example 6
Fifty parts of Compound No. 67 or 84, 3 parts of
calcium ligninsulfonate, 2 p~rts of sodium laurylsulfate
and 45 parts of synthetic hydrated silicon dioxide are well
mixed while being powdered to obtain a wettable powder.
Formulation Example 7
86320
Ten parts of Compound No. 68 or 81, ]4 parts of
polyoxyethylene stvrylphenyl ether, 6 parts of calcium
dodecylbenzenesulfonate, 30 parts of xylene and 40 parts of
cyclohexanone are well mixed while being powdered to obtain
an emulsifiable concentrate.
Formulation Example 8
~wo part of Compound No. 75 or 85, 1 part of
synthetic hydrated silicon dioxide, 2 parts of calcium
ligninsulfonate, 30 parts of bentonite and 65 parts of
kaolin clay are well mixed while being powdered. The
mixture is then kneaded with water, granulated and dried to
obtain a granule.
Formulation Example 9
Twenty-five parts of Compound No. 71 or 84, 3
parts of polyoxyethylene sorbitan monooleate, 3 parts of
carboxymethyl cellulose and 69 parts of water are well mixed
and pulverized until the particle size of the active
ingredient becomes less than 5 microns to obtain a granule.
These compositions comprising the tetrahydro-
phthalimides (I) may be applied as such, or after diluted
with water, to the weeds in suitable application modes such
as spraying, perfusion, etc. For instance, they may be
spread over, perfused into or admixed with soil. Further,
for instance, they may be applied for foliar treatment. If
necessary, they may be used together with other herbicides
to improve their activity as herbicides, and in some cases,
a synergistic effect can be expected. They may be also
~18~320
- 32 -
( applied in comhination with insecticides, acaricides,.
nematocides, fungicides, plant growth regulators,
fertiLizers, soil controlling agent, etc.
A dosage rate of the tetrahydrophthalimide (I) as
S the active ingredient may be generally from 0.01 to 100
grams, preferably from 0.1 to 50 grams, per are. In the
practical usage of the tetrahydrophthalimide ~I) as emulsi-
fiable concentrates, wettable powders or suspensions, it may
be diluted with 1 to 10 liters of water (optionally includ-
ing an auxiliary agent such as a spreading agent) per are.
When formulated into granules or dust, it may be used as
such without dilution.
The application of the tetrahydrophthalimides (I)
as herbicides will be illustratively shown in the followng
Examples wherein the phytotoxicity to cultivated plants and
the herbicidal activity on weeds were evaluated as follows:
the aerial parts of the test plants were cut off and weighed
(fresh wei~ht3; the percentage of the fresh weight of the
treated plant to that of the untreated plant was calculated
with the latter fresh weight taken as 100; and the phyto-
to~icity and the herbicidal activity were evaluated by the
standard given in the table below.
' 1~86320
Rating Fresh weight
value (percentage to untreated plot) (%)
_ ~ Herbicidal activity ¦ Phytotoxicity
O 91- I 91-
1 71 - 90 71 - gO
2 41 - 70 51 - 70
3 11 - 40 31 - SO
4 1 - 10 11 - 30
_ _ _ O - 10
The following compounds were used in the Examples
for comparison:
1~863ZO
- 34 -
Compound
o.Structuxe Remarks
(a) F 1 4;032,326
Cl ~ ~
!
o
(b) O U;S pa ent
Cl ~ N ~
~c) O EP 00~9$08A
Il
C1 ~ N
(n)H7C3-S-C-CHo
O C3H~ (n )
(d) Cl Commerc ally
Cl ~ OCH COONa herbicide
~ 2 known as
Cl/ . "2,4,5-T"
(Na salt)
O Commercially
(e) 11 available
N-CH(CH )2 herbicide
I 11 1 3 known as
N'SO2 "Bentazone"
¦ (Na salt)
Na
(f) Cl Commercially
I available
N~N herbicide
I 1I known as
(cH3)2Hc~N~N~NHc2Hs "Atrazine"
1 ~8~320
- 35 -
( Compound
1`70. Structure Remarks
(g) O Commercially
¦l available
R N-N'~_C(CH )3 herbicide
2 j ll 3 known as
~ N,N llr~etribuzin~
~3CS
(h)Cl COONa Commercially
, ~ available
F3C ~ ~O ~ \~-NO2 herbicide
known as
"Acifluorren-
sodium"
Test Exam~le 1
. _
Trays (33 x 23 cm2) were filled with upland field
soil, and the seeds of sovbean, tall morningglory, velvet~
leaf, black nightshade, cocklebur and hemp sesbania were
sowed therein and grown for 18 days in a grePnhouse.
designed amount of the test compound formulated into an
emulsifiable concentrate and diluted with water was sprayed
to the foliage of the test plants o~er the top by means,o a
small hand sprayer at a spray volume of 10 liters per are.
At the time of application, the test plants were generally
at the 2 to 4 leaf stage and had a height of 2 to 1~ cm.
Twenty days thereafter, herbicidal activity and phvto-
toxicitv were ex~mined. The results are ~hown in Table 2.
.~
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-- 37 --
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-- 40 -
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- 42 - ~186320
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- 43 ~ 3632(~
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~ ~86320
'rest Exam~el 2
~ agner's pots tl/SOOO are) were filled with field
soil, and the seeds of tall morning~lory, velvetleaf,
redroo~ pigweed, soybean and corn were sowed therein and
covered with soil in 1 cm depth. A designed amount of the
test compound formuLated into an emulsifiable concentrate
and diluted with water was sprayed to the soil surface at a
spray volume of 10 liters per are. The test plants were
grown outdoors for 3 weeks, and herbicidal activity and
phytotoxicity were examined. The results are shown in Table
3.
`-` 1186320
- 45 -
; Table 3
. _
Com- DosageHerbiciclal activity Phvto-
pound (weight of toxicity
No. active in- _ l
gredient, Tall ~Telvet- Redroot Soy- Corn
g/are) glorv leaf pigweed bean
_ .
1 20 5 5 5 0 0
0 0
2 150 5 5 5 oo oo
13 10 55 55 5 oo l oo
14 10 5 5 5 ~ 0
0 0
22 150 55 55 S 0 0
24 15 S 5 5 oo 0
26 10 5 5 5 0 0
0 0
29 10 5 55 5 oo oo
0 0
31 10 s5 5 55 0 0
32 150 5 5 5 0 oo
34 15 5 5 55 0 oo
0 0
~4 20 5 5 5 0 0
S 0 0
2~ 5 ' 5 5 0 0
S 0 0
47 15 55 5 5 0 0
48 20 5 5 5 0 0
~ 5 S 0 0
49 15 5 55 5 0 0
51 150 5 5 5 0 0
52 10 5 5 5 0 i 0
0 1 0
i3~0
- 46 -
(Continued)
. . . . .
Com- Dosage l~erbicidal activity i Phyto-
pound (weight of toxicity
No.active in- _ ~ - !
qredient, Tall Velvet- ¦Redroot Soy- Corn
g/are) lorn n~- leaf! pi~.~eed bean ',
57L5 5 5 5 0 i 0
6315 5 5 5 o I o!
6410 5 5 5 0 ~ 0
Test Example 3
Plastic pots (diameter, 10 cm; height, 10 cm) were
filled with upland field soil, and the seeds of soybean,
cotton, tall morningglory and velvetleaf were sowed therein
and covered with soil. A designed amount of the test
compound formulated into an emulsifiable concentrate and
diluted with water was sprayed to the soil at a spray volume
of 10 liters per are and then the soil was well mixed to the
depth of 4 cm. The test plants were further grown for 20
days in a greenhouse, and herbicidal activity and phyto-
toxicity were examined. The results are shown in Table 4.
~1~632~
- ~7 -
Tahle 4
Com- IDosageHerbicidal activity j Phyto- !
pound (weight ofj toxicity
No. active in- . I
gredient, Tall morning- Velvet- ! ~oY- !Cotton
_ gtare) glory : leaf , bean I
67 20 5 , 5 j 0 2
6~ ~0 5 li 5 1 0
69 25 5 ~ 5 jo2
1 5 0 0
71 20 5 i. 5 0 2
72 20 5 5 0 0
73 20 5 5 0 0
74 20 5 5 0 0
0 2
76 20 5 ~ 5 0 0
77 20 5 5 0 0
78 20 5 5 0
89 20 5 5 0 2
91 20 S 5 0
92 20 5 5 0 0
93 20 5 5 0
Test Example 4
Plastic pots (diameter, 8 cm; height, 12 cm)
filled with paddy field soil, and the seeds of barnyardgrass
and broad-leaved weeds (e.g. false pimpernel, toothcup,
waterwort) were sowed therein to a depth of 1 to 2 cm. The
pots were placed under a flooded condition, and the tubers
of arrowhead and the rice seedlings of the 2-leaf stage were
transplanted therein at a depth of 1 to 2 cm and grown for 6
days in a qreenhouse. A designed amount of the test
compound formulated into an emulsifiable concentrate and
diluted with water was perfused into the pots at a perfusion
~8~3~0
~,~
volume o 5 ml per pot. The test plants were ~urther arown
for 20 davs in the greenhouse, an~ phytotoxicity and herh,i-
cidal activity were e~amined. The results are shown in
Table 5.
S Tah]e 5
Com~ Dosage l~er~icidal activity ! Phy~o-
pound (weight of I toxicitv
No. active in-
gredient, Barnyard- Broad- Arrow- P~ice
g/are) ¦ glass leevded head plant
___ _ _ _
26 5 4 5 9
44 5 3 5 S
j 48 55 3 5 4
67 10 5 5 4
68 10 4 5 5 0
! 7l 10 5 55 55
! 1 89 10 ~ 5 5 0
gl 10 5 S S
93 10 4 _ 5 4 0
Test Example S
The seeds of soybean, cocklebur, tall morning-
glory, velvetleaf, jimsor. weed, redroot pigweed, sunflower,
common ragweed and common lambsquarters were sowed in the
field as previously laid up in ridges, each ridge plotted in
3 m . When soybean, cocklebur and other plants were grown
at 1-2 compound leaf stage, 6-leaf sta~e and 4-9 leaf stage,
respectively, a designed amount o the ~est compound
formulated into an emulsifiable concentrate and diluted with
water (including a spreading agent) was sprayed to the
foliage of the test plants by means of a small hand spraver
at a spray volume of 5 liters per are with three replica-
~18~i3;~0
- 49 -
tions. Thirty days thereafter, herbicidal activity and
phytotoxicity w~re examined. The results are shown in Table
6.
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- 51 -
Test Example 6
-
The seeds of corn, cocklebur, tall morning~lory,
velvetleaf, jimson weed and redroot pigweed were sowed in
the field as previously laid up in ridges, each ridge being
plotted in 3 m2. When corn, cocklebur and other plants were
grown at 6-7 leaf sta~e, 4-leaf stage and 3-6 leaf stzge,
respectively, a designed amount of the test compound
formulated into an emulsifiable concentrate and diluted with
water (including a spreading agent) was sprayed to the
foliage of the test plants by means of a small hand sprayer
at a spray volume of 5 liters per are with three repli-
cations. Thirty days thereafter, herbicidal activity and
phytotoxicity were e~amined. The results are shown in
Table 7.
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Test ~xample 7
Seeds of soybear., tall mornin~lory, velvetleaf,
common lamhsquarters, redroot pigweecl, black n.i~htshade,
common ra~weed and common purslane were sowed in the field
as previously laid up in ridges, each ridge being plotted in
3 m2. A designed amount of the test compound Cormulated
into an emulsifiable concentr~te and diluted with water
(including a spreading a~ent~ was spraved to the soil
.surface by means of a small hand sprayer at a spray volume
of 5 liters per are with three replications. Thirty days
thereafter, herbicidal activity and phytotoxicity were
exam.ined. The results are shown in Table 8.
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