USRE32550E - Halophenoxy benzamide herbicides - Google Patents
Halophenoxy benzamide herbicides Download PDFInfo
- Publication number
- USRE32550E USRE32550E US06/075,367 US7536779A USRE32550E US RE32550 E USRE32550 E US RE32550E US 7536779 A US7536779 A US 7536779A US RE32550 E USRE32550 E US RE32550E
- Authority
- US
- United States
- Prior art keywords
- nitro
- benzamide
- compound
- trichlorophenoxy
- benzoate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
- C07C205/57—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C205/59—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton the carbon skeleton being further substituted by singly-bound oxygen atoms
Definitions
- This invention is concerned with certain phenoxybenzoic acid compounds and their use as herbicides.
- This invention provides herbicidal compound having the formula: ##STR1## wherein X is halogen, n is 1 to 5, and R is amido, alkylamido (C 1 --C 6 ) preferably C 1 --C 4 , or dialkylamido (C 1 --C 6 ) preferably C 1 --C 4 .
- the compounds of this invention are readily prepared by the Ullmann ether synthesis reaction between the alkali metal (Na, K) salt of a halophenol and a 5-halo (Cl, Br)-2-nitrobenzoic acid or an ester, amide, or salt thereof.
- the 5-halo-2-nitrobenzoic acid is readily prepared by nitrating a m-halotoluene, followed by oxidation of the methyl group by well-known procedures.
- Non-limiting examples of the compounds of this invention are:
- Example 1 The ester of Example 1 was hydrolyzed to the corresponding acid and using known procedures for the preparation of amides, twelve other compounds within the scope of this invention were prepared. These compounds are:
- the compounds of the invention can be applied in various ways to achieve herbicidal action. They can be applied, per se, as solids or in vaporized form, but are preferably applied as the toxic components in pesticidal compositions of the compound and a carrier.
- the compositions can be applied, as dusts; as liquid sprays, or as gas-propelled sprays and can contain, in addition to a carrier, additives such as emulsifying agents, binding agents, gases compressed to the liquid state, odorants, stabilizers, and the like.
- additives such as emulsifying agents, binding agents, gases compressed to the liquid state, odorants, stabilizers, and the like.
- a wide variety of liquid and solid carriers can be used.
- Non-limiting examples of solid carriers include talc, bentonite, diatomaceous earth, pyrophyllite, fullers earth, gypsum, flours derived from cotton seeds and nut shells, and various natural and synthetic clays having a pH not exceeding about 9.5.
- Non-limiting examples of liquid carriers include water; organic solvents, such as alcohols, ketones, amides and esters; mineral oils, such as kerosene, light oils, and medium oils and vegetable oils, such as cottonseed oil.
- herbicidal application is measured in terms of pounds of herbicide applied per acre.
- the compounds of this invention are effective herbicides when applied in herbicidal amounts, i.e., at rates between about 0.2 pounds and about 10 pounds per acre.
- All crop and weed species are planted individually in 3" plastic pots containing potting soil. Four seeds of each of corn, cotton, and snapbeans are seeded to a depth equal to the diameter of the seed. All other species are surface seeded and sprinkled with screened soil in an amount sufficient to cover the seeds. Immediately after planting, all pots are watered by sub-irrigation in greenhouse trays. Pots for the pre-emergence phase are seeded one day before treatment.
- Planting dates for the post-emergence phase are varied so that all the seedlings will reach the desired stage of development simultaneously.
- the proper stage of seedling development for treatment in the post-emergence phase is as follows:
- Pigweed & Turnips 1 or 2 true leaves visible above cotyledons.
- Cotton first true leaf 1 inch in length; expanded cotyledons.
- Beans primary leaves expanded, growing point at primary leaf node.
- Spray applications are made in a hood containing a movable belt and fixed spray nozzle.
- pre-emergence phase For passage through the spray hood, one pot of each species (pre-emergence phase) is placed on the forward half of a wooden flat and one pot of established plants (post-emergence phase) is placed on the rear half of the flat.
- Treatments are moved to the greenhouse after spraying. Watering during the observation period is applied only by sub-irrigation.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
2-Nitro-5-(halophenoxy)benzoic acids and esters, salts, amides, and acyl halides thereof comprise a class of compounds that are highly effective pre- and post-emergence herbicides.
Description
This application is a continuation-in-part of copending application Ser. No. 194,481, filed Nov. 1, 1971, now abandoned, which is a division of application Ser. No. 819,412, filed Apr. 25, 1969, now U.S. Pat. No. 3,652,645.
This invention is concerned with certain phenoxybenzoic acid compounds and their use as herbicides.
It has been proposed to use as herbicides 2-methoxybenzoic acids (U.S. 3,013,054) and 4-phenoxybenzoic acids (French 1,502,538). It is the discovery of this invention, however, that benzoic acids having a phenoxy substituent in the 5-position are very effective herbicides.
This invention provides herbicidal compound having the formula: ##STR1## wherein X is halogen, n is 1 to 5, and R is amido, alkylamido (C1 --C6) preferably C1 --C4, or dialkylamido (C1 --C6) preferably C1 --C4.
The compounds of this invention are readily prepared by the Ullmann ether synthesis reaction between the alkali metal (Na, K) salt of a halophenol and a 5-halo (Cl, Br)-2-nitrobenzoic acid or an ester, amide, or salt thereof. The 5-halo-2-nitrobenzoic acid is readily prepared by nitrating a m-halotoluene, followed by oxidation of the methyl group by well-known procedures.
Non-limiting examples of the compounds of this invention are:
2-nitro-5-(2',4',6'-trichlorophenoxy)benzoic acid;
methyl 2-nitro-5-(2',4',6'-trichlorophenoxy)benzoate;
propyl 2-nitro-5-(2',4',6'-tribromophenoxy)benzoate;
phenyl 2-nitro-5-(2',4',5'-trifluorophenoxy)benzoate;
2-nitro-5-(2',4',6'-triiodophenoxy)benzoic acid;
2-nitro-5-(2',4',6'-trichlorophenoxy)benzoyl chloride;
2-nitro-5-(2',4',6'-trichlorophenoxy)benzamide;
N-ethyl 2-nitro-5-(2',4',6'-trichlorophenoxy)benzamide;
N-isopropyl 2-nitro-5-(2',4',6'-trichlorphenoxy)benzamide;
N,N-dimethyl 2-nitro-5-(2',4',6'-trichlorophenoxy)benzamide;
sodium (or potassium) 2-nitro-5-(2',4',6'-trichlorophenoxy)benzoate;
ethylammonium 2-nitro-5-(2',4',6'-trichlorophenoxy)benzoate;
ethanolammonium 2-nitro-5-(2',4',6'-trichlorophenoxy)benzoate;
sodium 2-nitro-5-(2',4',6'-trichlorophenoxy)benzoate;
methyl 2-nitro-5-(2',4',5'-trichlorophenoxy)benzoate;
methyl 2-nitro-5-(2',4'-dichlorophenoxy)benzoate; and
methyl 2-nitro-5-(2',3',4',5',6'-pentachlorophenoxy)benzoate.
The following example illustrates the preparation of a typical compound of this invention and demonstrates a method for product recovery.
A stirred solution of methyl 5-chloro-2-nitro-benzoate (17.0 g., 0.079 mole) and the potassium salt of 2,4,6-trichlorophenol (18.6 g., 0.079 mole) in dimethyl sulfoxide (100 ml.) was heated at 90° for 17 hours. The cooled reaction mixture was diluted with water (500 ml.) and then extracted with ether (3×100 ml.). The combined ether fractions were washed with 10% sodium hydroxide solution (2×30 ml.) and then with a saturated aqueous sodium chloride solution. The ether solution was dried (Na2 SO4) and the solvent evaporated to give a dark oil. Two crystallizations (petroleum ether) gave 1.91 g. of a pale yellow solid, m.p. 101°-103°.
I.R. (Nujol): c═o 1723, c═o 1240, and 1260 cm.-1
NMR (CDCl3): methyl 3.91 p.p.m. (3H), quartet
6.96 p.p.m. (1H, J=2.5 and 8 c.p.s.), doublet
7.05 p.p.m. (1H, J=2.5 c.p.s.), broad singlet
7.05 p.p.m. (2H), and doublet 8.01 p.p.m. (1H, J=8 c.p.s.).
The ester of Example 1 was hydrolyzed to the corresponding acid and using known procedures for the preparation of amides, twelve other compounds within the scope of this invention were prepared. These compounds are:
(2) 2-nitro-5-(2',4'-dichlorophenoxy)benzamide.
(3) N-methyl 2-nitro-5-(2',4'-dichlorophenoxy)benzamide.
(4) N,N-dimethyl 2-nitro-5-(2',4'-dichlorophenoxy)benzamide.
(5) N-propyl 2-nitro-5-(2',4'-dichlorophenoxy)benzamide.
(6) 2-nitro-5-(2',4',6'-trichlorophenoxy)benzamide.
(7) N-methyl 2-nitro-5-(2',4',6'-trichlorphenoxy)benzamide.
(8) N,N-dimethyl 2-nitro-5-(2',4',6'-trichlorophenoxy)benzamide.
(9) N-propyl 2-nitro-5-(2',4',6'-trichlorphenoxy)benzamide.
(10) N-isopropyl 2-nitro-5-(2',4',6'-trichlorphenoxy)benzamide.
(11) N,N-diethyl 2-nitro-5-(2',4',6'-trichlorophenoxy)benzamide.
(12) N,N-dimethyl 2-nitro-5-(2',4'-dichloro-6'-fluorophenoxy)benzamide.
(13) N-secbutyl 2-nitro-5-(2',4'-dichloro-6'-fluorophenoxy)benzamide.
For comparison, the following position isomer of Example 4 was prepared, the acid of which is disclosed in U.S. 3,475,427.
(14) N,N-dimethyl-2-nitro-3-(2',4'-dichlorophenoxy)benzamide.
The compounds of the invention can be applied in various ways to achieve herbicidal action. They can be applied, per se, as solids or in vaporized form, but are preferably applied as the toxic components in pesticidal compositions of the compound and a carrier. The compositions can be applied, as dusts; as liquid sprays, or as gas-propelled sprays and can contain, in addition to a carrier, additives such as emulsifying agents, binding agents, gases compressed to the liquid state, odorants, stabilizers, and the like. A wide variety of liquid and solid carriers can be used. Non-limiting examples of solid carriers include talc, bentonite, diatomaceous earth, pyrophyllite, fullers earth, gypsum, flours derived from cotton seeds and nut shells, and various natural and synthetic clays having a pH not exceeding about 9.5. Non-limiting examples of liquid carriers, include water; organic solvents, such as alcohols, ketones, amides and esters; mineral oils, such as kerosene, light oils, and medium oils and vegetable oils, such as cottonseed oil.
In practice, herbicidal application is measured in terms of pounds of herbicide applied per acre. The compounds of this invention are effective herbicides when applied in herbicidal amounts, i.e., at rates between about 0.2 pounds and about 10 pounds per acre.
Crabgrass Digitaria sanguinalis
Yellow Foxtail grass Seteria glauca
Johnson grass Sorgum Halepense
Barnyard grass Echinochloa crus-galli
Amaranth pigweed Amaranthus retroflexus
Turnip Brassica sp.
Cotton Gossypium hirsutum var. DPL smooth leaf
Corn Zea Mays var. Golden Bantam
Bean Phaseolus vulgaris var. Black Valentine
All crop and weed species are planted individually in 3" plastic pots containing potting soil. Four seeds of each of corn, cotton, and snapbeans are seeded to a depth equal to the diameter of the seed. All other species are surface seeded and sprinkled with screened soil in an amount sufficient to cover the seeds. Immediately after planting, all pots are watered by sub-irrigation in greenhouse trays. Pots for the pre-emergence phase are seeded one day before treatment.
Planting dates for the post-emergence phase are varied so that all the seedlings will reach the desired stage of development simultaneously. The proper stage of seedling development for treatment in the post-emergence phase is as follows:
Grasses: 2 inches in height
Pigweed & Turnips: 1 or 2 true leaves visible above cotyledons.
Cotton: first true leaf 1 inch in length; expanded cotyledons.
Corn: 3 inches-4 inches in height.
Beans: primary leaves expanded, growing point at primary leaf node.
Spray applications are made in a hood containing a movable belt and fixed spray nozzle. For passage through the spray hood, one pot of each species (pre-emergence phase) is placed on the forward half of a wooden flat and one pot of established plants (post-emergence phase) is placed on the rear half of the flat. Treatments are moved to the greenhouse after spraying. Watering during the observation period is applied only by sub-irrigation.
Compounds are screened initially at a rate of application equivalent to four to eight pounds per acre. Two weeks after treatment the pre- and post-emergence percent injury is visually rated. Subsequent testing was carried out at 2.1 and 0.5 pounds per acre.
Herbicidal testing of the compounds of Examples 2 through 13 and of the comparative compound showed the results set forth in Table I. The plants are tablulated using the following abbreviations:
TABLE I
__________________________________________________________________________
PRE-POST-EMERGENCE
Compound
Dosage,
Example No.
lbs./acre
CG JG BG PW TP CT CN BN
__________________________________________________________________________
2 4 80/70
40/40
40/30
100/100
20/70
100/40
0/20
100/100
3 8 80/90
60/80
70/40
--/--
90/100
30/80
0/30
0/100
4 8 90/90
40/30
20/30
--/--
90/100
30/50
40/0
80/100
4 4 30/40
20/20
0/20
--/--
20/80
80/50
0/20
0/90
5 8 80/90
30/40
20/40
--/--
0/100
80/50
40/0
0/100
6 8 0/50
20/30
20/30
0/100
70/100
70/70
0/30
50/100
6 4 --/--
--/--
--/--
0/100
0/80
--/--
--/--
--/--
6 2 --/--
--/--
--/--
0/80
0/90
--/--
--/--
--/--
7 8 80/70
0/20
50/40
--/--
20/100
100/20
0/20
0/100
7 4 --/--
--/--
--/--
--/--
--/70
--/--
--/--
--/--
8 8 70/60
20/30
40/30
--/100
80/100
50/70
0/30
50/100
9 8 30/60
0/20
0/20
--/--
0/90
30/30
0/0 0/100
9 4 --/--
--/--
--/--
--/--
0/30
--/--
--/--
--/--
10 8 40/50
0/20
20/30
--/--
70/80
50/0 0/70
0/90
11 8 30/40
0/--
--/--
--/--
20/100
--/30
--/--
0/50
12 8 100/0
20/--
60/--
--/--
100/80
100/50
70/--
--/--
12 4 0/--
0/--
0/--
--/--
100/--
100/--
70/--
--/--
12 2 70/--
40/--
30/--
--/--
60/--
30/20
20/--
--/--
13 8 90/0
0/--
0/--
--/--
100/90
100/100
80/--
--/--
13 4 80/--
0/--
0/--
--/--
90/--
100/--
40/--
--/--
13 2 30/--
0/--
0/--
--/--
80/--
30/--
80/--
--/--
14 8 40/0
0/--
0/--
.sup. 20/.sup.1 --
20/20
0/0 0/--
0/0
__________________________________________________________________________
.sup.1 Bindweed.
Crabgrass CG
Johnson grass JG
Barnyard grass BG
Bean BN
Pigweed PW
Turnip TP
Cotton CT
Corn CN
Although the present invention has been described with preferred embodiments, it is to be understood that modifications and variations may be resorted to, without departing from the spirit and scope of this invention, as those skilled in the art will readily understand. Such modifications and variations are considered to be within the purview and scope of the appended claims.
Claims (4)
1. An herbicidal compound having the formula: ##STR2## wherein X is halogen, n is 1 to 5, and R is amido, alkylamido .[.(C1 --C6).]. .Iadd.(C1 --C3).Iaddend., or dialkylamido .[.(C1 --C6).]. .Iadd.(C2 --C6).Iaddend.wherein each alkyl of the dialkylamido contains 1 to 3 carbon atoms. .[.
2. A compound of claim 1, wherein said compound is N-methyl 2-nitro-5-(2',4'-dichlorophenoxy)benzamide..]. .[.3. A compound of claim 1, wherein said compound is N,N-dimethyl
2-nitro-5-(2',4'-dichlorophenoxy)benzamide..]. 4. A compound of claim 1, wherein said compound is N,N-dimethyl 2-nitro-5-(2',4',6'-trichlorophenoxy)benzamide. .[.5. A compound of claim 1, wherein said compound is N,N-dimethyl 2-nitro-5-(2',4'-dichloro-6'-fluorophenoxy)benzamide..]. .[.6. A compound of claim 1, wherein said compound is N-sec-butyl
2-nitro-5-(2',4'-dichloro-6'-fluorophenoxy)benzamide..]. 7. A compound of claim 1, wherein said compound is 2-nitro-5-(2',4',6'-trichlorophenoxy)benzamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/075,367 USRE32550E (en) | 1969-04-25 | 1979-09-14 | Halophenoxy benzamide herbicides |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US81941269A | 1969-04-25 | 1969-04-25 | |
| US19448171A | 1971-11-01 | 1971-11-01 | |
| US06/075,367 USRE32550E (en) | 1969-04-25 | 1979-09-14 | Halophenoxy benzamide herbicides |
Related Parent Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US19448171A Continuation-In-Part | 1969-04-25 | 1971-11-01 | |
| US00334528A Reissue US3839444A (en) | 1971-11-01 | 1973-02-22 | Halophenoxy benzamide herbicides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE32550E true USRE32550E (en) | 1987-11-24 |
Family
ID=27372671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/075,367 Expired - Lifetime USRE32550E (en) | 1969-04-25 | 1979-09-14 | Halophenoxy benzamide herbicides |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USRE32550E (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3013054A (en) * | 1958-08-04 | 1961-12-12 | Velsicol Chemical Corp | 2-methoxy-3, 6-dichlorobenzoates |
| FR1502538A (en) * | 1965-12-09 | 1967-11-18 | Ciba Geigy | New pesticide agents |
| US3475427A (en) * | 1966-02-03 | 1969-10-28 | Smithkline Corp | Phenoxazines |
| DE2019821A1 (en) * | 1969-04-25 | 1970-11-12 | Mobil Oil Corp | Halophenoxybenzoic acids as herbicides and processes for their use |
-
1979
- 1979-09-14 US US06/075,367 patent/USRE32550E/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3013054A (en) * | 1958-08-04 | 1961-12-12 | Velsicol Chemical Corp | 2-methoxy-3, 6-dichlorobenzoates |
| FR1502538A (en) * | 1965-12-09 | 1967-11-18 | Ciba Geigy | New pesticide agents |
| US3475427A (en) * | 1966-02-03 | 1969-10-28 | Smithkline Corp | Phenoxazines |
| DE2019821A1 (en) * | 1969-04-25 | 1970-11-12 | Mobil Oil Corp | Halophenoxybenzoic acids as herbicides and processes for their use |
Non-Patent Citations (1)
| Title |
|---|
| Deshpande et al, Chemical Abstracts, 53 (1959), column 14,100. * |
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