US3692805A

US3692805A - Aromatic sulfonyl azides

Info

Publication number: US3692805A
Application number: US109681A
Authority: US
Inventors: Kurt H G Pilgram
Original assignee: Shell Oil Co
Current assignee: Shell USA Inc
Priority date: 1971-01-25
Filing date: 1971-01-25
Publication date: 1972-09-19
Anticipated expiration: 1989-09-19
Also published as: GB1369705A

Abstract

Certain novel 4-amino-3,5-dinitrobenzenesulfonyl azides are described, with their preparation and use as herbicides.

Description

United States Patent Pilgram 1 Sept. 19, 1972 [54] AROMATIC SULFONYL AZIDES [56] References Cited [72] Inventor: Kurt H. G. Pilgram, Modesto, UNITED STATES PATENTS Calif. 95350 '1 3,367,949 2/1968 Soper ..260/397.7 [731 Ass1gnee= Cmpany, New YOrk, 3 376127 4/1968 McConnell ..260/249 x NIY. [22] Filed: Jan. 25, 1971 Primary Examiner-John M. Ford [21] Appl.No.: 109,681 Attorney-Frank R. La Fontaine and Marion W.

Western [52] U.S.Cl ......260/349 71/103 51 Int. Cl. ..c07a109l00 [57] ABSTRACT [58] Field of Search ..260/349 Certain novel 4-amino-3,S-dinitrobenzenesulfonyl azides are described; with their preparation and use as herbicides.

6 Claims, No Drawings AROMATIC SULFONYL AZIDES BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a novel class of benzenesulfonyl azides ring substituted with a secondary amino and two nitro groups which exhibit high herbicidal activity. 2. Description of the Prior Art No art is known which anticipates the herbicidal amino-dinitrobenzenesulfonyl azides of this invention. 1

U5. Pat. No. 3,376,127 discloses the use of alkali metal azides, alkali earth metal azides, hydrazoic acid, ammonium and quaternary ammonium azide, double azide salts and carbonyl-azides as aquatic herbicides. Other related art includes US. Pat. No. 3,367,949 which discloses a series of substituted 3,5- dinitrosulfanilamides as herbicides.

SUMMARY OF THE INVENTION DESCRIPTION OF THE PREFERRED EMBODIMENTS The novel compounds of this invention can be represented by the general formula I:

wherein R and R each represents alkyl of up to four carbon atoms, alkenyl of up to four carbon atoms or cycloalkyl of up to six carbon atoms. Any of these alkyl groups can be of either branched-chain or straight chain configuration. I

Exemplary species of the class of the invention include:

4-(dimethylamino)-3,S-dinitrobenzenesulfonyl azide 4-(dibutylamino)-3,5-dinitrobenzenesulfonyl azide 4-(diisopropylamino)-3,S-dinitrobenzeriesulfonyl 4-( lfi jlmethylaminoy3,5-dinitrobenzenesulfonyl 4-( stfl islpropylamino )-3 ,S-dinitrobenzenesulfonyl 4-( clig clopropylamino)-3,S-dinitrobenzenesulfonyl 4-f3i25clopentylamino )-3 ,5-dinitrobenzenesulfonyl 4-( i ;clohexylamino)-3,S-dinitrobenzenesulfonyl azide 4-(cyclopentylcyclohexylamino)-3,5-

dinitrobenzenesulfonyl azide 4-( ethylcyclopropylamino )-3,5-dinitro benzenesulfonyl azide 4-(diallylamine)-3,5-dinitrobenzenesulfonyl azide 4-(dicrotylamino)-3,5-dinitrobenzenesulfonyl azide 4-(allylpropylamino)-3,5-dinitrobenzenesulfonyl azide Preferred because of their especially effective herbicidal properties are the sulfonyl azide compounds in the subclass wherein R is alkyl of up to four carbon atoms or cycloalkyl of up to four carbon atoms and R is alkyl of up to four carbon atoms or alkenyl of up to three carbon atoms.

Examples of such preferred herbicides are:

4-(dipropylamino)-3,S-dinitrobenzenesulfonyl azide 4-( diethylamino)3,5-dinitrobenzenesulfonyl azide 4-(ethylpropylamino)-3,5-dinitrobenzenesulfonyl azide 4(butylethylamino)-3,S-dinitrobenzenesulfony azide 4-(allylcyclopropylamino)-3,S-dinitrobenzenesulfonyl azide 4(butylpropylamino)-3,5-dinitrobenzenesulfonyl azide 4-(allylcyclobutylamino)-3,S-dinitrobenzenesulfonyl azide 4-(dimethylamino)-3,S-dinitrobenzenesulfonyl azide 4-(methylpropyl)-3,5-dinitrobenzenesulfonyl azide The compounds of the invention are solid at ambient temperature. They may be suitably formulated for use as herbicides, as wettable powers, dusts, granules, solutions, emulsifiable concentrates, emulsions and pastes.

Wettable powers are usually compounded to contain 25, 50, or up to percent of toxicant and usually contain, in addition to solid carrier, 3-10 percent of a dispersing agent and, where necessary, 0-10 percent of stabilizer(s) and/or other additives such as penetrants or stickers. Dusts are usually formulated as a dust concentrate having a similar composition to that of a wettable power but without a dispersant, and are diluted in the field with further solid carrier to give a composition usually containing fz-IO percent of toxicant. Granules are usually prepared to have a size between 10 and BS mesh, and may be manufactured by agglomeration or impregnation techniques. Generally, granules will contain ya-25 percent of toxicant plus additives such as stabilizers, slow-release modifiers, binding agents, etc. Emulsifiable concentrates usually contain, in addition to the solvent, and, when necessary co-solvent, lO-SO percent s/v toxicant, 2-20 percent w/v emulsifiers and 0-20 percent of appropriate additives such as stabilizers, penetrants and corrosion inhibitors. Pastes are compounded so as to obtain a stable flowable product and usually contain lO-60 percent toxicant, 220 percent of appropriate additives and, as carrier, water or an organic liquid in which the toxicant is substantially insoluble. Except where indicated otherwise, all precentages given in this paragraph are percentages by weight.

The herbicidal compounds of this invention may be prepared by the reaction of a benzenesulfonyl chloride of the formula 11:

chloride being introduced in a solvent which is miscible with water, e.g., lower alkanols or dioxane. The reaction will proceed satisfactorily at temperatures ranging from about 25 to 100 C. Dependent on the reaction temperature utilized, the reaction is ordinarily complete in l to hours.

The substituted benzenesulfonyl chlorides described by formula ll are known compounds and can be prepared from p-chlorobenzene-sulfonic acid using a four-step synthesis scheme. In the initial reaction step the p-chloroben zenesulfonic acid is nitrated in the 3 and 5 position on the ring with a mixture of 90 percent nitric acid in 65 percent oleum. The dinitro intermediate is then converted to an alkali metal salt, e.g., sodium or potassium, by neutralizing with the corresponding hydroxide and the salt compound is reacted with a secondary amine of the formula RF NH wherein R and R are as defined above to yield the alkali metal salt of a 4-(N,N-disubstituted amino)-3,5- dinitrobenzenesulfonic acid. This alkali metal salt is then converted to the corresponding sulfonyl chloride by treatment with phosphorus pentachloride in a solution of phosphoryl chloride.

The compounds of the invention, processes for their preparation and their herbicidal activity, are, illustrated by the following examples, in which parts by weight (w) and parts by volume (v) bear the same relation as the kilogram to the liter and all temperatures are in degrees centigrade.

EXAMPLE I 4-( Dipropylamino )-3,5dinitrobenzensulfonyl azide To a solution of 3,5-d initro-4- (dipropylamino)benzenesulfonyl chloride (9.15 w) in ethanol (200 .v) was added at room temperature a solution of sodium azide (6.5 w) in water v) in one portion. After 1 hour, water (300 v) was added and the yellow crystalline solid which precipitated was filtered and dried to give 4-dipropylamino-3,S-dinitrobenzenesulfonyl azide (5.5 w) melting at 70-75. The structure was confirmed by infrared spectra] and elemental analyses.

Analysis (Percent by Weight) Calculated: C 38.7 H 4.7 N 22.6 Found: C 28.5 H 4.7 N- 22.7

, EXAMPLE [I 4-(Butylethylamino)-3,5dinitrobenzenesulfonyl azide N 02 4-(Butylethylamino)-3,5dinitrobenzenesulfonyl chloride (18.3 w) in dioxane (50 v) was added dropwise with stirring to a solution of sodium azide (3.9 w) in water (50 v). The mixture was heated to for 3 hours, poured over ice water and extracted with 3 X v portions of methylene chloride. The combined methylene extracts were dried over anhydrous magnesium sulfate, filtered and concentrated to 18 g of red oil. This oil was crystallized from ether to yield a yellow crystalline solid, 4-(butylethylamino)-3,5- dinitrobenzenesulfonyl azide (16 w) melting at 75-78 The structure was confirmed by infrared spectrum, nuclear magnetic resonance and elemental analyses.

Analysis (Percent by Weight) Calculated: C 38.7; H 4.7; N 22.6 Found: C- 39.0; H 4.6; N- 23.0

EXAMPLE III 4-( Diethylamino )-3 ,S-dinitrobenzenesulfonyl N02 Na- --N (021-15) 2 0 l ,7. ..N Qz A solution of 4-(diethylamino)-3 ,5-

dinitrobenzenesulfonyl chloride (18.4 w) in dioxane (100 v) was added rapidly with stirring to a solution of sodium azide (4 w) in water (100 v). This mixture was heated to for 3 hours, poured over ice water and filtered. Recrystallization from ether afforded an orange crystalline solid 4-( diethylamino )-3 ,5 dinitrobenzenesulfonyl azide (17 w), melting at 9 9l01. The structure 1 was confirmed by infrared spectrum, nuclear magnetic resonance and elemental analyses.

Analysis (Percent by Weight) Calculated: C 34.9; H 3.5; N 24.4 Found: C 34.8; H 3.6; M 25.0

EXAMPLE IV 4-(Allylcyclopropylamino)-3,S-dinitrobenzensulfonyl azide N O CHr-CH=CH;

structure was confirmed by infrared spectrum, nuclear magnetic resonance and elemental analyses.

Analyses (Percent by Weight) Calculated: C 39.2; H 3.3; N -.22.8 Found: C 38.7; H 3.3; N 23.2

EXAMPLE V Pre-emergence herbicidal activity of the typical compounds of the invention was evaluated by planting weed seeds in soil held in large test tubes, the soil having been treated with the test compound at the rate-of l and milligrams of test compound per tube, respec: tively. Seeds of watergrass (Echinochloa crusaglli) and cress (Lepidium sativum) were germinated in treated soil under controlled conditions of temperature and light for 12 to 13 days prior to evaluation of the effectiveness of the treatments. At that time, the germination was noted and the treatments were rated on a 0 '(no effect) to 9 (all dead) scale. The results are sum- TABLE I Pre-em ergence Water- Post-Emergence grass Cress Crabgrass Pigweed Compound I I0 l 10 l 10 1 l0 4-(dipropylamino)-3,5-

dinitrobenzenesultonyl azide 4-( butylethylamino dinitrobenzenesulfonyl azide 7 8 4 7 8 8 8 8 4-(diethylamino)-3,5

dinitrobenzenesulfonyl azide 4-(allylcyclopropyl)- dinitrobenzenesulfonyl azide 8 8 7 7 7 9 4 9 We claim as our invention: 1. A compound of the formula:

wherein R and R each represents alkyl of up to four carbon atoms, alkenyl of up to four carbon atoms or cycloalkyl of up to six carbon atoms.

2. A compound according to claim 1 wherein R is alkyl of up to four carbon atoms or cycloalkyl of up to four carbon atoms and R is alkyl of up to four carbon atoms or alkenyl of up to three carbon atoms.

3. The compound according to claim 2 wherein R and R each is propyl.

4. The compound according to claim 2 wherein R is butyl and R is ethyl.

5. The compound according to claim 2 wherein R and R each is ethyl.

6. The compound according to claim 2 wherein R is cyclopropyl and R is allyl.

Claims

2. A compound according to claim 1 wherein R1 is alkyl of up to four carbon atoms or cycloalkyl of up to four carbon atoms and R2 is alkyl of up to four carbon atoms or alkenyl of up to three carbon atoms.
3. The compound according to claim 2 wherein R1 and R2 each is propyl.
4. The compound according to claim 2 wherein R1 is butyl and R2 is ethyl.
5. The compound according to claim 2 wherein R1 and R2 each is ethyl.
6. The compound according to claim 2 wherein R1 is cyclopropyl and R2 is allyl.