DE2120629A1 - Process for the preparation of 4-chloro-3,5-dinitrobenzenesulfonamide - Google Patents

Description

PAT E N TA N WS LT E

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BANK H. AUFKKUSE-R

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US 33,859
95 / Si

ESSO RESEARCH AND ENGINEERING CONPAUY

Linden, New Jersey, U.S.A.

Process for the production of 4 ~ chlorine - 3,5-di-

nitrobenzenesulfonamide

The present invention relates to a process for the preparation of 4-chloro-3,5-dinitrobenzenesulfonamide.

The present invention also relates to transfer of the 4-chloro ~ 3,5-di: nitrobenzenesulfonate unid with the help of

Il Ll

The amines in N, N -disubstituted ^ s ^ -Dinitrosulfanilamides.

3,5-Dinitro-N, N "-di (n-propyl) -Bulfanilamide is a highly effective one Pre-emergent herbicide. This compound has already been described in U.S. Patent 3,367 94-9. The production this connection according to the method described in this patent specification is very labor-intensive and expensive. The preparation of many analogous compounds according to this process is also extremely difficult «

The present invention therefore relates to a new process for the preparation of a new intermediate product, which the Herste1-

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development of the compounds described in the above patent specification as well as other compounds with pesticidal properties considerably simplified.

Accordingly, it is an object of the present invention to provide a process for the preparation of 4-chloro-3,5-dinitrobenzene- to create sulfonamide.

Another object of the present invention _s an improved process for the preparation of Jsi -Einitro ^ H-l _t? -di ~ (n-propyl) -sulfanilamide and other 3j5-dinitro II \ E -disubstituted sulfanilamides also enable "

Another object of the present invention is to to create a new interconnection in syntlicsen and is useful as a soil fungicide.

According to the present invention, a. manufacturing process created by 4-chloro-3,5 ™ dinitrobeiizolsulionaiiiid.

This process consists in dissolving 4-chloro-3,5-dinitrobenzium-olefinyl chloride in a solvent, the solvent being a ketone with 3 to 8 carbon atoms, a carboxylic acid ester with 2 to 8 carbon atoms, ΙΙ, Ιί-biasthylformaide, dimethyl sulfoxide or is a cyclic itiier with 4 Ms 8 carbon atoms, one cools the mixture to a temperature of -50 to +10 ⁰ G, ammonia either in the gaseous state or as a solution in one of the rhymed solvents, which can also contain water, in a sufficient amount slowly so that the ammonia reacts with a binitrobenzenesulfonyl chloride compound at the rate at which it is added, suitably the total amount of ammonia added at / ei equivalent per equivalent of binitrobenzenesulfonylchloride of this reaction corresponds to this amount and then the excess animonia was separated off

It has been described in the literature that the ice leaching of immoniac gas in a hot Eensol solution you 4-öhlor-3,5- <iiß3 · -

109846/19 55

trobensο1sulfonylChlorid results in two products, which according to the following schematic equation can be given.

O ₀ N

-NO ₂

NH,

SOoCl

SO ₂ NH ₂

This reaction has been described in the Journal of the American Chemical Society, Vol. 77 »page 5652 (1955) by JRE Hoover and AE Day. It should be noted that no 4-chloro-3 _? 5-dinitrobenzenesulfonamide is formed or at least has not been detected. Under the previous conditions, the nuclear chlorine atom between the two nitro groups, which is referred to below as the 4-chlorine atom, was substituted before the chlorine atom of the sulfonyl group is replaced.

Under the conditions according to the invention, the sulfonyl chloride is substituted without attacking the chlorine atom in the 4-position will.

One of the most critical conditions for successful selective amination is the use of a particular solvent. The solvents can be ketones with 3 to 8 carbon atoms, such as acetone, carboxylic acid esters with 2 to 8 carbon atoms, such as acetic acid ethers, aprotic solvents such as Ν, Ν-dimethylformamide, or cyclic ethers with 4 to 8 carbon atoms, such as tetrahydrofuran. Other solvents tested gave a mixture of products.

Another one of the critical factors of the present process is that the mixture to a temperature of -50 to +10 ⁰ C, must be preferably -20 ° to 5 ° C, cooled, before the solution was aminated. It was found that under

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under these conditions the chlorine atom bonded to the sulfonyl group preferably exclusively, not the nuclear chlorine atom _; has been replaced, resulting in the desired connection. Below ~ 50 ° G the reaction does not start and above 10 ° C both chlorine atoms are replaced at sufficiently equal ^{rates that 1} - chloro-3,5-dinitrobenzoisulfonamide is contaminated with increasing amounts of undesirable and difficult to separate 5,5-dinitrosulfonylamide .

The starting product 4-chloro-3,5-dinitrobenzenesulfonyl chloride used in the process according to the invention can, according to Vervon If. Ullmann and E. Kuhn (Justus Liebig ¹ s Annalen der 'Chemie, Vol. 566, page 104 (1909)) or by other methods known to the person skilled in the art.

The 4-chloro-3,5-dinitrobenzenesulfonyl chloride is in one of the Dissolved solvent specified above and then the solution to a temperature between -50 and 10 ° G, preferably -20 Cooled to 5 ° C. Gaseous ammonia or a solution of Ammonia in one or more of the solvents specified above, which may also contain water, is then added to the solution. The rate of addition can depend on on the stirring speed, the size of the reaction vessel and the concentration of ammonia in the reaction participant solution to the reaction added solvent can be varied. A suitable speed can be made visible. That is, if ammonia is added slowly enough, shows the reaction mixture at the point of addition is perishable orange color, which quickly turns into a pale yellow color. On the other hand, if the rate of addition is too large, the reaction mixture shows a red-orange color which does not disappear on standing. The total amount of ammonia added should not exceed two equivalents per equivalent of the sulfonyl chloride compound and not consumed Ammonia should be separated to facilitate product isolation.

The ammonia can be separated either by

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that you can get it under certain pressure conditions, so that the partial pressure of ammonia is lower than that of the surrounding air, allows it to escape from the solution, or the ammonia can after completion of the addition by adding any acid that is sufficiently acidic to convert ammonia to an ammonium ion, are neutralized, after which the ammonium salt can be filtered off. It is understood that the method for Separation of the excess ammonia is not intended to restrict the process according to the invention and is customary and known Procedures can be used at this stage.

The solution containing 4-chloro-3,5-dinitrobenzenesulfonamide can then, if necessary, be dried. The drying can with a conventional drying agent such as magnesium sulfate, sodium sulfate or molecular sieves etc. The solution is then concentrated to constant weight and the sulfonamide is then recovered.

In many cases the product is pure enough to continue to be used, but additional cleaning may be required be carried out in the usual way as follows? A solvent can be the unreacted 4-chloro-3,5-dinitrobenzenesulfonyl chloride dissolves without the product 4 ~ chloro-3,5-dinitrobenzenesulfonamide to be used to dissolve, and such solvents include aromatic hydrocarbons, such as benzene, toluene and the like. Those considered critical in the conversion of the benzenesulfonyl chloride to the benzenesulfonamide specified solvents are excluded, but any other solvent could easily be determined by a person skilled in the art Manner to be used in this extraction stage.

The final product is then 4-chloro ~ 3,5-dinitrobenzenesulfonamide separated by filtration. It has been found that this compound has soil-fungicidal properties.

The fungicidal compositions according to the invention are prepared by mixing the active ingredient specified above in fungicidally effective amounts with a conditioning agent

108846 / .1955

'Such as it is as a weed adjuvant or modifier Used by those skilled in the art * manufactured to formulations for easy and effective application on the floor using common application equipment are suitable. The formulation of the compounds according to the invention can be done in the same way as e.g. in the German patents. ... .... (patent applications P 19 32 699, P 19 26 768 and P 19 36 61J).

Thus, the fungicidal compositions or formulations are made in the form of solids or liquids. Solid compositions are preferably in the form of granules) laten or dust.

The compositions can be compounded to give a homogeneous free-flowing powder by mixing the active compound with finely divided solids, preferably talc ,, natural clays _t pyrophyllite, Dia1; L ^ enerede or flours, such as' walnut shell flour, wheat flour, Eotholzmehl (Sedwood) , SoyabötoLezunehl or Bauiax-Rollameniueiil. Other inert solid conditioning agents or carriers of the type conventionally used in the manufacture of powdered pest control compositions can be employed.

Granules can be co-pounded by absorbing the compound in liquid form on a pre-formed granular diluent. There can be diluents; natural clays such as _t Pjxophyllit, Diatosieenerde, such as walnut scarf enmehl j used as sand and granular flour ,.

In addition, granulates can also be made by _s mixing the active ingredient with a mas of the above bescnriebenen pisiiferförmigen diluent and the mixture is transferred either into pellets or extriicliort "

Liquid egg storage liquid according to the invention would be produced in the usual way by y-arBr-r-sne & sos active ;, wiskstoffs kit

10S846 / 1SSS

a suitable liquid diluent medium. With certain Solvents such as alkylated naphthalene or other aromatic solvents Petroleum solvents, dimethylformamide or cycloketone, can be relatively high concentrations of up to 50 Achieved wt .-% or more of active ingredient in the solution will.

The fungicidal compositions according to the invention, whether they are present in the form of dusts or liquids preferably a surfactant known in the art sometimes referred to as wetting, dispersing or emulsifying agents " will. These agents, hereinafter referred to as surface-active dispersants for the sake of simplicity, cause the compositions to disperse easily in water can be used to give aqueous sprays which are a desirable composition for the application.

The surface-active dispersants used can be anionic, cationic or non-ionic. Generally, the surfactant will make no more than about 5 to 15% by weight of the composition from and in certain compositions the percentage is 1% or less. Usually the minimum lower concentration is 0.1%.

The fungicidal compositions are either used as spray material? as granules or as dust on the undesirable Fungal growth applied to the area or place to be protected. Such an application can be done directly on the place or area and the fungi on it are applied during the period of fungal attack, to destroy the fungi, but the recitation is preferred before a fungal attack to be feared in order to prevent such an attack. Thus, the compositions be applied in the form of aqueous foliar sprays or can also be applied directly to the surface of the floor in spray form, or the dry powdery Compositions directly on the plants or on the

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Ground to be dusted.

The active compound will, of course, be used in an amount sufficient to exert the desired fungicidal effect. The amount of active compound included in compositions applied to destroy or prevent fungi will vary depending on the mode of application, the particular fungi being restricted from growing, the intended use, and the like. In general, contain the fungicidal compositions which are applied in the form of a spray in the form of dusts or granules, about 0.1 to 100 wt -.% Of active compound.

) The terms "carrier material" or "diluent" such as Hereafter used v / earth, described a material that is inorganic, or organic, and synthetic or natural May be of origin with which the active ingredient for ease of storage, transportation and handling and applying it to the plants to be treated, mixing or formulating. The carrier material is preferably biological and chemically inert and, in use, can be a solid or a fluid.

Fluid carriers can be liquids, for example water or an organic fluid, including a liquefied one, usually. vapor or gaseous material, or vapor or gaseous material, and these materials may be a solvent or a non-solvent for the active material. For example, the Erdölsprühöle used in horticulture, in the range from about 135 to about 302 ⁰ C (275 to 575 ° F) or in the range of about 302 ⁰ C to about 538 ° C (575 to about 1000 ⁰ F) boil and an unsulfonable residue of at least about 75 % and preferably at least about 90% or mixtures of these two types of oils are particularly suitable liquid carrier materials.

The compositions according to the invention can be in the form of concentrates that are suitable for storage or transport

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port are suitable and, for example, about 5 "to about 90% by weight of the active Constituent, preferably about 20 to about 80 wt .-% included. These concentrates can be made with the same or one dilute other carrier material to a concentration suitable for application. The compositions according to the invention can also be dilute compositions suitable for application. In general, concentrations are from about 0.1 to about 10% by weight of the active material based on the total weight of the composition is satisfactory, although lower and higher concentrations can be used if necessary.

The compositions of the invention can be formulated as wettable _<powder, a major proportion of the active ingredient, mixed with a dispersing agent, ie, a deflocculating or suspending agents, and if desired, contain a finely divided solid carrier and / or a wetting agent. The active ingredient can be in particulate form or adsorbed to the carrier and preferably constitutes at least about 10%, preferably at least about 25% by weight of the composition. The concentration of dispersant should generally be between about 0.5 and about 5 percent by weight of the total composition, although greater or lesser amounts can be used if desired.

The dispersant or dispersant used may be a protective colloid such as gelatin, glue, casein, resin or a synthetic polymeric material such as polyvinyl alcohol or methyl cellulose. The dispersants used are preferably or dispersants sodium or calcium salts of high molecular weight sulfonic acids such as the sodium or Calcium salts of lignin sulfonic acids, which are derived from sulfite cellulose lye. The calcium or sodium salts condensed aryl sulfonic acids, e.g. the products known under the name "Tamol 731" are also suitable.

The wetting agents used can be non-ionic surface-active Be medium, such as the condensation products of

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- ίο -

'Fatty acids containing at least 12, preferably 16 Ms 20 carbon atoms in the molecule, or abietic acid or naphthenic acid, obtained by refining petroleum lubricating oil fractions with alkylene oxides, such as ethylene oxide or propylene oxide, or with both ethylene oxide and propylene oxide, e.g. B. the condensation product of oleic acid and ethylene oxide, which contains about 6 to 15 ethylene oxide units in the molecule. Other non-ionic surfactants _not like Polyalkyleiioxydpolymerisate known commercially as "Pluronics", "may also be used.! Teilester the above acids with polyvalent j alcohols such as glycerol, polyglycerol, sorbitol or mannitol, can also be used v / Ground .

Suitable anionic wetting agents include the alkali metal salts, preferably the sodium salts of sulfuric acid esters or Sulphonic acids that have at least 10 carbon atoms in the molecule contain, one, e.g. the sodium sec.-alkyl sulfates, dialkyl sodium sulfosuccinate, available under the trademark "Teepol", sodium salts of sulfonated eicine oil or Sodium dodecylbenzenesulfonate.

The compositions of the invention can also be used as Solutions of the active ingredient in an organic solvent or in a mixture of solvents such as alcohols, ketones, especially acetone, ethers, hydrocarbons etc., can be formulated.

Petroleum hydrocarbon fractions used as solvent should preferably have a flash point above about 22.8 ° G (73 ° F), an example of such materials is a refined aromatic extract of kerosene. Additional solvents such as alcohols, ketones and polyalkylene glycol ethers and esters, can be used together with these petroleum solvents be used.

The compositions of the invention can also be formulated as emulsifiable concentrates, the concentrated Solutions or dispersions of the active ingredient in

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an organic liquid, preferably a water-insoluble one organic liquid containing an added emulsifier contains, represent. These concentrates can also contain a proportion of water, e.g., up to about 50 percent by volume on the total composition, to facilitate subsequent dilution with water. Suitable organic liquids include, for example, the petroleum hydrocarbon fractions mentioned above.

The following examples are intended to further illustrate the present invention without, however, restricting it.

Example 1 A typical synthesis is given below.

Cl \

O ₂ N

- NO ₂

O ₂ NH ₂

A solution of ^ -Chlor- ^ j ^ -dinitrobenzenesulfonyl chloride (60 g) in 500 ml of acetone was in a dry ice / acetone bath cooled to -15 ° C. Then was added dropwise over the course of 2 hours a solution of a concentrated ammonium hydroxide solution (53 * 6 ml) in 500 ml of acetone was added, with the temperature was kept between -15 and -5 ° C. 15 minutes behind Upon completion of the addition, 5 ml of concentrated hydrochloric acid solution was added, followed by anhydrous magnesium sulfate admitted. The suspension was stirred and then filtered to separate magnesium sulfate and ammonium chloride. Then became the acetone removed. Then 200 ml of benzene were added and the suspension was heated to reflux and the product separated from the hot suspension by filtration. M.p. 185-189 ° C.

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- .12 -

ber .: C. 25, 59 H 1 A3 N 12th , 59 found: C. 25, 26th H 1 , 76 Έ 12th , 66

example

A solution of 30 g of 4-chloro ^, 5-dinitrobenzenesulfonyl chloride in 500 ml of tetrahydrofuran was stirred in a dry ice / acetone bath and cooled to -10.degree. Then was in the course a solution of 25 ml of concentrated - trated ammonium hydroxide solution in 500 ml of tetrahydrofuran added, the temperature between -15 and -5 ° 0 was kept. One hour after the addition was finished, were "5 ml of 5% hydrochloric acid solution and finally anhydrous Magnesium sulfate added. After drying, the suspension was filtered to remove magnesium sulfate and ammonium chloride to separate. The tetrahydrofuran was removed to give the product with a melting point of 192-196 ° C. The melting point was not lowered by mixing with the product of the previous example.

One use of the claimed intermediate is to use IP, N -disubstituted ^^ - Dinitrosulfanilamidderivate, which have pesticidal properties.

) The following example explains this connection further without However, to limit the present invention.

Example 3 Preparation of N, IP-Di-n-propTl-3 + 5-dinitrosulfanilamide

H, N-di-n-propylamine (5.6 g, 0.05 mol), 8 ml of triethylamine and 14.1 B (0.05 mol) of 4-chloro-3,5-dinitrobenzenesulfonamide and 250 ml of methanol were mixed and the mixture was refluxed with vigorous stirring. After 8 hours the mixture was poured into water and extracted with benzene. The benzene solution was washed with dilute hydrochloric acid and water, dried with anhydrous magnesium sulfate, filtered off

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trated and narrowed. A purified sample had a melting point from 132 Ms 133 ° C.

Another use of the "claimed 4-chloro-3,5-C benzenesulfonamids "consists in use as a soil fungicide. The test procedure is given below.

Example 4

Separate samples of sterilized soil are inoculated with Fusarium and Sclerotium. The inoculated soil is placed in a 118.4 ecm (4 oz.) Jar and soaked with 20 ml of a formulation containing sufficient of the active ingredient to give treatment levels of 11.2, 5.6 , 2.8 and 1.4 kg / 1000 m ² (100, 50, 25, 12.5 lbs./acre). The treated dishes are incubated for 2 days at 21.1 ° C (70 ⁰ F). The amount of mycelium growth on the soil surface is then rated according to a scale of 0 to 10, where 0 means no interference and 10 means total prevention of mycelium growth.

Under these conditions, the compound of the present invention, 4-chloro-3,5-dinitrobenzenesulfonamide, shows the following activity.

Control of soil fungi by 4-chloro-3,5-dinitrobenzenesulfonamide.

Organism 11.2 (100) 5.6 (50) 2.8 (25) 1.4kg / 1000m ²

(12.5lbs / acre)

Fusarium 10 10 10 8

Sclerotium 10 9 8 6

1U9846 / 1955

Claims (1)

Sponsorship claims / [". / Process for the preparation of 4-chloro-3,5-cLmitro - (, ^ jpnzenesulfonamide, characterized in that 4-chloro-3 _} 5-dinitrobenzenesulfonyl chloride in a solvent such as ketones with 3 to 8 carbon atoms, Carboxylic acid esters with 2 to carbon atoms, Ν, Ν-dimethylformamide, dimethyl sulfoxide and cyclic ethers with 4 to 8 carbon atoms dissolve, the resulting solution is ^{cooled to a temperature of -50 to +10 0} C, ammonia either in a gaseous state or in at least one of the said solvents, which may contain in addition ser Vas- f dissolved at a sufficiently slow rate added so that the ammonia in the extent to which it is added, is reacted with the dung Dinitrobenzolsulfonylchloridverbin- and separating one then excess ammonia. 2. The method according to claim 1 _$, characterized in that the solvent is acetone, ethyl acetate, N, N-dimethylformamide or tetrahydrofuran. 3- The method according to claim 1, characterized in that the mixture is cooled ^{to a temperature of -20 to +5 0 C.} 4. The method according to claim 1, characterized in that at least 2 molar equivalents of ammonia per molar equivalent Dinitrobenzenesulfonyl chloride can be added to the solution of dinitrobenzenesulfonyl chloride. 5. A method of combating soil fungi, characterized in that a soil containing the fungi is with a fungicidally effective amount of 4-chloro-3 »5-dinitrobenzenesulfonamide, mixed with an inert carrier. 6. The method according to claim. 5 »characterized, 109846/1955 that the inert carrier material is an aromatic petroleum solvent. ?. 4-OhIor-Ji5-dinitrobenzenesulfonamide. 8. Fungicidal compositions, characterized in that that they are 4-chloro-3 »5-dinitrobenzenesulfonamide and a carrier material included for it. 109846/1955