USRE26178E - Co-crz-br - Google Patents

Description

United States Patent 26,178 METHOD OF CONTROLLING MICROORGANISMS WITH Z-HALO-SUBSTITUTED ACETOPHENONES George E. Lukes, Kentfield, and Thomas B. Williamson,

Santa Clara, Caliii, assignors to Staulfer Chemical 5 Company, New York, N.Y., a corporation of Delaware N0 Drawing. Original No. 3,184,379, dated May 18. 1965, Ser. No. 172,849, Feb. 13, 1962. Application for reissue Oct. 4, 1965, Ser. No. 493,309

6 Claims. (Cl. 167-30) Matter enclosed in heavy brackets appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.

This invention pertains to a method of controlling pest microorganisms by contacting them with certain substituted Z-halomethyl aryl ketones. The invention is also concerned with the preparation, use and application of biocidally active compositions containing as the toxic component thereof at least one of the aforementioned halomethyl aryl ketones.

The present invention is predicated on the finding that certain halomethyl aryl ketones, particularly 2-bromoacetophenones, are highly toxic to microorganisms of the type which affect commercial food crops. We have, for instance, ascertained that these chemical compounds are especially effective in combating certain varieties of destructive soil fungi such as Rhizoctonia solani, Fusarium solani and the like. Other deleterious microorganisms which are susceptible to the toxicants of the 3 invention include bacteria and, in this case, reference is made to Aspcrgillus niger, Penicillium and Escherichia coli.

The halomethyl aryl ketones, the biocidal properties and use of which are contemplated herein, can be depicted by the following formulae:

C 0CII2 X 4 and COOH:X

wherein R R R and R designate hydrogen, a lower alkyl radical, a lower alkoxyl radical, amino, nitro and halogen e.g. fluorine, chlorine or bromine, it being understood at least one of said R R R and R is a substituent other than hydrogen and X can be chlorine or bromine. Specific configurations falling within the ambit of Formulae I and II are exemplified in the list of structures below:

Compound 1 HaC CO CIII BI' GHQ Compound 2 Re. 26,178 Reissued Mar. 21, 1967 Compound 3 Compound 4 on, C 0on,nr

Compound 5 n,o- 4: OCH2BI Compound 6 c H, Q-o o-o urn;

Compound 7 c1- -0 o-on, nr

Compound 8 a c OCI-I]3r Compound 9 oils-Go o-o Hi-Bt Compound 11 Compound 12 Compound 13 11.0 oo 0-0 Ha-Br Compound 14 @CMM l CH;

3 Compound Compound 16 Compound 17 Compound 1 8 Compound 19 Compound 20 Compound 21 Compound 22 Compound 23 (1H3 (llll l C Ii: C H:

Compound 24 o c in 0 Hz Compound 25 O CH:

Compound 26 0 (l; in

OCII

OCH

may be encountered wherein the halogenation proceeds at an impractically low velocity and, in such instances, the reaction is accelerated by the use of catalysts, and for this purpose, certain anhydrous heavy metal salt halides, i.e. ferric chloride, zinc chloride etc. are especially efiicacious. An alternate procedure whereby one may arrive at the compounds of the invention comprises the chloroacetylation of the requisite aromatic ring compound having the appropriate number and arrangement of substituents. Further details of the aforedisclosed reactions can be had by resorting to the original technical literature of which the various chemical journals and patent literature are particularly useful.

In using the 2-halomethyl aryl ketones as contemplated herein, it is merely necessary to contact, with these toxicants, the microorganism, the growth of which it is desired to control. This can be accomplished by a variety of procedures which are known to the art. For instance, a solution of the compound in an organic solvent may be applied directly to the soil in the form of a spray. Alternately dispersions of the compounds in a water media may be advantageously employed. In the latter case, the use of various surface active agents or soaps may be desirable for the purpose of stabilizing the dispersions. Since the compounds of the invention have been found to be nonphyto-toxic, the non-volatile representatives can be mixed with talc or other inert binder and the resultant mixture combined with the cotton or bean seed before planting into fungus infected soil. Fumigation techniques may also be resorted to if the volatility of the compound is sufiiciently high. The biocidal activity of the compounds of the invention are set forth in the table below:

In ascertaining the bactericidal activity of the herein contemplated compounds, 1 oz. bottles were partially filled with 10 ml. of malt or nutrient broth, the containers capped with aluminum foil, sterilized and a solution of the compound to be tested injected by means of a syringe through the foil into the broth. Water suspensions of such typical bacteria as Aspergillus niger, Penicillium and Escherichia coli were injected into the broth and the botties sealed and held for one week, after which the bacteria count was recorded.

The activity of the compounds of the invention against such soil fungi as Rhizoctonia solani and Fusarium solani was determined by incorporating the microorganisms into sterilized soil and 1 lb. portions of this admixture were placed in quart jars. A small depression was formed in the soil and filled with coarse sand. 1 ml. of 5% acetone solution of the compound to be tested was introduced on to the sand and the jar sealed. The contents of the container were then thoroughly shaken and the infected soil seeded with representative commercial crops such as cotton or Pinto beans. After an interval of about 2 or 3 weeks, the plants were examined and the treated plants compared with the controls, having no treatment.

We claim:

1. A method of inhibiting the growth of microorganisms which comprises applying thereto a small but effective amount of a 2-halomethyl aryl ketone of the following formula:

2. A method of inhibiting the growth of microorganisms which comprises applying thereto a small but effective amount of Z-halomethyl naphthyl ketone of the following formula:

wherein X is selected from the class consisting of chlorine and bromine.

3. A method of inhibiting microorganism growth comprising, applying to said microorganism habitat a morebiologically effective amount of a compound of the formula:

wherein X is selected from the group Consisting of bromine and chlorine.

4. A method of inhibiting the growth of microorganisms comprising applying to said microorganism habitat a microbiologically ejjective amount of a compound of the formula:

5. A method of inhibiting the growth of microorganisms comprising applying to said microorganism habitat a microbiologically eflective amount of a compound of the formula:

o o-crns' References Cited by the Examiner The following references, cited by the Examiner, are of record in the patented file of this patent or the original patent.

UNITED STATES PATENTS Re. 26,009 5/1966 Buckman et a1. l62l61 2,901,394 8/1959 Rosher l6730 3,021,256 2/1962 Bollenback et al. 162-161 FOREIGN PATENTS 1,330,953 6/1962 France.

ALBERT T. MEYERS, Primary Examiner. JULIAN S. LEVITT, Examiner.

GEORGE A. MENTIS, Assistant Examiner.

Z gz g? UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 26,178 Dated March 21, 1967 Inventor(s) George E. Lukes and Thomas B. Williamson .4- It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

r- In Column 2, Compound 13, the formula should mac:

co-cn -sr In Column 3, Compound 24, the formula should read:

CO-CH -Br In Column 3, Compound 25, the formula should read:

OCH

73 3 UNITED STATES PATENT OFFICE Y CERTIFICATE OF CORRECTION Patent No. 26 178 Dated March 21, 1967 Invemm-(S) George E. Lukes and Thomas B. Williamson It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In Column 1, under line 47, the formula (II) should read as follows:

woo-W 41 In Column 1, Compound 20, the formula should read:

In Column 3, Compound 26, the formula should read:

H CO O-CH -Br (continued on Page 2) mg? UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Page 2 Patent; No. Dated March 21,

lnventoz-(s) George E. Lukes and Thomas B. Williamson identified patent It is certified that error appears in the aboveshown below:

and that said Letters Patent are hereby corrected as In Columri 3, Compound 27, the formula should read:

HBCO CO-CH2-C1 OCH3 5; Cu. nova "I70 EAL) Attest:

EdwardMFl wllgh mm; x. 50mm, .112. Minimum- 01 Patents