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Publication numberUS2588969 A
Publication typeGrant
Publication dateMar 11, 1952
Filing dateNov 26, 1949
Priority dateNov 26, 1949
Publication numberUS 2588969 A, US 2588969A, US-A-2588969, US2588969 A, US2588969A
InventorsJr Harry W Coover, Joseph B Dickey
Original AssigneeEastman Kodak Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Certain acylamino-acrylates and-crotonates as insecticides
US 2588969 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

Patented Mar. 11, 1952 CERTAIN ACYLAMINO-ACRYLATES AND -CROTONATES AS INSECTICIDES Joseph B. Dickey and Harry W. Coover, Jr., Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey N Drawing. Application November 26, 1949, Serial No. 129,694

6 Claims.

This invention relates to compositions useful for insecticidal purposes. More specifically, the invention is concerned with insecticidal compositions containing acylaminoacrylates and crotonates, together with a carrier therefor.

Compounds to be of value for insecticidal purposes should ordinarily be light stable, easy to apply, free from harmful effects to plants, free of a tendency to stain walls, fabrics, etc., and non-offensive to human beings. Many of the insecticides which are known at the present time are either short-lived in eifectiveness or have other characteristics which prevent those insecticides from being of general application.

One object of our invention is to provide insecticidal compositions which are highly toxic to insects but are of low toxicity to man and other warm-blooded animals. Another object of our invention is to provide insecticidal compositions which are simple to use but are highly effective against the various insects which are of a destructive nature, such as to plant life, foodstuffs, or fabric materials. A further object of our invention is to provide acylaminoacrylates and crotonates in a form in which they are useful for combating harmful insect life. Other objects of our invention will appear herein.

We have found that acylaminoacrylates and crotonates are particularly effective for insecticidal purposes. The compounds which are useful are either the esters or the organic or inorganic base salts thereof. We have found that the water-soluble compounds are the most desirable for use. The compounds which we have found to be most desirable for use as insecticides are those having the following formulas:


in which formulas a is an acyl group, R is hydrogen, alkyl, preferably of 1-4 carbon atoms, cycloalkyl or aryl is H or methyl and X is a basic substituent which preferably renders the compound water-soluble. Among the acyl groups which may be employed the following are suitable for the substituent a: HC=O, CHsCO, CzHsCO, C3HlCO, C4H9CO, CsHmCO, CH31C0, C1'1H33CO, and C1-7H35CO. The acyls used may be either branched or straight chain radicals. For the substituent R, besides hydrogen, there may be employed methyl, ethyl, propyl, butyl, isopropyl, cyclohexanyl, phenyl, benzyl, or the like. For the X substituent there may be employed 2 either an alkyl radical, such as methyl, ethyl, propyl, isopropyl or butyl, or a well-recognized basic substituent. If the substituent is inorganic, any of the metals of the periodic table capable of forming salts may be employed although for most purposes the alkali metals, such as sodium or Dotassium are preferred. Other substituents which may be used are ammonium, ethanolamine, methyl or ethylamine, aniline, guanidirie, dibutylamine, tetramethylamine, or the like.

The preparation of acylaminoacrylic acid may be by the method described by Bergmann and Grafe, Z. Physiol. Chem. 187, 183 (1930); C. A. 24, 2150. Instead of the a-acetaminoacrylic acid,

, other acids of this type, such as the a-propionyl aminoacrylic acid may be prepared by this method. e-Propionyl aminoacrylic acid has a melting point of l52-154 C. The alcohol esters of these acids may be formed by heating with the alcohol in the presence of sulfuric acid in the manner ordinarily employed for preparing alcohol esters. The salts of these acids may be prepared by reacting thereupon with the appropriate base. For instance, the sodium salt may be prepared by reacting the acid with aqueous or alcoholic sodium hydroxide. The B-acylamino crotonic acid esters may be prepared by various methods described in the prior art as follows:

1. B-Acetamino crotonic esterBer. 42, 3913; Ann. 226, 309.

2. fl-Benzoylamino crotonic esterBer. 42, 3913.

3. fl-Phenylureido crotonic esterBer. 33, 622; Ann. 314, 209.

4. B-Amino-a-benzeneazo crotonic ester-Ber. 34, 3600.

5. fi-Carbethoxyamino 244, 235.

6. p-Ureido crotonic ester-Ann. 229, 5.

7. fi-Carbethoxymethylamino crotonic ester Ber. 33, 266; Ann. 318, 380.

These esters and salts described above are formed into insecticidal compositions by mixing with pyrophyllite in case a dust is desired or by mixing with water if to be used in spray form. Ordinarily these salts will be water-soluble, but, in the case of water-insoluble compounds a dispersion in water can be formed by using a well-known dispersing agent, such as sodium lauryl sulfate. If the insecticide is to be emplayed as an aerosol, it is mixed with dichlorodifiuoromethane. Ordinarily, the proportion of acylaminoacrylate or crotonate used is 210% based on the carrier therefor although as little as 0.5% thereof will be effective, especially against insects which are readily susceptible to the effect thereof. If desired, other insecticidal materials may be employed as an additive to or to displace part of the acylaminoacrylate in the insecticidal composition. For instance, insecticides crotonic esterAnn.

such as pyrethrum, rotenone, nicotine, calcium or lead arsenate, paradichlorobenzene or the like may be included in the insecticidal compositions in accordance with our invention. Also, fungicidal materials such as lime-sulfur, sulfur, Bordeaux mixture, mercury compounds or the like may be included as can be incorporated in the composition at hand. Also, if desired, a synergist may be added, such as piperonyl butoxide, piperonyl propoxide and piperonyl butyl carbitol oxide. This synergist is effective in small proportions, such as 0.5-2% of the composition but may be added in a proportion up to 5%, if desired.

The effectiveness of the compounds disclosed for insecticidal purposes is illustrated by the following: methyl-aacetamino methacrylate was dissolved in water and kept in a Petri dish for twenty-four hours and was then employed as a contact insecticide for tribolium. 100% paralysis was obtained in eighteen hours. In another test the material was allowed to stand in a Petri dish for thirteen days but, nevertheless, when used as a contact insecticide for tribolium, 100% paralysis was obtained, both in an 18-hour and a 4-hour treatment. This material was also tested as regards plant injury on beans, tomatoes, and chrysanthemums. Used in concentrations both of 1:200 and 1:600 it was found that there was no plant injury.

To illustrate the effectiveness of these compounds in dust form a dust was formed of ethyl acetamino crotonate in a concentration of 1:100 using pyrophyllite as the carrier. This test was carried out by placing fruit flies in a bottle, sprinkling the insects with the dust and observing them at intervals. It was found that 100% kill of the fruit flies was obtained in one-half hour. Using methyl aacetaminoacrylate in the same test gave an 85% kill of the fruit flies in three hours.

The following examples illustrate insecticidal compositions and their preparation in accordance with our invention: I

ExampZe 1.--One part of ,B-acetaminomethyl crotonate was dissolved in 99 parts of water and was found to be useful as a spray for insecticidal purposes. In some cases the addition of wetting agents such as soap, sodium cetyl sulfate, sulfonated castor oil or the like, and sticking agents such as polyvinyl alcohol, methyl cellulose, gelatin, gum arabic, carboxymethyl-cellulose, and the like was found to be desirable.

Example 2.One part of the compound having the formula:

was mixed with 100 parts of water, 0.5 part of 12% of refined petroleum distillate and 85% of an inert propellant, namely, difiuorodichloromethane. The composition obtained was particularly useful as an aerosol. Other compounds which are useful for insecticidal purposes in addition to those mentioned above are the following:

R is hydrogen, alkyl or aryl R is alkyl or aryl CHz-C=%C O O R C-G JEN-C oi t Y is oxygen, sulfur, or nitrogen and HN-a O in which a is an acyl group, R. is selected from H, alkyl of 1-4 carbon atoms, cycloalkyland aryl, Q is selected from H and methtyl and X is selected from alkyl, organic basic substituents and inorganic basic substituents.

2. An insecticidal composition comprising an insecticidal proportion of ethyl beta-acetamino crotonate in finely divided pyrophyllite.

3. An insecticidal composition comprising an insecticidal proportion of an a-acylaminoacrylate in dichlorodifiuoromethane.

4. An insecticidal composition comprising an insecticidal proportion of a methyl a-acetamino acrylate in finely divided pyrophyllite.

5. An insecticidal composition comprising an insecticidal proportion of an a-acylaminoacrylate in pyrophyllite.

6. An insecticidal composition comprising 1 part of ethyl beta-acetamino crotonate in parts of finely divided pyrophyllite.



REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,195,712 Jacobson Apr. 2, 1940 2,218,181 Searle et al. Oct. 15, 1940 FOREIGN PATENTS Number Country Date 577,771 Great'Britain May 30, 1946

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2195712 *Oct 29, 1935Apr 2, 1940Du PontHalogenation of unsaturated carboxylic acid esters
US2218181 *Jun 15, 1939Oct 15, 1940Du PontPest control
GB577771A * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2696496 *Jul 5, 1952Dec 7, 1954Rohm & HaasS-crotonyl alkylxanthates
US2743262 *Jul 11, 1952Apr 24, 1956Eastman Kodak CoA-(chloroacetamido)-acrylic esters and their homo- and co-polymers
US3096237 *May 11, 1960Jul 2, 1963Bayer AgMethods of combating mites and fungi
US3959356 *Mar 18, 1975May 25, 1976Richardson-Merrell Inc.Acetylene derivatives of amino acids
US3960927 *Mar 18, 1975Jun 1, 1976Richardson-Merrell Inc.Olefinic derivatives of amino acids
US4039549 *Mar 8, 1976Aug 2, 1977Merrell Toraude Et CompagnieOlefinic derivatives of amino acids
US4041041 *Mar 8, 1976Aug 9, 1977Merrell Toraude Et CompagnieAcetylene derivatives of amino acids
US4216008 *May 22, 1978Aug 5, 1980Hoffmann-La Roche Inc.Butenoic acid derivatives
USRE31980 *Jan 14, 1983Sep 3, 1985Merrell Toraude Et CompagnieOlefinic derivatives of amino acids
DE1120802B *May 13, 1959Dec 28, 1961Bayer AgSchaedlingsbekaempfungsmittel
DE1137896B *Nov 11, 1959Oct 11, 1962Bayer AgPilzbekaempfungsmittel
U.S. Classification424/45, 560/38, 514/464, 548/537, 560/149, 549/72
International ClassificationA01N37/46
Cooperative ClassificationA01N37/46
European ClassificationA01N37/46