US1986218A - Insecticide and fungicide - Google Patents

Description

Patented Jan. 1, 1935 msnc'rlomn AND FUNGICIDE' Theron P. Remy, Los Angeles, Calilfi, assignor The Texas Company, New York, N. Y., a corporation of Delaware No'Drawing. Application June 16, 1931 Serial No. 544,926

Claims. (Cl. 167-22) This invention relates to insecticides and fungithese materials. A method that is applicable for cides and more particularly to insecticides and this purpose is the formation of double comfungicides in the form of substantially dry dusts pounds with heavy metal salts. comprising mixtures of gaseous, liquid or solid Sulfones and sulfoxides are compounds which 5 toxic organic sulfur compounds and an active correspond to the formulae 5 powdered carrying medium. This invention con- R templates the manufacture of an insecticide and SO and S0 fungicide composed essentially of an activated R R dust carrier and certain groups of organic sulfur D V Y, d usua ly result W Organic compounds. fides are subjected to oxidizing conditions, as in 10 All crude oils contain some compounds of sulfur treating the pet u fid s W Sodium yp which are more or less undesirable insofar as h te d u peroxidethe general commercial use of the refined pe- Thiophene and sulfonic acids are best obtained troleum products is concerned. During the procby their separation from sulfuric acid tars and l5 esses of distillation, cracking and refining these ud Distillation y means of steam is one compounds may be altered in chemical onstitumethod that is useful for this purpose. tion, and the synthesis of new organic sulfur Insecticides and fungicides'comprising certain compounds may occur. It is desirable to remove organic and inorganic chemicals combined with a these sulfur compounds during the refining proc d carrier are Widely known and used t the esses. present time. In ordinary commercial practice, 20

A study of the sulfur compounds contained in such insecticides and fungicides take the form of petroleum reveals some of them to be highly toxic a dry dust which is used without dilution of any to insect and fungus life. Among the more toxic kind in various types of power or hand driven sulfur compounds found in petroleum or its dedusting machines. The more finely divided these rivatives are the mercaptans, the thiophenols and dusts, the more Pronounced are their insecticidal 25 thiocresols, the alkyl sulfides or thio ethers, the and fungicidal properties. This is due to the disulfides, the thiophenes, the sulfones, the sulgreater qu y of insecticidal and fungicidal foxides and the sulfonic acids. terials capable of being adsorbed on the increased These organic sulfur compounds may be sepasurface.

rated from petroleum or its derivatives or from- Too fine a state of subdivision of the dust car- 30 the p ducts of the cracking and refining procrier, however, results in material losses during the esses by well-known chemical reactions. dusting operations caused by the Ca being It is known that freshly distilled naphthas conhome away by air currents. This is an important tain sulfur compounds of the mercaptan, thiopheconsideration when the dusting of large areas by I101 and thiocresol classes, which are readily acted airplane is contemplated. 35 upon by caustic soda. This reagent is usually Organic sulfur compounds are readily adsorbed used in the form of a solution with which the inlarge qua titi s by c tai otherwise inert -untreated naphthas are washed, and with which terials which have the further characteristic .the organic sulfur compounds react to form the property of tenaeibllsly retaining these 40 corresponding sodium salts. By acidification of pounds and rel a g t em O y y Slowly in 40 the separated sodium salts it is possible to bring vapor form. This is a characteristic of such adabout their reconversion to the original, corresorbents as, carefully dehydrated fullers earths, sponding mercaptans, thiophenols and thiosilica gel, acid-treated clays, activated bauxite cresols. and activated charcoals and carbons.

Disulfldes are produced when mercaptans are I have found that when Organic sulfur com- 45 subjected to the doctor-treatment. This consists pounds recovered from petroleum, from its derivprincipally in reacting them with sodium p1um-' atives or from the products obtained by cracking bite and sulfur. Recovered mercaptans may in petroleum are usedinconjunction with any of the this manner be converted into the corresponding enumerated adsorbents, a very superior type of fid insecticide and fungicide results. Much greater 50 Organic sulfides are present as such in some quantities of the organic sulfur compounds are petroleum distillates'andinthe products obtained capable of admixture without detracting from by cracking petroleum, though they may be ob- .the substantially dry character of the dust and tained more readily from the tars and sludges without having recourse to too high a degree of resulting f e-S u c acid treatment of subdivision. The relative superiorityofthese in- 66 secticides and fungicides may in part be due to the fact that the toxic materials are released over a relatively long period of time assuring a continned toxic condition. A sudden, rapid release of the insecticidal and fungicidal materials, which may have a deleterious effect on the plant life, is thereby likewise averted. In preparing dust mixtures various methods of incorporating the organic sulfur compound or sulfur compounds with the dust carrier may be used. I prefer to bring about this result by placing a suitable carrier of a mesh which may vary over wide range but preferably of between 200 and 400 mesh in a suitable mixer, such as a ball mill, and slowly adding the organic sulfur compound or sulfur compounds while the dust carrier is being agitated or mixed. The percentage of sulfur compound or sulfur compounds added to the activated carrier during this mixing operation, may

vary widely depending on the desired use to which the finished dust is to be put, and accordingly, the average percentage of sulfur compound or sulfur compounds carried in the completed dust. mixture will vary widely depending on the intended use. The present invention, therefore is not limited tcthe use of any specific percentages of these elements with the dust carrier.

I have impregnated activated fullers earth with very small percentages of representative compounds of several groups of organic sulfur compounds. As an example, a dust composed of 99.8

per cent of fullers earth of- 200 mesh and 0.2 per cent of ethyl mercaptan recovered from petroleum oil was dusted on citrus trees and killed thrips, red spiders, aphis and scale insects in various stages of development.

The disulfides are less toxic than the members of the mercaptan series, from which they are often formed during the refining processes. The toxic relationship for general insect and fungus use is practically the same. While I do not wish to limit myself to the amount of organic sulfur compound carrled by the dust medium, I have found that a mixture of 99.5 per cent of activated fullers earth of 200 mesh with 0.5 per cent of ethyl disulfide recovered during the refining of petroleum products will kill aphis, scale insects and many species of worms and beetles, as well as grape leaf hopper, spiders and mites.

I claim:

1. An insecticide and fungicide in the form of a substantially dry dust which comprises a finely divided activated adsorbent selected from the group consisting of dehydratedfullers earth, acid-treated clay and silica gel impregnated with readily vaporizable organic sulfur compounds recoverable from petroleum and the products of refining "the same selected'from the group consisting of mercaptans and organic disulfides.

2. An insecticide and fungicide in the form of a substantially dry dust comprising a finely divided activated adsorbent selected from the group conssting of dehydrated fullers earth, acid-treated clay and silica gel impregnated with readily vaporizable mercaptan compounds recoverable from petroleum and the products of refining the same.

3. An insecticide and fungicide in the form of a substantially dry dust comprising a finely divided activated adsorbent selected from the group consisting of dehydrated fullers earth, acid-treated clay and silica gel impregnated with organic disulfides recoverable from petroleum and the products of refining the same.

4. An insecticide and fungicide in the form of a substantially dry dust consisting of finely divided dehydrated fullers earth impregnated with readily vapcrizable m'ercaptans recoverable from petroleum and the products of refining the same.

5. An insecticide and fungicide in the form of a substantially dry dust consisting of finely divided dehydrated fullers earth impregnated with readily vaporizable organic disulfides recoverable from petroleum and the products of refining the same.

THERON P. REMY.