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United States Patent (19) 11 3,923,868 Henrick (45) Dec United States Patent (19) 11 3,923,868 Henrick (45) Dec. 2, 1975 54 SUBSTITUTED ALKYLTHO BUTENOIC 3,078,298 2/1963 Gregory et al.................. 260f481 R ACIDS AND ESTERS 3,097,998 7/1963 Miller.............................. 260/481 R s A. 3,466,322 9/1969 Elam............................... 260f48l R 75) Inventor: Clive A. Henrick, Palo Alto, Calif. 3,476,665 4/1969 Ottenheyim et al............. 260/481 R 73) Assignee:- r - - - Zoecon Corporation,rare Paloto. Alto, 3,737,4423,732,264 4/19736f 1973 Baum ..............................et al...................... 260/481260/535 R Calif. 3,773,823 l l l 1973 Jarolim et al................... 26O1535 R 22 Filed: June 6, 1973 (21) Appl. No.: 367,613 FOREIGN PATENTS OR APPLICATIONS 898,098 6/1962 United Kingdom............. 260/481 R 52 U.S. Cl. ......... 260/481 R; 260/399; 260/456 P; 260/468 R; 260/470; 260/471 R; 260/473 R; Primary Examiner-Lorraine A. Weinberger 260/473 G. 260/476; 260/482 R; 260/486 R; Assistant Examiner-John F. Terapane 260/487; 260/488 H; 260/535 R; 260/608 I; Attorney, Agent, or Firm-Donald W. Erickson 260/609 R; 260/614 R; 260/615 R; 260/632 R; 260/516; 424/305; 424/308; 424/309; 424/3 1; 424/312; 424/314; 424/317 51 int. Cl........................................... CO7 c 149/20 57 ABSTRACT (58) Field of Search......... 260/48 R, 535 S, 535 R, 260/488 H Aliphatic 5-thia esters and acids, and derivatives thereof, useful for the control of insects. (56) References Cited UNITED STATES PATENTS 11 Claims, No Drawings 3,040,086 67962 Miller.............................. 260/481 R 3,923,868 1 2 In the description hereinafter, each of n, n, R-R", Z SUBSTITUTED ALKYLTHIO BUTENOIC ACIDS and Z' is as defined hereinabove unless otherwise spec AND ESTERS ified. This invention relates to novel 5-thia aliphatic unsat The compounds of formula A can be prepared ac urated esters and acids, derivatives thereof, syntheses 5 cording to the following outlined syntheses: - R : R R R---ch-high-st + X-CH-C=CH -OR." Z’’ Z. (l (II) 4 D3 R2 R1 O R---Ichi-ch-ch-s-ch-e-ch- - OR' Z' Z' (II) thereof and the control of insects. In the above formulas, X is a leaving group, such as More particularly, the novel 5-thia compounds of the bromo or chloro; R' is lower alkyl; Z' is hydrogen, present invention are represented by the following for lower alkyl or -OR" and Z' is hydrogen or taken with mula A: Z' is a carbon-carbon bond. In the practice of the above-outlined syntheses, an R: R R . O alkylating agent of formula II is reacted with the mer capto compound of formula I in the presence of a base, R---(CH-CH=CH-s-ch, -C A such as sodium hydride, potassium hydride, sodium A. v." methoxide, sodium ethoxide, and the like, in an organic solvent inert to the reaction, such as tetrahydrofuran, wherein, dimethylformamide, methanol, ethanol, and the like. R is hydrogen, lower alkyl, lower alkenyl, lower alky The compounds of formula I and II are reacted in a nyl, cycloalkyl, aryl or aralkyl; 30 mole for mole level and the reaction can be carried out each of R', R, R and R is lower alkyl; from about room temperature or above, such as reflux R’ is hydrogen or methyl; temperature. n is one or two; The esters of formula III are converted into the corre n is zero, one or two; sponding free acid by hydrolysis with base, such as po Z is hydrogen, lower alkyl, chloro, fluoro, bromo, or 35 tassium carbonate, sodium carbonate, sodium hydrox the group -OR" in which R is hydrogen, lower al ide, and the like, in an organic solvent, such as a lower kyl, cycloalkyl, aralkyl, aryl or carboxylic acyl; and alcohol. Other esters or the present invention can be Z" is hydrogen or taken with Z, a carbon-carbon prepared by transesterification of conversion of the bond. acid into the acid halide by treatment with thionyl chlo The compounds of formula A are useful for the con 40 ride, oxalyl chloride, phosphorus pentabromide, or the trol of insects. The utility of these compounds as insect like, and then reacting the acid halide with the alcohol control agents is believed to be attributable to their ju corresponding to the ester moiety desired. venile hormone activity. They are preferably applied to Compounds of formula A, in which Z is halogen, can the immature insect, namely - during the embryo, lar be prepared from a compound of formula A having a vae or pupae stage, in view of their effect on metamor 45 terminal double bond (Z' taken with Z is a carbon-car phosis and otherwise cause abnormal development bon bond) by treatment with a hydrogen halide or ace leading to death or inability to reproduce. These com tyl halide in an organic solvent, such as a lower alcohol pounds are effective control agents for Hemipteran, or halogenated hydrocarbon. such as Lygaeidae, Miridae and Pyrrhocoridae; Lepi A mercapto compound of formula I can be prepared dopteran, such as Pyralidae, Noctuidae and Gele 50 from the corresponding C-1 halide of formula I" using chiidae; Coleopteran, such as Tenebrionidae, conventional methods. Thus, by treating the respective Crysomelidae and Dermestidae; Dipteran, such as mos halide with thiourea in an alcohol solvent followed by quitos, flies; Homopteran, such as aphids and other in alkaline hydrolysis, or with sodium hydrosulfide in di sects. The compounds can be applied at low dosage lev methylformamide, or the like, the corresponding mer cls of the order of 0.01 ug. to 25.0 pug. per insect. Suit 55 captan is obtained. able carrier substances include liquid or Solid carriers, such as water, acetone, xylene, mineral or vegetable R R: R oils, talc, vermiculite, natural and synthetic resins and (l') silica. Treatment of insects in accordance with the rich --- CH)-X present invention is accomplished by spraying, dusting 60 or exposing the insects to vapor of the compounds of formula A. Generally, a concentration of less than 25% In formula I, each of n, , R-R, X, Z' and Z' is as of the active compound is employed. The formulations defined hereinabove. can include insect attractants, emulsifying agents or The respective C-1 bromide or chloride of formula I' wetting agents to assist in the application and effective 65 can be prepared according to the procedures of U.S. ness of the active ingredient. In the application of the Pat. Nos. 3,709,914 and 3,732,254. Briefly stated, a compounds, there is generally employed a mixture of halide of formula I" can be prepared by reducing the the C-2,3 trans and cis isomers. corresponding ketone (m is zero) or aldehyde (n is one 3,923,868 3 4 or two) precursor with, for example, sodium borohy bon atoms. Typical aromatic groups include phenyl, dride in ethanol, to yield an alcohol which is then con tolyl, xylyl, mesityl, naphthyl, lower alkylphenyl, such Verted into a compound of formula I" by treatment with as methylphenyl, ethylphenyl, t-butylphenyl and iso phosphorus trihalide, phosphorus pentahalide, lithium propylphenyl. chloride or bromide in acetone, or the like. When lith The term “carboxylic acyl,' as used herein, refers to ium chloride or lithium bromide is used, the alcohol is the acyl group of a carboxylic acid, anhydride or hal first converted into the corresponding mesylate or tosy ide. The acyl group is determined by the particular car late according to the procedure of Crossland et al., J. boxylic acid halide or carboxylic acid anhydride em Org. Chem. 35, 3195 (1970) and then reacted with the ployed in the esterification. Although no upper limita lithium halide as described by Cornforth et al., J. O tion need be placed on the number of carbon atoms Chem. Soc. (London) 2539 (1959) and Weiberg and contained in the acyl group within the scope of the Lowry, J. Amer. Chem. Soc. 85, 3188 (1963). present invention, generally it contains from one to 18 Compounds of formula A wherein Z is -OR (R is carbon atoms. Typical esters of the present invention hydrogen) can be prepared from a compound of for include formate, acetate, propionate, enanthate, ben mula A having a terminal double bond (Z' taken with Z 15 zoate, trimethylacetate, trichloroacetate, trifluoroace is a carbon-carbon bond) by the addition of water to tate, t-butylacetate, phenoxyacetate, cyclopentylpropi said terminal olefinic bond using a mercuric salt fol onate, aminoacetate, (3-phenylpropionate, 3,4-dime lowed by reduction of the oxymercurial intermediate in thylbenzoate, p-isopropylbenzoate, cyclohexylacetate, situ. Suitable mercuric salts include mercuric acetate, stearate, methacrylate, p-choromethylbenzoate, p mercuric nitrate, mercuric trifluoroacetate, mercuric methoxybenzoate and p-nitrobenzoate. acylates and mercuric halides. Suitable reducing agents The following examples are provided to illustrate the include the borohydrides, hydrazine and sodium amal practice of the present invention. Temperature is given gam. See Brown and Rei, J. Amer. Chem. Soc. 91, in degrees Centigrade. 5646 (1969); Brown et al., J. Amer. Chem. Soc. 89, 1522 and 1524 (1967); and Wakabayashi, J. Med. EXAMPLE Chem. 12, 191 (1969). By conducting the reaction in To 319 g. of mercuric acetate in 1,000 ml. of dry the presence of an alcohol (R-OH) such as methanol, methanol, cooled in an ice-water bath, is added drop ethanol, isopropyl alcohol, benzyl alcohol, cyclopentyl wise over ten minutes 126 g. of 6-methyl-5-hepten alcohol, and the like, the corresponding ether is pre 2-one. The mixture is stirred for two hours at 5-10 pared.
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