BE525010A - - Google Patents

Description

       

   <Desc / Clms Page number 1>
 



  UNION CARBIDE AND CARBON CORPORATION, residing in NEW YORK.



   INSECTICIDES.



   The present invention relates to improvements relating to insecticides and more particularly to a process for preparing a substituted cyclopentenolone intended to enter into reaction with the chrysanthemum-monocarboxylic acid, anhydride or chloride so as to form. ester having insecticidal activity, and in insecticidal compositions, containing such ester associated with vehicles or synergists, or both.



   One of the major uses of pyrethrum is in the manufacture of insecticidal compositions intended for the destruction of flying or crawling insects such as flies, mosquitoes, moths, cockroaches and various other types of insects. Pyrethrum is obtained in the form of a concentrate by depleting the flowers of pyrethrum or chrysanthemum cinerariaefolium with a suitable solvent which is then removed by evaporation to obtain a residual concentrate. Because of the high cost of manufacturing pyrethrum, the concentrate is spread with a suitable solvent so as to obtain a liquid for household sprays at such dilution that it tends to paralyze insects instead. to kill them.



  To increase the insecticidal effectiveness of these sprays, various known insecticidal agents have been incorporated such as rotenone, thiocyanates or D.D.T.



   Two of the active constituents of pyrethrum flowers are the esters of substituted 3-methyl-2-cyclopenten-4-ol-1-one and chrysanthemum monocarboxylic acid. In the process applied to the manufacture of allethrin, chrysanthemum-monocarboxylic acid and 2-allyl-3-methyl-2-cyclopenten-4-ol-1-one are separately prepared and then reacted together. ble so as to make an ester, as follows:

 <Desc / Clms Page number 2>

 
 EMI2.1
 (r'H, 3) 20 = CHGH - e (CH) 3 2 qH2 - cH \ c (cH3> z CH "2 - co CH-COOH HOCH OCH20H = CH2 / fi 3 (cH3) zc = cAçH (CE- ) - #L - (GH3) 2C CHI (!! - C (CH3) 2 C xa "2: CI !;

   CH3 2 '-CO 0 CCH2CE = ri 2 + H-0 (allethrin) G "3
Although allethrin is not as expensive as pyrethrum, it is not currently possible to activate or make it as sensitive as desirable by known synergists.



   A process is known for the manufacture of an ester of chry- santhemum-monocarboxylic acid by reacting chry- acid anhydride.
 EMI2.2
 santhemuin-monocarboxylic with a cyclopentenolone of the formula:
 EMI2.3
 wherein R is an unsaturated organic radical of 3 to 7 carbon atoms, free from elements other than carbon, hydrogen and oxygen. It has now been discovered that if R is a cyclopentene radical, the chrysanthemum monocarboxylate thus obtained has improved insecticidal properties, in the sense that the addition of synergistic or activating agents can give it an insecticidal power greater than that which is obtained. would get if R were another radical falling within the definition above.



   The present invention provides a method of making a 2-
 EMI2.4
 (2-cyclopentenl) -2-methyl-2-cyclopenten li.-ol 1-one of the formula:
 EMI2.5
 this process comprising reacting cyclopentadiene with hydrochloric acid so as to obtain 2-cyclopentenyl chloride, reacting the acetylacetic ester with 2-cyclopentenyl chloride in the presence of an alkali metal alkoxide with production of a 2- (2-cyclo-
 EMI2.6
 pentenyl) -2-lower keto-butyrate, subjecting this compound to ketone hydrolysis in the presence of an alkali metal hydroxide with formation of 2-cyclopentenyl-acetone, reacting 2-cyclopentenyl -acetone with diethyl carbonate in the presence of an alkali metal alkoxide so as to form 4- (2-cyclo-pentenyl)

  Ethyl-3-ketobutyrate, converting this compound to an alkali metal salt and reacting it with
 EMI2.7
 pyruvic aldehyde so as to make 6- (2-cyclopantenyl-3-hydroxyhexane-2.5-dione and the treatment of this compound with an extended base to

 <Desc / Clms Page number 3>

 converting it to 2- (2-cyclopentenyl) -. 3-methyl-2-cyclopenten-4-ol-1-one.



   The invention further provides a process for making an insecticidally active ester by reacting said 2- (2-cyclopentenyl) -3-methyl-2-cyclopenten-4-ol-1-one with chrysanthemum monocarboxylic acid chloride in the presence of an acid binding agent such as pyridine, or with chrysanthemum-monocarboxylic acid or its anhydride.



   Finally, the invention provides insecticidal compositions containing a vehicle or a synergist, or both, and 3- (2-cyclopentenyl) 2-methyl-4-oxo-2-cyclopentenyl-chrysanthemumate. active insecticide, combined if desired with a known insecticide.



   The synthesis of 3- (2-cyclopentenyl) 2-methyl-4-oxo-2-cyclopentenyl-chrysanthemumate involves a number of steps which can be schematically represented as follows.



   Stage 1
Hydrochloric acid is reacted with cyclopentadiene, a relatively inexpensive raw material, so as to obtain 2-cyclopentenyl chloride:
 EMI3.1
 cyclopentadiene ac. hydrochloric 2-cyclopentenyl chloride.



   Stage 2.



   2-Cyclopentenylacetone is obtained by reaction of sodium 1-acetylacetic ester with 2-cyclopentenyl chloride obtained in step 1, followed by ketone cleavage.
 EMI3.2
 CH = é CH GOGH CH = CH COCH first first: CHC1 + HCNa ethoxide of: CE CE NaOH î l sodium il 'then CH2 -OR2 COOEt CH2 - CH2 COOEt 504HZ ester chloride Ester alpha- (2-cyclo - 2-'cyclopen- acetyl-pentenyl) acetylacetic tenyl acetic sodium CH = CH >> i> CH CH2COCH3 + EtOH + C02 C2 z 2-cyclopentenyl-acetone
Stage 3.



   Ethyl 4- (2-cyclopentenyl) -3-ketobutyrate is obtained by reaction of diethyl carbonate with 2-cyclopentenyl-acetone produced in stage 2
 EMI3.3
 

 <Desc / Clms Page number 4>

 
 EMI4.1
 4- (2-cyclopentenyl) -3-ketobutyacetone diethyl 2-cyclopentenyl carbonate ethyl spleen
Stage 4.



   The pyruvic aldehyde is reacted with the ethyl 4- (2-cyclo-pentenyl) -3-ketobutyrate obtained in Step 3 in the presence of an extended aqueous solution of an alkali metal hydroxide to form the 6- (2-
 EMI4.2
 cyclopentenyl) 3 hydroxyhexane-2.5-dione. The ester is saponified so as to obtain the sodium or potassium salt of the corresponding acid, which is then condensed with pyruvic aldehyde.
 EMI4.3
 
 EMI4.4
 4- (2-Cycloaldehyde 6 (2-cyelopentenyl- bydroxyhexapentenyl) -3-keto-pyruvic acid ne-2.5-dione butyric
Stage 5.



   The product of stage 4 is treated with sodium hydroxide
 EMI4.5
 extended to form 2- (2-cyelopentenyl) -3-methyl-2-cydopenten-4-0l 1-one.
 EMI4.6
 
 EMI4.7
 



  6- (2-oolopentenyl) -3- 2- (2-cyc1opentenyl) -3-methyl-hydroxyhexane-2.5-dione 2-cyclopenten-4-ol-1-one
Stage 6.
 EMI4.8
 



  Finally, the cydopentenolone obtained in Example 5 is reacted with chrysanthemum monocarboxylic acid chloride in the presence of pyridine or other acid binding agent, as follows:
 EMI4.9
 2- (2-Cyclopentenyl) acid chloride -
 EMI4.10
 Chrysanthemum-mono- 3-methyl-2-c7clopenten-4-carboxylic ol-1-one

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 EMI5.1
 
 EMI5.2
 3- (2-cyclo-pntenyl) 2-methyl-4-oxo-2-cyelopentenyl-chrysanthemamate.



  + c5H5N HCL (pyridine hydrochloride) or with chrysanthemunt-monocarboxylic acid or anhydride, as follows:
 EMI5.3
 For reasons of brevity, the ex-
 EMI5.4
 Pressure of "cyclopentenyl chrysanthemumate" to denote 3- (2-cyclopentenyl) 2-methyl-4-oxo-2-cyclopentenyl-chrysanthemumate.
 EMI5.5
 The results of biological tests carried out using cyclopentenyl hry- santhemumate not added with a synergistic agent show that it is of the same order of efficiency (as furethrin '(2-methyl-4-oxo
 EMI5.6
 -2-cyclopenfcenyl-chrysanthemum-monocarboxylate de '3-furfuryae) or allethrin, both not supplemented with a synergist.



   The biological results also show that synergistic agents with a higher efficacy than pyrethrin can also be used as such with cyclopentenyl chrysanthemumate. In general, pyrethrin with a synergist paralyzes more flies than cyclopentenyl chrysanthemumate with the same synergists added. However, bioassays reveal that, compared to allethrin, only half of the cyclopentenyl chrysanthemumate is needed with the "sulfoxide" or "n-propyl-isome". Another advantage of cyclopentenyl chrysanthemumate is that it is less toxic to mammals at absolute concentration than allethrin.

   Thus, cyclopentenyl chrysanthemumate appears to show one fifth of the toxicity of allethrin in rats at a single dose administered orally, in absolute concentration, and even less at actual doses.



   Compounds of interest as synergists in combination with cyclopentenyl chrysanthemumate are:
A. Piperonyl butoxide, which is the technical grade of
 EMI5.7
 3.4-methylenedioxy-6-propylbenzyl ether of diethylene glycol monobutyl ether, the structure of which is represented by the formula:

 <Desc / Clms Page number 6>

 
 EMI6.1
 Compounds closely related to the above compound amount to about 20% by weight of the piperonyl butoxide.



   B. Normal propyl-isome, name given to 2-methyl-6.7-methylene-
 EMI6.2
 Di-n-propyl dioxy-1.2.3.-hexahydronaphthalene 3.1-d.icarbo $ ylate. Its structure can be represented by the following formula:
 EMI6.3
 C. Synergic 6266, number assigned to N- (hexoxyethqxypropyl) -
 EMI6.4
 bicyclo # 2,2 l-5-h.eptene-2.3- <îicart> oxiinide, the structure of which can be represented graphically as follows:
 EMI6.5
 
Do Sulphoxide, name given to the n-octylsulphoxide of isosafrol and whose structure can be represented graphically as follows:
 EMI6.6
 E. N-isobutyl-undecylene-amide, of general formula:
 EMI6.7
 CH2 = GH (CH2) 8C0MG4H9 F. Ether of pinene and ethylene glycol, of empirical formula CHO # CHCH G.

   Piperonyl-cyclonene, mixture of, 3-isoaml-5- (34-methyler-dioxyphenyl) -2-cyclohexenone and its 6-carbethoxy derivative:

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 EMI7.1
 
 EMI7.2
 3-isoamyl-5- (3o4-methylenedioxyphenyl) -2-cyclohexenone
H. Butoxypolypropylene glycol, which denotes the monobutyl ether of polyoxypropylene glycol, with a viscosity of about 100 S.U.S. at 38 C and an average molecular weight of approximately 850.



   I. Sulfone, name given to the nomal octylsulfone of isosafrol, of formula:
 EMI7.3
 J. Synergique 264, number assigned to N- (2-ethylhaptyl) -bicyclo-
 EMI7.4
 (2.2.1) -5-heptene-2. 3-di carboximide. at
 EMI7.5
 
K. Sedame oil, name given to sesame indicium oil. of which approximately 0.25% is constituted by sesamin. The structure of sesamin can be represented graphically by the formula:
 EMI7.6
 
Of these eleven synergists, preference is given to sulfoxide and piperonyl butoxide.



   In the examples which follow, example 1 describes the preparation
 EMI7.7
 of cyclopentenolone and its reaction to give rise to the ester with insecticidal activity, the other examples relating to its uses in insecticidal compositions.



  Example 1.



   Part a- Anhydrous hydrochloric acid is added to a

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 mixture formed from 99 g. (1.5 mol) of monomeric cyclopentadiene in 380 g. of carbon tetrachloride. The mixture is maintained at a temperature of 0 ° C. during the addition, which is continued for about an hour, until a weight gain of about 58 g is obtained. After distillation of the carbon tetrachloride at atmospheric pressure, 138 g are obtained. 2-cyclo-pentenyl chloride (1.35 mol), distilling at 52-53 ° C. under an absolute pressure of 100 mm. of mercury. The yield is 90% of the theoretical yield.



   Part b- 306 g are gradually added. sodium ethoxide (4.5 mol) in the form of a 19.5% solution (1570 g.) in 650 g ethanol.
 EMI8.1
 



  (5 mols) ethyl ddiaoekylacetate, with stirring, over thirty minutes. The mixture is maintained at a temperature of 20 ° C. during the addition. After stirring the mixture for a further hour at 20 ° C., it is heated to the temperature of 50 C. and added to it over the course of one hour and
 EMI8.2
 half 459 e..of 2-cyclo-pentenyl chloride (4.5 mols). To complete the reaction, the mixture is maintained at its reflux temperature under atmospheric pressure for three hours.



   At the end of this time, the ethanol was removed from the mixture by distillation under atmospheric pressure at a flask temperature of 125 ° C.
 EMI8.3
 



  The residue, which contains ethyl 2-cyclopentenyl-acetylacetate, is cooled to 20 ° C. and 2,500 g are added over a period of ten minutes. 10% aqueous sodium hydroxide solution (6; 5 mols). To complete the ketone cleavage of the compound, the mixture is stirred for four hours while
 EMI8.4
 maintaining the temperature at 200C. 400 cc is then added. 50% aqueous sulfuric acid so as to reduce the pH of the mixture to 3.5. The mixture is treated with 200 cc. of benzene and distillation is carried out at atmospheric pressure using a rectifying column fitted with a 175 cc separating funnel. filled with benzene. During the distillation, a total of one liter of water is gradually added to the vapor pipe, just before the condenser.

   The bottom layer of the separating funnel is continuously removed, while the oil present is refluxed back into the distillation flask. We continue the operation
 EMI8.5
 ration until the temperature reaches 6800., so that all of the ethanol is drained from the system and all of the 2-cyclo-pentenylacetone remains in the flask.



   Distillation of the oil contained in the residue, which is added to the oil present in the decanter, gives 440 g. 2-cyclopentenyl-
 EMI8.6
 acetone having the following properties: boiling range, ** under an absolute pressure of 15 mm. mercury, 66-68OC; density (20/20), 0.940. Dosing of ethyl acetylacetate in the distilled product by the sodium methoxide method gives a value of 8.3% by weight. Determination of the ketone by the hydroxylamine method gives a cyclopentenyl acetone content of 89.1% by weight, after correction for ethyl acetylacetate.

   Since the boiling points of 2-cyclopentenyl-acetone and ethyl acetylacetate are very close, the separation of these two compounds by fractional distillation is difficult. After removal of ethyl acetylacetate from 2-cyclopentenyl-acetone by saponification, the pure ketone has a specific gravity (20/20) of 0.934 and a refractive index (n3) of 1.45431- Le yield of 2-eyelo-pentenyl-acetone is 72% relative to 2-cyclo-pentenyl chloride, which corresponds to an efficiency of 72%.



   Part c - Load 2240 g. (19 months) of diethyl carbonate in a flask fitted with a reflux condenser and refluxed under reduced pressure to 100 mm. of mercury (absolute). 185.6 g are introduced into the flask. (2.73 months) sodium ethoxide as a 19.3 solution in ethanol (776.4 g. ) within 2 hours, the ethanol continuously distilled.

   The total distillate collected is 1033 g. All of the ethanol solvent being removed, it remains in the tank.

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 lon a suspension of sodium ethoxide in diethyl carbonate, to which 340 g is added over the course of 2 hours. of 2-cyclopentenyl-acetone (purity, 91.7%, 2.51 mols) while continuing the distillation of ethanol as above. The total amount of distillate removed in this o-
 EMI9.1
 pereration is 289 g. The residue is cooled to 25 ° C., 174 g is added.



  (2.9 months) of acetic acid, then 620 cc. of water so as to dissolve the sodium acetate. The oily layer is separated and rapidly distilled under reduced pressure. 400 g are obtained. ethyl 4- (2-cyclopentenyl) -3-ketobutyrate, boiling range from 100 to 155 ° C. under an absolute pressure of 5 mm. of mercury. Titration with sodium methoxide in the breast
 EMI9.2
 of pyridine indicates a purity of 94.6%. Analysis of the average fraction (183 gb) shows a product content of 82.4 g. The yield based on 2cyclopentenyl-acetone is 85%.



  Part fl-Gn ga: tt: #. Â drop within one hour 819 g. of ethyl 4- (2-cyclopentenyl) -3-ketobutyrate, 93.1% (3.89 mol) purity at 2.180 g. a well-stirred aqueous solution of 9.5% sodium hydroxide (5.18 months)
 EMI9.3
 maintained at 20-2500. After 16 hours, the solution is neutralized to pH 7.5 with carbon dioxide.



  1500 g are loaded into the neutralized solution of bgta-keto-acid. of an aqueous solution of pyruvic aldehyde (22.4, 4.67 months) neutralized to pH 7 using 26 g. of sodium bicarbonate, over the course of an hour and a quarter, while maintaining the reaction mixture at a temperature of 25 C.



  To terminate the reaction, the mixture is allowed to stand for 21 hours and then exhausted four times with successive 1 liter portions of diisopropyl ether. The four extracts are mixed and the volatile material removed therefrom at a flask temperature of 100 ° C., under an absolute pressure reduced to 4 mm. of mercury. A residue of 742 g is obtained. from 6- (2-
 EMI9.4
 cyclopentenyl) -3-hydroxyhexan-2.5-dione which analysis shows that it is of a purity of 75.8. The yield is 74% based on ethyl 4- (2-cyclopentenyl) -3-ketobutyrate.



   Part e. 368 g are introduced dropwise. of 6- (2-Cyclopentenyl) -3-hydrohexane-2.5-dione with a purity of 75.8% (1.42 mol) over 30 minutes in 3312 g. a 2% aqueous solution of sodium hydroxide, with vigorous stirring, at a temperature maintained between 20 and 25 C.



  After a period of four hours, to allow the reaction to complete, one. saturate the mixture with sodium chloride and four successive extractions are carried out, each with 1 liter portions of diisopropyl ether. The four extracts are mixed, neutralized with 2 g. of acetic acid and distilled off under reduced pressure. We obtain 139 g. a fraction distilling at 120 C. under an absolute pressure of 2.5 mm. of mercury at 170 C. under an absolute pressure of 5 mm. of mercury. On analysis, this product was found to contain 72.8 percent of 2- (2-cyclopentenyl) -3-
 EMI9.5
 methyl-2-cyclopenten-4-ol-1-one. Yield, 40%.



   Part f - We make a mixture of 275 g. of 2- (2-cyclopentene) -4-ol-1-one (purity, 70.8%; 1.094 mol), 156 g. of pyridine and 0.905 liters of ethanol. To this mixture is added a solution of 183 g. of semi-carbazide hydrochloride (1.64 mol) in 220 cc. of water. The mixture was allowed to stand for 16 hours and at the end of this time the crystals formed of semi-carbon were filtered off and washed with 4 liters of water to remove the chloride. This is obtained by crystallization from 181g ethanol.
 EMI9.6
 colorless crystals with a melting point of 2089C. at 210 ° C. The yield of pure semicarbazone of 2- (2-cyclo-pentenyl) -3-methyl -! '2'-cyclopenten-4-ol-1-one is 71 ".



  Stirred at 600C-650C. for two and a half hours a mixture of 181 g. of pure semicarbazone (0.77 mol), 1.6 liters of water, 1.6 liters of diisopropyl ether and 1047 g. potassium acid sulfate (7.7 months). At the end of this period, all of the semi-carbon is dissolved, indicating that the hydrolysis is complete. The aqueous layer is separated and

 <Desc / Clms Page number 10>

 exhaust it three times in portions of 200 cc. diisopropyl ether. The three extracts are mixed with the oily layer resulting from the hydrolysis and the whole is washed with 200 cc. saturated sodium chloride solution.

   Distillation of the ethereal solution gives 101 g. of
 EMI10.1
 2- (2-cyclopentenyl) 3-methyl-2mcyelopentèn 4-0l 1-one, characterized by the following properties: Boiling point under an absolute pressure of 1 mm. mercury, 131 C; in-
 EMI10.2
 refractive index (nD0) 1.5350; purity according to the determination of hydroxyl) 96.7%. The yield relative to the semi-carbon is 84%, taking into account the 17 g. of product contained in the intermediate fraction and the column.



   Part g- A mixture of 244 g is stirred at a temperature of 19 to 21 C. 87.5% (1.2 mol) 2- (cyclopentenyl) -3-methyl-2-cyclopenten-4-ol-1-ohe, 115 g of pyridine (1.46 mol) and 500 g. dry dibutyl ether. To the stirred mixture was added over 30 minutes a solution containing 235 g. (1.22 mol) of newly distilled chrysanthemum-monocarboxylic acid chloride, 96.8% purity, and 235 g. dry dibutyl ether.



  After a reaction period of two hours at a temperature of 20 to 24 ° C., the reaction mixture is washed successively first with 500 g. - water, then twice using 500 g. 1% hydrochloric acid, twice using 500 g. of a 2.1% aqueous solution of sodium hydroxide, finally using 500 g. of water. Each of the washing liquors is exhausted, after use, by means of the same portion of 200 g. dibutyl ether. The washed crude product is then mixed and the extract with dibutyl ether and the mixture is distilled under reduced pressure so as to remove the dibutyl ether and accidental impurities.

   The residue is then subjected to stripping with water vapor under reduced pressure and 388 g are obtained. 2- (2-cyclopentenyl) -3-methyl-2-cyclopenten-4-ol-1-one, with a purity of 91.7% according to the method of analysis with ethylene diamine, and (nD30) of 1.5160.



   Part h - Instead of carrying out the following procedure (g), the substituted cyclopentenolone can be reacted with chry- santhemum-monocarboxylic acid anhydride as follows: boil under reflux at 165 C for four hours a mixture of 92 g. of 2- (2-cyclopente-
 EMI10.3
 nyl) -3-methyl-2-cyclopenten 4-0l-1-one, of a purity of 96.7% (0.5 mol), 168 gb of chrysanthemum-monocarboxylic acid anhydride of a purity of 94.8% (0.5 mol) and 119 g. dry butyl ether. The solution is spread with 42 g. of butyl ether and washed successively with 263 g. of a 7.6% aqueous solution of sodium hydroxide (0.5 mol), 0.25 liter of a 2% aqueous solution of sodium hydroxide (0.125 mol) and 0.25 liter of water.

   Each of the washing liquors is then exhausted, successively by means of a single portion of 100 cc. dibutyl ether to minimize product loss. The washed oil and the extracts are mixed, the volatile material removed therefrom at a final flask temperature of 80 ° C. and under reduced pressure to 5 mm. of mercury, then it is rectified with steam. 162 g are obtained. of residual product characterized by the following properties: refractive index, (n3D) = 1.5120; density (20/20) 1.033, purity according to the ethylene diamine method, 87.1%, chrysanthemum-monocarboxylic acid content, 0.1%, chrysanthemum-monocarboxylic acid anhydride content, 0, 2%.

   The yield based on the reagents is 88%, taking into account the 4.3 g. of product consumed for the analysis of the reaction mixture for the determination of the anhydride content.



   A number of formulas have been prepared by which cyclopentenyl chrysanthemumate has been tested to determine its effectiveness in admixture with various compounds which exert synergistic action. These formulas were tested by the method of Peet-Grady (Official Method of the Chemical Specialties Manufacturers Association). The results of these tests compared with those provided with the official reference insecticide

 <Desc / Clms Page number 11>

 (Official Test Insecticide, known as OTI) and with allethrin in formulas also supplemented with synergists are provided in the examples which follow.



  Example 2.
 EMI11.1
 
<tb>



  Formula <SEP> A <SEP> B <SEP> OTI
<tb>
<tb>
<tb> Chrysanthemumate <SEP> of <SEP> cyclopentenyl <SEP> (mg.) <SEP> 25 <SEP> - <SEP> -
<tb>
<tb> Allethrine, <SEP> mgo <SEP> - <SEP> 25-
<tb>
<tb> pyrethrin, <SEP> mgo <SEP> - <SEP> - <SEP> 100
<tb>
<tb> piperonyl <SEP> butoxide <SEP>, <SEP> mgo <SEP> 200 <SEP> 200-
<tb>
<tb> kerosene <SEP> deodorized, <SEP> ce. <SEP> 100 <SEP> 100 <SEP> 100
<tb>
 Large group Peet-Grady trial.
 EMI11.2
 
<tb>



  Formula <SEP> number <SEP> deaths <SEP>% <SEP> paralysis <SEP>% <SEP> Difference <SEP> / <SEP> OTI
<tb>
<tb>
<tb>
<tb> ¯¯¯¯¯¯¯¯¯ <SEP> testing <SEP> 24 <SEP> h. <SEP> 10 <SEP> raina <SEP> killed <SEP> paralyzed
<tb>
<tb>
<tb>
<tb>
<tb> A. <SEP> Chrysanthe-
<tb>
<tb>
<tb>
<tb>
<tb> mumate <SEP> from <SEP> cy-
<tb>
<tb>
<tb>
<tb> clopentenyl <SEP> 5 <SEP> 61.3 <SEP> 92, <SEP> 2 <SEP> + <SEP> 25 <SEP> - <SEP> 2.8
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> B.

   <SEP> allethrin <SEP> 5 <SEP> 40, <SEP> 90, <SEP> 0 <SEP> + <SEP> 4 <SEP> - <SEP> 4 <SEP>
<tb>
<tb>
<tb>
<tb>
<tb> OTI <SEP> 8 <SEP> 35.5 <SEP> 94.0
<tb>
 
The results of these tests show that the added value for death and the loss for paralysis of cyclopentyl chrysanthemumate with synergist are, compared to OTI, respectively 21 and 1.2 percentage points, compared with to the similar comparison made between allethrin with synergist and OTI.



  Example 3.
 EMI11.3
 
<tb>



  Formula <SEP> A <SEP> B <SEP> OTI
<tb>
<tb> Cyclopentenyl <SEP> Chrysanthemumate <SEP>, <SEP> mg. <SEP> 50-
<tb>
<tb> allethrin, <SEP> mg. <SEP> - <SEP> 50-
<tb>
<tb> pyrethrins, <SEP> mg. <SEP> - <SEP> - <SEP> 100
<tb>
<tb> isosafrol <SEP> n-octyl-sulfoxide <SEP>, <SEP> mg. <SEP> 250 <SEP> 250-
<tb>
<tb> fract. <SEP> kerosene <SEP> deodorized, <SEP> ce. <SEP> 100 <SEP> 100 <SEP> 100
<tb>
 Large group Peet-Grady trial.
 EMI11.4
 
<tb>



  Formula <SEP> number <SEP> Death <SEP>% <SEP> paralysis <SEP>% <SEP> Difference <SEP> OTI
<tb>
<tb> ¯¯¯¯¯¯ <SEP> testing <SEP> 24 <SEP> h. <SEP> 10 <SEP> min. <SEP> killed <SEP> paralyzed.
<tb>
<tb>



  A. <SEP> Chrysan- <SEP> 6 <SEP> 74.9 <SEP> 96.5 <SEP> + <SEP> 38 <SEP> + <SEP> 1.4 <SEP>
<tb>
<tb> themumate <SEP> from
<tb>
<tb> cyclopentény-
<tb>
<tb> the
<tb>
<tb>
<tb> B. <SEP> Allethrin <SEP> 6 <SEP> 37, <SEP> 2 <SEP> 90.6 <SEP> 0 <SEP> - <SEP> 4.5 <SEP>
<tb>
<tb>
<tb> OTI <SEP> 8 <SEP> 37.0 <SEP> 95.1
<tb>
 
The results of these trials show that the added values for death and paralysis of cyclopentenyl chrysanthemumate with sy- nergic over OTI are 38 and 5.9 percentage points, respectively, compared to a similar comparison made between l allethrin with synergist and OTI.
 EMI11.5
 
<tb>



  Formula <SEP> A <SEP> B <SEP> OTI
<tb>
<tb> Chrysanthemumate <SEP> of <SEP> cyclopentenyl, mgo <SEP> 42- <SEP> -
<tb>
<tb> allethrin, <SEP> mgo <SEP> - <SEP> 42 <SEP> -
<tb>
<tb> pyrethrins, <SEP> mgo <SEP> - <SEP> - <SEP> 100
<tb>
<tb> @ <SEP> n-propyl-isome, <SEP> mg. <SEP> 600 <SEP> 600 <SEP> -
<tb>
<tb> fracto <SEP> kerosene <SEP> deodorized, <SEP> ce. <SEP> 100 <SEP> 100 <SEP> 100
<tb>
 the n-propyl-isome is 2-methyl-6.7-methylenedioxy-1.2.3.4-

 <Desc / Clms Page number 12>

 
 EMI12.1
 di-n-propyl hexahydronaphthalene 3e5-dicarboyl .ate.



  Large group Peet-Grady trial.
 EMI12.2
 
<tb>



  Formula <SEP> number <SEP> deaths <SEP>% <SEP> paralysis <SEP>% <SEP> Difference <SEP> OTI
<tb>
 
 EMI12.3
 ¯¯¯¯¯¯¯¯¯¯¯¯ 24 hrs 10 min. death from paralysis
 EMI12.4
 
<tb> A. <SEP> Chrysanthemumate
<tb>
<tb> of <SEP> cydopentenyl <SEP> 4 <SEP> 65.1 <SEP> 92.1 <SEP> + <SEP> 33 <SEP> -3.9
<tb>
<tb> B. <SEP> allethrin <SEP> 4 <SEP> 47.2 <SEP> 94.0 <SEP> + <SEP> 15 <SEP> -2.0
<tb>
<tb>
<tb> OTI <SEP> 4 <SEP> 32.6 <SEP> 96.0
<tb>
 
The results of these tests show that the added value of deaths for cyclopentenyl chrysanthemumate with synergist compared to OTI is 18 percentage points compared to a similar comparison between allethrin with synergist and OTI; there is a slight decrease in paralysis, which is 1.9 point per cent.



  Example 5.
 EMI12.5
 
<tb>



  Formula <SEP> A <SEP> B <SEP> OTI
<tb>
<tb>
<tb>
<tb>
<tb> Cyclopentenyl <SEP> Chrysanthemumate <SEP>, <SEP> mg. <SEP> 40 <SEP> - <SEP> -
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> allethrin, <SEP> mgo <SEP> - <SEP> 40-
<tb>
<tb>
<tb>
<tb>
<tb> pyrethrins, <SEP> mg, <SEP> - <SEP> - <SEP> 100
<tb>
<tb>
<tb>
<tb>
<tb> <SEP> sesame oil <SEP>, <SEP> mg. <SEP> 150 <SEP> 150-
<tb>
<tb>
<tb>
<tb>
<tb> fracto <SEP> kerosene <SEP> deodorized, <SEP> ce. <SEP> 100 <SEP> 100 <SEP> 100
<tb>
 
 EMI12.6
 Peet-Grady trial. in a large group.
 EMI12.7
 
<tb> Formula <SEP> number <SEP> death <SEP>% <SEP> paralysis <SEP>% <SEP> Difference <SEP> OTI
<tb>
 
 EMI12.8
 ¯¯¯¯¯¯¯ was training 24 hours. 10 min, death paralysis A. -cllirysantheIBlllJate cyclopentenyl 3 26.1 89.8 -11 -6.4.
 EMI12.9
 
<tb>



  B. <SEP> Allethrin <SEP> 3 <SEP> 18.8 <SEP> 90.8 <SEP> -18 <SEP> -5.4
<tb>
<tb> OTI <SEP> 5 <SEP> 37.4 <SEP> 96, <SEP> 2 <SEP>
<tb>
 
The results of this trial show that the value of deaths obtained with cyclopentenyl chrysanthemumate with sesame oil as a synergist, although less than that obtained with OTI, is 7 percentage points higher than that obtained. allethrin with synergy compared with OTI; the figure for paralysis is only slightly worse (-1).



  Example 6
 EMI12.10
 
<tb> Formula <SEP> A <SEP> B <SEP> OTI
<tb>
<tb>
<tb> Cyclopentenyl <SEP> Chrysanthemumate <SEP>, <SEP> mg. <SEP> 30- <SEP> -
<tb>
<tb>
<tb> allethrin, <SEP> mg. <SEP> - <SEP> 30 <SEP> -
<tb>
<tb> pyrethrins, <SEP> mg. <SEP> - <SEP> - <SEP> 100
<tb>
<tb>
<tb> @ <SEP> synergistic <SEP> 6266, <SEP> mg. <SEP> 1000 <SEP> 1000 <SEP> -
<tb>
<tb> fract. <SEP> kerosene <SEP> deodorized, <SEP> ce <SEP> 100 <SEP> 100 <SEP> 100
<tb>
   @ chemical identification:

     N- (hexoxyethoxypropyl) -bicyclo-2.2.1-
 EMI12.11
 5-heptene-203-dicarboximide Large group Peet-Gradv assays *
 EMI12.12
 
<tb> Formula <SEP> Number <SEP> death <SEP>% <SEP> paralysis <SEP>% <SEP> difference <SEP> OTI
<tb>
 
 EMI12.13
 ¯¯¯¯¯¯¯¯¯¯¯ of 2G tests. ho 10 mino deaths' paralysis
 EMI12.14
 
<tb> A.

   <SEP> Chrysanthemumate <SEP> from
<tb>
<tb> cyclopentenyl <SEP> 5 <SEP> 46.6 <SEP> 94.2 <SEP> + <SEP> 13 <SEP> + <SEP> 0.2
<tb>
<tb> Bo <SEP> Allethrin <SEP> 5 <SEP> 31.4 <SEP> 92.1 <SEP> -3 <SEP> - <SEP> 1.9
<tb>
<tb>
<tb> OTI <SEP> 8 <SEP> 34.3 <SEP> 94.0 <SEP> - <SEP> -
<tb>
 

 <Desc / Clms Page number 13>

 
The results of these tests show that the added values for death and paralysis of cyclorentenyl chrysanthemumate with synergism relative to OTI are respectively 16 and 2.1 percentage points compared to a similar comparison made with allethrin. with synergetic about OTI.



  Example 7.
 EMI13.1
 
<tb>



  Formula <SEP> A <SEP> B <SEP> OTI
<tb>
<tb> Cyclopentenyl <SEP> Chrysanthemumate <SEP>, <SEP> mg. <SEP> 51 <SEP> - <SEP> -
<tb>
<tb> allethrin, <SEP> mg. <SEP> - <SEP> 51-
<tb>
<tb> pyrethrins, <SEP> mg. <SEP> - <SEP> - <SEP> 100
<tb>
<tb> @ <SEP> synergistic <SEP> 264, <SEP> mg. <SEP> 1000 <SEP> 1000 <SEP> -
<tb>
<tb> fract. <SEP> kerosene <SEP> deodorized, <SEP> ce., <SEP> 100 <SEP> 100 <SEP> 100
<tb>
 
 EMI13.2
 chemical identification:. # N- (2 (ethylhexyl) -bicyclo-2.2.1-5-liep-tene-2.3-dicarboximide.



   Large group Peet-Grady trials.
 EMI13.3
 
<tb>



  Formula <SEP> Number <SEP> deaths <SEP>% <SEP> paralysis <SEP>% <SEP> Difference
<tb>
<tb>
<tb>
<tb>
<tb> testing <SEP> OTI
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> death <SEP> para-
<tb>
 
 EMI13.4
 ¯¯¯¯¯¯¯¯¯¯¯¯¯¯ # ¯¯¯¯¯ ¯¯¯¯ ¯¯¯¯¯¯¯ ----- lysia.
 EMI13.5
 
<tb>



  Ao <SEP> chrysanthemumate <SEP> from <SEP> 5 <SEP> 31.8 <SEP> 93.0 <SEP> + <SEP> 7 <SEP> -1.5
<tb>
<tb> cyclopentenyl
<tb>
<tb> B. <SEP> Allethrin <SEP> 5 <SEP> 29.0 <SEP> 90.7 <SEP> +4 <SEP> -3.8
<tb>
<tb>
<tb> OTI <SEP> 8 <SEP> 24.9 <SEP> 94.5 <SEP> - <SEP> -
<tb>
 
In accordance with these tests, the official test insecticide (OTI) shows only a 1.5 point per cent gain over cyclopentenyl chrysanthemumate with synergistic, the gain over allethrin being 3.8, ie a superiority of 2.3 percentage points in favor of cyclopentenyl chrysanthemumate over allethrin with regard to paralysis.



  Example 8.



   Tests were carried out using a composition containing cyclopentenyl chrysanthemumate intended for spraying onto cattle in an oily vehicle, compared with a commercial oily composition of the same destination containing pyrethrins. The proportions of the ingredients appearing in the composition are as follows.
 EMI13.6
 
<tb>



  Formula <SEP> A <SEP> B <SEP> OTI
<tb>
 
 EMI13.7
 Cyclopentenyl chrysanthemumate, mgo - - 15
 EMI13.8
 
<tb> pyrethrins, <SEP> mgo <SEP> 25 <SEP> 15-
<tb>
<tb> piperonyl <SEP> butoxide <SEP>, <SEP> mg. <SEP> 200 <SEP> 120 <SEP> 120
<tb>
<tb> polyoxypropy <SEP> monobutyl <SEP> <SEP> <SEP>
<tb>
<tb> lene <SEP> glycol <SEP> - <SEP> 5 <SEP> 5
<tb>
 
 EMI13.9
 Spray oil, Qaa, oFo (cc) 100 100 100
The tests are carried out on dairy cows, ten in number for each formula. Cows are given twelve sprays which are applied at three to four day intervals at the rate of 57 g. about per animal. The sprays are done in the middle of the afternoon and the counts are made the next day at noon.

   They relate to the ox fly (h), the stable fly (s) and the house fly (H). The ratios of the various species of flies in the total population are 50, 20, and 30, respectively.



   The following table gives the results obtained as a repellent effect.

 <Desc / Clms Page number 14>

 
 EMI14.1
 
<tb>



  Pulvéri- <SEP> Species <SEP> of <SEP> Repellency <SEP> <SEP>% <SEP> p. <SEP> repellent
<tb>
<tb>
<tb>
<tb> sation <SEP> fly <SEP> 24 <SEP> h. <SEP> 48 <SEP> h. <SEP> 72 <SEP> h. <SEP> by <SEP> period,
<tb>
<tb>
<tb> average.
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>



  A <SEP> h, <SEP> S, <SEP> H <SEP> 65.7 <SEP> 55.4 <SEP> 31.8 <SEP> 50.9
<tb>
<tb>
<tb>
<tb>
<tb> pyrethrins <SEP> S, H <SEP> 44.4 <SEP> 41.7 <SEP> 3.0 <SEP> 29.7
<tb>
<tb>
<tb>
<tb> S <SEP> 50.9 <SEP> 41.2 <SEP> 21.5 <SEP> 37.9
<tb>
<tb>
<tb>
<tb> H <SEP> 40.0 <SEP> 35.3 <SEP> 43.1 <SEP> 39.5
<tb>
<tb>
<tb>
<tb> h <SEP> 90.0 <SEP> 76.8 <SEP> 47.8 <SEP> 71.5
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> B
<tb>
<tb>
<tb>
<tb> pyrethrin <SEP> s <SEP> h, <SEP> S, <SEP> H <SEP> 71.5 <SEP> 63.8 <SEP> 50, <SEP> 2 <SEP> 61.8
<tb>
<tb>
<tb>
<tb>
<tb> S, H <SEP> 49.7 <SEP> 50.0 <SEP> 27.7 <SEP> 42.1
<tb>
<tb>
<tb>
<tb> S <SEP> 71.1 <SEP> 35.8 <SEP> 40.5 <SEP> 49.1
<tb>
<tb>
<tb>
<tb> H <SEP> 57.3 <SEP> 44.5 <SEP> 48.8 <SEP> 50.2
<tb>
<tb>
<tb>
<tb> h <SEP> 88.0 <SEP> 88.1 <SEP> 74.6 <SEP> 81.6
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> C <SEP> h, <SEP> S, <SEP> H <SEP> 74,

  2 <SEP> 63.0 <SEP> 52.0 <SEP> 63.1
<tb>
<tb>
<tb>
<tb>
<tb> chrysanthemu- <SEP> S, <SEP> H <SEP> 60.0 <SEP> 43, <SEP> 0 <SEP> 0 <SEP> 34.7
<tb>
<tb>
<tb>
<tb> mate <SEP> de <SEP> cyclo- <SEP> S <SEP> 74.9 <SEP> 47.1 <SEP> 52.3 <SEP> 58.1
<tb>
<tb>
<tb>
<tb> pentenyl <SEP> H <SEP> 65.2 <SEP> 41.4 <SEP> 55.5 <SEP> 54.0
<tb>
<tb>
<tb>
<tb> h <SEP> 84.7 <SEP> 88.6 <SEP> 93.7 <SEP> 89.0
<tb>
 
The above repellency percent values are based on the number of counts made, as follows.
 EMI14.2
 
<tb>



  Fly <SEP> species <SEP> <SEP> 24 <SEP> h. <SEP> 48 <SEP> h. <SEP> 72 <SEP> h. <SEP>
<tb>
<tb>
<tb>
<tb>
<tb> h, <SEP> S, <SEP> H, <SEP> number <SEP> of <SEP> counts <SEP> 120 <SEP> 110 <SEP> 100
<tb>
<tb>
<tb>
<tb> S, <SEP> H, <SEP> 30 <SEP> 30 <SEP> 20
<tb>
<tb>
<tb>
<tb> S <SEP> 90 <SEP> 80 <SEP> 80
<tb>
<tb>
<tb>
<tb> H <SEP> 90 <SEP> 80 <SEP> 80
<tb>
<tb>
<tb>
<tb> h <SEP> 120 <SEP> 110 <SEP> 100
<tb>
 
In accordance with these tests, the composition based on cycloentenyl chrysanthemumate as an oily vehicle spray for cattle is shown to be superior in repellent activity against ox flies, stable flies and house flies in the formulations of the com. - merchandise based on pyrethrins with synergy.

   It will be noted that spray C is greater than spray B and at the same time cheaper than spray B, and therefore than spray A. Thus, given the current prices of the ingredients of the various formulas, this increase in activity obtained with cyclopentyl chrysantemumate with synergist is obtained without price increase.



  Example 9.



   The formulas below use the same proportions of ingredients as in Example 8, but the spray oil is here replaced by the deodorized kerosene.
 EMI14.3
 
<tb>



  Formula <SEP> OTI <SEP> A <SEP> B <SEP> C
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> piperonyl <SEP> butoxide <SEP>, <SEP> mgo <SEP> - <SEP> 200 <SEP> 120 <SEP> 120
<tb>
<tb>
<tb>
<tb>
<tb> pyrethrins, <SEP> mg. <SEP> 100 <SEP> 25 <SEP> 15-
<tb>
<tb>
<tb>
<tb>
<tb> <SEP> fly repellent <SEP> agent <SEP>, <SEP> ce. <SEP> * <SEP> - <SEP> - <SEP> 5 <SEP> 5 <SEP>
<tb>
<tb>
<tb>
<tb>
<tb> chrysanthemumate <SEP> of <SEP> cyclopentenyl, mgo <SEP> - <SEP> - <SEP> - <SEP> 15
<tb>
<tb>
<tb>
<tb>
<tb> kerosene <SEP> deodorized, <SEP> Q.S.P., <SEP> ce. <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
<tb>
   @ polyoxypropylene glycol monobutyl ether Large group Peet-Grady trials on the destruction of flies.

   

 <Desc / Clms Page number 15>

 
 EMI15.1
 
<tb> Formula <SEP> number <SEP> paralyzes <SEP>% <SEP> Death <SEP>% <SEP> Diff. <SEP> OTI <SEP> and
<tb> of tests <SEP> 3 <SEP> min. <SEP> 5 <SEP> mine <SEP> 10 <SEP> min. <SEP> 24 <SEP> h. <SEP> estimate
<tb>
<tb>
<tb>
<tb>
<tb> A <SEP> 6 <SEP> 86.1 <SEP> 90.2 <SEP> 95.2 <SEP> 67.9 <SEP> + <SEP> 31 <SEP> AA <SEP>
<tb>
<tb> B <SEP> 6 <SEP> 87.0 <SEP> 92.6 <SEP> 96.0 <SEP> 72.3 <SEP> + <SEP> 36 <SEP> AA
<tb>
<tb>
<tb> C <SEP> 6 <SEP> 80.8 <SEP> 85.4 <SEP> 93.6 <SEP> 70.3 <SEP> + <SEP> 34 <SEP> AA <SEP>
<tb>
<tb> OTI <SEP> 10 <SEP> 91.5 <SEP> 93.9 <SEP> 94.9 <SEP> 36.7 <SEP> - <SEP> B <SEP>
<tb>
 
These tests show that Formula C is as effective at paralysis and death as Formula B, while being less expensive.



  Example 10.



   The efficacy with respect to Blatella germanica of cyclopentenyl chrysanthemumate alone and combined with sulfoxide (n-octyl-isosafrol sulfoxide) as a synergist is determined.



   Formulas, Series 1
 EMI15.2
 
<tb> Formula <SEP> Chrysantheimimate
<tb>
<tb>
<tb>
<tb> (x) <SEP> of <SEP> cyclopentenyl <SEP> Allethrin <SEP> Sulfoxide
<tb>
<tb>
<tb>
<tb>
<tb> mg. <SEP> mg. <SEP> mg.
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>



  A <SEP> 80
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> B <SEP> 40 <SEP> -
<tb>
<tb>
<tb>
<tb>
<tb> C <SEP> 20- <SEP> -
<tb>
<tb>
<tb>
<tb> D <SEP> 10 <SEP> - <SEP> -
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> E <SEP> 10 <SEP> - <SEP> 50 <SEP>
<tb>
<tb>
<tb>
<tb>
<tb> F <SEP> 5 <SEP> - <SEP> 25 <SEP>
<tb>
<tb>
<tb>
<tb>
<tb> G <SEP> 2.5 <SEP> - <SEP> 12.5
<tb>
<tb>
<tb>
<tb>
<tb> H- <SEP> 40
<tb>
<tb>
<tb>
<tb>
<tb> I <SEP> - <SEP> 20
<tb>
<tb>
<tb>
<tb>
<tb> J- <SEP> 10-
<tb>
<tb>
<tb>
<tb>
<tb> K <SEP> - <SEP> 5-
<tb>
<tb>
<tb>
<tb>
<tb> L- <SEP> 5 <SEP> 25
<tb>
<tb>
<tb>
<tb>
<tb> M <SEP> - <SEP> 2.5 <SEP> 12.5
<tb>
<tb>
<tb>
<tb>
<tb> N- <SEP> 1.25 <SEP> 6.25
<tb>
   @ In addition, each of the solutions contains 0.02 cc of "Triton", 5 cc. acetone and enough water to make a total volume of 100 cc.



   A second series of tests is carried out, using the following formulas:

 <Desc / Clms Page number 16>

 
 EMI16.1
 
<tb> Chrysanthemumate
<tb>
<tb>
<tb>
<tb> Cyclopentenyl <SEP> formula. <SEP> mg. <SEP> Allethrin. <SEP> mg. <SEP> Tallow <SEP> oxide, <SEP> mg.
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>



  A <SEP> 80 <SEP> -
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> B <SEP> 40 <SEP> - <SEP> -
<tb>
<tb>
<tb>
<tb>
<tb> C <SEP> 20- <SEP> -
<tb>
<tb>
<tb>
<tb> D <SEP> 10 <SEP> - <SEP> -
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> E <SEP> 5- <SEP> -
<tb>
<tb>
<tb>
<tb>
<tb> F <SEP> 10 <SEP> - <SEP> 50
<tb>
<tb>
<tb>
<tb>
<tb> G <SEP> 5- <SEP> 25
<tb>
<tb>
<tb>
<tb>
<tb> H <SEP> 2.5 <SEP> - <SEP> 12.5
<tb>
<tb>
<tb>
<tb> I <SEP> - <SEP> 20-
<tb>
<tb>
<tb>
<tb>
<tb> J <SEP> - <SEP> 10-
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> K <SEP> 5 <SEP> -
<tb>
<tb>
<tb>
<tb>
<tb> L <SEP> - <SEP> 2.5
<tb>
<tb>
<tb>
<tb>
<tb> M <SEP> - <SEP> 1,25 <SEP> - <SEP>
<tb>
<tb>
<tb>
<tb>
<tb> N- <SEP> 5 <SEP> 25
<tb>
<tb>
<tb>
<tb>
<tb> 0 <SEP> - <SEP> 2.5 <SEP> 12.5
<tb>
<tb>
<tb>
<tb>
<tb> P <SEP> - <SEP> 1,25 <SEP> 6,

  25
<tb>
 
The following table gives the results expressed in the dose necessary to obtain a cockroach mortality of 50% in 24 hours.



   Results, series 2.
 EMI16.2
 
<tb>



  Formulas <SEP> mg. <SEP> for <SEP> mortality <SEP> 50 <SEP>%
<tb>
<tb>
<tb> in <SEP> 24 <SEP> hours
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> A <SEP> to <SEP> E <SEP> 15
<tb>
<tb>
<tb>
<tb> F <SEP> to <SEP> H <SEP> 4.5
<tb>
<tb>
<tb>
<tb> I <SEP> to <SEP> M <SEP> 3
<tb>
<tb>
<tb>
<tb> N <SEP> to <SEP> P <SEP> 2.7
<tb>
 
In both series, cyclopentenyl chrysanthemumate is synergistically activated more efficiently than allethrin. In the case of al- lethrin, the saving achieved by synergy is only half or less, whereas in the case of cyclopentenyl chrysanthemumate, it is possible to save two-thirds to three-quarters of the quantity needed without synergy.



  Example 11.



   The efficacy against Aphis rumicis on the cres- son of cyclopentenyl chrysanthemumate alone and cyclopentenyl chrysanthemumate in combination with tallow oxide (isosafrol n-octylsulphoxide) as a synergist and with synergistic 6266 (N- (Hexoxyethoxypropyl) bicyclo-2.2.1-5-heptene-2.3-dicarboximide.



  Similar tests were also carried out using allethrin.



  Formulas, series 2.

 <Desc / Clms Page number 17>

 
 EMI17.1
 
<tb> (@) <SEP> Formula <SEP> Allethrin <SEP> Chrysanthemumate <SEP> of <SEP> Sulfoxide <SEP> Synergistic
<tb>
 
 EMI17.2
 ¯¯¯¯¯¯¯ mo cyclopenténY1e. Ingo mgo 6266 Ingo
 EMI17.3
 
<tb> A <SEP> 100 <SEP> - <SEP> - <SEP> -
<tb>
<tb>
<tb>
<tb> B <SEP> 50 <SEP> - <SEP> -
<tb>
<tb>
<tb>
<tb>
<tb> C <SEP> 25 <SEP> - <SEP> -
<tb>
<tb>
<tb>
<tb>
<tb> D <SEP> 12.5 <SEP> - <SEP> -
<tb>
<tb>
<tb>
<tb>
<tb> E <SEP> 6,

  25 <SEP> - <SEP> - <SEP> -
<tb>
<tb>
<tb>
<tb>
<tb> F <SEP> 12 <SEP> - <SEP> 60-
<tb>
<tb>
<tb>
<tb>
<tb> G <SEP> 6 <SEP> - <SEP> 30-
<tb>
<tb>
<tb>
<tb>
<tb> H <SEP> 3 <SEP> - <SEP> 15
<tb>
<tb>
<tb>
<tb>
<tb> I <SEP> - <SEP> 100 <SEP> - <SEP> -
<tb>
<tb>
<tb>
<tb>
<tb> J <SEP> - <SEP> 50-
<tb>
<tb>
<tb>
<tb>
<tb> K <SEP> - <SEP> 25 <SEP> -
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> L- <SEP> 12.5 <SEP> - <SEP> -
<tb>
<tb>
<tb>
<tb> M <SEP> - <SEP> 6,

  25
<tb>
<tb>
<tb>
<tb>
<tb> M- <SEP> 12 <SEP> 60-
<tb>
<tb>
<tb>
<tb>
<tb> 0 <SEP> - <SEP> 6 <SEP> 30-
<tb>
<tb>
<tb>
<tb>
<tb> P <SEP> - <SEP> 3 <SEP> 15 <SEP> -
<tb>
<tb>
<tb>
<tb>
<tb> Q <SEP> 12 <SEP> - <SEP> - <SEP> 60
<tb>
<tb>
<tb>
<tb>
<tb> R <SEP> 6 <SEP> - <SEP> - <SEP> 30 <SEP>
<tb>
<tb>
<tb>
<tb>
<tb> S <SEP> 3- <SEP> 15
<tb>
<tb>
<tb>
<tb>
<tb> T- <SEP> 12 <SEP> - <SEP> 60
<tb>
<tb>
<tb>
<tb>
<tb> U <SEP> 6 <SEP> - <SEP> 30 <SEP>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> V <SEP> - <SEP> 3 <SEP> - <SEP> 15
<tb>
<tb>
<tb>
<tb> W <SEP> 12 <SEP> - <SEP> - <SEP> 60
<tb>
<tb>
<tb>
<tb>
<tb> X <SEP> 6- <SEP> - <SEP> 30
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Y <SEP> 3 <SEP> - <SEP> - <SEP> 15
<tb>
<tb>
<tb>
<tb> Z <SEP> - <SEP> 12- <SEP> 60
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> AA <SEP> - <SEP> 6- <SEP> 30
<tb>
<tb>
<tb>
<tb>
<tb> BB- <SEP> 3-

  <SEP> 15
<tb>
   (@) In addition, each of the formulas contains 10 cc. acetone, an amount of emulsifying agent representing 10% by weight of the toxic agent (cyclopentenyl allethrin or chrysanthemumate, plus any synergist) and an amount of water sufficient to make 100 cc.



   The resulting mixture was stirred and sprayed on potted watercress plants, each of the pots being infested with about 250 Aphis rumicis. nymphs and adults. The pots are placed on a turntable. 80 cc is applied. of the 100 cc of the formula using a sprayer at a pressure of 2.8 kg./cm2. The dead aphids are numbered twenty-four hours after application of the treatment. The results of the tests are plotted on a logarithmic probability scale.



  Here are the results obtained for a mortality of 50% and for a mortality of 95% after 24 hours.
 EMI17.4
 
<tb>



  Formula <SEP> Mg. <SEP> for <SEP> death <SEP> in <SEP> 24 <SEP> hours
<tb>
<tb>
<tb>
<tb> -------- <SEP> to <SEP> 50 <SEP> to <SEP> 95 <SEP>%
<tb>
<tb>
<tb>
<tb>
<tb> A <SEP> to <SEP> E <SEP> 10 <SEP> 70
<tb>
<tb>
<tb>
<tb>
<tb> F <SEP> to <SEP> H <SEP> 2 <SEP> 20
<tb>
<tb>
<tb>
<tb> I <SEP> to <SEP> M <SEP> 10 <SEP> 80
<tb>
<tb>
<tb>
<tb>
<tb> N <SEP> to <SEP> P <SEP> 1 <SEP> 11
<tb>
<tb>
<tb>
<tb>
<tb> Q <SEP> to <SEP> S <SEP> 6 <SEP> 14
<tb>
<tb>
<tb>
<tb> T <SEP> to <SEP> V <SEP> 2 <SEP> 12
<tb>
<tb>
<tb>
<tb>
<tb> W <SEP> to <SEP> Y <SEP> 5 <SEP> 13
<tb>
<tb>
<tb>
<tb> Z <SEP> to <SEP> BB <SEP> 3 <SEP> 9.5
<tb>
 
These results show that cyclopentenyl chrysanthemumate is made much more active by synergists than is allethrin.



  Example 12
A comparison is made of cyclopentenyl chrysanthemumate

 <Desc / Clms Page number 18>

 le and allethrin against the house fly following the large group Peet-Grady test. The results obtained, which are the means of five tests, are shown in the following table.



   Paralysis
 EMI18.1
 
<tb> Death <SEP>% <SEP>%
<tb>
<tb> Material <SEP> Concentration <SEP> 24 <SEP> hours <SEP> 10 <SEP> minutes
<tb>
<tb> Allethrin <SEP> 200 <SEP> 48.6 <SEP> 97.5
<tb>
<tb> Chrysanthemumate <SEP> from <SEP> cy'clopen-
<tb>
<tb> tenyl <SEP> 200 <SEP> 44.1 <SEP> 96.5
<tb>
<tb>
<tb> Allethrin <SEP> 100 <SEP> 25.8 <SEP> 91.4
<tb>
<tb> Chrysanthemumate <SEP> of <SEP> cyclopentenyl <SEP> 100 <SEP> 26; <SEP> 6 <SEP> 89.6
<tb>
 
 EMI18.2
 Allethrin 50 14.7 g 3.1
 EMI18.3
 
<tb> Chrysanthemumate <SEP> of <SEP> cyclopentenyl <SEP> 50 <SEP> 16.4 <SEP> 78.8
<tb>
   @ in mg. for 100 this. of solution in a fraction of deodorized kerosene.



   An analysis of the variations of the above results shows that there is no clear difference in behavior between allethrin and cyclopentenyl chrysanthemumate used without synergist against the house fly.



  Example 13.
 EMI18.4
 



  Syclopentenyl chrysanthemumate was compared synergistically with synergistically allethrin for their efficacy against house fly, following the large group Peet-Grady trial. Synergistic u-
 EMI18.5
 used are piperonyl butoxide ((3.4-methylenedioxy-6-propyl) benzyl - butyl-diethylene-glycol ether), synergist 6266 (N-hexoxyethoxypropyl- (bicyclo-2.2.1-5-heptene -2.3-bicarboximide), sulfoxide (isosafrol n-octyl-sulfoxide) and n-propyl-isome (2-methyl-6.7-methylenedior-1.2.3.



  Di-n-propyl 4-hexahydronaphthalene-3.4-dicarbo2ylate).
 EMI18.6
 



  Formula Garlic Ag Bl Z CL C2 Dl D2
 EMI18.7
 
<tb> Allethrin, <SEP> mg. <SEP> 25 <SEP> - <SEP> 30 <SEP> - <SEP> 50 <SEP> 50 <SEP> -
<tb>
<tb> Chrysanthemumate <SEP> from <SEP> cyclo-
<tb>
<tb>
<tb> pentenyl, <SEP> mg.- <SEP> 25- <SEP> 30 <SEP> - <SEP> 50- <SEP> 50
<tb>
<tb>
<tb> Piperonyl <SEP> Butoxide <SEP>, <SEP> mg. <SEP> 200 <SEP> 200- <SEP> - <SEP> - <SEP> - <SEP> - <SEP> -
<tb>
<tb>
<tb> Synergistic <SEP> 6266, <SEP> mg.- <SEP> - <SEP> 1000 <SEP> 1000 <SEP> - <SEP> -
<tb>
<tb>
<tb> sulfoxide, <SEP> mg.- <SEP> - <SEP> - <SEP> - <SEP> 250 <SEP> 250-
<tb>
<tb> n-propyl-isome, <SEP> mg. <SEP> - <SEP> - <SEP> - <SEP> - <SEP> 250 <SEP> 250
<tb>
<tb>
<tb> kerosene <SEP> deodorized, <SEP> cc.

   <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
<tb>
 
The results, which are the means of four tests, are given in the following table.
 EMI18.8
 
<tb>



  Formula <SEP> Death <SEP>% <SEP> Paralysis <SEP>% <SEP>
<tb>
<tb>
<tb>
<tb> ¯¯¯¯¯ <SEP> 24 <SEP> h. <SEP> 10 <SEP> min.
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>



  Al <SEP> (allethrin <SEP> + <SEP> piperonyl <SEP> butoxide <SEP>) <SEP> 40.0 <SEP> 90.0
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> A2 <SEP> (chrysanthemumate <SEP> of <SEP> cyclopentenyl
<tb>
<tb>
<tb>
<tb>
<tb> + <SEP> piperonyl <SEP> butoxide <SEP> <SEP> 61.3 <SEP> 91.2
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Bl <SEP> (allethrin <SEP> + <SEP> synergistic <SEP> 6266) <SEP> 31.4 <SEP> 92.1
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> B2 <SEP> (chrysanthemumate <SEP> of <SEP> cyclopentenyl
<tb>
<tb>
<tb>
<tb>
<tb> + <SEP> synergistic <SEP> 6266) <SEP> 46.6 <SEP> 94.2
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Cl <SEP> (allethrin <SEP> + <SEP> sulfoxide) <SEP> 37.2 <SEP> 90.6
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> G2 <SEP> (cyclopentenyl <SEP> chrysanthemumate <SEP>
<tb>
<tb>
<tb>
<tb>
<tb> + <SEP> sulfoxide <SEP> 74.9 <SEP> 96,

  5
<tb>
<tb>
<tb>
<tb>
<tb> Dl <SEP> (allethrin <SEP> + <SEP> n-propyl-isome) <SEP> 42.3 <SEP> 92.0
<tb>
 
 EMI18.9
 D2 (cyclopentenyl cbx7santhemumat-e + n- 63.4 92.8
 EMI18.10
 
<tb> propyl-isome)
<tb>
 

 <Desc / Clms Page number 19>

 
We can estimate the amount of cyclopentenyl chrysanthemumate without synergist and allethrin without synergist that it would take to obtain the same percentage of death and paralysis as with the same toxicants containing a synergist by plotting the results. as in Example 12 and by deducing from the curves thus obtained the quantities corresponding to the deaths and paralysis provided by the toxicants with synergism. The following table gives the quantities thus estimated.



   Equivalent amount in mg. toxic for the same effect.
 EMI19.1
 
<tb>



  Death. <SEP> 24 <SEP> hours <SEP> Paralysis. <SEP> 10 <SEP> minutes
<tb>
<tb> @ <SEP> Chrysanthemumate <SEP> Chrysanthemum.
<tb>
 
 EMI19.2
 



  Formula Cyclopentenyl Allethrin Allethrin, Cyclopentenyl
 EMI19.3
 
<tb> Al <SEP> (allethrin <SEP> 25,
<tb>
<tb> butoxide <SEP> pip-
<tb>
<tb> ronyle <SEP> 200) <SEP> 160- <SEP> 78 <SEP> -
<tb>
<tb> A2 <SEP> (chrysanth. <SEP> from
<tb>
<tb> cyclopentenyl
<tb>
 
 EMI19.4
 25 / -but-oxide pi-
 EMI19.5
 
<tb> peronyle, <SEP> 200) - <SEP> 350- <SEP> 98
<tb>
<tb>
<tb>
<tb>
<tb> Bl <SEP> (allethrin <SEP> 30,
<tb>
<tb>
<tb>
<tb> synergistic <SEP> 6266
<tb>
<tb>
<tb>
<tb>
<tb> 1000) <SEP> 112- <SEP> 107-
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> B2 <SEP> (chrysanthemum.
<tb>
<tb>
<tb>
<tb>
<tb> cyclopentenyl <SEP> 30,
<tb>
<tb>
<tb>
<tb> synergistic <SEP> 6266,
<tb>
<tb>
<tb>
<tb> 1000) <SEP> - <SEP> 205- <SEP> 140
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Cl <SEP> (allethrin <SEP> 50,
<tb>
<tb>
<tb>
<tb>
<tb> tallow <SEP> oxide, <SEP> 250)

   <SEP> 143 <SEP> - <SEP> 94 <SEP> -
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> C2 <SEP> (chrysantho <SEP> from
<tb>
 
 EMI19.6
 cyclopentenyl, 50,
 EMI19.7
 
<tb> sulfoxide, <SEP> 250- <SEP> 620- <SEP> 180
<tb>
<tb>
<tb> Dl <SEP> (allethrin <SEP> 50,
<tb>
<tb>
<tb> n-propyl-isome,
<tb>
<tb>
<tb> 250) <SEP> 175- <SEP> 106 <SEP> -
<tb>
<tb>
<tb>
<tb> D2 <SEP> (chrysanthemum.
<tb>
<tb>
<tb>
<tb> cyclopentenyl <SEP> 50,
<tb>
<tb>
<tb> n-propyl-isome <SEP> 250) <SEP> - <SEP> 380 <SEP> - <SEP> 112
<tb>
   @ values in mg. for 100 this. deodorized kerosene fraction.



   The efficacy ratios of the toxicant with synergist to the toxicant without synergist (allethrin with synergist allethrin without synergist and cyclopentenyl chrysanthemumate with synergistic cyclopentenyl chrysanthemumate without synergist), according to the table above, are as follows;
 EMI19.8
 
<tb> Death <SEP> ¯¯¯Paralysis¯¯¯¯¯¯¯
<tb>
<tb>
<tb>
<tb> Chrysanthemm. <SEP> chrysanthemum.
<tb>
<tb>
<tb>



  Synergistic <SEP> allethrin <SEP> cyclopentenyl <SEP> allethrin <SEP> cyclopentenyl,
<tb>
<tb>
<tb>
<tb> Butoxide <SEP> of <SEP> 6.4 <SEP> 14.0 <SEP> 3.1 <SEP> 3, <SEP> 9 <SEP>
<tb>
<tb>
<tb> piperonyl
<tb>
<tb>
<tb> Synergistic <SEP> 6266 <SEP> 3.7 <SEP> 6.8 <SEP> 3, <SEP> 6 <SEP> 4, <SEP> 7 <SEP>
<tb>
<tb>
<tb>
<tb> Sulphoxide <SEP> 2.9 <SEP> 12.4 <SEP> 1.9 <SEP> 3.6
<tb>
<tb>
<tb>
<tb>
<tb> n-propyl-isome <SEP> 3.5 <SEP> 7.6 <SEP> 2.1 <SEP> 2.2
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> average <SEP> 4.1 <SEP> 10.2 <SEP> 2.7 <SEP> 3, <SEP> 6 <SEP>
<tb>
 

 <Desc / Clms Page number 20>

 
It appears from this that, in the whole of its behavior, cyclopentenyl chrysanthemumate is ten times more effective with a "synergist than without synergist, while allethrin is only four times more effective. .

   For paralysis alone, cyclopentenyl chrysanthemumate is four times more effective synergistically than without synergist, while allethrin is only three times.



  Example 14
These tests were carried out on the house fly using aerosol formulas based on cyclopentenyl chrysanthemumate, in accordance with the official specifications of the Standard Aerosol Test Method for Flying Insects. Comparative trials were also carried out using allethrin.

   85 parts by weight of equal parts of dichloro-difluoromethane (Freon 11) and trichlorofluoromethane (Freon 12) are made with the remaining 15 parts by weight, in each formula, being:
 EMI20.1
 
<tb> Chrysan- <SEP> Goal- <SEP> Sova-
<tb>
<tb> them. <SEP> of <SEP> oxide <SEP> cide
<tb>
<tb> Formula <SEP> cyclopen- <SEP> All- <SEP> Stro- <SEP> pip- <SEP> Sulf- <SEP> Bayol <SEP> 544
<tb>
<tb> ¯¯¯¯¯ <SEP> tenyl <SEP> thrine <SEP> DDT <SEP> bane <SEP> ronyl <SEP> oxide <SEP> D <SEP> C
<tb>
<tb> A <SEP> 0.4 <SEP> - <SEP> 2.0 <SEP> - <SEP> - <SEP> 7.6 <SEP> 5.0
<tb>
<tb> B <SEP> - <SEP> 0.4 <SEP> 2.0 <SEP> - <SEP> - <SEP> - <SEP> 7.6 <SEP> 5.0
<tb>
<tb> C <SEP> 0.34 <SEP> - <SEP> 2.0 <SEP> - <SEP> 1.6 <SEP> - <SEP> 4.56 <SEP> 6.5
<tb>
<tb> D- <SEP> 0.4 <SEP> 2.0 <SEP> - <SEP> 1.6 <SEP> - <SEP> 4.56 <SEP> 6.5
<tb>
<tb> E <SEP> 0.34 <SEP> - <SEP> 2,

  0 <SEP> - <SEP> - <SEP> 1.6 <SEP> 4.56 <SEP> 6.5
<tb>
<tb> F- <SEP> 0.4 <SEP> 2.0 <SEP> - <SEP> - <SEP> 1.6 <SEP> 4.56 <SEP> 6.5
<tb>
<tb> G <SEP> 0.34 <SEP> - <SEP> - <SEP> - <SEP> 1.6 <SEP> - <SEP> 6.56 <SEP> 6.5
<tb>
<tb> H- <SEP> 0.4 <SEP> - <SEP> - <SEP> 1.6 <SEP> - <SEP> 6.56 <SEP> 6.5
<tb>
<tb> I <SEP> 0.34 <SEP> - <SEP> - <SEP> - <SEP> - <SEP> 1.6 <SEP> 6.56 <SEP> 6.5
<tb>
<tb> J <SEP> - <SEP> 0.4 <SEP> - <SEP> - <SEP> - <SEP> 1.6 <SEP> 6.56 <SEP> 6.5
<tb>
<tb> K <SEP> 0.34 <SEP> - <SEP> - <SEP> 2.0 <SEP> - <SEP> 1.6 <SEP> 4.56 <SEP> 6.5
<tb>
<tb> L <SEP> 0.34 <SEP> 0.4 <SEP> - <SEP> 2.0 <SEP> - <SEP> 1.6 <SEP> 4.56 <SEP> 6.15
<tb>
 
Note.

   The D.D.T. is dichloro-diphenyl-trichloroethane, Bayol D is highly refined kerosene, Stroban is a chlorinated hydrocarbon containing 65% chlorine by weight, and Sovacide 544-0 is an aromatic petroleum solvent.



   Large group Peet-Grady trials.



   Paralysis
 EMI20.2
 
<tb> Death <SEP>% <SEP>% <SEP> Reported <SEP> to <SEP> Deferred / <SEP> test <SEP> TOTA
<tb>
<tb>
<tb>
<tb> Formula <SEP> 24 <SEP> hours <SEP> 15 <SEP> min. <SEP> nb. <SEP> TOTA <SEP> Death <SEP> Paralysis
<tb>
<tb>
<tb>
<tb>
<tb> A <SEP> 91.8 <SEP> 80.3 <SEP> 1 <SEP> + <SEP> 2 <SEP> + <SEP> 7 <SEP>
<tb>
<tb>
<tb>
<tb> B <SEP> 93.2 <SEP> 83.0 <SEP> 1 <SEP> + <SEP> 4 <SEP> + <SEP> 10 <SEP>
<tb>
<tb>
<tb>
<tb> C <SEP> 96.9 <SEP> 94.2 <SEP> 2 <SEP> + <SEP> 6 <SEP> + <SEP> 19 <SEP>
<tb>
<tb>
<tb>
<tb>
<tb> D <SEP> 91.0 <SEP> 85.5 <SEP> 3 <SEP> + <SEP> I <SEP> + <SEP> 8 <SEP>
<tb>
<tb>
<tb>
<tb> E <SEP> 94.0 <SEP> 89.9 <SEP> 2 <SEP> + <SEP> 3 <SEP> + <SEP> 14 <SEP>
<tb>
<tb>
<tb>
<tb> F <SEP> 93, <SEP> 5 <SEP> 87.6 <SEP> 3 <SEP> + <SEP> 4 <SEP> + <SEP> 10 <SEP>
<tb>
<tb>
<tb>
<tb> G <SEP> 85.8 <SEP> 91,

  9 <SEP> 4 <SEP> - <SEP> 5 <SEP> + <SEP> 12 <SEP>
<tb>
<tb>
<tb>
<tb> H <SEP> 77.1 <SEP> 83.3 <SEP> 4 <SEP> -13 <SEP> + <SEP> 4
<tb>
<tb>
<tb>
<tb> I <SEP> 85.9 <SEP> 90.6 <SEP> 4 <SEP> - <SEP> 5 <SEP> + <SEP> 11
<tb>
<tb>
<tb>
<tb>
<tb> J <SEP> 78.7 <SEP> 84.9 <SEP> 4 <SEP> -12 <SEP> + <SEP> 5 <SEP>
<tb>
<tb>
<tb>
<tb> K <SEP> 89.2 <SEP> 87.3 <SEP> 3 <SEP> - <SEP> 1 <SEP> + <SEP> 10 <SEP>
<tb>
<tb>
<tb>
<tb> L <SEP> 86.9 <SEP> 81.9 <SEP> 3 <SEP> - <SEP> 3 <SEP> + <SEP> 5 <SEP>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> TOTA-1 <SEP> 89.6 <SEP> 73.5 <SEP> - <SEP> - <SEP> -
<tb>
<tb>
<tb>
<tb>
<tb> TOTA-2 <SEP> 90.9 <SEP> 75.5 <SEP> - <SEP> - <SEP> -
<tb>
<tb>
<tb>
<tb> TOTA-3 <SEP> 90, <SEP> 0 <SEP> 77.3 <SEP> - <SEP> -
<tb>
<tb>
<tb>
<tb> TOTA-4 <SEP> 90.5 <SEP> 79.5
<tb>
      The number of tests carried out is five for each formula,

   except in TOTA-3 and TOTA-4 where it is 10. Same dose in each test,

 <Desc / Clms Page number 21>

 i.e. 0.1 mg. per liter.



   It emerges from the above results obtained with the aerosol type formulas that cyclopentenyl chrysanthemumate with synergist is superior in all cases to allethrin with the same synergist.



  Example 15
The efficacy against Epilachna corrupta in the larval state on French bean of cyclopentenyl chrysanthemumate alone and in combination with the synergists MGK 264 (N-2-ethylhexyl) -bicydo-2.2.1-5 was determined. -heptene-2.3-dicarboximide) and 6266 (N-hexoxyethoxypropyl) bicyclo-2.2.1-5-heptene-2.3-dicarboximide). Similar tests are carried out with allethrin and pyridine.



   The preparation of the formulas and the spraying on the plants are given in Example 11 with regard to the evaluation of cyclopentenyl chrysanthemumate on Aphis rumicis. Two bean plants are used per concentration. Each of them being sprinkled in this way, then dried, it is locked in a spherical wire mesh cage where four larvae have already been placed in the third stage of development. Plants and insects are kept under fluorescent light at room temperature. The count of dead larvae is carried out after 72 hours of exposure. The results of the dose tests are recorded on logarithmic probability paper. Here are the results obtained in dose for a mortality of 50%.



   Chrysanth. of
 EMI21.1
 
<tb> cyclo-pent- <SEP> Allethrin <SEP> Synergic <SEP> Synergic
<tb>
<tb>
<tb>
<tb> Formula <SEP> (@) <SEP> nyle <SEP> mg. <SEP> mg. <SEP> Triton <SEP> 264 <SEP> 6266
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> A <SEP> 25 <SEP> - <SEP> 2.5 <SEP> -
<tb>
<tb>
<tb>
<tb> B <SEP> 12.5- <SEP> - <SEP> 1.25
<tb>
<tb>
<tb>
<tb>
<tb> C <SEP> 6, <SEP> 25 <SEP> - <SEP> 0.625 <SEP> - <SEP> -
<tb>
<tb>
<tb>
<tb> D <SEP> 3.125 <SEP> - <SEP> 0.3125 <SEP> -
<tb>
<tb>
<tb>
<tb>
<tb> E- <SEP> 25 <SEP> 2.5 <SEP> - <SEP> -
<tb>
<tb>
<tb>
<tb>
<tb> F- <SEP> 12.5 <SEP> 1.25
<tb>
<tb>
<tb>
<tb> G- <SEP> 6.25 <SEP> 0, <SEP> 625 <SEP> - <SEP> -
<tb>
<tb>
<tb>
<tb>
<tb> H- <SEP> 3.125 <SEP> 0.3125 <SEP> - <SEP> -
<tb>
<tb>
<tb>
<tb> I <SEP> 12- <SEP> 7,2 <SEP> - <SEP> 60
<tb>
<tb>
<tb>
<tb>
<tb> J <SEP> 6- <SEP> 3,

  6 <SEP> - <SEP> 30
<tb>
<tb>
<tb>
<tb> K <SEP> 3- <SEP> 1.8 <SEP> - <SEP> 15
<tb>
<tb>
<tb>
<tb>
<tb> L- <SEP> 12 <SEP> 7,2- <SEP> 60
<tb>
<tb>
<tb>
<tb> M <SEP> - <SEP> 6 <SEP> 3,6- <SEP> 30
<tb>
<tb>
<tb>
<tb>
<tb> N
<tb>
<tb>
<tb>
<tb>
<tb> 0 <SEP> 12 <SEP> 3 <SEP> 1.8 <SEP> - <SEP> 15
<tb>
<tb>
<tb>
<tb> P <SEP> 6- <SEP> 7,2 <SEP> 60-
<tb>
<tb>
<tb>
<tb>
<tb> Q <SEP> 3 <SEP> 3,6 <SEP> 30-
<tb>
<tb>
<tb>
<tb> R- <SEP> - <SEP> 1.8 <SEP> 15-
<tb>
<tb>
<tb>
<tb>
<tb> S <SEP> - <SEP> 12 <SEP> 7,2 <SEP> 60-
<tb>
<tb>
<tb>
<tb>
<tb> T- <SEP> 6 <SEP> 3,6 <SEP> 30-
<tb>
<tb>
<tb>
<tb> U <SEP> - <SEP> 3 <SEP> 1.8 <SEP> 15
<tb>
   (@) Each of the compositions additionally contains 10 cc. of acetone and enough water to make a total of 100 cc.



   Here are the results obtained:
 EMI21.2
 
<tb> Lethal <SEP> dose <SEP> for <SEP> Epilachna
<tb>
<tb> Formula <SEP> oorrupta <SEP> (larva), <SEP> in <SEP> mg.
<tb>
<tb>



  A <SEP> to <SEP> D <SEP> 10
<tb>
<tb> E <SEP> to <SEP> H <SEP> 6
<tb>
<tb> I <SEP> to <SEP> K <SEP> 6
<tb>
<tb> L <SEP> to <SEP> 0 <SEP> 5
<tb>
<tb> BY <SEP> 8
<tb>
<tb> S <SEP> to <SEP> U <SEP> 12
<tb>
 

 <Desc / Clms Page number 22>

 
In accordance with the above results, the activation of cyclopentenyl chrysanthemumate by synergists 264 and 6266 is more intense.
 EMI22.1
 than that experienced by 1 '(allethrin.



  Example 16.



   The toxicity to rice charangon was determined with respect to cyclopentenyl chrysanthemumate alone, and with sulphoxide, piperonyl butoxide and sulfone as a synergist. Similar tests were carried out for comparison using allethrin, with and without synergist. To prepare these compositions, the active ingredient and the synergist are dissolved in acetone. An inert powder, in this case wheat bran, is added to the whole to make 100 g. Mix thoroughly to obtain homogeneity and then allow the acetone to evaporate completely from the mixture. Mix again in a ball mill for half an hour. The table below gives the formulas in question.
 EMI22.2
 
<tb>



  Material <SEP> A <SEP> B <SEP> C <SEP> D <SEP> E <SEP> F <SEP> G <SEP> H
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Chrysanthemumate <SEP> from <SEP> cyclo-
<tb>
<tb>
<tb>
<tb>
<tb> pentenyl, <SEP> mg. <SEP> 500- <SEP> 100 <SEP> 100 <SEP> 100 <SEP> -
<tb>
<tb>
<tb>
<tb> Allethrin <SEP> - <SEP> 500- <SEP> - <SEP> - <SEP> 100 <SEP> 100 <SEP> 100
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Piperonyl <SEP> Butoxide <SEP>, <SEP> mg. <SEP> - <SEP> - <SEP> 1600- <SEP> - <SEP> 1600- <SEP> -
<tb>
<tb>
<tb>
<tb>
<tb> Sulfoxide, <SEP> mg. <SEP> - <SEP> - <SEP> - <SEP> 1600 <SEP> - <SEP> - <SEP> 1600
<tb>
<tb>
<tb>
<tb>
<tb> Sulfone, <SEP> mg. <SEP> - <SEP> - <SEP> - <SEP> - <SEP> 1600- <SEP> - <SEP> 1600
<tb>
<tb>
<tb>
<tb> Thinner <SEP> inert <SEP> (bran <SEP> of <SEP> wheat)
<tb>
 
 EMI22.3
 grams, .3 D li ts.9 'i I-) tsil -3 JZ5> .3' j, j 'j <:

  5, i j, j
The above compositions are placed in 115 g bottles. approximately containing 56 g. of wheat bran and mix everything together, shaking for half an hour. 100 adult charangons are then introduced into each flask and allowed to feed for a week. We proceed to count the dead bodies at the end of this exhibition. The results of the tests are plotted on logarithmic probability paper. Here are the results for seven days in dose necessary for a mortality of 50%.
 EMI22.4
 
<tb>



  Dose <SEP> required <SEP> for <SEP> 50 <SEP>% <SEP>
<tb>
<tb>
<tb> Formula <SEP> of <SEP> death <SEP> in <SEP> seven <SEP> days, <SEP> mg.
<tb>
<tb>
<tb>
<tb>
<tb>



  A <SEP> 500
<tb>
<tb>
<tb>
<tb> B <SEP> 260
<tb>
<tb>
<tb>
<tb> C <SEP> 70
<tb>
<tb>
<tb>
<tb> D <SEP> 50
<tb>
<tb>
<tb>
<tb> E <SEP> 52
<tb>
<tb>
<tb> F <SEP> 62
<tb>
<tb>
<tb>
<tb> G <SEP> 58
<tb>
<tb>
<tb>
<tb> H <SEP> 51
<tb>
 
Consistent with the above data, cyclopentenyl chrysanthemumate, although its activity is only one-third that of allethrin when used alone, is much more overactivated than allethrin by the synergists used. . Under actual conditions of use, both must be used with synergists because of the prohi- bitive cost of these compounds without synergists. Cyclopentenyl chrysanthemumate, because of its harmlessness to mammals, has the advantage of being able to be used for grain protection.



  Example 17
Cyclopentenyl chrysanthemumate can furthermore (which shows the extent of its use) be used as a larvicide for the destruction of mosquito larvae. In the laboratory tests carried out, cyclopentenyl chrysanthemumate or allethrin is stirred, alone or with the addition of tallow oxide as a synergist; in 100 cc. of water containing 20 larvae in the third stage of the yellow fever mosquito, Aedes Ae- gypti L. The dead larvae are counted 48 hours after stay

 <Desc / Clms Page number 23>

 larvae in the aqueous medium.

   The results given below show the efficacy of cyclopentenyl chrysanthemumate compared to that of al- lethrino
 EMI23.1
 
<tb> Dose <SEP> required <SEP> for <SEP> pu <SEP>% <SEP> of
<tb>
<tb>
<tb>
<tb> Formula <SEP> death <SEP> in <SEP> 48 <SEP> hours <SEP>; <SEP> p.p. <SEP> million.
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>



  Allethrin <SEP> 0.08
<tb>
<tb>
<tb>
<tb> Chrysanthemumate <SEP> of <SEP> cyclopentenyl <SEP> 0.07
<tb>
<tb>
<tb>
<tb>
<tb> @ <SEP> Allethrin <SEP> + <SEP> sulfoxide <SEP> 0.046
<tb>
<tb>
<tb>
<tb>
<tb> @ <SEP> Chrysanthemumate <SEP> of <SEP> cyclopentenyl <SEP> 0.043
<tb>
<tb>
<tb>
<tb> + <SEP> sulfoxide
<tb>
<tb>
<tb>
<tb> No <SEP> processed <SEP> 0
<tb>
   @ 1 part of allethrin to 5 parts of tallow oxide @ 1 part of cyclopentenyl chrysanthemumate + 5 parts of tallow oxide.



  Example 18.



   The synergistic effect of a fly repellent agent of polyoxypropylene glycol monobutyl ether (viscosity at 38 ° C., 100 S.U.S.; average molecular weight, approximately 850) was tested.



  Here are the preferred formulas.
 EMI23.2
 
<tb>



  Formula <SEP> A <SEP> B <SEP> OTI
<tb>
<tb>
<tb> Chrysanthemumate <SEP> of <SEP> cyclopentenyl, <SEP> mgo <SEP> 84 <SEP> 84 <SEP> -
<tb>
<tb> Allethrin, <SEP> mg. <SEP> - <SEP> - <SEP> -
<tb>
<tb> Fyrethrins, <SEP> mg. <SEP> - <SEP> - <SEP> 100
<tb>
<tb> <SEP> fly repellent <SEP> agent <SEP>, <SEP> ce. <SEP> 10 <SEP> 10 <SEP> -
<tb>
<tb> kerosene <SEP> deodorized, <SEP> ce .. <SEP> 90 <SEP> 90 <SEP> 90
<tb>
 Peet-Grady trials. big group.
 EMI23.3
 
<tb>



  Number <SEP> Death <SEP>% <SEP> Paralysis <SEP>% <SEP> Diff. <SEP> OTI
<tb>
<tb>
<tb>
<tb>
<tb> Formula <SEP> of tests <SEP> 24 <SEP> h. <SEP> 10 <SEP> min. <SEP> Death <SEP> Paralysis
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Ao <SEP> Chrysanthemumate
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> of <SEP> cyclopentenyl <SEP> 3 <SEP> 84 <SEP> 96.8 <SEP> +40 <SEP> + <SEP> 0.3
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> B. <SEP> Allethrin <SEP> 3 <SEP> 73.2 <SEP> 98.1 <SEP> +29 <SEP> + <SEP> 1.6 <SEP>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> OTI <SEP> 6 <SEP> 44.0 <SEP> 96.5 <SEP> -
<tb>
 
The results of this trial show that the added value of insured deaths by cyclopentenyl chrysanthemumate over OTI is 11 percentage points relative to allethrin; the loss of paralyzes is only 1.3 percentage point.



  Example 190
Biologically active materials such as polyoxypropylene glycol monobutyl ether with a molecular weight of 850 can be used to protect livestock from ectoparasites such as flies, flies and ticks; beta-butoxy-beta'-thio-cyanodiethyl ether and a mixture of beta-thiocyanoethyl esters of higher fatty acids of 10 to 18 carbon atoms (known under the trade name "Lethanes"); terpene thiocyanates (known as Thanite-Isobornyl Acetate); "methoxychlor"; and a synergist. Here are formulas containing these ingredients.
 EMI23.4
 
<tb>



  Parts <SEP> in <SEP> weight
<tb>
<tb>
<tb> A <SEP> B
<tb>
<tb>
<tb> Chrysanthemumate <SEP> from <SEP> cyclopentenyl <SEP> 0.1 <SEP> to <SEP> 10 <SEP> 0.1 <SEP> to <SEP> 10
<tb>
<tb> Polyoxy- monobutyl <SEP> <SEP> <SEP> ether
<tb>
<tb> propylene <SEP> glycol <SEP> (p.mol. <SEP> average <SEP> 800) <SEP> 20 <SEP> to <SEP> 80 <SEP> 20 <SEP> to <SEP> 80
<tb>
<tb> Butoxide <SEP> of <SEP> piperonyl <SEP> 2 <SEP> to <SEP> 20 <SEP> 2 <SEP> to <SEP> 20
<tb>
<tb> Emulsifying agent <SEP> <SEP> 0 <SEP> to <SEP> 20 <SEP> 0 <SEP> to <SEP> 20
<tb>
<tb> "Methoxychlor" <SEP> - <SEP> 0 <SEP> to <SEP> 10
<tb>
 

 <Desc / Clms Page number 24>

 
This composition can be applied directly to cows, for example, in a proportion of 0.5 to 2 g. per animal and per day.

   The concentrate can be sprayed with water if desired, usually in such proportions that the diluted water product can be sprayed in the amount of 570 to 2280 cc. per animal and per week to protect them against flies.



   It is also possible to dilute a concentrate of the above formula, with or without an emulsifying agent, using a petroleum or water distillate and apply the dilution in local sprays to paralyze and kill flies, mites, etc., or even to crops to protect them against insects. In particular beans, corn, wheat, cabbage, apples and apple trees, reasons, etc. can be protected against worms, beetles, aphids and spiders. Sprays can also be made on surfaces such as the inside of chests or grain elevators to kill insects attacking grain, or directly on cows or other livestock to protect them from attack by flies.

   These same concentrates can be spread with oil or water and applied to packaged products such as cereals or flour in cloth or paper bags to prevent penetration and invasion by insects. . Good results have been obtained in this regard with concentrates having the following compositions:

   Example 20. parts by weight
 EMI24.1
 
<tb> formula <SEP> C <SEP> formula <SEP> D
<tb>
<tb>
<tb> Chrysanthemumate <SEP> of <SEP> cyclopentenyl <SEP> 0.5 <SEP> 0.7
<tb>
<tb> Piperonyl <SEP> Butoxide <SEP> <SEP> 5 <SEP> 7
<tb>
<tb> Agent <SEP> repellent <SEP> of <SEP> flies <SEP> 50 <SEP> 75
<tb>
<tb> Emulsifying agent <SEP> <SEP> 12 <SEP> 15
<tb>
<tb> Distillate <SEP> of <SEP> petroleum <SEP> 32.5 <SEP> 3.5
<tb>
<tb>
<tb>
<tb> 100 <SEP> 100
<tb>
 
Polyoxypropylene glycol monobutyl ether, wt. mol. medium 800.



   Cyclopentenyl chrysanthemumate can also be used synergistically and as a propellant in aerosols or pressure sprays to kill insects such as flies, moths, mosquitoes, bedbugs, ants, cockroaches, pests. flour snails, silverfish, etc. This aerosol or this pressurized spray may also contain one or more toxicants of the halogenated type such as DDT,
 EMI24.2
 inethoxychlor or "stroban", for example, or thiocyanates or thiocyanacetates, with or without a solvent such as methyl naphthalene, petroleum distillates, etc., ad libitum. Here is a composition formula for this type of aerosol or pressure spray.



  Example 21
Pressure spraying. parts by weight.



  Cyclopentenyl chrysanthemumate 0.01 to 6.0 Synergistic 0.05 to 10.0 Toxic 0, 0 to 6, 0 Polypropylene glycol monobutyl ether 0.0 to 55.0 Solvent
Spraying agent (Q.S.P. 100 p. By propulsion weight)

 <Desc / Clms Page number 25>

 
DDT, "methoxychlor", "Stroban", thioxyanates, thiocyanacetates.



   Viscosity at 100oCo, 250 SoUoSo; wt. mol. medium, 850.



   Freon 11; Freon 12.



   The present new insecticide can also be used in dry compositions, particularly suitable for the protection of cereals and flour against insects, with inert powdered vehicles such as wheat bran, kaolin, talc, powder. pyrophyllite, diatomaceous earth, kieselguhr, bentonite, crushed walnut shells, sawdust, etc. Here is an example of a composition of this type.



  Example 22.



   Protective powder for grains.
 EMI25.1
 
<tb>



  Parts <SEP> in <SEP> weight.
<tb>
<tb>
<tb>



  Cyclopentenyl <SEP> Chrysanthemumate <SEP> <SEP> 0.02 <SEP> to <SEP> 0.5
<tb>
<tb> Synergistic <SEP> 1 <SEP> to <SEP> 5.0
<tb>
<tb> Vehicle <SEP> inert <SEP> in <SEP> powder, <SEP> QoSoPo <SEP> 100
<tb>
<tb>
<tb>
<tb> Total <SEP> 100
<tb>
 

** ATTENTION ** end of DESC field can contain start of CLMS **.


    

Claims (1)

ABSTRACT I. Process for the manufacture of a substance having insecticidal activity, said process being characterized by the following points, separately or in combinations: EMI25.2 10) 2- (2-eyclopentenyl) -, 3-méthyL-2-cyclopentén L, .- ol-1-one, of formula: EMI25.3 by reacting cyclopentadiene with hydrochloric acid so as to obtain 2-cyclopentenyl chloride, reacting the acetylacetic ester with 2-cyclopentenyl chloride in the presence of an alkali metal alkoxy with production of a lower 2 - (? - cyclopentenyl) -3-keto-butyrate, subjecting this compound to ketonic hydrolysis in the presence of an alkali metal hydroxide with formation of 2-eyclopentenyl- acetone, reacting 2-cyclopentenyl-acetone with diethyl carbonate in the presence of an alkali metal alkoxide so as to form ethyl 4- (2-cyclopentenyl) -3-ketobutyrate, converting this compound into an alkali metal salt and reacting it with the pyruvic aldehyde of ma- EMI25.4 to make the 6 (2-eyclopentenyl) -3-hydroxy-hexane-2,5-d.ione and treat this compound with an extended base to convert it to 2- (2-cyclopentenyl). ) 3-methyl-2-cyc7, openten / -0l-1-oneo 2) 2- (2-cyclopentenyl) -3-methyl-2-cyclopenten-4-ol-1-one is reacted with chrysanthemum carboxylic acid or anhydride; EMI25.5 3) 2- (cy clopentenyl) -3-methyl-2-cyclopenten-4-ol-1-one is reacted with chrysanthemum mono-carboxylic acid chloride in the presence of an acid binding agent such as pyridine II - As new industrial products, insecticidal compositions characterized by the following points, separately or in combinations; <Desc / Clms Page number 26> 1) they contain a vehicle and (or) a synergist and 3- (2-cyclopentenyl) 2-methyl-4-oxo-2-cyclopentenyl-chrysanthemumate obtained by the above process; 2) the proportion of cyclopentenyl chrysanthemimate is between 0.01 and 10 parts by weight of the composition; 3) said composition contains 0.1 to 10 parts by weight of cyclopentenyl chrysanthemumate, 20 to 80 parts by weight of polyoxypropylene glycol monobutyl ether with an average molecular weight of 800, 2 to 20 parts by weight of butoxide of piperonyl and 0 to 20 parts by weight of an emulsifying agent 4) the vehicle is a petroleum distillate; 5) composition for pressure sprays comprising 0.01 to 6 parts by weight of cyclopentenyl chrysanthemumate, 0.05 to 10 parts by weight of one of the synergists mentioned, 0 to 6 parts by weight of a toxic agent as described 0 to 55 parts by weight of polypropylene glycol monobutyl ether with an average molecular weight of 850, the remainder being sufficient of a known solvent to make 100 parts by weight of the composition; 6) composition comprising 0.02 to 0.5 part by weight of cyclopentenyl chrysanthemumate, 1 to 5 parts by weight of a synergist and the remainder being an inert powder carrier in an amount sufficient to make 100 parts by weight. weight; 7) A composition for paralyzing and killing flies, comprising 25 to 100 mg. of cyclopentenyl chrysanthemumate, 150 to 1000 mg. a synergist and deodorized kerosene in an amount sufficient to make 100 cc; 8) the composition contains pyrethrin or another known insecticidal agent.