BE590265A - - Google Patents

Description

       

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  "IMPROVEMENTS IN THE FIGHT AGAINST INSECTS".

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   The present invention relates to compounds and compositions for controlling insects.



   The 3-chloropropyl octyl sulphoxides and the corresponding 2-methyl compounds have been found to be effective insect repellants. The invention relates to the aforementioned compounds and their preparation from the corresponding sulphides, as well as the production of these sulphides. It also relates to compositions for combating insects which contain the aforementioned sulfoxides. Such compositions may also contain an N-alkyl imide of bicyclo [2,2,1] -5-heptene-2,3-dicarboxylic acid and / or a condensation product of an alkylene oxide with a mercaptan, as will be described later.



   The invention particularly relates to the following compounds: 3-chloropropyl n-octyl tallow oxide; 3-chloropropyl sec-octyl sulfoxide; 3-chloropropyl tert-octyl sulfoxide; 3-chloro-
 EMI2.1
 2-methylpropyl n-octyl sulfoxide; s3-chloro-2-mathylpropyl sec-octyl sulfoxide; 3-chloro-2-methylpropyl tert-octyl sulfoxide.



   The present invention relates to: - a process for preparing a 3-chloropropyl octyl sulfide, which consists in reacting an octene with 3-chloropropyl mercaptan; - A process for preparing 3-chloro-2-methylpropyl octyl sulfide comprising the reaction of an octene with 3-chloro-2-methylpropyl mercaptan.

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   The invention relates to a process for the preparation of the last two types of compounds, which comprises carrying out the reaction in the presence of ionizing rays, for example ultraviolet light.



   In the process for preparing 3-chloropropyl octyl sulfide, an alkali metal mercaptide of an octyl mercaptan is reacted with 1-bromo-3-chloropropane.



   The process for preparing 3-chloro-2-methyl-propyl octyl sulfide is further characterized by the fact that it consists of reacting an alkali metal mercaptide of an octyl mercaptan with 1-bromo-2- methyl-3-chloropropane, this reaction being carried out, for example, in the presence of methanol and under substantially anhydrous conditions.



   Insecticidal mixtures as well as mixtures having an insect repellant reaction are currently known and are used for controlling insects, such as flies, mosquitoes, cockroaches, etc. Agents used to control insects generally fall into two categories, namely agents used in agriculture and agents used in the home. Although the usual principal role of an agent of both categories is to kill insects, it is very desirable, particularly in certain applications, especially those involving dwellings, man or livestock, to have 'an agent which mainly combats insects by effectively removing it from the area or animal to be protected.



  For example, the housewife is particularly desirous of having a control agent which prevents insects from infesting a specific place. Likewise, with regard to the attack

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 the main goal of man or livestock is to prevent insects from attacking animals. In many other applications a control agent which repels insects is much more desirable than an agent which is toxic and which stuns or kills insects precisely in the area to be protected.

   So, for example, when setting up a table for the picnic, a repellant that prevents flies from landing on the table and on food is clearly more desirable than another product that will stun or kill flies or other insects. , which will then infest the area to be protected. Obviously, the contamination of food and the disgusting presence of dead or paralyzed insects should be avoided whenever possible.



   The sulfoxides according to the invention have been found to be extremely effective as insect repellants, which is surprising, since other sulfoxides that have been tried have been found to be shown to be effective. quite unsuitable for insect repellency.



   The improved repellent composition according to the invention can be used to repel a large number of different species of insects with the same effectiveness, for example house flies, stable flies, ticks, fleas, midges. , cockroaches, mosquitoes, etc. The improved repellant compositions according to the invention are particularly effective in repelling house flies (Musca domestica) and stable flies (Stomoxys calcitrans).

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   In accordance with the invention, new sulfoxides containing chlorine have been discovered which correspond to the formula
 EMI5.1
 in which R represents an n-octyl, aec-octyl or tert-octyl radical and R 1 represents H or CH3.



   The invention also relates to a method of controlling insects, which consists in subjecting these insects to the action of an effective amount of at least one compound having the characteristic structure indicated above.



   In accordance with another feature of the invention, a process has been devised for increasing the repellency of compositions based on 3-chloropropyl-n-octyl sulfoxide, and having a repellency against. insects, a process which consists in incorporating into these compositions an N-alkyl imide of bicyclo acid
 EMI5.2
 2,2,1> -, 5-heptene-2,3-dicarboxylic, taken in a proportion ensuring a marked increase in repellency.



   In addition, the invention relates to a process for increasing the repellency of compositions based on 3-chloropropyl-n-octyl sulfoxide and having a repulsive power with respect to insects, by incorporating therein at least one. mercaptan of formula.
 EMI5.3
 
 EMI5.4
 where 8z, R3 ,. ¯R. And ¯R are taken from the group consisting of hydrogen and alkyl radicals in any combination such that the total number of carbon atoms in the R groups does not exceed 4.

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   Examples of compounds of structure II which can be incorporated into the repellant compositions according to the invention are 2-hydroxyethyl-n-octyl sulfide, 2-methyl-2-hydroxypropyl-n-octyl sulfide, 2- (3-hydroxybutyl) n-octyl sulfide, 3- (4-hydroxyhexyl) n-octyl
 EMI6.1
 sulfide, 2- (3-hydroxy-4-methylpentyl) n-octyl sulfide, 2- (1-hydroxyhexyl) n-octyl sulfide, 2-hydroxy-3,3-dimethylbutyl n-octyl sulfide, 2-hydroxybutyl n-octyl sulfide, 2-hydroxy-3-methylbutyl n-octyl sulfide and
2-hydroxypropyl n-octyl sulfide.



   The weight ratio of chlorine-containing tallow oxides to alkylene-mer-captan oxide condensation products contained in the repellant compositions can range from 3: 1 to 1: 4. Weight ratios of less than 1: 4 can be used if desired, but, in general, this is not the case. Weight ratios greater than 3: 1 should not be used, but only because they are no more effective than the alkylene mercaptan oxide condensation products alone.



   Those skilled in the art will readily understand that when compounds are found to be synergistic in some proportion, the same compounds are generally synergistic in all proportions. Thus, the invention relates to the preparation and use of compositions in which very variable ratios or proportions of the ingredients forming the composition of the invention are used. The ratios which will be indicated must therefore be considered as preferred ratios.



   Such a mercaptan compound enables a process to be applied which increases the effectiveness of a chlorine-containing sulfoxide, especially when used as a repellant.

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 sif for stable flies. Thus, although a sulfoxide is very effective against flies, it is considerably more effective against house flies than against stable flies. The incorporation of the mercaptan compound in question makes it possible to raise the effectiveness of a sulfoxide to a level which is more close to that of a repellent when used against house flies.



   It is also possible to incorporate a synergistic product, such as a silica gel, with the sulfoxides according to the invention.



   To prepare the chlorine-containing sulphides from which the sulphoxides are obtained by oxidation, several different synthetic methods can be used. One of the methods that can be used consists in reacting the allyl chloride with the desired octyl mercaptan (normal, secondary and tertiary) in the presence of ultra-violet light. This reaction is carried out at a temperature of between -50 and 200 ° C., preferably between 0 and 100 ° C. under atmospheric pressure and in the presence of ultraviolet light. Ultraviolet light with a wavelength of 100 to 2900 Angstroms is satisfactory.

   In the formation of 3-chloropropyl octyl sulfide by this reaction, the molecular ratio of allyl chloride to octyl mercaptan is generally between 0.5: 1 and 2: 1. It is actually preferred to use a slight excess of allyl chloride, i.e., 1.1 to 1.3 moles of allyl chloride per mole of octyl mercaptan.



   In another method of preparing 3-chloropropyl octyl sulfide, allyl chloride is reacted with hydrogen sulfide in the presence of ultraviolet light to form 3-chloropropyl mercaptan.

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  This compound is then reacted with an octene in the presence of ultraviolet light to form the sulfide.



  In this synthesis, the temperatures and the wavelengths of the ultraviolet light already mentioned are used for the implementation of the first phase. The pressures used in the reaction will be the autogenous pressures created upon loading of the hydrogen sulfide.



  The molecular ratios of hydrogen sulfide to allyl chloride are generally from 1: 1 to 5: 1.



  The pressures generated by the use of the above products in the ratios indicated generally reach from 7 to 35 kg / cm 2. After the formation of 3-chloropropyl mercaptan by reaction between allyl chloride and hydrogen sulfide, this mercaptan is reacted with an octene, for example 1-octene, in the presence of ultraviolet light. Atmospheric pressure is satisfactory for carrying out this reaction, and the temperatures and ultraviolet wavelengths already indicated can be used. The molecular ratio of 3-chloropropyl mercaptan to octene is usually between 0.5: 1 and 2: 1. It is preferred to use a molecular ratio of 1: 1.



   In another variation of the process for the preparation of the sulfides, an alkali metal mercaptide is formed from an octyl mercaptan and this marcaptide is reacted with 1-bromo-3-chloropropane. For example, tert-octyl mercaptan is reacted with caustic soda to form sodium octyl-mercaptide, and this compound is reacted with 1-bromo-3-chloropropane to form 3-chloropropyl tert. -octyl sulfide.



   Regardless of the process used for the formation of the sulphide, the oxidation of this product to sulphoxide

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 is the same. The oxidizing agents used are currently the peroxygen compounds chosen from hydrogen peroxide and organic peracids. Examples of suitable paracids are performic acid, peracetic acid and perbenzoic acid. These acids can be introduced into the reaction zone as they are, or they can be produced in situ. A molecular ratio of the peroxygen compound to sulfide of between 0.5: 1 and 1.5: 1 is usually used. A preferred ratio is currently between 0.8: 1 and 1: 1.

   When this oxidation is carried out, the sulfide is dissolved in a product which is also a solvent for the peroxygen compound. Examples of suitable solvents are methanol, ethanol, isopropanol and acetone. Usually the oxidation is carried out at a temperature between 0 and 100 C, preferably between 50 and 80 C. The reaction usually takes less than an hour, although longer reaction times can be used. . It is preferable to add the oxidizing agent to the sulfide while constantly maintaining an excess of sulfide. It is preferred to apply the above procedure to avoid loss of sulfoxide due to formation of a sulfone.

   A convenient method of determining the end of the reaction is to test for the peroxygen compound by means of a paper impregnated with a mixture of potassium iodide and starch.



   Another suitable method for the oxidation of sulfides is to oxidize the sulfide with oxygen or an oxygen-containing gas, for example with air. This process is advantageously carried out by adding a small amount of NO 2 or of concentrated nitric acid to which a compound containing bromine has been added.



  In US Pat. No. 2,859,248, a process for the production of an organic sulfoxide is described which comprises the oxidation of an organic sulfide.

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 with a gas containing elemental oxygen, that sulfur having the formula RSR (in which each group R contains not more than 20 carbon atoms and the total of carbon atoms does not exceed 30, and in which each group R represents an alkyl, cycloalkyl, aryl, aralkyl or alkaryl residue, one of these residues containing a hydroxy group as a substituent) in the presence of a catalyst system comprising a nitrogen compound containing at least one of groups HNO3 and NO2 'and a halogenated compound containing at least one of the groups CuCl2' CuBr, CuBr2 and
HBr,

   with the proviso that when one of the H groups contains a hydroxy group, HBr is not used.



   In addition, when preparing the sulfides by any of the methods described above, it is useful to add a small amount of a hydrochloric acid scavenger, such as ethylene oxide. or propylene oxide.



   In the patent application filed in the United States of America, March 26, 1959 under No. 802031, a process for activating a reaction between a sulfur-containing compound which is capable of reacting is described. on a halogenated olefinic compound in the presence of activating rays, to produce a compound consisting of a thiol or a sulphide, which process comprises carrying out the reaction in the presence of a product consisting of an anion exchange resin or a organic compound containing epoxy groups.



   In accordance with the invention, the above alkylene oxides may be present in the reaction mixture in which the sulfides are oxidized to sulfoxides.



  In addition, a small amount of these alkylene oxides in the new chlorine-containing sulfoxides according to the invention is advantageous for preventing dehydroha-

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 accommodation during storage. These compounds appear to inhibit decomposition due to dehydrohalogenation, or they sweep away the hydrochloric acid that is formed.



  In any event, the use of these alkylene oxides helps to prevent corrosion from hydrochloric acid generated during storage of these new chlorine-containing sulfoxides. The effectiveness of these alkylene oxides in stabilizing 3-chloropropyl octyl sulfoxides will be demonstrated later.



   When applying the repellant compositions according to the invention to a surface to repel insects, such as flies, the method of application, as those skilled in the art will readily understand, depositing approximately from 0.010 to 2, 1 g of active ingredient per m 2 of surface. The application of the repellant compositions according to the invention by spraying, for example using an aerosol canister, in a space should be adjusted to obtain the suspension of about 0.035 to 176.5. g of active ingredients per 100 m3. Larger or smaller amounts can be applied if desired, but generally it is not economical to use larger amounts, and it is not efficient to use larger amounts. weak due to lack of repellent action.



   Those skilled in the art will readily understand that a general preparation for the control of insects may contain both an insecticide and a product having an insect repellency action and that, for this reason, agents conforming to the invention can be used either alone or in admixture with other agents for controlling insects, such as

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 agents are repellents or insecticides or both.



   The agents according to the invention possess extremely good repellency activity, which is actually surprising, due to the ineffectiveness of closely related compounds, as shown in Table V below.



   Furthermore, the agents according to the invention exhibit many desirable qualities for their use in various compositions for the control of insects. Not only are they very effective in repelling flies, as well as house flies. than stable flies, but still they are substantially non-toxic to animals in the amounts normally used. They have excellent heat and light stability, even in the presence of moisture.



   There is shown in the single figure of the attached drawing, a graph relating to an accelerated aging test of repellents under the action of a sun lamp, the number of hours of exposure being plotted on the abscissa and the power percentage. initial repellent being worn on the ordinate; layer A refers to 3-chloropropyl-n-octyl sulfoxide plus N- (2-ethylhexyl) bi-
 EMI12.1
 cyclo 2,2,1> -5-heptene-2,3.-dicarboximide and curve B with 3-chloropropyl n-octyl sulfoxide.



   These agents are soluble at high concentrations in many common solvents. Because they are compatible with many other commonly used insecticides or repellants, they can be mixed with such products. We can apply

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 the agents according to the invention in the usual way while obtaining good results. Thus, solutions, emulsions, fine powders, wettable powders and aerosols containing the agents according to the invention can be used.



   The insect control agents of the invention are effective when used in very small amounts. Thus, when it is applied in the usual manner to a certain area or in a given volume, an amount as little as about 0.05% by weight of the overall composition is found to be effective. this. Still smaller amounts or concentrations can be used, however, and when applying to control insects there is virtually no upper limit other than that imposed by economic and aesthetic considerations.



   Solvents which are suitable for the application of the repellents in accordance with the invention include naphtha, kerosene and in particular the so-called deodorized kerosene, toluene, xylene, cyclohexanone, acetone, etc.



   A particularly effective and presently preferred composition is obtained when substantially odorless "Soltroln (trade mark)" which is a fraction of an isoparaffinic hydrocarbon solvent boiling at approximately 127 to 425 ° C. and which has been prepared is used. preferably by hydrofluoric acid alkylation of an isoparaffin with an olefin, under dealkylation conditions which are known in the alkylation art.

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   Solutions prepared with the aforementioned solvents and related liquids can be conveniently distributed in the form of sprays sent into space by means of aerosol type cans, using the pressure of an appropriate propellant. - prayed, such as butane, as is well known in the art.



   The repellency of the repellent composition based on 3-chloropropyl-n-octyl sulfoxide is enhanced by adding the N-alkyl imide already mentioned, at least in two ways. First, the reinforcing component increases the effectiveness of the repellant composition by "synergy" as the term goes, resulting in fewer insects moving closer to the area or space containing. a synergistic proportion of the reinforcing component.

   Second, the duration of the repellant action of the repellant composition is increased in a manner generally referred to as "stabilization" because the reinforced repellant composition containing a stabilizing proportion of the reinforcing component retains the property of repelling insects for a long time. .a longer period of time.



   We can represent the N-alkyl imides of the acid
 EMI14.1
 bicyclo r2,2,1> -5-heptene-.2,3-dicd¯rhxyl by- the formula
 EMI14.2
 in which R1 is an alkyl radical containing not more than 12 carbon atoms.

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  Representative examples of N-alkyl imides
 EMI15.1
 bicyclo -2,2,1¯7-5-heptene-2,3-dicarboxylic acid comprising N-methyl bicyclo r2,2,1J-5-reptene-2,3-dicarboximide; N-ethyl bicyclo [2,2,1] -5-heptene-2,3-dicarboximide; N-isopropyl bicyclo [2,2,1] -5-heptene-2,3-dicarboximide; N-2-ethylhexyl bicyclo [2,2,1] -5-heptene-2,3-dicarboximide; N-t-dodecyl bicyclo [2,2,1] - 5-heptene-2,3-dicarboximide; N-isoheptyl bicyclo
 EMI15.2
 f2,2,1 f-5-heptene-2,3-dicarboximide; N-tert-butyl bicyclo f2,2,1> -5-heptene-dicarboximide; N- (3-propyl-octyl) bicyclo [2,2,1] 5-heptene-2,3-dicarboximide and N- (2,3-dimethyldecyl) bicyclo [2,2,1] -5-heptene -2.3- dicarboximide.

   N- (2-ethylhexyl) bicyclo [2,2,1] -5-heptene-2,3-dicarboximide is the preferred strengthening compound of this type.



   The N-alkyl imides of the acid can be prepared
 EMI15.3
 bicyclo r2,2,1> -5-Heptene-2,3-dicarboxylicated by condensing cyclopentadiene with maleic anhydride dissolved in benzene at room temperature. The product resulting from the condensation is then reacted with an appropriate alkyl amine to obtain the desired product. For example, the condensation product of cyclopentadiene and maleic anhydride is reacted with a tert-butyl amine to obtain N-tert-butyl acid.
 EMI15.4
 bicyclo f2,2,1 f-5-heptene-2,3-dicarboxylic.



   The proportions in which the reinforcing compound can be mixed with the repellent composition based on 3-chloropropyl-n-octyl sulfoxide can vary widely. Repellency enhancement appears to be obtained with as little as 1% by weight of the strengthening compound in the mixture. Usually, this compound is used in the mixture in an amount equivalent to 5 to about 95% by

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 total mixture weight. Thus the weight ratio of
 EMI16.1
 Bic acid N-alkyl imide; rclo f2,2,1 f-5-heptene-2,3-dicarboxylic to 3-chloropropyl n-octyl sulfoxide is usually from 5:95 to 95: 5.

   Preferably, an amount of N-alkyl imide of the acid is used.
 EMI16.2
 bicyclo f2,2,1 f-5-heptene-2,3-dicarboxyliqiae between 25 and 75% by weight of the total mixture.



   The non-limiting examples above relate to processes for obtaining the new chlorine-containing tallow oxides, to their stabilization and to their use as repellents. Compounds according to the invention containing a methyl group can be prepared easily by any skilled person using the corresponding 2-methyl compounds, for example 3-chloro-2-methyl-propyl mercaptan in place of 3-chloropropyl. mercaptan.



   EXAMPLE I.-
A test is carried out in which 3-chloropropyl n-octyl sulfide is prepared, then this product is oxidized to obtain the corresponding sulfoxide.



   In this test, 365 g (2.5 moles) of n-octyl mercaptan and 200 g (5% molecular excess) of allyl chloride are introduced into a reactor which is formed by a 75 mm "Pyrex" glass tube. mm, with a section of 23 cm, closed at one end and fitted with a standard 40/50 female conical connector which is fixed at the other end. A glass cooling coil is disposed within the tube to allow temperature control.

   Stopcock plugs are fixed near each end and perpendicular to the axis of the 75 mm tube, so that the reactor can be evacuated before a test and an additional product can be introduced during such a test. small stopper with valve in the end, of the reactor containing the conical seal, so as to

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 be able to take small samples. A quartz cup 15 cm long and 33 mm in outer diameter with a flanged gasket is placed on the corresponding gasket of the reactor, and a mercury vapor lamp is fixed in this cup. The capacity of the reactor is approximately 700 cc.



   After loading the reagents, a reactor is set in / horizontal shaking frame and shaken at about 120 cycles per minute with the mercury vapor lamp on. The contents of the reactor are irradiated at approximately room temperature with light from a mercury vapor lamp of
100 watts until the refractive index of the reaction solution no longer increases. It takes about an hour. During irradiation, some hydrochloric acid is released and the reaction solution which was colorless turns bright orange.

   The reaction solution is then transferred to a distillation flask and most of the unreacted allyl chloride is distilled off under atmospheric pressure. by heating to 150 ° C. The remaining product is distilled off under reduced pressure to give 302 g of 3-chloropropyl n-octylsulfide, boiling point 145 under 7.0 mm of mercury (absolute pressure) nD20 1.4770. These results correspond to a concentration of 62.7% of the mercaptan. Also recovered 136 g of unreacted n-octyl mercaptan and 41 g of a high boiling product.



   Thus, the final yield of 3-chloropropyl n-octyl sulfide is 86.3%, by moles based on the mercaptan.



   In a similar test, an identical load is irradiated with light from a 450 watt mercury lamp instead of the 100 watt lamp. Irradiation is carried out again with shaking.

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 ge until a constant refractive index is obtained.



  In this test, a reaction time of less than 15 minutes is required.



   The oxidation of this sulphide to the corresponding sulphoxide, that is to say to 3-chloropropyl n-octyl sulphoxide, is carried out in a three-necked flask equipped with a stirrer, a reflux condenser and of a drip feed funnel. In a typical test, we in
 EMI18.1
 Add 222.5 g of 3-chloropropyl n-octyl sulfide and 300 cc of methanol to the balloon, and the mixture is heated to reflux.



  At this time, 113.3 g of a 30% by weight aqueous solution of hydrogen peroxide is added over 20 minutes. While the hydrogen peroxide is being added, the reaction mixture is vigorously refluxed. When the hydrogen peroxide has been completely added, the solution is allowed to stand for at least 2 hours to complete the oxidation. About 500 cc of water is then added to precipitate this product as a second liquid phase.



   Other methods can be used to recover the product. One is to extract the product with a solution of 500 cc of n-pentane mixed with 250 cc of ether. The product is then crystallized from pentane-ether solution at carbonate snow temperature. In another process, the product resulting from the oxidation by hydrogen peroxide of 3-chloropropyl n-octyl sulfide is extracted with 250 cm3 of chloroform, then the chloroform is removed by heating the mixture to 80 ° C. under an absolute pressure of 2 mm of mercury. The results of the process using crystallization are shown in Table I below.

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  TABLE I.-
 EMI19.1
 
<tb> Physical <SEP> properties <SEP> of the
<tb>
<tb>
<tb> ¯¯¯¯¯¯¯suif <SEP> oxydē¯¯¯¯ <SEP>
<tb>
<tb>
<tb>
<tb>
<tb> Efficiency <SEP> in
<tb>
<tb> sulfoxide <SEP> <SEP> index of
<tb>
<tb>
<tb> (by <SEP> ratio <SEP> Point <SEP> of <SEP> fusion <SEP> refraction
<tb>
<tb>
<tb> Process <SEP> from <SEP> to <SEP> sulphide) <SEP> approximate <SEP> 50
<tb>
<tb>
<tb> recovery <SEP> moles <SEP>% <SEP> C <SEP> n50D
<tb>
<tb>
<tb>
<tb>
<tb> Crystallization <SEP> 83.4 <SEP> 37 <SEP> - <SEP> 40 <SEP> 1.4740
<tb>
 
EXAMPLE II. -
Several runs are carried out to prepare 3-chloropropyl n-octyl sulfide by another synthetic method.



   In these tests, the allyl chloride and the alkylene oxide are charged to a 5.60 liter capacity stainless steel reactor which has a device for irradiating the contents with ultraviolet light.



  After charging the allyl chloride, hydrogen sulfide is introduced into the reactor and the contents are irradiated with a 450 watt mercury lamp. After irradiation, unreacted hydrogen sulfide is removed and the remaining reaction solution distilled.



  Most of the unreacted allyl chloride is removed by heating the solution to 150 ° C. under atmospheric pressure. The product, which is 3-chloropropyl mercaptan (boiling at about 68 C under an absolute pressure of 50 mm of mercury and at about 145 C under an absolute pressure of 760 mm of mercury; nD20 = 1.4935 is obtained by distillation under 50 mm of mercury (absolute pressure) of the reaction solution from which most of the allyl chloride is removed The results of the two aforementioned tests are shown in the table below.

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  TABLE II
 EMI20.1
 
<tb> Test <SEP> A <SEP> Test <SEP> B
<tb>
<tb>
<tb>
<tb> Load
<tb>
<tb>
<tb> Allyl chloride <SEP> <SEP> (g) <SEP> 1.910 <SEP> 1. <SEP> 910
<tb>
<tb>
<tb> Hydrogen <SEP> sulphide <SEP> (g) <SEP> 1.700 <SEP> 1.700
<tb>
<tb>
<tb> Propylene <SEP> <SEP> oxide <SEP> cm3) <SEP> 100 <SEP> ..
<tb>
<tb>
<tb>



  Ethylene oxide <SEP> (cm3) <SEP> - <SEP> 100
<tb>
<tb>
<tb> Molecular <SEP> <SEP> ratio of <SEP> reagents
<tb>
<tb>
<tb> molecular <SEP> port <SEP> 2 <SEP> 2
<tb>
<tb>
<tb> Irradiation time <SEP>, <SEP> minutes <SEP> 40 <SEP> 120
<tb>
<tb>
<tb> Temperature <SEP> 25 C <SEP> 25 C
<tb>
<tb> Product
<tb>
<tb>
<tb>
<tb> 3-chloropropyl <SEP> mercaptan <SEP> (g) <SEP> 1.130 <SEP> 1.180
<tb>
<tb>
<tb>
<tb> By-product
<tb>
<tb>
<tb> 3,3'-dichlorodipropyl
<tb>
<tb>
<tb> sulphide <SEP> (g) <SEP> 346 <SEP> 423
<tb>
<tb>
<tb> Conversion <SEP> of <SEP> chloride <SEP> from al-
<tb>
<tb>
<tb> lyle <SEP> (%) <SEP> 58 <SEP> 61
<tb>
 
Several tests were carried out, one in which the 3-chloropropyl mercaptan, prepared as above, was reacted with 1-octene in the presence of ultra-violet light.

   In these tests, the reactants are loaded into a reactor and then the latter is purged with nitrogen. The reaction mixture is irradiated for the desired time, then the reaction solution is distilled under reduced pressure. Most of the unreacted l-octene and 3-chloropropyl mercaptan is collected at the top as a fraction between 5D and 74 C under 75 mm of mercury (absolute pressure) when the flask is heated. at about 150 C under 75 mm of maccure (absolute p-ression). The pressure is then reduced to 18 mm of mercury and, after having collected times small intermediate fractions (boiling point under 12 mm: 39-158 C), it is collected by expansion distillatin, as overhead product, the 3-chloroproyl n-octyl sulfide remaining at about 158-160 C under 12 made mercury (absolute pressure).

   The tests are summarized in the table below:

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 TABLE III
 EMI21.1
 
<tb> Test <SEP> n <SEP> C <SEP> D <SEP> E <SEP> F <SEP> G <SEP>
<tb>
<tb>
<tb>
<tb>
<tb> Volume <SEP> of the <SEP> reactor <SEP> 750 <SEP> cm3 <SEP> 750 <SEP> cm3 <SEP> 750 <SEP> cm3 <SEP> 750 <SEP> cm3 <SEP> 5.67 <SEP> liters
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Ultraviolet <SEP> light-
<tb>
<tb>
<tb> te <SEP> (watts) <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 450
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Load
<tb>
<tb>
<tb> 3-chloropropyl
<tb>
<tb>
<tb> mercaptan <SEP> (g) .... <SEP> 277 <SEP> 277 <SEP> 277 <SEP> 277 <SEP> 1. <SEP> 197
<tb>
<tb>
<tb> l-octene (g) ...... <SEP> 280 <SEP> 280 <SEP> 280 <SEP> 280 <SEP> 1.215
<tb>
<tb>
<tb> Addendum ..........

   <SEP> none <SEP> none <SEP> a <SEP> b <SEP> none
<tb>
<tb>
<tb> Quantity <SEP> of addi-
<tb>
<tb>
<tb> tif ...... <SEP> - <SEP> 0.1 <SEP> g <SEP> 10 <SEP> cm3
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Molecular <SEP> report
<tb>
<tb>
<tb> of the <SEP> reagents .... <SEP> 1 <SEP> 1 <SEP> 1 <SEP> 1 <SEP> 1
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Irradia <SEP> time
<tb>
<tb>
<tb> tion (minutes) ... <SEP> 90 <SEP> 90 <SEP> 90 <SEP> 90 <SEP> 120
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Product <SEP> retrieved
<tb>
<tb>
<tb> (g) <SEP> c ..... <SEP> 394 <SEP> 402 <SEP> 401 <SEP> 420 <SEP> 1. <SEP> 612
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Conversion <SEP> of
<tb>
<tb>
<tb> reagents <SEP> (%) <SEP> .....

   <SEP> 70.0 <SEP> 72.2 <SEP> 72.0 <SEP> 75.3 <SEP> 66.8
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Final <SEP> efficiency {%) <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
<tb>
 
 EMI21.2
 a - alpha, alpha'-azodiisobutyronitnle. b - propylene oxide c - 3-chloropropyl n-octyl sulfide
A portion of the 3-chloropropyl n-octyl sulfide, prepared by the above process, is then oxidized by means of hydrogen peroxide to give 3-c @ loropropyl n-octyl sulfoxide. The apparatus used is identical to that which was used for the oxidation in Example I. In this test, an amount of hydrogen peroxide is used which is less than the theoretical amount necessary for oxidation.

   As a result, 222.5 g of 3-chloropropyl n-octyl sulfide, 300 cm3 of methanol and 102 g of 30% by weight hydrogen peroxide are charged to the oxidation reactor, the addition of hydrogen peroxide taking about 10 minutes.



    After 16 minutes, the peroxide reaction was negative on the KI-starch paper, so the reaction was considered complete.

 <Desc / Clms Page number 22>

 



   The reaction solution is diluted with 500 cm3 of water; the phase containing the product is separated and extracted with 500 cm3 of n-pentane. Pentane is then removed by distillation under reduced pressure. 232.1 g of 3-chloropropyl n-octyl sulfoxide are obtained.



     EXAMPLE III.-
A test is carried out in which 3-chloropropyl sec-octyl sulfide is prepared and this product is then oxidized to 3-chloropropyl sec-octyl sulfoxide.



   In this test, 138.6 g of sec-octyl mercaptan, 80 g of allyl chloride and a trace of thio- (3-naphthol) are charged to the reactor of Example I, then the mixture is irradiated. with ultraviolet light. Thio- (3-naphthol) is used to activate the reaction, but no activating effect is obtained. After 70 minutes the lamp was turned off and the contents removed from the reactor. The distillation of the product obtained leads to the isolation of 94.6 g of 3-chloropropyl sec-octyl sulfide, boiling at 132 ° C. under 5.5 mm of mercury (absolute pressure); refractive index of the product nD20 = 1.4765.



   This sulfide is then oxidized to obtain the sulfoxide described in Example I, using a charge of 75 g of 3-chloropropyl-sec-octyl sulfide, 115 cm3 of methanol and 36 g of 30% aqueous hydrogen peroxide. in weight. 69.8 g of crude 3-chloropropyl sec-octyl sulfoxide, nD20 - 1.4820 are obtained. By purifying the sulphoxide by crystallization at low temperature, the pure compound is obtained.



   EXAMPLE IV.-
In another run, 3-chloropropyl tert-octyl sulfide is prepared and then oxidized to 3-chloropropyl tert-octyl sulfoxide.

 <Desc / Clms Page number 23>

 



   In this test, 197 g of ter-octyl mercaptan, 250 cm3 of methanol and 59 g of NaOH are charged to a one-liter three-neck flask equipped with a stirrer, and the mixture is then heated under reflux to that all of the caustic soda dissolves. The solution is transferred to a drop-in funnel and 212 g of 1-bromo-3-chloropropane are charged to the flask. The sodium mercaptide is then added dropwise in 20 minutes. The reaction is very vigorous and the sodium bromide precipitates out. After stirring for a few minutes to complete the reaction, about 250 cm3 of water are added to dissolve the salt formed (BaBr). The phases are then separated and the oily phase is washed with dilute hydrochloric acid, then with water.

   The product is then subjected to distillation. The main fraction, amounting to 282.0 g, has a refractive index nD20 = 1.4855 and a boiling point of 117 C under 5 mm of mercury (absolute pressure).



   The 3-chloropropyl tert-octyl sulfide, prepared as above, is oxidized to form the sulfoxide as in Example I. For this oxidation, the charge comprises 100 g of 3-chloropropyl tert-octyl sulfide, 150 cm3 of methanol. and 48 g of 30% by weight aqueous hydrogen peroxide.



  The product is treated by fractionating (according to Example I) and 87.3 g of 3-chloropropyl tert-octyl sulfoxy- de (nD20 = 1.4993) are obtained.



   EXAMPLE V.-
Several runs were carried out by mixing 3-chloropropyl n-octyl sulfoxide, prepared by the method described in Example I, with varying amounts of additives, and the product was heated to determine its stability.

 <Desc / Clms Page number 24>

 



   In these tests, small amounts of sulfoxide containing certain amounts of propylene oxide are heated in an oil bath to 115-120 ° C. and the time taken to produce the decomposition is recorded. At this temperature the decomposition point is very sharp, as the product begins to turn yellow with evolution of gas, and the color quickly turns from yellow to black.



  When decomposition has started, it only takes 15 to 30 seconds for the product to fully undergo these changes. The results of the tests are shown in the following table.



   TABLE IV.-
 EMI24.1
 
<tb> Sample <SEP> Additive <SEP> Quantity <SEP> of <SEP> Time <SEP> before
<tb> n <SEP> the additive <SEP> the <SEP> decount
<tb> ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ (weight <SEP>%) <SEP> tion <SEP> minutes
<tb>
<tb> 1 <SEP> none <SEP> 0 <SEP> 11,
<tb>
<tb> 2 <SEP> Propylene <SEP> <SEP> oxide <SEP> 0.5 <SEP> 29.5
<tb>
<tb> 3 <SEP> "<SEP> 1.0 <SEP> 55.0
<tb>
<tb> 4 <SEP> "<SEP> 5.0 <SEP> 180
<tb>
<tb> 5 <SEP> "<SEP> 10.0 <SEP> 180
<tb>
 
The above tests demonstrate that an alkylene oxide, for example propylene oxide, is very effective in preventing decomposition of the novel sulfoxides according to the invention.



    EXAMPLE VI.-
A test is also carried out in which 3-chloro-2-methylpropyl n-octyl sulfide is prepared which
 EMI24.2
 then oxidizes to 3-chloro-2-methylpropyl-n-oyl sulfoxide.



   In this test, 100 g of methallyl chloride and 146 g of n-octyl mercaptan are reacted in the presence of ultraviolet light, using substantially the same method as in Example I. recovery by extraction and fractionation, sensitive

 <Desc / Clms Page number 25>

 ment identical to that of Example I, gives 3-chloro-2-methylpropyl n-octyl sulfide, boiling point 147 C under 5 mm of mercury (absolute pressure). The refractive index of the compound is nD20 = 1.4751.



   The sulfoxide sulfide is then oxidized, by the oxidation method of Example I, using 75 g of 3-chloro-2-methylpropyl n-octyl sulfide, 100 cm3 of methanol and 36 g of aqueous hydrogen peroxide. 20% by weight.



  The reaction mixture is extracted, after the completion of the reaction, with pentane, and the sulphoxide is recovered by fractionation of pentane at 62 ° C. under 1 mm of mercury (absolute pressure). 3-Chloro-2-methylpropyl n-octyl sul. the oxide which is obtained weighs 79.9 g; refractive index nD20 = 1.4826.



   The following example brings to light the unexpected excellent repellant properties of the compounds prepared according to the invention, compared to other compounds.



   EXAMPLE VII.-
Olfactometer test.
The olfactometer is an instrument used to introduce two currents of air into a cage. One of the streams passes through a filter on which a small amount of repellant to be tested has been placed. The other air stream is not treated and serves as a control. To perform an olfactometer test, 0.1 g of the repellant is dissolved in acetone and this solution is used to saturate a filter pad (manufactured and sold by the American Optical Company, under the designation OR filter pad. -7 "of the type used for breathing apparatus). This tampon is air dried and secured around a metal tube. A glass cylinder is then secured around the tampon.

   This cylinder, which. has about 10 cm internal diameter and 15 cm long, is in turn set

 <Desc / Clms Page number 26>

 contact with the surface of the wire mesh of the cage containing the insects. Similarly, an untreated tampon is also attached to serve as a control.



   Air is blown with the same volumetric flow through the two buffers. The number of house flies resting on the wire mesh in the area bounded by the glass cylinder is counted after 5, 10 and 15 minutes and then at 15 minute intervals until ten counts have been made. The average of these ten readings is taken to determine the percentage increase or decrease in the number of flies on the treated circles.



   The results of the olfactometer tests show that the flies do not land on the wire mesh when the air is filtered through a plug treated with 3-chloro-propyl n-octyl sulfoxide. The control test gives an average of 16.2 flies. The sulfoxide is entirely effective in repelling flies in the above test.



     EXAMPLE VIII.-
Test of the "sandwich" appftt .-
This test consists of placing a porous screen treated with the insecticide to be tested between the hungry insects (house flies) and the food. If the chemical is repellent, the flies will not eat. If the chemical is not repellent, the insects will pick up food through the screen.



   This bait is prepared as follows: A smooth, thin film of molasses containing no sulphide product is placed on a 2.5 x 10 cm strip of cardboard, leaving on each side a margin of at least 6.35 mm.



  The role of this margin is to prevent insects from feeding without actually being on the strip, making it easier to count. We dry the strips thus prepared

 <Desc / Clms Page number 27>

 in an oven at 45 C.



   Porous filter paper cover strips are impregnated with the chemical to be tested and placed on the bait. The paper used is thin, porous and very absorbent. The loose fibrous structure of this paper allows flies to pick up molasses through the paper. In order to uniformly impregnate the bands, they are immersed in an acetone solution of the product to be tested.



  They are then hung on glass rods and dried for 6 hours.



   Just before the start of the test, the dried cover strips are carefully placed over the baits and secured with staples. When assembling the bait, care should be taken not to squeeze it or touch it with your fingers, as the molasses is easily squeezed out through the cover strip.



  Two sandwich baits are fixed on a cardboard support.



  The entire assembly is then applied to one of the covers which fit into the opening in the rubber bottom of the cages containing the insects.



   The cover with the baits is placed in the opening of a cage so that the baits are exposed to attack. We take flies over five days old that have been starved for 6 hours. The number of flies feeding on the strips is counted after 5 and 15 minutes and then every 15 minutes for 2 1/2 hours. In cases where the chemical is not repellent, the flies will eat all the molasses before the 2 1/2 hours have passed. In this case, we stop counting them. Non-repellent samples turn black from flies very soon after they are placed in the cages. Repellents with good activity are not affected. The difference is striking.

 <Desc / Clms Page number 28>

 



   Table V shows the results of the tests with the sandwich baits; tests 1, 2, 3 and 4 in which 1% acetone solutions are used as well as tests 5 and 6 in which 0.5% solutions are used show the effectiveness of the compounds in which one of the substituents is a 3-chloropropyl or 2-methyl-3 -chloropropyl group and the second substituent of which is a normal, secondary or tertiary octyl group. Related compounds, such as those applied in Tests 7 and 18, are ineffective at comparable doses.

 <Desc / Clms Page number 29>

 
 EMI29.1
 



  "JJ.1..s ... l \\.
 EMI29.2
 
<tb>



  TEST <SEP> WITH <SEP> BAIT <SEP> EN <SEP> SANDWICH <SEP> PERFORMED <SEP> WITH <SEP> DES <SEP> FLIES <SEP> DOMESTIC <SEP> IN <SEP> USING <SEP> MISCELLANEOUS < SEP> SULFOXYDES.Etest <SEP> Sulfoxides <SEP> Number <SEP> of <SEP> flies <SEP> getting <SEP> feeding <SEP> in <SEP> the <SEP> time <SEP> indicated <SEP> Bait < SEP> residual
<tb> n <SEP> minutes <SEP> Appat <SEP> after <SEP> exposa
<tb> 5 <SEP> 15 <SEP> 30 <SEP> 45 <SEP> 60 <SEP> 75 <SEP> 90 <SEP> 105 <SEP> 120 <SEP> 135 <SEP> 150 <SEP> 165 <SEP > tion <SEP> during <SEP> a
<tb> A)

   <SEP> Sulfoxides <SEP> used <SEP> under <SEP> form <SEP> night <SEP>
<tb> of <SEP> solutions <SEP> to <SEP> 1% <SEP> in <SEP> acetone
<tb> 1 <SEP> 3-chloropropyl <SEP> n-octyl <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP > 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 100
<tb> 2 <SEP> 3-chloropropyl <SEP> sec-octyl <SEP> 0 <SEP> 0 <SEP> 1 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP > 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> -
<tb> 3 <SEP> 2-methyl-3-chloropropyl <SEP> n-octyl <SEP> 0 <SEP> 0 <SEP> 1 <SEP> 1 <SEP> 1 <SEP> 1 <SEP> 0 <SEP > 0 <SEP> 1 <SEP> 0 <SEP> 1 <SEP> 4 <SEP> 94 (a)
<tb> 4 <SEP> 3-chloropropyl <SEP> tert-octyl <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP > 0 <SEP> 4 <SEP> 1 <SEP> 4 <SEP> 98 (a)
<tb> B) <SEP> Sulfoxides <SEP> used <SEP> in <SEP> form <SEP> of
<tb> solutions <SEP> to <SEP> 0,

  5% <SEP> in <SEP> acetone
<tb> 5 <SEP> 3-chloropropyl <SEP> n-octyl <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP > 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 100
<tb> 6 <SEP> 2-methyl-3-chloropropyl <SEP> n-octyl <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 1 <SEP> 0 <SEP> 0 <SEP> 0 <SEP > 0 <SEP> 1 <SEP> 1 <SEP> 4 <SEP> C) <SEP> Sulfoxides <SEP> used <SEP> in <SEP> form <SEP> of
<tb> solutions <SEP> to <SEP> 1% <SEP> in <SEP> acetone
<tb> 3-chloropropyl <SEP> n-amyl <SEP> 0 <SEP> 4 <SEP> 12 <SEP> 32 <SEP> 3 <SEP> 2 <SEP> 8 (b)
<tb> 3-hydroxypropyl <SEP> n-oct;

  yl <SEP> 50 <SEP> 50 <SEP> 28 <SEP> 12 <SEP> 8 <SEP> 6 <SEP> 8 (b)
<tb> 9 <SEP> 3-chloropropyl <SEP> n-butyl <SEP> 19 <SEP> 42 <SEP> 28 (b)
<tb> 10 <SEP> 3-chloropropyl <SEP> tert-butyl <SEP> 2 <SEP> 50 <SEP> 25 <SEP> 12 <SEP> (b)
<tb> 11 <SEP> 3-chloropropyl <SEP> isobutyl <SEP> 10 <SEP> 50 <SEP> 22 (b)
<tb>.

   <SEP> 12 <SEP> 3-chloropropyl <SEP> 2-ethylhexyl <SEP> 0 <SEP> 12 <SEP> 15 <SEP> 6 <SEP> (b)
<tb> 13 <SEP> 3-chloropropyl <SEP> 2,4,4-trimethyl-1-pentyl <SEP> 3 <SEP> 15 <SEP> 22 <SEP> 8 <SEP> (b)
<tb> 14 <SEP> 3-chloropropyl <SEP> ter-dodecyl <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 5 <SEP> 13 <SEP> 18 <SEP> 18 <SEP> 12 <SEP > (b)
<tb> 15 <SEP> 3-chloropropyl <SEP> dicyclopentadienenyl <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 14 <SEP> 8 <SEP> 1 (b)
<tb> D) <SEP> Allyl <SEP> sulfoxides <SEP> used <SEP> in <SEP> form <SEP> of <SEP> solutions <SEP> at <SEP> 1% <SEP> in <SEP> l 'acetone
<tb> 17 <SEP> di-n-butyl <SEP> 0 <SEP> 0 <SEP> 4 <SEP> 20 (b)
<tb> 18 <SEP> n-octyl <SEP> n-propyl <SEP> 3 <SEP> 3 <SEP> 3 <SEP> 3 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> - <SEP > 1 <SEP> - <SEP> 1 <SEP> 6
<tb> 19 <SEP> tert-octyl <SEP> methyl <SEP> 15 <SEP> 28 <SEP> 30 <SEP> 25 (b) <SEP> 9
<tb>
   (at)

   - Observation made after depriving the flies of food for 165 minutes (b) - The food is consumed for the time indicated and therefore the test is considered to be terminated.



  (c) - After overnight exposure to hungry flies.

 <Desc / Clms Page number 30>

 
EXAMPLE IX. -
Stability or light exposure test.
This test consists in exposing the insecticide in a himid atmosphere to the action of an ultraviolet lamp (of the "General Electric Sunlight S-1" type). The lamp is suspended in a sleeve above a phonograph platter, rotating at 33 revolutions per minute, on which a flat aluminum container has been placed. Two large cellulose pads are placed in this container and covered with gauze having 4.76 mm openings. Keep the pads moist by keeping water in the cup. Clean filter paper is placed on the gauze and the strips of repellent impregnated blotting paper are pinned.

   The distance between the test strips and the lamp, which is 22.5 cm, is set to maintain a temperature of about 38 C. The decomposition is determined using the bait method. sandwich for house flies. The chemicals are deposited on strips of blotting paper by soaking them in acetone solutions. All the quantities of chemicals are noted as a function of the concentration of the solution used for soaking. The strips are soaked and dried overnight. The next morning, the strips are exposed for 4 hours to the effect of light and the repellency is determined in the afternoon.



   A test comparable to Test 1 of Table V is also carried out after exposure of the control sample to ultraviolet light, as described.



  The results obtained are the same as with the unexposed sample. These tests show that exposure to sunlight, even hot and in the presence of humidity, is not detrimental to the effectiveness of the products.

 <Desc / Clms Page number 31>

 



   EXAMPLE X.-
Toxicity test.
Two chicks (about 3 days old) are given a commercial feed mixed with 0.5% by weight of 3-chloropropyl n-octyl sulfoxide. The quantity of feed consumed and the increase in the weight of the chicks are determined and compared with the results obtained with chicks having received the same commercial feed not containing added sulphoxide. As shown in Table VI, chicks fed the feed containing sulfoxide consumed more feed, but with somewhat less efficiency. The weight gain is about the same -849 versus 850- for both groups of chicks.



  There is no adverse effect of the sulfoxide in the food.



   TABLE VI.-
 EMI31.1
 
<tb> Test <SEP> of <SEP> toxicity <SEP> with <SEP> two <SEP> chicks <SEP> fed <SEP> during <SEP> 28
<tb>
<tb>
<tb>
<tb> days <SEP> with <SEP> a <SEP> food <SEP> from <SEP> commerce <SEP> containing <SEP> 0.5% <SEP> from <SEP> 3-
<tb>
<tb>
<tb>
<tb> chloropropyl <SEP> n-octyl <SEP> tallow <SEP> oxide.-¯¯¯¯¯¯¯¯¯¯ <SEP>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Repellent <SEP> Food <SEP> Weight <SEP> Gain <SEP> of <SEP> Efficacy
<tb>
<tb>
<tb>
<tb> consumed <SEP> final <SEP> weight <SEP> tee <SEP> (x)
<tb>
<tb>
<tb>
<tb>
<tb> g <SEP> g <SEP> g <SEP>%
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> None <SEP> 1664 <SEP> 970 <SEP> 849 <SEP> 51
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 3-chloropropyl <SEP> n-
<tb>
<tb>
<tb>
<tb> octyl <SEP> sulfoxide <SEP> 1807 <SEP> 984 <SEP> 850 <SEP> 46
<tb>
 (x)

   The effectiveness is evaluated in% of food = consumed producing the increase in weight.



   EXAMPLE XI.-
Repellant compositions containing varying amounts of 3-chloropropyl n-oc- are tested.
 EMI31.2
 tyl sulfoxide and N-2- (ethylhexyl) bicyclo 2,2-5 .. heptene-2,3-dicarboximide to establish the repellency against stable flies and to demonstrate the synergistic effect. We impregnate organdy bags, made with

 <Desc / Clms Page number 32>

   'of organdy tiwsu and having 25 cm2, so that one end of the bag remains open with the desired amount of the repellent composition to be tested, dissolved in 6 to 7 cm3 of acetone, then these bags are hung up. a rope to air dry them.

   After 24 hours, the bags are put on the hand and exposed to attack by several thousand stable flies confined in cubic cages 45 cm in size. The flies were reared according to the method described by Campau, Baker and Morrison in "Journal of Economic Entomology", 46, 524, (1953).



   The time to the first bite is recorded, and if the bites do not continue within 5 minutes, the bag is removed and the same process is repeated the next day. Whenever a bite occurs, the bag is shaken to drive off the flies and the bag is left in the cage until no more bites occur within 5 minutes or until two more bites are noted, in which case the time in seconds elapsing until the second and the third bite is recorded. The time of effective repulsion is indicated by the number of days elapsed from the time the bags were impregnated until the day the flies were constantly biting. Random bites are not considered to be an indication of the loss of effective repellency.

   The results of these tests are shown below in Table VII.

 <Desc / Clms Page number 33>

 
 EMI33.1
 l'AbLbAU Vll.-
 EMI33.2
 
<tb> Tests <SEP> to <SEP> bag <SEP> of organdy <SEP> with <SEP> of <SEP> flies <SEP> of stable <SEP> in <SEP> using <SEP> the <SEP > 3-chloropropyl-
<tb>
 
 EMI33.3
 n-octyl sulfoxide, N- (z-ethylhexyl) bicyclo-2, z, -5-heptene-2,3-dicarboximide
 EMI33.4
 
<tb> and <SEP> of <SEP> mixtures <SEP> of <SEP> these <SEP> two <SEP> compounds. Test <SEP> n <SEP> Quantity <SEP> of <SEP> product <SEP> Seconds <SEP> before <SEP> the <SEP> bites <SEP> n <SEP> 1,2 and <SEP> 3 <SEP> during <SEP> of tests <SEP> to <SEP> of the <SEP> moments
<tb> used <SEP> for <SEP> trai- <SEP> variables <SEP> after <SEP> the <SEP> processing <SEP> of the <SEP> bag <SEP> (1)
<tb> ter <SEP> the <SEP> bag,

   <SEP> g <SEP> ¯¯¯¯¯¯¯¯¯
<tb> ¯¯¯ <SEP> Dicarbo- <SEP> Sulfoxi- <SEP> 1 <SEP> day <SEP> 2 <SEP> days <SEP> 3 <SEP> days <SEP> 4 <SEP> days <SEP > 5 <SEP> days <SEP> 6 <SEP> days <SEP> 7 <SEP> days <SEP> 8 <SEP> days
<tb> ximide <SEP> of
<tb> 1 <SEP> 2 <SEP> 0 <SEP> 50, <SEP> 15, <SEP> '<SEP> 10
<tb> 2 <SEP> 0.9 <SEP> 0.1 <SEP> N <SEP> N <SEP> 60, <SEP> 60, <SEP> 30
<tb> 3 <SEP> 0.75 <SEP> 0.25 <SEP> N <SEP> N <SEP> 45, <SEP> 20, <SEP> N
<tb> 4 <SEP> 0.5 <SEP> 0.5 <SEP> N <SEP> N <SEP> N <SEP> N <SEP> 80, <SEP> 50, N <SEP> 65,180, N < SEP> 200, N <SEP> 60.30.30
<tb> 5 <SEP> 0.1 <SEP> 0.9 <SEP> N <SEP> N <SEP> N <SEP> 180, <SEP> 63, <SEP> N <SEP> 17, <SEP> 8.60
<tb> 6 <SEP> 0 <SEP> 1.0 <SEP> 150, <SEP> 200, <SEP> N <SEP> 185,170,25
<tb>
   (1)

   N indicates in the table above that no bites occur during the 5 minute exposure period.

 <Desc / Clms Page number 34>

 
As shown in Table VII, dicarboximide alone, even used at a rate of 2 g, does not confer total repellency, because bites are recorded after
50, 15 and 10 seconds in a test performed at the end of the first day. Since bites occur in all three operations, the test is stopped. Sulfoxy. de Seul exhibits good repellency at the end of the first test period (as shown in Test 6), but on the second day bites are obtained in all three operations.

   Tests 2, 3 and 4 show that the mixtures of dicarboximide and of sulphoxide taken in the same total quantity equivalent to 1 g of sulphoxide used separately, are more repellent than the sulphoxide or the dicarboximide used alone. Thus, mixtures of dicarboximide and sulfoxide have a higher repulsive efficiency compared to sulfoxide alone or dicarboximide alone.



   EXAMPLE XII.-
The increase in the duration of the repellent effect obtained by mixing the dicarboximide with the
Insect repelling 3-chloropropyl n-octyl sulfoxide by exposing sandwich bait samples containing only sulfoxide and sulfoxide mixed with dicarboximide to an ultraviolet lamp in a humid atmosphere, then determining the effect repellent of exposed samples using the bait sandwich method.



   The prepared strips, that is to say its sandwich baits, are placed in cages which contain 5 day old house flies, which have been deprived of food for 6 hours. The highly porous paper web containing the impregnation composition to be tested is thus exposed to flies, and the loose fiber structure of the impregnated paper allows the flies to eat.

 <Desc / Clms Page number 35>

 molasses through this strip. A molasses bait covered with a strip of blotting paper impregnated with a non-repellent product becomes covered with flies immediately after exposure and the bait is consumed within 5 minutes. In these tests, the number of flies feeding on the strip is recorded periodically for 2 hours and 45 minutes.



   The accelerated aging of the compositions to be tested in order to determine the duration of the repellency effect can be achieved by exposing these compositions to the action of an ultraviolet lamp ("General Electric Sun Lamp S-1") in a humid atmosphere. The lamp is suspended in a sleeve above a phonograph plate, rotating at 33 revolutions per minute, on which is placed a flat aluminum container. Two large cellulose pads are placed in this container and covered with gauze having 4.76 mm openings. The pads are kept moist by placing excess water in the container. Place clean filter paper on the gauze and pin the strips of blotting paper impregnated with the repellant.



  The distance between the test strips and the lamp, which is 22.5 cm, is set to maintain the temperature at about 38 ° C. These strips were exposed to light for varying periods of time.



   The strips to be tested are impregnated, on the one hand, with a solution containing 0.2% by weight of the sulfoxide and 0.2% by weight of dicarboximide or, on the other hand, with a solution containing 0.2% by weight sulfoxide alone. A portion of the bands are exposed to the UV lamp and the repellency of the exposed bands, as well as the unexposed bands, determined by the bait sandwich method.

   The percentage of the initial repellency that remains after exposure is estimated

 <Desc / Clms Page number 36>

 with the ultraviolet lamp by comparing the repellency of the exposed bands with that of the bands which contain varying concentrations of the composition to be tested and which have not been exposed to the effect of the lamp, assuming that the bands which are impregnated with 0.4% by weight of the composition have a repellency of 100%.



  In this way, it is possible to estimate with a difference of approximately # 10% the efficiency of the bands exposed to the lamp compared to that of the unexposed bands; Accelerated aging tests are illustrated by the graph of the appended drawing, which shows the percentage of the initial repellency on the ordinate as a function of the number of hours of exposure under the lamp, on the abscissa.



   The curves in this graph demonstrate that the effectiveness of the repellant sulfoxide can be increased considerably when used in admixture with the dicarboximide (curve A: 3-chloropropyl-n-octyl sulfoxide + N- (2 -.
 EMI36.1
 ethylhexyl) bicyclo 2,2,> 5-heptene..2,3-dicarboximide, and curve B: 3-chloropropyl n-octyl-sulfoxide). Thus, for example, the repellency of the strips treated only with the sulfoxide is reduced to about 20% of the initial value by an exposure of -5 hours. Comparatively, the repellency of the bands impregnated with a mixture of sulfoxide and dicarboxymide is only reduced to about 50% of the initial value after exposure for the same period of time.



   EXAMPLE XIII. -
In this example, the effectiveness of an emulsifiable concentrate for spraying on dairy animals is demonstrated. The concentrate which can be emulsified has the following composition:

 <Desc / Clms Page number 37>

 
 EMI37.1
 
<tb> Ingredient <SEP> in <SEP> weight <SEP> content
<tb>
<tb> ¯¯¯¯¯¯¯. <SEP> in <SEP> the concentrated <SEP>.-
<tb>
<tb> 3-chloropropyl <SEP> n-octyl <SEP> sulfoxide <SEP> 10
<tb>
 
 EMI37.2
 Id- (2..ethylhexylybicyclo, 2,2, 5-.heptene-233-.dicarboximide 40
 EMI37.3
 
<tb> "Triton <SEP> X-100" <SEP> 7.45
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Xylene <SEP> 42.5
<tb>
 
1 part of this concentrate is mixed with 19 parts water prior to spray application.

   A group of six cows is chosen as a control and a second group is sprayed with 113 g of the emulsion in water per cow and per day. Cows are sprayed during milking between 1:00 p.m. and 2:30 p.m. daily, using a pressure sprayer, which covers each animal well with a fine spray. Each cow receives a total of five sprays per week from Monday to Friday. The number of stable flies and ox flies on each animal is counted at 9 a.m., 10 a.m. and 11 a.m., as well as at 3 p.m. and 4 p.m. Monday through Friday of each week, and only at 9 , 10 and 11 a.m. on Saturday. The average number of flies counted per cow is calculated from the observations obtained in a two-week period.

   The group of six cows which were sprayed with the emulsion during the first week serves as a control during the second field, and conversely, the group of cows which served as a control during the first week are sprayed. of the emulsion during the second week.

   The results of the test show that spraying an emulsion containing the sulfoxide-dicarboximide mixture on the cows is very effective in lowering the number of barn flies and ox flies that land on each cow. The average of the daily counts for the control group and the treated group is as follows:

 <Desc / Clms Page number 38>

 
 EMI38.1
 
<tb> Average <SEP> number <SEP> of <SEP> flies
<tb> flies <SEP> from- <SEP> flies <SEP> to
<tb> table <SEP> oxen <SEP>
<tb>
<tb> Group <SEP> witness <SEP> 1.97 <SEP> 27.24
<tb> Group <SEP> processed <SEP> 0.16 <SEP> 3.94
<tb>
 
EXAMPLE XIV.-
The repellency of a mixture of dicarboximide with 3-chloropropyl n-octyl sulfoxide against ticks results from the present example.



   We divide a piece of filter paper 9 cm in diameter into four quarters by drawing pencil lines passing through the center. 1 cc of a 1% by weight acetone solution of the chemical to be tested is applied uniformly to two opposite quadrants, while the other two quadrants are left untreated. The solution is applied carefully with a pipette and care is taken that it does not encroach on the adjacent quadrants. The acetone is allowed to evaporate and the filter paper is then placed in a Petri boot. It is calculated that the dose of 1 cm3 of a 1% solution of these chemicals on one quadrant, corresponds to approximately 5.1 g / m2.



  About 30 to 60 Texas ticks in the larval state (Amblyomma americanum) are then placed on the paper. The number of ticks on the treated quadrants and their number on the untreated quadrants are counted at various time intervals. The repellency of the product is then expressed by the equation: Number of ticks on the untreated quadrants (100) Index Total number of ticks on the repellent paper
Therefore, if there are no ticks in the treated quadrants, the repellency index will be 100. If the number of ticks is equal in the treated and untreated quadrants, the repellency index will be 50 and the actual repulsion. from 0.

   Similarly, if the repellency index is less than 50, the chemical

 <Desc / Clms Page number 39>

 actually exerts an attraction on ticks.



   When the filter paper is treated with an acetone solution which contains 0.5% by weight of 3-chloropropyl n-octyl sulfoxide and 0.5% by weight of N - (2-ethylhexyl)
 EMI39.1
 bicyclo-Z-2,2., 17-5-heptene-2,3-dicarboximide and when used in the above test, the repellency is 80% and more for a period of as long as 80 days.



   EXAMPLE XV.-
Several tests were carried out in which the repellency of Stomoxys Calcitrans (Linn.) Stable fly compositions were determined. In these tests, organdy bags, made with a 25 cm piece of organdy so as to leave one end of the bag open, are impregnated with 1 g of the sulfoxide to be tested dissolved in 6 to 7 cm3 of acetone , then we hang the bags to dry them. After 24 hours, the bags are put on the hand and exposed to the attack of several thousand hungry stable flies, which are locked in cubic cages 75 cm square. The flies were bred according to the method reported by Campau, Baker and Morrison in the "Journal of Economics Entomology", 46, 524, (1953).

   The time to the first bite is noted and if no bites occur for 5 minutes, the bag is removed and the process repeated the next day.



  The effective repellency period is noted in the number of days elapsing from the day of impregnation of the bags until the day when the flies are constantly biting.



  Occasional bites are not considered to be a loss of effective repellency. The results of these tests are shown in Table VIII below.

 <Desc / Clms Page number 40>

 



  TABLE VIII.- -.
 EMI40.1
 
<tb> Compound <SEP> tried <SEP> Seconds <SEP> elapsing <SEP> until <SEP> the first <SEP>, <SEP> 2nd
<tb>
<tb>
<tb>
<tb> and <SEP> dose <SEP> by <SEP> and <SEP> 3rd <SEP> bite <SEP> in <SEP> a <SEP> delay <SEP> of <SEP> 5 <SEP> minutes
<tb>
<tb>
<tb>
<tb> bag <SEP> 1st <SEP> 2nd <SEP> 3rd <SEP> 4th <SEP> 5th <SEP> 6th
<tb>
<tb>
<tb>
<tb>
<tb> day <SEP> day <SEP> day <SEP> day <SEP> day <SEP> day
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 1.0 <SEP> g <SEP> of <SEP> 3-chloro-
<tb>
<tb>
<tb>
<tb> propyl-n-octyl
<tb>
<tb>
<tb>
<tb> sulfoxide <SEP> cty <SEP> 32,43,20
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 1.0 <SEP> g <SEP> from <SEP> 2-hydro-
<tb>
<tb>
<tb>
<tb> xypropyl <SEP> n-octyl
<tb>
<tb>
<tb>
<tb> sulfoxide <SEP> (B)

   <SEP> 130 <SEP> 150 <SEP> 120
<tb>
<tb>
<tb>
<tb>
<tb> PM <SEP> x <SEP> 30.145
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 0.5 <SEP> g <SEP> A <SEP> + <SEP> 0.5 <SEP> g <SEP> B <SEP> PM <SEP> PM <SEP> PM <SEP> 85, PM <SEP> PM <SEP> 35,16,218
<tb>
<tb>
<tb>
<tb> 0.25 <SEP> g <SEP> A + 0.75 <SEP> g <SEP> B <SEP> PM <SEP> PM <SEP> PM <SEP> PM <SEP> 80.6720
<tb>
<tb>
<tb>
<tb> 0.75 <SEP> g <SEP> A + 0.25 <SEP> g <SEP> B <SEP> PM <SEP> PM <SEP> 30,7,10
<tb>
 x PM - no bites CLAIMS.-
1.- Sulfoxide of formula
 EMI40.2
 in which R2 is an n-octyl, sec-octyl, or tert-octyl radical and R1 represents H or CH3.



   2. - Process for preparing a sulfoxide of general formula:
 EMI40.3
 in which R1 represents H or CH3 and R2 an n-octyl, sec-octyl or tert-octyl radical, characterized in that the corresponding sulphide is oxidized with the aid of an oxidizing agent in order to form the sulphoxide.


    

Claims (1)

3. A process according to claim 2, characterized in that the sulfide is subjected to the action of a peroxygen compound in the presence of a solvent which dissolves both the sulfide and the peroxygen compound. 4. A process according to either of claims 2 and 3, characterized in that the oxydaJ is carried out <Desc / Clms Page number 41> tion at a temperature between 0 and 100 C. 5. - A method according to either of claims 2 to 4, characterized in that the molecular ratio of the peroxygen compound to the sulphide is between 0.5: 1 and 1.5: 1. 6. A process according to claim 2, characterized in that the sulphide is oxidized with oxygen in the presence of an oxygen compound of nitrogen, which acts as a vehicle for fixing oxygen on the sulphide. 7.- Process for preparing a sulphide having the general formula: EMI41.1 in which R1 represents H or CH3 and R2 represents an n-octyl sec-octyl or tert-octyl radical, characterized in that it consists in reacting an octene with a 3-chloropropyl mercaptan or a 2-methyl derivative thereof , or to react allyl chloride with an octyl mercaptan or else to react an alkali metal mercaptide of an octyl mercaptan with 1-bromo-3-chloropropane or with its 2-methyl derivative. 8. A process according to claim 7, characterized in that the reaction between octane and mercaptan is carried out in the presence of ultraviolet light. 9. A process according to either of Claims 7 and 8. characterized in that a molecular ratio of 3-chloropropyl mercaptan or of its 2-methyl derivative to octene of between 0, is used. 5: 1 and 2: 1. 10. A method according to claim 8, characterized in that the ultraviolet light has a wavelength of between 100 and 2900 Angstroms. II.- A method according to claim 7. <Desc / Clms Page number 42> terized in that the reaction between mercaptide and bromopropane is carried out in the presence of methanol and under substantially anhydrous conditions. 12. - Process according to claim 11, charac- terized in that reacting an octyl mercaptan dissolved in methanol with an alkali metal hydroxide, the reaction product obtained is added to 1-bromo-3-chlo - ropropane or its 2-methyl derivative, which produces a precipitate of sodium bromide, an oily phase is separated by adding water in order to form two phases, the aqueous phase which contains this is eliminated. The sodium bromide is removed and the sulphide is isolated from the oil phase. 13. - Composition for combating insects, which contains a sulfoxide of general formula EMI42.1 in which R1 represents H or CH3 and R2 a noctyl, sec-octyl or tert-octyl radical. 14.- Composition according to claim 13, characterized in that it contains as additive an alkylene oxide as stabilizer. 15. - Composition according to claim 13, characterized in that it contains as additive a vehicle or support. 16. - Composition according to either of Claims 13 to 15, characterized in that it contains as additive a mercaptan of formula EMI42.2 in which R2 'R3'R4 and R5 represent hydrogen or alkyl radicals, the total number of atoms of <Desc / Clms Page number 43> carbon present in the four radicals not exceeding 4. . 17. - Composition according to claim 16, characterized in that the ratio of sulfoxide to mercaptan in the composition is approximately between 3: 1 and 1: 4. 18.- Composition according to either of Claims 16 and 17, characterized in that the mercaptan used is 2-hydroxypropyl n-octyl sulfide. 19.- Composition according to any one of claims 13 to 15, characterized in that the composition for combating insects contains as additive an N-alkyl imide of bicyclo [2,2 , 1] -5-heptene-2,3-dicarboxylic. 20. - A method for combàttre insects, characterized in that they are subjected to a composition according to one or the other of claims 13 to 18, 21. Sulfoxides, in substances, as described above, in particular in specific examples 1 to VI. 22.- Compositions for combating insects, in substance, as described above, in particular in specific examples VII to XV.