CA1340767C - Perfumes containing n-lower alkyl neoalkanamides(s) - Google Patents

Abstract

N-lower alkyl neoalkanamides of 1 to 4 carbon atoms in the lower alkyl thereof, and of 5 to 14 carbon atoms in the noealkanoyl group, e.g., N-methyl- and N-ethyl neodecanamides, are new compounds which have insect repellent properties, being especially effective against cockroaches, e.g., the German cockroach. However, they are also useful as repellents for other insects, including, for example, American cockroaches, mosquitoes, flies, fleas, ants, and lice. The most effective of the described amides for insect repellency are normally liquid and are sufficiently volatile to be detectable in air by insects. They may be applied directly to surfaces to be treated or they may be incorporated in detergent compositions, such as laundry detergents, floor and wall cleaners, rug cleaners and shampoos, hair shampoos, and liquid and bar soaps, and have been found to be sufficiently substantive to the substrate being washed so as to impart insect repelling properties to it. The invented N-lower alkyl neoalkanamides have been found to be of long lasting effectiveness, with significant and measurable insect repellency being obtainable for as long as two weeks after application. They are stable during normal trees, relatively low in manufacturing cost, of high substantivities to substrates, economical to use, unobjectionable in odor to humans, and safe to humans and animals, and to the environment. In addition to insect repelling uses, the invented N-lower alkyl neoalkanamides are also useful components of perfumes. Various products, such as detergent compositions, shampoos, waxes and polishes, pet care items, insect repellents and insecticides, may be perfumed with the invented perfumes, which results in such products and compositions being made insect repellent so that surfaces to which they have been applied also become insect repellent, as well as perfumed.

Description

1340~1~'~
N-ALKYL-NEOALKANAMIDES
This invention relates to N-alkyl neoalkanamides, which are novel. chemical compounds that possess insect repel-ling properties, and are useful components of perfumes. More specifically, this invention relates to N-lower alkyl neoalkan-amides. The mentioned neoalkanamides, especially N-methyl and N-ethyl neodecamamides and neotridecanamides, have been found to be especial7.y effective in repelling insects, such as German cockroaches, when applied to surfaces of structures, items and materials to be: protected. The present invention also relates to various compositions containing such N-alkyl neoalkanamides, which compositions may be perfumes or may be insect repelling, employed as a rneans for depositing such active compounds onto surfaces to be made repellent to insects.
Some prior art insect repellent materials are toxic .
and others are foul smelling and discoloring, which adverse properties can seriously limit their utilities. Most of the useful insect repellents reported in the literature are tertiary amides and of these the one~heretofore regarded as the most effective all-purpose insect repellant is N,N-di-ethyl-m-toluamide, which is often referred to as "DEET".

1340'67 However, the F~resent neoalkanamides, and N-methyl neodecanamide and N-methyl n.eotridecanamide in particular, are superior to DEFT in long lasting effectiveness, and in at least one entomological laboratory, have replaced DEFT as the standard of repellent action (against roaches). Additionally, such neoalkanamidee; are also effective to repel other insects, including mosquitoes, and have been found to be of greater effectiveness against Anopheles guadrimaculatus than DEFT. In view of the relatively small number of useful insect repellents known, effort:; continue to be made to discover additional repellents which would be of greater repellent actions and of longer lasting effects. Desirably, such compounds also would i be of improved physical characteristics, such as of more pleasant aroma, desirable volatility, non-staining character, liquid state (preferable), improved stability, greater substantivity to substrates, and longer lasting repellent effect.
In <3ccordance with the present invention N-alkyl noealkanamide;s that are intended for use as insect repellents, have been discovered. The invention provides an insect repelling composition useful for repelling insects from an area, location or item which comprises an insect repelling proportion of a compound of the formula:
R' H
R-C-CO-N-R "' R"
wherein R "' is methyl or ethyl, and the aryl moiety R' R-C-CO
R"
is neodecanoyl wherein the sum of the carbon atoms in R, R' and R" is eight or t ., ~34~7~7 is neodecanoyl wherein the sum of the carbon atoms in R, R' and R" is eight or is neotridecanoyl wherein the sum of the carbon atoms in R, R' and R" is eleven, and when the acyl moiety is neodecanoyl i:he composition is in a liquid state in association with an insect repellent compatible carrier. At present one of the most preferred of such compounds for employment as an insect: repellent, especially effective against German cockroaches, is methyl neodecanamide.
The invention also provides a process for repelling insects from an area, location or item which comprises applying to or nE~ar such area, location or item an insect repelling quantity of N-alkyl neoalkanamide(s), Wherein the alkyl is of 1 to 4 carbon atoms and the neoalkanoyl moiety is of 7 to 14 carbon atoms.
Also within the invention are detergent compositions (both particulate and liquid), carpet and upholstery shampoos, human hair shampoos, hard surface cleaners, and soap 2a ~a m 134fl'~E'~
and detergent bars comprising such N-alkyl neoalkanamide(s).
Also useful are' solutions and dispersions of the neoalkanamide(s) in liquid mediF~ or the neoalkanamides dispersed in a particulate or powdered carrier, which particulate or liquid products are ' S suitable for application to a location from which insects are to be repelled,. Also within the invention are processes for repelling insecas by applications of insect repelling amounts of neoalkanamides of this invention to or near a surface, area, location or ite=m from which such insects are to be repelled.
In some situations the present repellents may be used in conjunc-tion with insecticides, to repel the insects from one area and.
toward the location of the insecticide. Alternatively, they may be formulated with insecticides so that after the repellent effect is lost the treated area will still not be safe for insects.
Perf~,unes of this invention . in which such N-lower alkyl neoalkanamides are present comprise a N-lower alkyl neo-alkanamide or a mixture of a plurality of such N-lower alkyl neoalkanamides, wherein the lower alkyl is o~ or averages 1 to 4 carbon atoms and the neoalkanoyl moiety thereof is of or averages 5 to 14 carbon atoms, and at least one pexfu~e component which is of a type selected from the group consist-ing of essential oils, esters, ethers, aldehydes, alcohols, hydrocarbons, ketones and lactones, in which the content o~
such neoalkanamide(s) is in the range of 0.1 to 98%.

1340"lG7 Computer and manual searches of the prior art have not resulted in the finding of any reports of volatile primary or secondary amidles that were recognized to be perfume or repellent components. Such searches indicated that the N-lower alkyl neoalkanami.des of the present invention are novel and unobvious. The closest compounds to the N-lower alkyl neoalkanamides o1. this invention appear to be those described in Canadian patent application 505,117 (Steltenkamp and Camara) filed March 26, :1986, which relates to N-higher alkyl neoalkanamides. However, the neoalkanamides of that patent application are ltaught therein to be useful as antistatic agents, not as insect repellents. Also, such application had ;
not been published as of the priority date of the present application, and therefore is not applicable prior art.
The invented alkyl neoalkanamide compositions and processes include those wherein the alkyl is of 1 to 18 carbon atoms, but preferably such alkyl will be 1 to 4 carbon atoms, more preferably one or two carbon atoms (methyl or ethyl), and often most preferably such will be methyl. The neoalkanoyl moiety, which may be derived from any of the suitable neoalkanoic acids, several of which are available commercially, will normally be of 5 ar 7 to 14 carbon atoms (of a number of carbon atoms in the range of 5 or 7 to 14), such as neodecanoyl, neotridecanoyl or neoheptanoyl, and often will preferably be neodecanoyl. Among the available neoalkanoic acids are neopentanoic acid, neoheptanoic acid, neononanoic acid, neodecanoi.c acid, neododecanoic acid, neotridecanoic acid, and neotet;radecanoic acid, and the l3~Orlc~'~
corresponding alkyl neoalkanamides thereof, such as the methyl and ethyl neoalkanamides, may be made from such neoalkanoic acids. Usually the ethyl groups are straight chain but they can also branch. Pure neoalkanamides of the types described may also be made but often the commercial or technical grade acids, which may be used, and the amides made from them, will be mixtures.
The invented amides are of the formula R' H
R -C-CON -R"' R"
wherein R, R' and R° are alkyl groups, the sum of the carbon atom contents of which is in the range of 5 to 12, and R " ' is an alkyl, preferably a lower alkyl group, more preferably of 1 to 4 carbon atoms,. Further details with respect to R, R' and R " will be given later, in conjunction with a description of neoalkanoic acids which may be employed as starting materials for the production of the neoalkanamides.
Infrared absorption spectra for some representative and preferred N-lower alkyl neoalkanamides of this invention and shown in the drawing, in which:
FIG. 1 is an infrared absorption spectrograph of a sample of N-methy7_ neodecanamide;
FIG. 2 is an infrared spectrograph of a sample of N-ethyl neodecanamide;

13 4 0'7 ~'~
FIG. 3 is an infrared spectrograph of a sample of N-methyl neohepta.namide; and FIG. 4 is an infrared spectrograph of a sample of N-methyl neotridec:anamide.
Also shown in the drawing, in FIG. 5, is a plot of insect repelling action vs. time, in which repellent effects of N-methyl neodecanamide and "DEFT", a leading insect repel-lent, were compared.
To make the neoalkanamides of this invention neo- ' alkanoyl chloride reactant is slowly reacted with the appropriate primary amine, in ethyl ether, after which reaction the reaction mixture is washed with distilled water, dilute hydrochloric acid solution, dilute sodium hydroxide solution, and more disti7.led water, until it is neutral to pH paper.
The ether is then removed by means of a steam bath, followed by employment of a vacuum evaporator. The reaction product obtained is wager white to light amber in color and is essen-tially pure. 7:n an alternative method, the neoalkanoic acid may be reacted directly with the lower alkylamine.
Neoa7.kanoic acids, such as neodecanoic acid, neotri-decanoic acid, neoheptanoic acid and neopentanoic acid, are available from Exxon Chemical Americas, which synthesizes 'them by reacting a suitable branched alkene and carbon mo~oxide under higher pressurE: at elevated temperature in the presence of aqueous acidic catalyst: (Koch reaction). The general mechanism involved includes generation of carbonium ion, fol,l,ov~ted by com~lexation ~t3~0'~~'r with carbon monoxide and the catalyst to form a "complex°, which is subsequently hydrolyzed to generate free acid. The formula of the free acid is R' R-C-COOH
I
R"
In neodecanoic ac_~d, for example, the total number of carbon atoms in R, R' and R" is 8, 31% of the neodecanoic acid is of a structure wherein R' and R" are both methyl and R is hexyl, 67% is of a formula wherein R' is methyl, R" is alkyl of a carbon atoms conte=nt greater than that of methyl and less than that of R', and R is of a carbon atoms content less then that of hexyl and great=er than that of R"; and 2% is of the formula wherein R' and R" are both of a carbon atoms content greater than that of methyl and less than that of R' and R is of a carbon atoms conte=nt less than that of hexyl and greater than those of R' and R". Among other neoalkanoic acids that are available and uses=ul to make the present amides may be mentioned others in the 7 to 16 carbon atoms content range, such as neoheptanoic, neononanoic, neodecanoic, neododecanoic, neotridecanoic, and neotetradecanoic acids. In the various neoalkanoic acids mentioned, when R is alkyl of five or more carbon atoms, such alkyl is branched. The acyl chloride starting materials for the reactions to produce the invented N-lower alkyl neoalkanamides may be made from the neoalkanoic acids and suitable: chlorinating agents, such as phosphorus _ 7 _ .

1340'~~'~
trichloride (although sometimes thionyl chloride may be found preferable), and are available from the Lucidol Division of Pennwalt, Inc. and from White Chemical Corp.
Although or is possible for the insect repellents of this invention to be incorporated in various materials when such materials are being manufactured, as by mixed in with pulp for making paper, rubber and synthetic organic polymeric plastic batches, and chips for the manufacture of pressed boards, and while the invented insect repellents may also be injected or otherwise inserted into the bodies of items to be made insect repellent, usually the insect repellents will be applied to surfaces of areas, structures or items to be made insect repellent, either by direct application of the insect repelling N-alkyl neoalkanamide, in liquid solution or dispersion, or dispersed in a powdered carrier, or in a detergent composition, such as a laundry detergent, floor or wall cleaner, upholstery or rug shampoo, hair shampoo, liquid soap, bar soap, or in any other appropriate composition in which it may be u:~efully incorporated. Among such other appropriate compositions may be mentioned insecticidal and antibacterial washes or dips for humans, pets and farm animals, furniturE: polishes and finishes, floor waxes and finishes, ointment: s, salves and topical medicaments, insecticides, fungicides, bactericides, plant fertilizers, mulches and plant potting preparations, to name only a few.
In some instances means will be provided for recharging such items and compositions with the active alkanamide component to renew their repellent effects. In the majority of instances _ g _ y 1340~~7 the invented compositions will be applied directly or indirectly by external application to surfaces to be treated, and afterward such application will be made on a continuing basis to maintain a satisfactory degree of insect repellency.
Thus, the insect :repellent N-alkyl neoalkanamide, such as N-methyl neodecanam:ide and/or N-methyl neotridecanamide, may be painted onto a surface to be treated or may be applied to such surface by washing it with a detergent composition containing the active insect repellent. The invented compounds are in liquid state or pasty condition at normal ambient temperatures and are water insoluble, so they tend to be satisfactorily substantive to surfaces from detergent compositions and from other preparation:, even when such compositions are rinsed off, and normally,, after either direct or indirect application to such surfaces, a sufficient amount of the alkanamide will remain to be effectively insect repelling. While different application rates of the different alkanamides of this invention are desirably used for effective repelling of different insects from different surfaces under different conditions, it is generally considered that insect repellant effects are obtainable at surface concentrations of the active ingredient in the range of 0.002 to 100 g./sq. m. For economic reasons and for effectiveness against such insects there will normally be applied from 0.01 to 5 g./sq. m., preferably 0.1 to 2 g./sq. m, e.g., 1 g./sq. m., when roach repellency is desired. Higher application rates, such as 10 to 100 g./sq. m., will often be used against mosquitos.
Because the present insect repellents are volatile _ g _ ~3~Q'~~7 their presence can be detected in the air near a surface to which they have been applied. Therefore, not only are the surfaces repellent: to insects, which will avoid having their body parts contact. such surfaces, but the vapors from the N-lower alkyl neoalkanamines will tend to repel insects from the surrounding space. Thus, the application of the volatile repellent to walls of a china closet can repel roaches from the closet interior, thereby preventing them from contacting, soiling and contaminating contained dishes, utensils and l0 silverware. Similarly, coating of pantry surfaces, interior and/or exterior, with a furniture polish containing an invented volatile repellent, or use of shelf paper containing a repellent neoallcanamide can discourage roaches from entering the pantry and contaminating foods contained therein. Also, washing of clothing with detergent compositions containing the invented repellents may prevent insects from lighting on the clothing and its wearer, and from stinging or biting the wearer. Shampooing of rug with a rug shampoo or carpet cleaner containing the invented repellent will discourage insects from entering the room and from nesting and laying their eggs in or under the rug. Washing of floors and walls with insect repel:Lent detergent compositions formulated for such purpose will deposit thereon a substantive coating of the invented insect rE~pellent and will discourage insects from contacting the floor and wall surfaces and from entering the treated rooms. It~ is an important feature of the invented insect repellents that although they are sufficiently volatile to be effective, i:heir repellent properties are persistent, e~1 .~3407~'~
often lasting as :Long as three weeks or more (even longer if incorporated interiorly in a product). The invented repellents may be formulated with insecticides, such as by being sprayed onto the surfaces of insecticidal powers, e.g., boric acid powder,, which is effective against roaches. By use of the neoalkanam:ide-boric acid composition immediate effectiveness in repelling the roaches is obtained and subsequently, aftE~r the repellent activity may have diminished, due to exhaustion by volatilization, any roaches that return to the area will be killed by the insecticide. It is recognized that: a more normal practice is to incorporate an attractant with the insecticide but the repellent-insecticide composition also has utility.
It is apparent from the foregoing brief description that the invented insect repellents can be used in many compositions and <:an be applied in diverse ways. However, among the most useful products which can incorporate the invented neoalkanamides are detergent compositions, from which the neoalkanamides are surprisingly substantive to the surfaces of washed items. Such detergent compositions operate in several ways to counter insect contamination of the washed item. They remove: any earlier contamination, remove stains and soils, on whi<:h the insects might feed, and which could attract them, and leave behind the insect repelling neoalkanamide.
The prirnary component of the present detergent compositions, other than the insect repelling neoalkanamide, is an organic detergent material. Such material may be one of 1340'l~'~
the soaps, preferably a sodium and/or potassium higher (C10-18) fatty acid soap, but is preferably a synthetic organic detergent,, which may be of the anionic, nonionic, amphoteric, ampho:Lytic, zwitterionic or cationic type, or may be a mixture of two or more detergents within one or more of such classifications. Preferably, the detergent will be a synthetic organic detergent of the anionic or nonionic type and often the anionic detergents will be most preferred.
Descriptions of m<~ny such detergents are found in the text Surface Active Age~nts and Detergents, Vol. II, pages 25-138, by Schwartz, Perr;r and Berch, published in 1958 by Interscience Publishers, Inc. Such compounds are also described in a 19')3 publication by John W. McCutcheon, entitled Detergents and Emulsifiers, and they form an art-recognized class known to those of skill in the art.
The anionic detergents employed may be any such suitable detergents (or soaps), but normally will be salts of alkali metals, su<:h as sodium or potassium or ammonium or lower alkanolammonium salts, e.g., triethanolamine salts. The anionic detergent may be a sulfate, sulfonate, phosphate or phosphonate or sa:Lt of other suitable acid but usually will be a sulfate or sulfonate, which may be designated as "sulf(on)ate". Such anionic detergents will include a lipophilic group, which will normally have from 10 to 18 carbon atoms, preferably in linear higher alkyl arrangement, but other lipophi:Lic groups may be present instead, preferably including 12 to 16 carbon atoms, such as branched chain alkyl benzene. In some cases the anionic detergents may include I3~07~~
poly-lower alkoxy groups, as in ethoxylated higher fatty alcohol sulfates, e.g., triethoxylated lauryl alcohol sulfate.
Normally the number of ethoxy groups in such detergents will be in the range o:E 1 to 30, preferably 1 to 10. As examples of suitable anionic detergents there may be mentioned: higher fatty alcohol sulfonates, such as sodium tridecyl sulfonate;
sodium linear alkyl benzane sulfonates, e.g., sodium linear tridecylbenzene sulfonate; olefin sulfonates; and paraffin sulfonates. All of the anionic detergents will preferably be sodium salts for most of the particulate detergent compositions of this invention but potassium, ammonium and triethanolammoniurn salts may be more desirable for some liquid compositions. Usually the detergent will preferably include a lipophilic alkyl moiety of 12 to 16 carbon atoms, often preferably of or averaging 12 to 13 carbon atoms.
The suitable nonionic detergents will normally be condensation products of lipophilic compounds or moieties and lower alkylene oxides or polyalkoxy moieties. Highly preferable lipoph:files are higher fatty alcohols of 10 to 18 carbon atoms but alkyl phenols, such as octyl and nonyl phenols, may also be used. The alkylene oxide of preference is ethylene oxide and normally from 3 to 30 moles of ethylene oxide will be present per mole of lipophile.
In the built detergent compositions, in which builders are employed to improve the detergency of the synthetic organic detergent (or soap), there will be present a building proportion of a suitable builder. Builders used may be inorganic or organic, water soluble or water insoluble.

t ~3407~;~
Among such classes of builders may be mentioned water soluble inorganic salts, :including: polyphosphates, e.g., sodium tripolyphosphate; carbonates, e.g., sodium carbonate;
biocarbonates, e.c~., sodium bicarbonate; borates, e.g., borax;
and silicates, e.c~., sodium silicate; water insoluble inorganic buildera, including zeolites, e.g., hydrated zeolite 4A; and water soluble organic builders, including citrates, gluconates, NTA, and polyacetal carboxylates. In some cases, as when mildness of the product to the human body or to delicate fabrics :is important, alkaline builders and other "harsh" builders will be avoided, and in many cases no builders will be present at all.
Various adjuvants may be present in the detergent compositions of this invention to improve various characteristics o:E such products. Thus, for example, bentonite may be employed as a fabric softener, perfumes and colorants may be added for their aesthetic effects, soil anti-redeposition ageni~s may be employed, such as sodium carboxymethyl cel:Lulose, and solvents or co-solvents may be present, as in liquid compositions. Among other adjuvants there may be ment:LOned fluorescent brighteners, antistatic agents, antibacterial agents, fungicides, foaming agents, anti-foams, flow promoters, suspending agents, antioxidants, anti-gelling ageni~s, soil release promoting agents, and enzymes The detE~rgent compositions of this invention may be in particulate, powder, tablet, bar, liquid, paste, gel, capsule, leaf, foam or "aerosol° or other suitable form, as P

I3~01~7 may be best suited for the purpose intended. Methods for manufacturing products in such forms are well known in the art of processing soaps and detergents, and need not be further mentioned here.
While it: is possible to apply the present insect repelling N-lower alkyl neoalkanamides directly to surfaces and items to be made insect repellent, it is often more convenient and also more efficacious to utilize the repellent neoalkanamide as a liquid solution or emulsion, or as a liquid or particulate or powder dispersion. To make such solutions the neoalkanamide may be dissolved in any suitable solvent, such as a lower alcohol, e.g., ethanol, or in an aqueous alcoholic medium. Of course, other solvents may also be employed, such as hydrocarbons, esters, ketones, aldehydes and halogenated hydrocarbons. Among the hydrocarbons and halogenated hydrocarbons there may be mentioned isobutane and the chlorofluorinated lower hydrocarbons, such as dichloro-difluoromethane, rnonofluorothrichloromethane and other chlorofluormethane:s, -ethanes and -propanes. Such compounds include the liquei'iable gases, which can be maintained in liquid state in pressurized dispensing containers, for ready application as sprays or in other suitable forms to locations which are to be made insect repellent. The neoalkanamides may also be in aqueous or other emulsion form, when a suitable emulsifier, hydrot:rope or surface active agent is utilized, too. The invented neoalkanamides may be also dispersed in particulate or powdered inert or active materials. Among such inert materials may be mentioned silica, calcium carbonate, 1340'~~7 clay, expanded po:Lystyrene, wood chips and sawdust. Also, the neoalkanamides may be dispersed in active materials, such as detergent composition beads, bentonite (a fabric softener) and boric acid (a roach poison) .
Other modes of use of the invented insect repellents, some of which have already been mentioned, include incorporation in materials which are intended for use at or near sites from which the insects are to be excluded. Thus, the repellents may be incorporated in shelf papers, wallpapers, wallpaper glues, rugs and carpeting, and carpet padding. They may be formulated in floor waxes, furniture polishes and other preparations that are intended for applications to surfaces in the areas to be treated. They may be automatically dispensed in certain areas, such as storerooms and warehouses, by timer-operated sprayers or other dispensers, and they may be renewably charged to containers, from which they may be vaporized, such as absorbers and other holders, as in thE: under sides of garbage can covers.
The detergent compositions of this invention, including those that are useful for washing hard surfaces, such as floors, amd also soft surfaces, such as those of carpets, laundry, and human hair, will include an insect repelling proportion of N-alkyl neoalkanamide or a mixture of such neoalkanamides, which proportion is sufficient so that of enough of the neoalkanamide is retained on the washed surface, after washing of :it with the detergent composition, to repel insects from such surface, and will also include a detersive proportion of soap or synthetic organic detergent (or any __ ~3~0~~'~
suitable mixture t=hereof). The neoalkanamide is preferably one wherein the lower alkyl is 1 of 4 carbon atoms (and that designation includes mixed lower alkyls, too averaging such numbers of carbon atoms, more preferably being methyl or ethyl, and usually most preferably being methyl. The neoalkanoyl moiety of the neoalkanamide is of 7 to 14 carbon atoms, preferably 9 to 11 or 13 carbon atoms, and most preferably is of :LO carbon atoms. Mixtures of such neoalkanoyl moieties and "average" moieties, averaging within such ranges or averaging 10 or 13 carbon atoms can also be used, and are to be considered as being within such descriptions. As was previously indicated, the more preferred neodecanamides are, N-methyl- and N-ethyl neodecanamides, of which N-methyl neodecanamide is most preferred, in most instances, although sometimes N-methyl neotridecanamide is preferred.
In part:iculate built laundry detergent compositions of the invention t:he active detergent component will usually be synthetic organic detergent selected from the group consisting of anionic, nonionic, amphoteric, ampholytic, and zwitterionic detergents and mixtures thereof, and the builder will be water soluble inorganic or organic builder or water insoluble inorganic builder. The proportions of synthetic organic detergent(s), builder(s), and neoalkanamide(s) to make an effective inse<a repellant particulate synthetic organic detergent composition will be 1 or 5 to 35%, 10 to 90%, and 0.2 to 10%, respe<:tively. Preferred compositions of such type will have the synthetic organic detergent selected from the 1340'~~i'~
group consisting of anionic and nonionic detergents, and mixtures thereof, may contain water soluble filler salts(s), such as sodium su:Lfate, and will contain N-methyl neotridecanamide or neodecanamide, or a mixture thereof. The proportions of su<:h components for best effects in such detergent composii:ions will often be 7 to 30% of the synthetic organic detergent(s), 20 to 75% of the builder salt(s), 0 to 50% of the filler salt(s), and 0.5 to 5% of the neoalkanamide ( s ) .
When liquid detergents containing the invented insect repellant neoalkanamide(s) are made, the same components may be used, plus a liquid medium, but the detergent will prE~ferably be non-soap. Sometimes a conventional emulsifying agent, such as an Emcol~, sold by Witco Chemical Co., Inc., will be employed, in emulsifying proportion. Also,, hydrotopes, such as sodium toluene sulfate, and other functional and aesthetic adjuvants, such as have been employed in :Liquid detergent compositions, and/or fillers, may be included, or not. In the built liquid detergents the synthetic organic detergent content will be in the range of 2 to 25%, the builder content will be 5 to 40%, the neoalkanamide content will be 0.2 to 10%, and the liquid medium content, p~_eferably aqueous, will be 40 to 90%. More preferably, the built liquid detergent compositions of the invention will comprise 3 to 20% of a synthetic organic detergent which is anionic and/or nonionic, 10 to 30% of builder salts) for such detergent(s), which may be water soluble, such as potassium pyrophosphate, sodium carbonate, or i .~

I340'~G'~
sodium polyacetal carboxylate, and/or water insoluble, such as sodium zeolite, 0 to 20% of water soluble filler salt, such as sodium sulfate, 0.5 to 5% of N-methyl neodecanamide and/or N-ethyl neodecanamide, or other suitable neoalkanamide, and 50 to 90% of water, preferably deionized water.
When an insect repelling shampoo for use on upholstery, rugs and carpets is to be made, it may comprise 1 to 35%, preferably 5 to 20%, of a detergent selected from the group consisting of water soluble soaps) and synthetic organic detergent:a, 0 to 40% of builders) for the soap and/or detergent, often preferably 0%, and 0.2 to 10% of N-lower alkyl neoalkanami<ie, preferably 0.5 to 5%, all being of the broad types previously mentioned, in a liquid medium, preferably aqueous, the percentage of which may be in the range of 40 to 90=~, preferably 70 to 90%, with water being 50 to 90% of the composition, preferably 70 to 90%.
Alternatively, the. shampoo may be in gel, paste or powder form.
When the. present insect repellents are used in shampoos intended for washing human hair on the head and for making the hair re:pellant of insects, the shampoos will preferably comprise 2 to 25% of soap and/or the previously described synthetic organic detergent(s), and 0.2 to 10% of N-lower alkyl neoallcanamide, of the type previously discussed in conjunction with t:he broad description of detergent compositions, in an aqueous medium such as 40 to 90% of water, preferably deionized water. The aqueous medium may include up to half thereof oiE a co-solvent, such as a lower alkanol, ____ _ ._.

~34~7~7 e.g., ethanol, or a glycol but normally the percentage of such co-solvent will be limited to 5 to 20% of the final product.
In more preferred embodiments of the shampoos for human hair, there will be present 5 to 22% of synthetic organic detergent, 0 to 20% of water soluble filler salt, 0.5 to 5% of N-lower alkyl neodecanamide or mixture thereof, preferably N-methyl neodecanamide or N-ethyl neodecanamide, and 50 to 90% of water, preferably deionized.
Solid o:r bar or cake insect repellant detergent products can also be made, which may be used for washing persons, animals, laundry, rugs, and/or hard surfaces, such as walls and floors, to make them insect repellant. Such products can comprise neoalkanamide repellant with soap and/or synthetic organic detergent, or may also include builders, fillers and other adjuvants, previously referred to herein.
The proportion of N-alkyl neoalkanamide in such products will normally be from 0.2 to 10%, and that of the detersive material will be :From 15 to 95%. Such bars will normally be of a moisture coni~ent in the range of 2 to 20% and the balance will be of builders) and/or fillers) and/or adjuvant(s), when such are present. Normally, the adjuvant(s) content of the various deter<~ent products will be in the range of 0.5 to 20%, total, with :individual adjuvants being 0.1 to 5% for the most part.
The various detergent compositions described above may be prepared by processes that are well known in the art and need not be described at length herein. Such processes include spray drying, dry mixing, spray applying and/or 1~40'~~7 coating, sequential dissolving and/or dispersing and/or emulsifying, mill_Lng, plodding and pressing.
When then insect repellant is to be sprayed or applied in a carr_~er, such as a liquid or particulate material or medium, the concentration of it therein will be an insect repellant proportion, so that when applied onto a surface of a material to be tre=ated (or into the interior or other portion thereof), by spra;ring, dusting, rubbing, wiping, pouring, depositing, or other mechanism, the repellant applied will be in such quantity and/or concentration that it will be effective in repe:Lling insects or a particular type of insect, so that such inse<a (s) will stay away from the treated location. Such rE~pelling is due to the insect being reluctant to contact the repellent and also in some measure is due to the repellant effect of the vapor from the repellant, which is at least partially volatile, although it may last for as long as two weeks or more, as normally applied, using the application concentrations that were previously given. Also, the lasting power of the repellant is increased when it is incorporated in the body of an article, such as in a mattress or absorbent sponge, rather than only on a surface that is exposed to the air.
The conc=entration of the repellent chemicals) in a liquid medium, suc=h as an aqueous medium, in which a dispersing agent or emulsifier may be employed, too, will usually be in the range of 0.2 to 10, 25 to 50%, but is often preferably in the range of 0.5 to 10%, e.g., about 1% or 5%, for roach repellency. 'The liquid medium may be water, lower alkanol, such as ethanol, lower ketone, such as acetone, lower hydrocarbon, such as isobutane, cyclopropane or mixture thereof, or halogE~nated lower hydrocarbon, such as chlorofluorinated,, fluorinated or chlorinated lower hydrocarbons, e.g., Propellants il and 12. The various "lower" compounds are of 1 to 4 carbon atoms per molecule, preferably 1 or 2 carbon atoms, and in the case of those that are normally in the gaseous state, they are under sufficient pressure to maintain them in liquid state.
Similar concentrations of the invented repellents may be employed in powdered or particulate carriers. Thus, the invented neoa:lkanamides may be applied as by spraying of liquid droplets onto powdered calcium carbonate, silica, clay or boric acid, onto grains of such materials, or onto detergent composition particles or synthetic organic polymer beads (preferably of particle sizes between 125 microns and 2.4 mm in diameters), in concentrations in the range of 0.2 to 10 or 25%, preferably 0.5 to 5 or 10%, for roach repellents.
In insect repelling processes or treatments in which the invented repellents are employed they will normally be applied to surfaces to be treated at concentrations such that 0.002 to 100 g./sq.m. initially remain on such surfaces after treatment, with such application rate preferably being 0.01 to 5 or 10 g./sq.m. and more preferably 0.1 to 2 g./sq.m., e.g., 1 g./sq.m. for act: ion against roaches. Concentrations outside such ranges may sometimes also be of at least partial effectiveness. When the repellant is in a detergent composition which is employed in an aqueous washing medium, f such as water, the: wash water will usually contain from 0.05 to 5% of the detergent composition but in some applications, such as shampooing of human hair or of carpets or rugs with foam preparations,, the concentrations may be greater, sometimes being a:~ high as 25%.
When the' repellents are incorporated in and applied to surfaces in other media or preparations, such as waxes or furniture polishes, the concentrations thereof will usually be in the same ranges as for detergent compositions, but may be increased, if desired, in some such instances to as high as 25%.
The invented repellents possess various significant advantages over various other repellent materials available.
They are essentia:Lly non-toxic and therefore are not hazardous to children or pei:s that might come into contact with them, after application. They are pleasantly aromatic (sometimes fruity, with N-mei~hyl neodecanamide and N-ethyl neodecanamide resembling apples and pears in odor) and therefore do not usually adversely affect the aromas of preparations into which they are formulated. In fact, they may be useful in giving such preparations acceptable aromas, and thereby permit the omissions of expensive perfumes from such products. They are substantially colorless and therefore can be employed in detergents, shampoos, polishes, sprays, and various compositions and preparations wherein the imparting of color would not be acceptable. They are effective both as contact and vapor repellents and are superior in repelling action to various commercial insect repellents, especially against ~3407b7 German cockroaches, which are considered to be the most difficult household insect pest to control. The present repellents are long lasting, with tests having shown both N-methyl neotride<:anamide and N-methyl neodecanamide to be effective to repe=L roaches for two weeks and more after topical application. Against Anopheles Quadrimaculatus N-methyl neodecanam_~de is effective for five weeks, by Dept. of Agriculture screening tests (a week longer than DEET).
Against Aedes aecr~,rpti the neoalkanamide is almost as effective as DEFT, using they same test. The N-alkyl neoalkanamides are sufficiently stable to be able to maintain their insect repelling properties despite being incorporated in various soap, detergent, polish wax, insecticide, cosmetic, and coating preparations, in liquid, paste, gel, foam, powder, particulate or solid bar form, or in aqueous or other solvent solutions, emulsions or dispersions, and they are highly substantive from :such media .
Experimental work to date has proven conclusively that members of the class of N-alkyl neoalkanamides, wherein the alkyl is lower alkyl and the neoalkanoyl moiety is 7 to 14 carbon atoms, are superior insect repellents, being especially effective against both the German cockroach and the American cockroach, and evaluations of such compounds indicate that they will also be effective repellents against other insects, such as those in i:he group of flies, fleas, lice, mosquitoes, bees, wasps, hornets, ants and beetles, and they may also be effective against arachnids, such as spiders, ticks and mites.
Because data are most complete and are very convincing for the ~3~0'~~'~
use of N-methyl ne~odecanamide against German cockroaches, and because such data were obtained from controlled tests, conducted in conne=ction with entomological research at a major university, such data, together with some mosquito repellency data, will be that: presented in most of working examples, which will follow., In the perfume composition aspect of this invention the perfumes made contain N-lower alkyl neoalkanamide(s) which modify the fragrance of the perfume, is substantive to surfaces - 24a -1340~~'~
to which the pexfuune is applied, is satisfactorily stable on storage and in contact with alkaline media, and increases the strengths of aromas of various other perfuming components. In accordance with that aspect of the invention a novel liquid perfume, suitable for perfuming soaps and detergent compositions, comprises a N-lower alkyl neoalkanamide or a mixture of a plurality of such N-lower alkyl neoalkanamides, wherein the lower alkyl is of 1 to 4 carbon atoms and the neoalkanoyl moiety thereof is of 5 to 14 carbon atoms, and at least one and preferably a plurality of perfume components) of types) selected from the group consisting of essential oils, esters, ethers, aldehyd,es, alcohols, hydrocarbons, ketones and lactones, in which the content of such neoalkanamide(s) is from 0.1 to 98$.
Also within the: invention are various household products that have been perfumed with the described perfume. Such products include built a.nd unbuilt soap and synthetic organic detergent compositions, i.n particulate, liquid, gel, paste, bar or cake, and other acceptable forms, hard surface cleaning detergent compositions, hair shampoos, rug and upholstery shampoos, floor .
polishes and waxes, furniture polishes and waxes, and shelving papers. Also within the invention are synthetic__organic golymeric "plastic". products containing a perfume of the invention, such as pet care articles, e.g., food dishes, bed frames, grooming aids, of perfumed plastic, and of other materials.
The described N-lower alkyl neoalkanamides are normally liquids and are of sufficient volatilities and lasting effects to be effective perfume materials. They are of pleasing aromas and are relatively long lasting. Additionallx, they interact with other perfume components and often strengthen -- 13~0~~7 and otherwise improve the aromas of such components in the total perfume. A preferred neoalkanamide, N-ethyl neodecanamide, is of a mild, somewhat rose-like fragrance, with a slight plunn or apple fruitiness. The fragrance of a drop, on a perfume:r's blotter strip, is still noticeable after two weeks. N-methyl neodecanamide possesses a light, fresh, fruity pear-like aroma with floral undertones. Its fragrance is also still detectable after two weeks. N-ethyl neoheptanamide has a "green", fruity, wine-like odor, which lasts one or two days, and N-methyl neoheptanamide has a fresh, clean, camphor-type odor, which also lasts one or two days. Other N-lower alkyl neoalkanamides of the class described herein are also aromatic and persistent, and tend to be substantive to surfaces to which they are applied.
Additionally, they are generally of satisfactory stabilities in a wide variety of preparations, even those which may be of substantial alkalinities.
With the, N-lower alkyl neoalkanamide(s) components) of the present perfumes there may be employed any of the various well-known aromatic perfuming components, fixatives, solvents, extenders, stabilizers and adjuvants. Of these the primarily perfuming materials will often fall in one or more of the following classes: essential oils, esters, ethers, aldehydes, alcoho:Ls, hydrocarbons, ketones, and lactones, but various other cla;~ses of materials may also be present, such as pyrrones, and pyrroles.
Among preferred components of rose, lily, tropical fruit and floral-woody-amber type perfumes are the following:

1340'~~~
essential oils - c:itrus, evergreen, jasmine, lily, rose, ylang ylang; esters - phenoxyethyl isobutyrate, benzyl acetate, p-tertiary butyl cy<:lohexyl acetate, guaiacwood acetate, linalyl acetate, dimethylbenzyl carbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycidate, allylcyclohexane propionate, styrallyl propionate, and benzyl salicylate; ethers - benzylethyl ether; aldehydes - alkyl aldehydes of 8 to 18 carbon atoms, bourgeional, citral, citronellal, citronellyl oxyacetaldehyde, cyclamen aldehyde, hydroxy citronellal, and lilial; alcohols - anethol, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol; hydrocarbons - balsams and terpenes; ketones -ionones, alpha-isomethyl ionone, and methylcedryl ketone;
lactones - gamma-alkyl lactone wherein the alkyl is of 8 to 14 carbon atoms; pyrrones - hydroxy lower alkyl pyrrone wherein the alkyl is of 1 to 4 carbon atoms; and pyrroles -benzopyrrole.
Although the components mentioned above are preferred in perfumes of the invention for producing the types of fragrances previously mentioned, various other perfumery materials may also be employed, including lemon oil, lime oil, orange oil, bergamot oil, sweet orange oil, petitgrain bigarade oil, rosemary oil, dimethyl anthranilate, indole, methyl anthranilat:e, jasmine oil, patchouly oil, vetiver bourbon oil, vanillin, ethyl vanillin, coumarin, 3-methyl nonan-3-yl-acetate, methyl ionone, synthetic lily of the valley oil, synth<aic red rose oil, 3-methyl nonan-3-ol, alpha-amyl cinnam:ic aldehyde, methyl salicylate, amyl .i I3~0'~~7 salicylate, lavandin, isobutyl heptenone, cedryl acetate, ethyl linalyl acet:ate, neryl acetate, nerol, d-limonene, cuminic aldehyde, linalyl propionate, nerolidyl acetate, nerolidyl formate,, alpha-pinene, isobutyl linalool, methylnaphthyl ket:one, linalyl isobutyrate, paracresyl caprylate, paracre:syl phenyl-acetate, sandalwood oil, coriander oil, sassafras oil, cassia oil, angelica root oil, Peruvian balsam, clove oil, mace oil, menthol, and almond oil.
In addit:ion to the named fragrance components there may also be emplo;red fixative type materials, including musk, civet, castoreum, ambergris, gum benzoin, musk ambrette, musk ketone, musk xylol, oleoresin orris root, resinoid benzoin Siam and resinoid opopanax, as well as various other resins, gums, synthetic masks and other fixatives. Also components of perfumes are alcohols and other suitable solvents and media, as well as preservatives, antioxidants, stabilizers and viscosity and volatility modifiers.
The pert°umes and perfuming materials of this invention may cont:ain from 0.1 to 98% of N-lower alkyl neoalkanamide(s), with the balance thereof being other fragrance materia:Ls and perfume constituents, which may include solvents, liquid media and/or particulate or powder bases, such as wood particles, sachet materials and clays.
Preferably the perfume will be in liquid state, more preferably in a lower alcoholic solvent, e.g., ethanol, and the concentration of N-lower alkyl neoalkanamide therein will be in the range o:E 1 to 60%. More preferably, such concentration wil:L be in the range of 2 to 30% and most i i3~o~~7 preferably it wil:L usually be in the range of 5 to 15%, e.g., 10%. Normally, the proportion of fixatives) will be less than that of the fragrance material, and will usually be in the range of 0.1 i~o 5%. The proportion of solvent may be variable but will usually be from 20 to 95%, preferably 50 to 90%, and may be omitted entirely from some perfumes which are to be employed as concentrates, as when the perfume is added to a product or composition, rather than being a handkerchief perfume .
Although the proportions of the various non-N-methyl neoalkanamide fragrance components of the perfume are variable, with individual components ranging from 0.01 to 30%
in some cases, and sometimes with certain of the classes of such materials be:Lng omitted from the formulas, normally there will be present in most perfume formulas at least one ester, at least one aldehyde and at least one alcohol representative of the fragrance classes. The proportions of each of such classes will usua:Lly be at least 1%, with at least one of such classes being present to the extent of at least 5% and sometimes at leash 10%. However, in other instances one or more of the three mentioned classes of fragrance components may be omitted, as in preferred floral-woody-amber perfumes which may comprise from 5 to 40% of citrenellol, 5 to 30% of geraniol and 2 to 40% of phenylethyl alcohol, with such proportions preferably being in the ranges of 5 to 20%, 5 to 25% and 2 to 15%, e.g., 8%, 10%, and 5%, respectively. The total of non-N-mei~hyl neoalkanamide fragrance components present in the imaented perfumes will usually be in the range f . ., ~J

I3~~76'~
of 5 to 99%, prefssrably 50 to 90%, with the greater percentages being present in the concentrates (from which solvent is omitted).
The proportion of perfume (usually as non-solvent concentrate) employed in various household and other products of this invention will usually be from 0.1 to 10%, preferably 0.5 to 5% and frequently 1 to 3%, with the content of N-lower alkyl neoalkanami<ie normally being within the range of 0.01 to 5%, preferably O.:l to 2% and often 0.2 to 1%. However, in perfuming, odorani~ or air freshening sprays the range of concentrations of perfumes may be increased to 5 to 25% and even to as high as 50%, and sometimes the perfume concentrate may be employed undiluted.
The invE:nted perfumes may be usefully employed in a wide variety of household products and in various other compositions and articles. Representatives of these are detergent compositions of various types, insect repellents, insecticides, papE:r items, textiles, surface treating compositions and :synthetic organic polymeric "plastic°
articles. The dei:ergent compositions include built and unbuilt particulai:e, liquid, gel, past and bar or cake detergents, such as are employed as laundry detergents, rug shampoos, human F ~i 1340'~~7 hair shampoos, upholstery cleaners, and hard surface cleaners (including scouring cleansers and wall and floor cleaners).
The insect repellent compositions may be in liquid, gel, paste, powder or other suitable form, as may be insecticides perfumed with the present compositions, although the insecti-cides will normally be in liquid solvent or liquefied gas solution or emu7.sion. From the above it is seen that the N-lower alkyl ne:oalkanamides can contribute both perfuming and insect repe7Lling properties to various household products.
The following examples illustrate but do not limit the invention. Unless otherwise stated, all parts are by weight and all temperatures are in °C., in such examples, and elsewhere in this specification and in the appended claims.

1340r~~'~

N-methyl neodecanamide was made from methyl amine and neodecanoyl chloride in a reaction conducted in a 3-necked glass one-liter flask equipped with a Chesapeake stirrer, a thermo-s meter, an additional funnel (a dropping funnel) and a condenser equipped with a Drierite~ desiccant tube. The flask was placed in an ice bath and was charged with 31 grams of methyl amine, 700 ml. of diethyl ether and 59 grams of triethyl amine (which functioned to remove from the reaction mixture any HCI that was produced). Then 190.5 grams of neodecanoyl chloride (obtained from Pennwalt C'orporation's Lucidol Division) were added dropwise to the flask ovex a period of one hour. After completion of the addition of the: neodecanoyl chloride the reaction mixture was allowed to come: to room temperature. The reaction mixture was then transferrESd to a 2-liter separatory funnel and was washed twice with deionized water to separate the N-methyl neodecanamide from the triethylamine chloride, once with 5% aqueous hydro-chloric acid, and once with 5% aqueous sodium hydroxide, after which it was further washed with distilled water until the ' washings were neutral to litmus paper. The ether was then removed from the mixture by heating it on a steam bath, followed by finishing such removal with a rotary vacuum evaporator.
The reaction product resulting, in essentially stoichiometric yield, is N-methyl neodecanamide. It was distilled at 235°C.
under 760 mm. ;Hg. The result is a pure, water white product.
An infrared spectrograph of the product is shown in FIG. 1.

13407G~
In similar manners there were made N-ethyl neodecan-amide, N-methyl neotridecanamide, N-ethyl neotridecanamide, N-methyl neohepta.namide and N-ethyl neoheptanamide, using gram-molar weights c~f the appropriate alkyl amine (ethyl amine, methyl amine, ethyl amine, methyl amine and ethyl amine, respectively), triethylamine, and neoalkanoyl chloride (neodecanoyl chloride, neotridecanoyl chloride, neotridecanoyl chloride, neoheptanoyl chloride and ne:oheptanoyl chloride, respectively). The same volume of diethyl ether 1700 ml.) is employed as in the prepara-tion of the N-methyl neodecanamide, the same equipment is used, and the same procedures of addition, reaction, separation, wash-ing, evaporation and distillation are followed. The products are obtained in essentially stoichiometric yields. Some of their infrared spectrographs are shown in FIG'S. 2-4.

The fcix compounds for which manufacturing methods are described i.n Example 1, are made, but the starting materials which act as sources of the neoalkanol moieties are the corresponding neoalkanoic acids instead of the acid chlorides, and no triethy7L amine is employed. In such reactions, in which stoichiometric proportions of neoalkanoic acid and alkyl amine are employed, with diethyl ether as the reaction solvent, a one-liter 3-necked flask is also used but the system is closed (to avoid loss of alkyl amine) and the flask is equipped with a heating mant:Le, a magnetic stirrer, a source o~ nitrogen gas with means for conveying it to below the surface o~ the reaction mixture, and a thermometer and thermostatic control, to regulate i3~o~r~7 the temperature o:E the reaction mixture, which is held at 240°C for five hours. The reaction products are separated, washed and have ei:her removed from them in the same manner as described in Example 1. The produces resulting have infrared spectrographs like those of the samples of corresponding products of Examp:Le 1, which are shown in FIG'S. 1-4.

The N-methyl neodecanamide made by the process of Example 1 was tesi:ed for cockroach repellency by dissolving one gram of it in 10 ml of acetone and then swabbing the inside of a Dixie« cup, having an internal surface area of 188.5 sq.cm., with the solution so that upon evaporation of the acetone there is left behind 0.0189 g of the N-methyl neodecanamide, ev<:nly coating the cup interior at a concentration of :L.O g/m2. Four equidistant openings, are cut in the drinking and edges of the cup so that when the cup is inverted and plat<:d on a flat surface, it will be possible for test insects (roac:hes) to crawl through them and under it. An identical control cup is prepared, with the sole difference being that the same proportion of acetone is applied to the cup and floor surface but no N-methyl neodecanamide is present with it. Each cup is placed in the middle of a half of a medially dividablE~ rectangular area in a box, to which there are next added 100 cockroaches. The box top is transparent and the roaches cannot escape from the box. Initially the 13~0~~7 box is in the dark but to test the effectiveness of the repellent applied to the cup interior the box is illuminated with a 100 watt: incandescent bulb positioned about 50 cm. above it. Each of the roaches, seeking to hide from the light, crawls under one of the inverted cups. It is considered that any significant difference in the number of roaches under the experimental and control cups indicates repellency or attrac-tion effected by the experimental cup because the control is essentially neytral, having nothing remaining on its surfaces).
After waiting one minute after illumination, a divider is slid across the box, separating the experimental and control areas, the cups are removed or knocked over, and the roaches in each section are coosnted. The number in the control area is the percentage eff~sctiveness of the repellent. By this test, after two days, N-methyl neodecanamide is 100% effective against the control. After two days, when N-methyl neodecanamide (NMNDA) is compared to DEFT, and to a successful cockroach repellent, identified as ;MGK-874, the N-methyl neodecanamide (NMNDA) is rated to be 9 times and 19 times as effective, respectively, as the other repellents. After five days after application of the repellent to the surfaces mentioned, a similar test shows the experimental NMNDA repellent to be even more effective, and such comparative effectiveness is still exhibited after 14 days. However, after 21 days none of the experimental and comparative repellents is of much repellent effect so I3407~'~
comparisons after that time are not considered to be significant .
FIG. 5 :is a graph showing comparative effectiveness (in %) of N-methy:L neodecanamide and DEFT in repelling roaches. The number of roaches hiding under the DEFT treated cup is plotted for each of the indicated days after the applications of the repellents. The comparative effectiveness of the experiment<~1 compound, NMNDA, in %, is the number (out of 100) of roache:a hiding under the DEET cup.
In a variation of the described test only the inner bottom parts (the upper parts when the cups are inverted) are coated with the various test, control, and comparison materials, at the same concentration, 1.0 g/m. The results are of the same t~,rpe and order as described above for the contact repellency tests but the absolute effectiveness of the experimental products are less than for the contact tests, as would be expected,, due to the lesser quantities of repellents applied and the facts that the repellents were not on the lower and side surfaces of the cups, which the roaches are more prone to occupy, so that repellant action is more due to a vapor effect than to contact.
In the described tests results are the same whether the repellents arES made by the direct condensation method, from neoalkanoic <~cids, or from the neoalkanoyl chlorides.
Similar results are obtainable when other neoalkanamides of the invented typea are employed, such as N-ethyl neodecanamide, N-butyl r a neodecanamide, 'N-methyl neotridecanamide, N-ethyl neotridecanamide, the N-methyl- and N-ethyl- neoheptanamides, -neononanamides, neo-undecanamides, and neododecanamides, and best contact and vapor repellency effects are obtained when the neoalkanamides are those which are normally in liquid state under atmospheric conditions, and are volatile enough to have the vapors thereof detectable to insects, and repugnant to them.
Instead of applying the repellents to the test surfaces in acetone solution they may be sprayed onto such surfaces by means of "aerosol" or pressurized sprays in 50:50 mixture of isob~utane and cyclobutane or 60:40 solutions of Freon 12 and Freon 11 (dichloridifluoromethane and trichloro-monofluorometha.ne, respectively? or in other pressurized solvents. Instead of applying the solution at the concentra-tion in the tests reported earlier in this example, concentra-tions in the range of 2% to 30% may often be used, depending to some extent on the solubity of the repellents in the solvent system employed, for example 15% in the Freon system, 20% in the hydrocarbon system, 5% in ethanol, and 25% in methyl ethyl ~, ketone. Aqueous systems may also be used, preferably with emulsifiers or suitable surface active agents being present to hold the repel7lent in homogeneous suspension as colloidal droplets, with its concentration usually being somewhat lower than for the oi-panic solvent solutions, e.g., 3%, ~% and 7%.
All such liquid systems may be applied with the aids of cloths, pads, spray cans and nozzles, and gels or pastes can also be used.

1340~r~'~
In practical tests, on actual kitchen floors, counters, drainboards and walls, and in kitchen cabinets and dishwashers, and under refrigerators, in roach-infested apartments, significantly fewer roaches will be observed on surfaces to which or near which the invented repellents are applied than on control surfaces, and fewer roaches are found on the bottoms and shelves of cabinets and pantries when walls thereof are treated with the invented repellents, especially when the repellent is N-methyl neodecanamide or N-methyl neotridecanamide, indicating that the repellents are vapor-effecitive too, as well as contact-effective. When floors, walls, counters, sinks, cabinets, appliances, windows, doors, rugs and carpets in the house or apartment are treated with the invented repellents, e.g., N-methyl neodecanamide, N-ethyl neodecanamide or N-methyl neotridecanamide, the incidence of cockroach infestation is reduced, compared to control apartments where no repellent is applied. However, .
because of the :initial presence of the pests in the premises, control of them may take as long as a week or two, and sometimes ' can require several applications of the repellent. In some instances the application rates are desirably increased to as high as 10 g./sq. m. but in other instances such rates may be dropped to 0,.01 g./sq. m. or lower. Of course, resuits are usually better with higher application rates.

N-met:hyl neotridecanamide (NMNTDA) was made from neotridecanoyl chloride and methyl amine by the method described in E~:ample 1 for the manufacture of N-methyl neodecanamide, using stoichiometrically adjusted proportions of the acid ch7.oride and the amine. The neotridecanoyl chloride starting material was made from neotridecanoic acid, obtained from Exxon Chemical Americas, which identifies such acid by the designation ECR-903. Such neotridecanoic acid is a mixture of neoacids of 12 to 14 carbon atoms, averaging about. 13. It has an acid value of about 273 and a specific gravit=y, at 20°C., of 0.9117 g./cu.cm. The N-methyl neotride:canamide resulting is purified by the method described in Example 1 and yields the infrared spectrograph of FIG. 9.
The N-methyl neotridecanamide made possesses a faint, pleasanit tobacco-like odor. When tested for insect repellency, according to the procedure described in Example 3, N-methyl neotridecanamide was found to be as.good as or better than N-methyl neodecanamide against German cockroaches, showing an average of about 14 days effectiveness at a 100%
repellency level, and about 25 days effectiveness at a 60%
repellency level, whereas comparable average test results for N-methyl neodecanamide are about 11 days and l7 days, respectively.
When the N-ethyl neodecanamide is made, employing essentially the saroe_synthesis, but with ethyl, amine reactant, it, too, is tested for insect repelling characteristics but is found to be significantly less.effective i.n this resQect than the N-methyl neotridecanamide.

I3~0'l67 N-Methyl neodecanamide (NMNDA), dissolved at a suitable concentration, e.g., 10i, in acetone, is applied, to a cotton otocking so that 1 g./ of the neoalkanamide is on 280 sq. cm, of stocking. Two hours after treatment of the stocking (during which period the acetone volatilizes off) the stocking is pulled over a previously installed nylon stocking on the arm of a human test subject and that so-covered arm io exposed in a cage of adult mosquitoes of a type against which DEFT is an effective repellent. Two ouch species are Aed~es aegypti and Anopheles quadrimaculatus. If fewer than five mosquitoes bite the subject through the stocking during a one-minute exposure the test is repeated 24 hours later, and if fewer than five mosquitoes then bite the subject the test is repeated weekly thereafter until five bites are received within a one-minute exposure period.
The degree of repellency of a treatment chemical or composi-tion is measured by the number of days from application of the chemical to the stocking until five mosquitoes bite the test arm within the one-minute exposure period.
In thes described test against Aedes aegypti DEFT
is rated 22 and NMNDA is rated 15, and when the test mosquito is Anopheles qua.drimaculatus the ratings are 29 and 36, respectively. Thus, the present N-lower alkyl neoalkanamide is about equivalent to tho DEET standard in mosquito repellency, as measured by the described Agricultural Research Sesvice .

1340~~0~
(U.S. Department of Agriculture) screening test, as employed by their Insects Affecting Man and Animals Research Laboratory at C~ainesville, Florida.
In acaual use on the human body, to which it is applied dissolved in a suitable solvent, in a skin lotion or cream, or in an "aerosol" spray, the NMNDA will be about equivalent to DEET, giving at least an hour's protection against Aedes a~egypti and Anopheles quadrimaculatus when 0.3 g. is applied t:o a humari forearm. Similar results are obtainable wits: other alkyl neoalkanamides, such as N-ethyl neodecanamide, N-methyl neotridecanamide, N-ethyl neotri-decanamide, N-methyl neononanamide and N-ethyl neoundecanamide, and mixtures of two or more thereof.

I3407~7 EXAIdPLE 6 (Built Particulate Detergent) Component percent Sodium linear t:ridecyl benzene sulfonate 20.0 Sodium tripolyphosphate 40.0 Sodium carbonate 10 , p Sodium bicarbonate 10.0 . Borax 5.0 Enzyme blend (proteolytic + amylolytic in , 1.0 powdered carries) Sodium carboxym,ethylcellulose 0.5 Fluorescent brightener 1.0 N-methyl neodecanamide 2.0 Water 10.5 15 All of the'components of the detergent composition except the enzyme powder and repellent are mixed together in a crutcher slurry, which is spray dried to hollow globular bead form, of pe~rticle sizes in the range of No'a. 10 to 100, U.S. Sieve Series. Subsequently, the enzyme powder is blended with they spray dried beads end the insect repellent, in liquid state, is sprayed onto the mixture, while it is being tumbled, to form a uniform composition. N-methyl neo-tridecanamide can be substituted for the NMNDA, if desired, ;
and clothes washed will be more insect repellent than control laundry. , l3~Orlo'~
EXAMPLE 7 (Scouring Cleanser) Component Percent t ,far Silex (finely divided silica powder) 97.5 Sodium linear dodecyl benzene sulfonate 2.0 N-ethyl neodecanamide ~ 0.5 100.0 EXAMPLE B (Built Liquid All-Purpose Detergent) Component Percent .

Nonionic detergent 1.0 Sodium linear dodecyl benzene sulfonate 2.0 Sodium cumene sulfonate . 5.0 Sodium carbonate 5,0 Sodium bicarbonate 1.0 Fluorescent bridhtener 0.02 Dye 0.01 N-methyl neononanamide or N-methyl neodecanamide 1.0 Water (deionized) ~ 84.97 100 , ' Condensation pra~duct of 1 mole of higher f$tty alcohol mixture averaging 10 carbon atoms, with 5 moles of ethylene oxide.' ~.~ Trace-n~ar~ ' 1340~0~

(Bu.ilt Liqui~A 1.-Purpose Cleaner) Component Percent Sodium linear dodecylbenzene sulfonate Sodium sulfate 3.3 Natural soda ash 4.0 Sodium bicarbonate 2.0 * Nonionic detergent 2.0 Isopropyl alcohol 1.8 Distilled coconut oil fatty acids 0.5 Dyes (as 0.1% ac;ueous solutions) 0.6 Perfume 08 Softened water 80.3 N-methyl neotridecanamide 1.0 100.0 * Condensation product of one mole of a mixture of higher fatty alcohols of 9-11 carbon atoms, with 6 moles of ethylene -oxide.
The p1~ of the insect repellent liquid all-purpose cleaner is adjusted with either sulfuric acid or caustic-soda to be 10.5 ~0.2.
The product made is an effective insect repellent cleaner, and surfaces and articles washed with it or to which it is applied,~~as a concentrated or diluted product, are left with a minor proportion of N-methyl neotridecanamide insect repellent thereon, so such surfaces and articles become insect repellent.

(Liquid Pirie Oil Cleaner) Component Percent Sodium paraffin sulfonate 6.8 Isopropanol * Neodol 23-6.5 (Shell Chemical Corporation) 4.0 Pine oil 10.0 N-methyl neotrid~ecanamide 10.0 Sodium sulfate 3.8 Deionized water 58.4 100.0 * Condensation product of one mole of higher fatty alcohol mixture averaging 12 or 13 carbon atoms, with 6.5 moles of ethylene oxide When t:he above composition is used as a cleaner it leaves surfaces to which it has been applied, in concentrated or diluted form, insect repellent for periods up to three weeks. .
~~ l-rcrcJ.~-h~ar~C

134~'~G7 EXAMPLE 11(Carpet Cleaner) Component Percent Sodium salt of l~auric,monoethanolamide 30.0 ' sulfosuccinate Mixed lipolytic, proteolytic and amylolytic ~ 2.0 enzymes Sodium tripolyphosphate 20.0 Sodium hexametaphosphate 5.0 Sodium monophosphate 3.5' Sodium bicarbonai:e 20.0 Urea B.0 * Micro-Ce~ . 10.0 N-methyl neoundec:anamide ~ 1.5 100.0 * Finely divided hydrated synthetic calcium silicate (Johns-Manville Products Corp. ) This product should be diluted 1:30 with water before use. One hundred grams will suffice to clean about ten square meters of soiled carpeting.
EXAMPLE 12 (Upholstery Cle$ner) Component Percent ... * Sulframin~0 S ' 10.0 Aqueous ammonia (286) 30.0 .
water 58.5 N-methyl neodecanamide 1.5 100.0 ~ ~' 'T~.G -Jri a r~,r~c 13407G~
~ Linear alkylaryl sulfonic acid (Witco Chemical Corp.) Before use this upholstery cleaner is mixed 1:3 by volume with Stoddlard solvent.
EXAMPLE 13(Hair Shampoo) Component ~ Percent Ammonium monoglyceride sulfate 22:0 Hydroxypropyl mee.hyl cellulose 1.0 Polyacrylamide 1.0 N-methyl neodecan.amide 1.0 ~r Deionized water 75.0 100.0 EXAMPLE 14 (Skin Cream) Component Amount (as indicated) Yellow ceresin wax 2.0 ounces Yellow beeswax w 2.0 Stearic acid 2.0 "
White petrolatum 4.0 White mineral oil 8.0 fluid ounces Water 6.0 Borax 0.3 ounce Triethanolamine 0.5 fluid ounce The ceresin, beeswax, petrolatum, stearic acid and white mineral oil are melted together by heating to 71'C.
The borax is dissolved in hot water and the triethanolamine is added to the solution, with the temperature being raised to 71'C. The aqueous solution is poured into the melted wax mixture with stirring 'and stirring is continued as the mixture is removed from the heat. When it begino to, thicken there are added t.o it 10 grams of N-methyl neodecanamide.
EXAMPLE 15 (Body Lotion) Component ~ Parts Glyceryl monostoa,rate 50Ø

Oleic acid 30.0 Mineral oil 15.0 Lanolin . 10.0 Triethanolamine ' 12.0 Sodium lauryl sulfate 10.0 Preservative 10.0 Water (deionized) 980.0 N-ethyl neononana,mide ~~ 12.0 EXAMPLE 16 (Bar Soap) Component Percent * Higher fatty acid, soap 88.0 N-methyl neoundecanamide 1.0 Titanium dioxide 1.0 Preservative (stannic chloride) ~ 0.2 9.8 Water * 80:20 tallow:coco sodium soap Instead of soap bar: and cakes, soap-synthetic bars can be made by substituting sodium coco-monoglyceride sulfate for up to 25~ of the soap content of the formula. Similarly, by employing t 1340r1~~
suitable plasticizer all-synthetic detergent bars can be made.
Preservative, titanium dioxide, repellent and some water are milled with the dried soap chips (which contain about 8% water) and the milled material is plodded to bar form, after which the bars are cut to lengths and pressed to cake shape. Laundry bars can be made by adding 20 to 40% of builder salt, such as sodium tripolyphosphate and/or sodium carbonate to the formula, usually with an increase in the moisture . content to improve plasticity during processing. Framed laundry bars an~i synthetic laundry bars can also be made and the content of the insect repellent will sometimes be increased in such bars, up to about 5%.
EXAMPLE 17 (Repellent Spray) Component Percent *ProPellant 12 45.5 **Propellant 11 45.5 Mineral Oil 4.0 N-methyl neodecanamide 5.0 100.0 *dichlorodifluoromethane **trichloromonofluoromethane The mineral oil and insect repellent are dissolved in the pressurized propellant mixture and such mixture is pressure filled into a dispensing container equipped with a spray nozzle designed for optimum spraying of the repellent solution.

1340~1~r1 EXAMPLE 18 (Powdered Repellent) Component Percent T
Clay, powdered ~ 99.0 N-methyl naodecanamide ~1.0 100.0 EXAMPLE '.19 (Floor Wax) Component Parts Montan based ester wax 6.0 Polyethylene wax ~ 4.0 Non-oxidized microcrystalline wax 5.0 Tall oil fatty acids 0.2 Aqueous potassium hydroxide solution 0.5 (43~) N,N-diethylaminoethanol 1.0 , Methyl carbitol 1.0 N-propyl neoheptanamide w 2.0 water 80.3 100.0 EXAMPLE 20 (Aerosol Furniture Polish) Component Parts Carnauba wax 5.0 Beeswax , 5.0 Ceresin wax 5.0 . .

Silicone oil (DC 7.00) 5.0 Stoddard solvent . 40.0 Sodium soap (75:25 tallow:coco) 2.0 Water 130.0 ~3~U~1~'~
A wax-s_Llicone concentrate is made by heating the Stoddard solvent t:o a temperature of about 52°C and gradually adding to it the pre-melted waxes and silicone oil, with agitation. Concurrently, the soap is dissolved in the water at a temperature of about 90°C, after which the hot soap solution is admixE~d with the wax dispersion, under vigorous agitation. The mixture is then cooled rapidly to room temperature, and .'385 parts of water, 71 parts of naphtha and parts of N-methyl neodecanamide are slowly added to it. 71 10 Parts of Propellant 12 are pressure loaded into dispensing containers after pre-loading of the balance of the composition.
EXAMPLE 21 (Shelf Paler) Rolls of shelf paper are sprayed on both sides 15 thereof with liquid N-methyl neodecanamide in volatile solvent, such as acetone, and are re-rolled after volatilization off of the solvent. The proportion of repellant is regu:Lated to be 2%, although in some instances as little as 0.1% may be employed. The shelf paper has a long "shelf life" prior to use because loss of the repellant by volatilization is inhibited by the rolling of the paper. In a modification of this example the neoalkanamide repellant is added to the paper pulp during the manufacturing process but care must be taken not to drive off the repellant during any drying operations.

r .

1340~1~'~
EXAMPLE 22 (Garbage Can Insect Repellent) A 2% concentration of N-methyl neodecanaanide in a sponge is made by injecting the neodecanamide into the interior of an open celled polyurethane foam, of flat cylindrical shape, which is inserted in an open holder affixed to the interior of the lid of a "step-on~ kitchen waste container.
EXAMPLE 23 (Repellent-Insecticide) Component Percent Boric acid 98'0 N-methyl neodeca~namide 2.0 100.0 The various products of Examples 5-23 are all effective in repelling insects, especially German cockroaches.
However, they rE:present only a few of the many repellent compositions anii articles of manufacture within the present invention.
The following examples relate to the uses of the invented N-alkyl neoalkanamides of this invention in perfumes.

13~0'Iu'~

Component Percent p-Tertiary butyl c:yclohexyl acetate 12.0 N-ethyl neodecanarnide 10.0 Linalool 10.0 Geraniol 10.0 Benzyl salicylate 10.0 Benzyl acetate 10.0 Citronellol 8.0 Terpineol 8.0 alpha-Isomethyl ionone 6.0 Linalyl acetate 5.0 Phenylethyl alcohol 5.0 Methylcedryl ketone 3.0 Ionone (alpha/beta) 1.0 Hydroxycitronella:l-methyl anthranilate Schiff base 1.0 Ambreine compound (CFE No. 2 [Colgate]) 1.0 100.0 The components are blended together in a conventional mixer and the resulting perfume compound is characterized as woody-floral-amber. In it the neodecanamide has a harmonizing effect and increases depth of odor. It also appears to strengi~hen the perfume and make it more persistent.
Similar good effecas are obtainable by substituting N-methyl neodecanamide for the ethyl homologue or by employing others of the described N-lower alkyl neoalkanamides in place thereof, or by using mixtures of such materials.
Specifically, the N-methyl neodecanamide harmonizes and E.

1340'~~7 floralizes the accord between the other perfume components and strengthens the fragrance.

Component Percent Styrallyl propionate 20.0 N-ethyl neodecanarnide 15.0 gamma-Undecalactone 10.0 Anethol 10.0 Benzyl acetate 10.0 Ethylmethylphenyl glycidate 5.0 Benzyl formate 5.0 Dimetol (Givaudan) 5.0 Hydroxyethyl pyrrone (1% in diethyl phthalate) 5.0 Allylcyclohexane propionate 5.0 gamma-Nonalactone 5.0 Linalyl benzoate 4.0 Ylang ylang extra 1.0 100.0 The components are mixed together to make a tropical fruit fragrance, suitable for use in household produ cts, such as detergent compositions, soaps and in cosmetics. The N-ethyl neodecanamide strengthens the fragrance and improves substantivity and persistence, while also making the accord more natural, jui<:ier and less lactonic. Instead of the N-ethyl neodecanamide there may be substituted in the above perfume formula oi~her N-lower alkyl neoalkanamides, such as N-methyl neodecanam:ide, N-ethyl neoundecanamide, N-ethyl 134Ur~~~
neononanamide, N-n-propyl neoheptanamide, and N-isopropyl neotetradecanamide;. While each of the mentioned neoalkanamides has a different fragrance and all are of different stabilit:ies, substantivities, persistences and fragrances, all are suitable for use in perfumes and contribute their properties to the final fragrances of the perfume compounds or handkerchief perfumes, which may be produced by dissolving in 5 parts of ethanol.

Component Percent Citronellol 25.0 Phenylethyl alcohol 25.0 N-ethyl neodecanarnide 10.0 Geraniol 10.0 Phenoxyethyl isobutyrate 3.9 Linalool 3.0 p-Tertiary butylc;rclohexyl acetate 3.0 Geranyl acetate 2.0 Eugenol 2.0 2 0 Phenylethyl acetate 2 . 0 Benzyl acetate 2.0 alpha/beta Ionone 2.0 Lauric aldehyde (:LO% solution in diethyl phthalate) 2.0 alpha-Isomethyl ionone 2.0 Dimethylbenzyl carbinyl acetate 1.0 Guaiacwood acetate 1.0 Rose oxide R (10% solution in diethyl phthalate) 1.0 °°

1340~1u'~
EXAMPLE 26 (cont.) Component Percent Ylang ylang (comp7Lete) 1.0 Undecylenic aldehyde (10% in diethyl phthalate) 1.0 Damascenone (Firme:nich, [1% solution in diethyl phthalate]) 1.0 Citral 0.1 100.0 The abo~re components are mixed together to form a perfume compound which is of a rose fragrance. In the perfume the N-ethyl neodec:anamide causes the fruity ester aspect of the rose fragrance. to take on a sugary, jam-like quality, while the ionones are subdued. Additionally, the perfume is strengthened and its substantivity and persistence are increased.

Component Percent Hydroxycitronella:L (synthetic) 28.0 N-methyl neodecanamide 20.0 Cyclamen aldehyde 1.0 Geraniol 20.0 Citronellol 15.0 Brahmanol 10 (Drac~oco) 5.0 Phenylethyl alcohol 3.0 Heliotropine 2.0 Indole (10% solution in diethyl phthalate) 2.0 alpha/beta Ionone 1.0 134U7~'~
EXAMPLE 27 (cont.) Component Percent gamma Nonalactone 1.0 Lilial (Givaudan) 1.0 Citronellyl oxyaceaaldehyde 0.5 Bourgeonal (Naarde:n) 0.5 100.0 The pert=ume compound of the above formula is made by mixing of the components, and the result is a lily fragrance.
l0 The presence of the N-methyl neodecanamide sweetens and naturalizes the a<:cord, particularly the drydown, and appears to strengthen the perfume and increase its substantivity to substrates, as well as its persistence after application or use. The perfume compound, when incorporated in household products, such as detergents, cleansers, polishes and shampoos, is fragrant, substantive, persistent and stable, and additionally possesses insect repellent properties, which are often desirable, especially in rug shampoos, floor and wall cleaners, cosmetic lotions and odorants.
Other N-lower alkyl neoalkanamides, when substituted for the N-methyl neodecanamide, such as N-ethyl neodecanamide, N-butyl neooctanamide, and N-methyl neotridecanamide, will have similar effects.

s .

134076' Component Percent Sodium linear tridecyl benzene sulfonate 20.0 Sodium tripolypho:~phate 37.0 Sodium carbonate 10.0 Sodium bicarbonate: 10.0 Borax 5.0 Enzyme blend (prot:eolytic + amylolytic in powdered carrier) 1.0 Sodium carboxymethylcellulose 0.5 Fluorescent bright:ener 1.0 Perfume (of Examp:Le 24 formula) 5.0 Water 10.5 100.0 All of t;he components of this built particulate detergent composition except the enzyme powder and perfume are mixed together in an aqueous slurry, which is spray dried to hollow globular bead form, of particle sizes in the range of No's. 10 to 100, U.S. Sieve Series. Subsequently, the enzyme powder is blended with the spray dried beads and the perfume, in liquid state, :is sprayed onto the mixture, while it is being tumbled, to form a uniform composition. As was mentioned earlier,, the N-alkyl neoalkanamide component of such detergent composii:ions helps to make washed laundry washed with such detergent compositions more insect repellant than laundry washed wii~h control products.
In addii~ion to the perfumes illustrated in Examples 24-27, a wide variety of other perfume types and formulas can ~3~076'l be made, utilizing the described N-lower alkyl neoalkanamide perfuming materia7.s. While properties of such materials will differ and their effects in various perfume formulas will be different, too, in general it may be said that the invented alkanamides will be satisfactorily volatile, of good substantivity so that they will be retained on surfaces to which they are applied, even from dilute liquid media, stable, so that they will not change substantially in fragrance when incorporated in various compositions and products, even when such are alkaline, persistent, so that they will last from a day to two weeks or more (being detectable after such times on a perfumer's blotter strip), and will desirably modify and often strengthen other perfumed materials, to produce a final perfume compound or perfumed product of modified or increased fragrance and increased strength of fragrance.
The various products described in Examples 6-23 and 28, while representative of those in which the N-lower alkyl neoalkanamides are. considered to be useful as insect repellents, are only a few of the many compositions and articles of manufacture within the present invention, wherein the described perfumes may be employed instead of the N-alkyl neoalkanamides per se. In such examples the described N-lower alkyl neoalkanamide ( s ) and the perfume ( s ) improve the - 58a -p~~~ 1 v J

134~76~
the product odor and also help to make such product~insect repellent. In addition to the compositions recited in Examples 6-23 anal 28, the described N-lower alkyl neoalkan-amides can be satisfactorily employed in perfumes in other products, some of which are considered to be exceptionally severe tests for perfumes. For example, at perfume concentra-tions corresponding to 0.3% of N-methyl neodecanamide or 0.3%
of N-ethyl neode:canamide in chlorinated powdered scouring cleansers, after two weeks of elevated temperature aging at 49°C. both neode:canamides exhibit excellent odor and color stability. Similar excellent odor and color stability are also noted at ne~oalkanamide concentrations of 0.2% in a particulate phosphate-built synthetic organic detergent compo-sitions and at 7.% in toilet soap. The proportions of perfumes employed will normally be from 2 to 20 or 5 to 10 times the proportions of i:he N-lower alkyl neoalkanamides in the mention-ed products. Generally, such products are not normally subjected to temperatures as high as 49°C. so the test is considered to be a severe one" especially When volatile materials are being tested. At room temperatures the alkanamides are stable. for much longer periods of time.
The invention has been described with respect to various illustrations and embodiments thereof but is dot to be limited to~tlzem because it is ev~.dent that one o~ ~kil1 in the art will be able to utilize substitutes and equivalents without departing from the invention.

Claims (24)

1. An insect repelling composition for repelling insects from an area, location or item, which comprises an insect repelling proportion of a compound of the formula:
wherein R''' is methyl or ethyl, and the acyl moiety is neodecanoyl wherein the sum of the carbon atoms in R, R' and R'' is eight or is neotridecanoyl wherein the sum of the carbon atoms in R, R' and R'' is eleven, and when the acyl moiety is neodecanoyl the composition is in a liquid state, in association with an insect repellant compatible carrier.

2. An isomeric, liquid state, insect repellant composition, which consists essentially of an insect repelling effective amount of a mixture of N-lower alkyl neoalkanamides having the formula:
wherein R''' is methyl or ethyl and the acyl moiety, of the formula is an isomeric mixture of acyls wherein the number of carbon atoms in R + R' + R'' is 8, in association with an insect repellent compatible carrier.

3. An isomeric, liquid state insect repelling composition, for repelling insects from an area, location or item, which comprises an insect repellant proportion of a compound of the formula:
wherein R''' is methyl or ethyl and is neotridecanoyl, wherein the sum of the carbon atoms in R, R' and R'', all of which are alkyl groups, is eleven, in association with an insect repellent compatible carrier.

4. An insect repellent composition according to claim 1, 2 or 3 wherein R''' is methyl.

5. An insects repellent composition according to claim 1, 2 or 3 wherein R''' is ethyl.

6. An insects repellent composition according to claim 1, 2 or 3 wherein the insect repelling compound is dispersed in an aqueous medium at a concentration in the range of 0.2 to 25%.

7. An insect repellent composition according to claim 1, 2 or 3 wherein the insect repelling compound is dissolved in a liquid solvent medium at a concentration in the range of 0.2 to 25%.

8. An insect repellent composition according to claim 7 wherein the concentration of the insect repelling compound in the liquid solvent medium is in the range of 0.5 to 10% and the liquid solvent medium is a normally gaseous hydrocarbon or halogenated hydrocarbon under sufficient pressure to be in liquid state at room temperature.

9. An insects repellent composition according to claim 1, 2 or 3 which is effective to repel insects from sites to which it is applied, at the rate of 0.1 to 10 grams per square meter, which comprises 0.2 to 50% of the insect repelling compound in a liquid aqueous or solvent medium.

10. An insect repellent composition according to claim 9 wherein the liquid medium is a C1-4chlorofluorocarbon or chlorofluorohydrocarbon and the concentration of the insect repelling compound in such liquid medium is in the range of 0.5 to 10%.

11. An insects repellent composition according to claim wherein the chlorofluorocarbon or chlorofluorohydrocarbon is of 1 or 2 carbon atoms and the concentration of insect repelling compound therein is in the range of 1 to 5%.

12. An insects repellent composition according to claim 10 wherein the liquid medium is a hydrocarbon and the composition is under superatmospheric pressure.
-62a-

13. An insect repellent composition according to claim 1 which is effective to repel insects from sites to which it is applied at a rate of 0.1 to 10 g./sq.m. and comprises 0.2 to 50% of the insect repelling compound in a particulate carrier.
-62b-

14. An insect repellent composition according to claim 13 wherein the particulate carrier is silica and the percentage of insect repelling compound in the composition is in the range of 0.2 to 25% thereof.

15. An insect repellent composition according to claim 13 wherein the particulate carrier is of particulate sizes in the range of 0.12 to 2.4 mm in diameter.

16. An insect repellent composition according to claim 13 wherein the particulate carrier is clay, the insect repelling compound is present in the composition at a concentration in the range of 0.5 to 10% and it was sprayed onto the clay.

17. An insect repellent composition according to claim 13 wherein the particulate carrier is boric acid, the insect repelling compound is present in the composition at a concentration in the range of 0.5 to 10% and it was sprayed onto the boric acid.

18. A process for repelling insects from an area, location or item which comprises applying to or near such area, location or item an insect repelling quantity of N-alkyl-neoalkanamide(s), wherein the alkyl is of 1 to 4 carbon atoms and the neoalkanoyl moiety is of 7 to 14 carbon atoms.

19. A process according to claim 18 wherein the alkyl of the neoalkanamide is of 1 or 2 carbon atoms and the neoalkanoyl moiety thereof is neodecanoyl.

20. A process according to claim 19, wherein the neoalkanamide is applied to the area, location or item by washing such area, location or item with a detergent composition which comprises a detersive proportion of soap or synthetic organic detergent, and an insect repelling proportion of an N-lower alkyl neoalkanamide so that the application rate of the neoalkanamide is in the range of 0.2 to 10 g./sq.m., the insect repelling proportion of the N-lower alkyl lower neoalkanamide being such that sufficient neoalkanamide is retained on the washed area, location or item, after washing with the detergent composition, to repel insects from such area, location or item.

21. An insect repellent detergent composition for washing a hard or soft surface, which comprises:
a detersive proportion of a soap or synthetic organic detergent; and an insect repelling proportion of an N-lower alkyl neoalkanolamide in which the alky moiety has 1 to 4 carbon atoms and the neoalkanoyl moiety has 7 to 14 carbon atoms, wherein the insect repelling proportion of the N-lower alkyl neoalkanolamide is such that the N-lower alkyl neoalkanolamide is retained on the washed surface in an amount enough to repel insects from such surface.

22. An insect repellant detergent composition according to claim 21, which is for washing a hard surface.

23. An insects repellent detergent composition according to claim 21, which is a liquid pine oil cleaner, a carpet cleaner or an upholstery cleaner.

24. An insect repellent detergent composition according to claim 21, 22 or 23 wherein the N-lower alkyl neoalkenolamide has the formula:
wherein R'" is methyl or ethyl, and the acyl moiety is neodecanoyl wherein the sum of the carbon atoms in R, R' and R" is eight or is neotridecanoyl wherein the sum of the carbon atoms in R, R' and R" is eleven.