AU607430B2 - Perfumes containing n-lower alkyl neoalkanamide(s) - Google Patents

Description

Roit Patt At imnoy Tot T1ho CommitJndner of Pntonts -COMMON1EALTH_OF _A1TRALIA SVdI V L Iuo( S Y dn*e.y 6 7 4 607430 COMMONWEALTH OF AUSTRALIA Patents Act 1952 C 0 M PL E T E S P E.C I F I A T I 0 N

(ORIGINAL)

4, 0 9 0# *4 I 4 4 Application Number Lodged Complete Specification Lodged Accepted Published This document contains the amendments made under Section 49 and is correct for printing.

Priority Related Art :8 August 1986; 8 August 1986; 16 July 1987

I

ar Iq Name of Applicant :COLGATE-PALMOLIVE

COMPANY

Address of Applicant :300 Park Avenue, New York, New York, 10022, U.S.A.

Actual Inventor/s :Robert J. Steltenkamp; Craig Field Eaton Address for Service F.B. RICE CO., Patent Attorneys, 28A Montague Street, Balmain N.S.W. 2041 Complete Specification for the invention entitled: PERFUMES CONTAINING N-LOWER ALKYL NEOALKANAMIDE(S) The following statement is a full description of this invention including the best method of performing it known to us:- Declared at this 13th day of juy 17 i COL E P MOLIVE COMPANY Assia ant General Counse-i .u a T: ndutrial Property F B. RICE V CO.) o Ile Commissioner of Patents Patent Attorneys, -la- This invention relates to N-alkyl neoalkanamides, which are novel chemical compounds that possess insect repelling properties, and are useful components of perfumes. More specifically, this invention relates to N-lower alkyl neoalkanamides. The mentioned neoalkanamides, especially N-methyl and N-ethyl neodecanamides and neotridecanamides, have been found to be especially 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 means 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 repellent is N,N-diethyl-m-toluamide, which is often referred to as "DEET".

4i cnp an -en fo eoiigsc cie opud nosrae -2- However, the present neoalkanamidos, and N-methyl noodecanamide and N-mothyl nootridecanamide in particular, are superior to DEET in long lasting effectiveness, and in at least one entomological laboratory, have replaced DEET as the standard of repellent action (against roaches).

Additionally, such neoalkanamides are also efffective to repel other insects, including mosquitoes, and have been found to be of greater effectiveness against Anopheles guadrimaculates than DEET. In view of the relatively small number of useful insect repellents known, efforts 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 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 accordance with the present invention N-alkyl neoalkanamides that are intended for use as insect repellents, have been discovered, in which the alkyl thereof is 1 to 4 carbon atoms, and the neoalkanoyl moiety is of 7 to 14 or 16 carbon atoms, preferably 9 to 11 or 13. At present one of the most preferred of such compounds for employment as an insect repellent, especially effective against German cockroaches, is methyl neodecanamide. Also within the invention are detergent compositions (both particulate and liquid), carpet and upholstery shampoos, human shampoos, hard surface cleaners, and soap and detergent bars comprising such N-alkyl neoalkanamide(s).

Also useful are solutions and dispersions of the neoalkanamide(s) in liquid media or the neoalkanamides dispersed in a particulate or powdered carrier, which particulate or liquid products are suitable for application to a location from which insects are to be repelled. Also within the invention are processes for repelling insects by applications of insect repelling amounts of neoalkanamides of this invention to or near a surface, area, location or item from which such insects are to be repelled.

In some situations the present repellents may be used in conjunction 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.

Perfumes of this invention in which such N-lower alkyl neoalkanamides are present comprise a N-lower alkyl neoalkanamide or a mixture of a plurality of such N-lower alkyl neoalkanamides, wherein the lower alkyl is of or averages 1 to 4 carbon atoms and t'ie neoalkanoyl moiety thereof is of or averages 5 to 14 carbon atoms, and at least one perfume component which is of a type selected from the group consisting of essential oils, esters, ethers, aldehydes, alcohols, hydrocarbons, ketones and lactones, in which the content of such neoalkanamide(s) is in the range of 0,1 to 98%, 3 i: V4 -4- 0000 0 00 0 1 0 0 00 0 0 0 0 a oo 0 a0 0 00 0 0 000 9 0 0 0 0 00 Computer and manual searches of the prior art have not resulted in the finding of any reports of volatile primary or secondary amides that were recognized to be perfume or repellent components. Such searches indicated that the N-lower alkyl neoalkanamides of the present invention are novel and unobvious. The closest compounds to the N-lower alkyl neoalkanamides of this invention appear to those described in U.S. patent app4l-ieaeon SNI7=l:6T8/ (Steltenkamp and Camara) filed March 27, 1985, which relates to N-higher alkyl neoalkanamides.

However, the neoalkanamides of that patent application are taught 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 15 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 or 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, neodecanoic acid, neododecanoic acid, neotridecanoic acid, and neotetradecanoic acid, and the i corresponding alkyl neoalkanamides thereof, such as the methyl and ethyl neoalkanamides, may be made from such neoalkanoic acids. Usually the alkyl groups are straight chain but they can also branch. Pure neoalkanamides of the types described may 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 1 0

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 00o0 o" to 4 carbon atoms. Further details with respect to R, R' and R" will be given later, in conjunction with a description of oa 0 o0.015 neoalkanoic acids which may be employed as starting materials 0.0 for the production of the neoalkanamides.

Infrared absorption spectra for some representative and preferred N-lower alkyl neoalkanamides of this o Ot invention are shown in the drawing, in which: 20 FIG. 1 is an infrared absorption spectrograph of a sample of -methyl neodecanamide; FIG. 2 is an infrared spectrograph of a sample of Nethyl neodecanamide; -i i'

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FIG. is an infrared spectrograph of a sample of Nmethyl neoheptanamide; and FIG. 4 is an infrared spectrograph of a sample of Nmethyl neotridecanamide.

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 "DEET", a leading insect repellent, were compared.

To make the neoalkanamides of this invention neoalkanoyl 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 distilled 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 water white to light amber in color and is essentially pure. In an alternative method, the neoalkanoic acid may be reacted directly with the lower alkylamine.

Neoalkanoic acids, such as neodecanoic acid, neotridecanoic acid, neoheptanoic acid and neopentanoic acid, are available from Exxon Chemical Americas, which synthesizes them by reacting a suitable branched alkene and carbon monoxide under higher pressure at elevated temperature in the presence of aqueous 25 acidic catalyst (Koch reaction). The general mechanism involved includes generation of carbonium ion, followed by complexation ii

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i i.

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6 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'

I

R-C-COOH

R"

In neodecanoic acid, 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 content greater than that of methyl and less than that of R, and R is of a carbon atoms content less than that of hexyl and greater than that of 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 content less than that of hexyl and greater than those of R' and Among other neoalkanoic acids that are available and useful 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 trichloride (although sometimes thionyl chloride may be found preferable), 7 and are available from the Lucidol Division of Pennwalt, Inc* and from White Chemical Corp.

Although it in possible for the insect repellents of this invention to be incorporated in various materials when such materials are being manufactured, as by being 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 neoalkenamide, in liquid solution or dispersion, or dispersed in a powdered carrier, or in a detergent composition, such as a laundry detergent, floor or 00 wall cleaner, upholstery or rug shampoo, hair shAmpoQ, liquid 00 soap, bar soap, or in any other Appropriate composition in which Sit may be usefully incorporated. Among such other appropriate compositions may be mentioned insecticidal and Antibacterial ,24 washes or dips for humans, pets And farm Animals, furniture polishes and finishes, floor waxes and finishes, ointments, oa salves and topical mnedicaments, insecticides, fungicides, owe bactericidest plant fertilizers, mulches and plant potting preparations, to name only a few. In some instances means will be provided for recharging such items Anid compositions with the active alkanaiide component to renew their repellent a.

.4 effects. In the majority of instancesthe invented comnpositions will be applied directly or indirectly by external application 00 coo 0 00 4 o p p p o 0 8to 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 neodecanamide 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 10 satisfactorily substantive to surfaces from detergent compositions and from other preparations, 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 repellent effects are obtainable at surface concentrations of the active ingredient 20 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. preferably 0.1 to 2 g,/sq. m., 1 g./sq. when roach repellency is desired, Higher application rates, such as 10 to 100 g,/sq, will often be used against mosquitoes.

Because the present insect repellents are volatile their presence can be detected in the air near a surface to (lClCL i i: 9 jr -C iv 1 which they have been applied. Therefore# not only are the surfaces repellent to insects# which will avoid having thAr body parts contact suph surfaces, but the vapors from the'Nlower alkyl neoalkanamides 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, Boiling and contaminating contained dishes, utensils and silverware.

Similarly, coating of pantry surfaces, interior and/or exterior, with a furniture polish containing an invented volatile repellent, or use of shelf '.,aper containing a repellent neoalkanamide can discourage roaches from e ntering the pantry and contaminating foods contained therein. Also, washing of o clothing with detergent compositions containing the invented ~'~5repellents may prevent insects from lighting on the clothing 0O and its wearer, and from stinging or biting the wearer.

Shampooing of a 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 repellent detergent compositions formulated for sujch purpose will deposit thereon a substantive coating of the invented insect repellent and will discourage insects from contacting the floor and wall surfaces and from entering th~e treated rooms. It in an important feature of the invented insect repellents that although they are sufficiently volatile to be effective, their 4 I in a product). The invented repellents may be formulated with insecticides, such as by being sprayed onto the surfaces of insecticidal powders, boric acid powder, which is effective against roaches. By use of the neoalkanamide-boric acid composition immediate effectiveness in repelling the roaches is obtained and subsequently, after 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 #114 the repellent-insecticide composition also has utility.

I r eIt is apparent from the foregoing brief description S" n5 that the invented insect repellents can be used in many compositions and can be applied in diverse ways. However, among the most useful products which can incorporate the invented t. neoalkanamides are detergent compositions, from which the neoalkanamides are surprisingly substantive to the surfaces of washed items. Such detergent compositions operate in several S ways to counter insect contamination of the washed item.

They remove any earlier contamination, remove stains and soils, I t on which the insects might feed, and which could attract them, t L and leave behind the insect repelling neoalkanamide.

The primary component of the present detergent compositions, other than the insect repelling neoAlkanamide, is an Sorganic detergent material. Such material may be one of the soaps, preferably a sodium and/or potassium higher (Ci 0 -18) fatty acid soap, but is preferably A synthetic organic detergent, which may be of the anionic, nonionic, amphoteric, ampholytic, zwitterionic or cationic type, or may be a mixture of two or 11 Li; i i i -i y rtA A.w I I and/or had surfaces and making them repellent to insects, which comprises soap and/or synthetic organic detergent and an insect repelling proportion of N-alkyl /2

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C C I f c 4

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40 It

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II I 4 4 *t I 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 many such detergents are found in the text Surface Active Agents and Detergents, Vol.

II, pages 25-138, by Schwartz, Perry and Berch, published in 1958 by Interscience Publishers, Inc. Such compounds are also described in a 1973 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, such as sodium or potassium or ammonium or lower alkanolammonium salts, triethanolamine salts. The anionic '15 detergent may be a sulfate, sulfonate, phosphate or phosphonate or salt 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 lipophilic 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 poly-lower alkoxy groups, as in ethoxylated higher fatty alcohol sulfates, triethoxylated lauryl alcohol sulfate. Normally the number of ethoxy groups in such detergents will be in the range of 1 to 30, preferably 1 to 10. As examples of suitable anionic detergents there may be mentioned: higher i 12 r 1--T -1 -40 q

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iI 44', 4 2 44 4 4r 4i 4 4.

4

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44 fatty alcohol sulfonates, such as sodium tridecyl sulfonate; sodium linear alkyl benzene sulfonates, 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 triethanolammonium 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 lipophiles 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. Among such classes of builders may be mentioned water soluble inorganic salts, including: polyphosphates, sodium tripolyphosphate; carbonates, sodium carbonate; bicarbonates, sodium bicarbonate; borates, borax; and silicates, sodium silicate; water insoluble inorganic builders, including zeolites, hydrated Zeolite 4A; and water soluble organic builders, 13 PERFUMES CONTAINING N-LOWER ALKYj NEOAI.KANAMIDE(S) The following statement is a full description of this invention including tile best method of perrorming it known to us:including citrates, gluconates, NTA, and polyacetal carboxylates.

In some cases, as when mildness of the product to the human body or to delicate fabric 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 of 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 agents may be employed, such as sodium carboxymethyl cellulose, and solvents or co-solvents may be present, as in liquid compositions. Among other adjuvants there may be mentioned fluorescent brighteners, antistatic agents, antibacterial agents, fungicides, foaming agents, anti-foams, flow promoters, suspending agents, antioxidants, anti-gelling agents, soil release promoting agents, and enzymes.

The detergent compositions of this invention may be in particulate, powder, tablet, bar, liquid, paste, gel, capsule, leaf, foam or "aerosol" or other suitable form, as 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, A 4 d need not be further mentioned here.

25 While it is possible to apply the present insect repelling N-lower alkyl neoalkanamides directly to surfaces

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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, 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 dichlorodifluoromethane, monofluorotrichloromethane and other chlorooo fluoromethanes, -ethanes and -propanes. Such compounds include S. the liquefiable gases, hich can be maintained in liquid state .015 in pressurized dispensing containers, for ready application '00 a* as sprays or in other suitable forms to locations which are to be made insect repellent. The neoalkanamides may also be in o, aqueous or other emulsion form, when a suitable emulisifier, o0 hydrotrope or surface active agent is utilized, too. The invented neoalkanamides may also be dispersed in particulate S or powdered inert or active materials. Among such inert materials may be mentioned silica, calcium carbonate, clay, °0 .p expanded polystyrene, 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).

15 ii

II

Ii y ii *1 jj: 4 r 4 ff4 .4' 4 4, .4 4 4 4 *48 4, 4, 4 4 4' 4 a a 44 a 4 IC 44 1 4 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 timeroperated sprayers or other dispensers, and they may be renew- It ably charged to containers, from which they may be vaporized, such an absorbers and other holders, as in the under sides of garbage can covers.

.15 The detergent compositions of this invention, including those that are useful for washing hard surfaces, such as floors, and also soft surfaces, such as those of carpets, laundry, and human hair, will include an insect repelling proportion of t4-alkyl neoalkananide or a mixture of such neo- 20 alkanainides, which proportion is sufficient so that enough of t 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 suitable mixture thereof). The neoalkanamide is preferAbly one wherein the lower alkyl is of 1 to 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 16 -3- -17most 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 carbon atoms. Mixtures of such neoalkanoyl moieties and "average" moieties, averaging within such ranges or averaging 10 or 13 carbon atoms 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 particulate built laundry detergent compositions of the invention the 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 insect repellent particulate synthetic organic detergent composition will be 1 or 5 to 35%, 10 to 90%, and 0.2 to respectively. Preferred compositions of such type will have the synthetic organic detergent selected from the group consisting of anionic and nonionic detergents, and mixtures thereof, may contain water soluble filler salts(s), such as sodium sulfate, and will contain N-methyl neotridecanamide or neodecanamide, or a mixture thereof. The proportions of such components for best effects in such detergent compositions will often be 7 to 30% of the synthetic organic detergent(s), 20 to of the builder salt(s), 0 to 50% of the filler salt(s), and to 5% of the neoalkanamide(s).

When liquid detergents containing the invented insect repellent neoalkanamide(s) are made, the same components may be used, plus a liquid medium,but the detergent will preferably be non-soap. Sometimes a conventional emulsifying agent, such ('EMc=V ai6C- agntrero- uh) as an Emcol/, sold by Witco Chemical Co., Inc., will be employed, in emulsifying proportion. Also, hydrotropes, 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 the neoalkanamide content will be 0.2 to 10%, and the liquid medium content, preferably aqueous, will be 40 to 90%. More I4 4 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 salt(s) for such detergent(s), which may be water soluble, such as potassium pyrophosphate, sodium carbonate, or 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 neodecansmide and/or N-ethyl neodecanamide, or other suitable neoalkanamide, and 50 to 90% of water, preferably deionized water.

It i. 18 pALbv When an insect repelling shampoo for use on upholstery, rugs and carpets is to be made, it may comprise 1 to 35%, preforably 5 to 20%, of a detergent selected from the group consisting of water soluble soap(s) and synthetic organic detergents, 0 to 40% of builder(s) for the soap and/or detergent, often preferably and 0.2 to 10% of N-lower alkyl neoalkanamide, preferably 0.5 to 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 with water being 50 to 90% of the composition, preferably 70 to Alternatively, the shampoo may be in gel, paste or powder for When the present insect repellents are used in shampoos intended for washing human hair on the head and for making the hair repellent of insects, the shampoos will prefer- '15 ably comprise 2 to 25% of soap and/or the previously described 4 44 synthetic organic detergent(s), and 0.2 to 10% of N-lower alkyl neoalkanamide, of the type previously discussed in conjunction with the 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 of a co-solvent, such as a lower alkanol, 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, U 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 to 90% of water, preferably deionized.

1 i i i i 19 -6i- I~ L I ui ~1 444 44 .41 4 *I

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114' 1 4 4. 4 Solid or bar or cake insect repellent detergent products can also be made, which may be used for washing persons, animals, laundry, rugs, and/or hard surfaces, su6h as walls and floors, to make them insect repellent.. Such products can comprise ncoalkanamide repellent 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 content in the range of 2 to 20% and the balance will be of builder(s) and/or filler(s) and/or adjuvant(s), when such are present. Normally, the adjuvant(s) content of the various detergent 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 coating, sequential dissolving and/or dispersing and/or emulsifying, milling, plodding and pressing.

When the insect repellent is to be sprayed or applied in a carrier, such as a liquid or particulate material or medium, the concentration of it therein will be an insect repellent proportion, so that when applied onto a surface of a material to be treated (or into the interior or other portion thereof), by spraying, dusting, rubbing, wiping, pouring, xi

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r i 20 -7- I LI. y -r depositing, or other mechanism, the repellent applied will be in such quantity and/or concentration that it will be effective in repelling insects or a particular type of insect, so that such insect(s) will stay away from the treated location. Such repelling is due to the insect being reluctant to contact the repellent and also in some measure is due to the repellent effect'of the vapor from the repellent, 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 repellent 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 I 4F surface that is exposed to the air.

The concentration of the repellent chemical(s) in a liquid medium, such as an aqueous medium, in which a dispersing r 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%, about 1% or for roach repellency. The liquid medium may be water, lower alkanol, such as ethanol, lower ketone, such as acetone, lower hydrocarbon, such 1, as isobutane, cyclopropane or mixture thereof, or halogenated S' lower hydrocarbon, such as chlorofluorinated, fluorinated or chlorinated lower hydrocarbons, Propellants 11 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, i j3 1~ ii 21 -8a-

I

0 r~ t* o 0 0' *0 o 0 Ii '*04 0 o 0 0 '4 Similar concentrations of the invented repellents may be employed in powdered or particulate carriers. Thus, the invented neoalkanamiges 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 comnposition particles or synthetic organic polymer beads (preferably of particle sizes between 125 microns and 2.4 mm. in diamters), in concentrations in the range of 0.2 to 10 or. 25%, preferably 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. mn. initially remain on such surfaces after treatment, with such application rate preferably being 15 0.01 to 5 or 10 g./sq. mn. and more preferably 0.1 to 2 g./sq. mn., 1 g./sq. mn. for' action against roaches. Concentrations outside such ranges may sometimes also be of at least partial effectiveness. When the repellent is in A detergent compositiQn which is employed in an aqucous srashing mnedium, such as water, 20 the wash water will usuAlly contain from 0.05 to 5% of the odetergent composition but in some Applications, such as shAmpooing of human hair or of carpets or rugs with foam preparations, O the concentration may be greater, sometimes being as high as 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 p.

a., 0e Li 0 04 4, 00 01

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1510 II 22 9 -I -23be in the same ranges as for detergent compositions, but may be increased, if desired, in some such in..tances to as high as The invented repellents possess various significant advantages over various other repellent materials available. They are essentially non-toxic and therefore are not hazardous to children or pets that might come into contact with them, after application. They are pleasantly aromatic (sometimes fruity, with N-methyl 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 prepartions wherein the imparting of colour would not be acceptable. They are effective both as contact and vapour repellents and are superior in repelling action to various commercial insect repellents, especially against German cockroaches, which are considered to be the most difficult household insect pest to control. The present repellents are long lasting, with 25 tests having shown both N-methyl neotridecanamide and N-methyl neodecanamide to be effective to repel roaches for two weeks and more after topical application. Against Anopheles quadrimaculatus N-methyl neodecanamide is effective for five weeks, by Dep't. of Agriculture screening tests (a week longer than DEET). Against rt

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li 00Q 0 0 0 o 0 o 0 o 0 0 oa 0 0 0 0 0.0 0 0 0 00 oe 0 0* 0 0 0 00 0 0 Aedes aegypti the neoalkanamide is almost as effective as DEET, using the 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 S 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 0 o evaluations of such crmpounds indicate that they will also be 15 effective repellents against other insects, such as those in the group of flies, fleas, lice, mosquitoes, bees, wasps, hornets, ants and beetles, and they may also be effective against arachnids, S such as spiders, ticks and mites. Because data are most complete and are very convincing for the use of N-methyl neodecanamide against German cockroaches, and because such data were obtained from controlled tests, conducted in connection with entomological research at a major university, such data, together with some 0 mosquito repellency data, will be that presented in most of the working examples, which will follow.

25 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 j t j: :1 24 Lii i. 1, l.c- zwitterionic or cationic type, or may be a mixture of two or 11 I to which the perfume 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 component(s) of type(s) selected from the group consisting of essential oils, esters, ethers, aldehydes, 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 and unbuilt soap and synthetic organic detergent 'compositions, in 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 polymeric "plastic", products containing a perfume of the invention, such as pet care articles, 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, Additionally, they interact with other perfume components and often strengthen 25 -e i, i .i 11 i.l*i 12 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 plum or apple fruitiness. The fragrance of a drop, on a perfumer'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 g days, and N-methyl neoheptanamide has a freih, clean, camphortype 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 0ooe surfaces to which they are applied. Additionally, they are 9 00 ,5 generally of satisfactory stabilities in a wide variety of preparations, even those which may be of substantial alkalinities.

o n With the N-iower alkyl neoalkanamide(s) component(s) of the present perfumes there may be employed any of the 0. various well-known aromatic perfuming components, fixatives, 0o *o 20 solvents, extenders, stabilizers and adjuvants. Of these the primarily perfuming materials will often fall in one or more oo of the following classes: essential oils, esters, ethers, aldehydes, alcohols, hydrocarbons, ketones, and lactones, but various other classes of materials may also be present, Si '25 such as pyrrones, and pyrroles.

i i i 26 13

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Among preferred components of rose, lily, tropical fruit and floral-woody-amber type perfumes are the following; essential oils citrus, evergreen, jasmine, lily, rose, ylang ylang; esterz phenoxyethyl isobutyrate, benzyl acetate, p-tertiary butyl cyclohexyl rcetate, guaiacwood acetate, linalyl acetate, dimethylbenzyl carbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formiate, uthymethyiphenyl glycidate, allylcyclohexane propionate, styrallyl propionate, and benzyl salicylate; ethers bonzylethyl ether; aldehydes alkyl Aldehydes of 8 to 18 carbon atoms, bourgeonal, citral, citronellal, citronellyl oxyacetaldehyde, cyclamen aldehyde, hydroxy citronellal, and lilial; alcohols anethol, citronellol, ougenol, 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 i4 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 anthranilate, jasmine oil, p~tchouly oil, vetiver bourbon oil, vanillin, ethyl vanillin, coum~rin, 3-methyl nonan-3-yl-acetate, methyl ionone, synthetic lily of th~e 27 14 valley oil# synthetic red rose oil, 3-methyl nonan-3-ol, alpha-axnyl cinnamic aldehyde, methyl salicylate, amyl salicylate, lavandin# isobutyl heptenone, cedryl Acetate, ethyl linalyl acetate, neryl acetate, nerol, d-limonene, cuminic aldehyde, linalyl propionate, nerolidyl acetate, nerolidyl formate, aipha-pinene, isobutyl linalool, nethylnaphthyl kcetone, linalyl isobutyrate, paracresyl caprylate, paracresyl phenylacetatef sandalwood oil, coriander oil, sassafras oi.lf cassia oil, angelica root oil, Peruvian balsam, clove oil, l0 ma~ce oil, menthol, and almond oil.

In addition to the named fragrance components there may also be employed 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 ru~sinsf gums synthetic musks and other fixatives. Also components of perfumes are alcohols and other suitable 4 solvents and media, as well as preservatives, antioxidants, ii stabilizers and viscosity and volatility modifiers.

4 ~2I022 perfumes and perfuming materials of this invention may contain from 0.1 to 98% of N-lower alkyl neoalkanamidet's), with the balance thereof being other fragrance materi~ls and perfume constituents, which may include solvents, liquid a a media and/or particulate or powder b~sest such as wood pArticles, L t t sachet materials and clays. Preferably the perfume will be in liquid state, more preferably in a lower alcoholic solvent, jJ- -28 15 ethanol, and the concentration of N-lower alkyl neoalkanamide therein will be in the range of 1 to 60%. More preferably, such concentration will be in the range of 2 to and most preferably it will usually be in the range of to 15%, 10%. Normally, the proportion of fixative(s) will be less than that of the fragrance material, and will usually be in the range of 0.1 to The proportion of solvent may be variable but will usually be from 20 to 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-Ne methyl neoalkanamide fragrance components of the perfume are o .15 variable, with individual components ranging from 0.01 to 0 00 o 30% in some cases, and sometimes with certain of the classes D 4 of such materials being 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 representa- .*oo0 tive of the fragrance classes. The proportions of each of such 0 0 classes will usually be at least with at least one of 0 0 such classes being present to the extent of at least 5. and sometimes at least 10%. However, in other instances one or °0o more of the three mentioned classes of fragrance components °.25 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 tQ -29 16 and 2 to 15%, 10%, and respectively. The total of non-N-methyl neoalkanamide fragrance components present in the invented perfumes will usually be in the range of 5 to 99%, preferably 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 with the content of Nlower alkyl neoalkanamide normally being within the range of 0.01 to preferably 0.1 to 2% and often 0.2 to 1%.

However, in perfuming, odorant or air freshening sprays the 4 f range of concentrations of perfume may be increased to 5 to 15 25% and even to as high as 50%, and sometimes the perfume 9 concentrate may be employed undiluted.

.494 The invented perfumes may be usefully employed in a wide variety of household products and in various other compositions and articles. Representative of these are detergent compositions of various types, insect repellents,.

insecticides, paper items, textiles, surface treating compositions and synthetic organic polymeric "plastic" articles.

The detergent compositions include built and unbuilt particulate, liquid, gel, paste and bar or cake detergents, such it t as are employed as laundry detergents, rug shampoos, human 30 31 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 insecticides will normally be in liquid solvent or liquefied gas solution or emulsion. From the above it is seen that the N-lower alkyl neoalkanamides can contribute both perfurming and insect repelling 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 oC., in such examples, and elsewhere in this specification and in the appended claims.

"DIXIE" and "MICRO-CEL" mentioned in the examples are registered trade marks.

t I I .1 a i i i jli- 18 EXAMPLE 1 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 thermometer, an additional funnel (a dropping funnel) and a condenser tLe\ of equipped with a Datrtt' edesiccant.atube 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 Penwalt Corporation's Lucidol Division) were added dropwise ir S" to the flask over a period of one hour. After completion of the addition of the neodecanoyl chloride the reaction mixture was 4$ allowed to come to room temperature. The reaction mixture was s0.15 then transferred to a 2-liter separatory funnel and was washed twice with deionized water to separate the N-methyl neodecanamide 4 9 from the triethylamine chloride, once with 5% aqueous hydro- ,4 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, 32- 19 In similar manners there were made N-ethyl neodecanamide, N-methyl neotridecanamide, N-ethyl neotridecanamide, Nmethyl neoheptanamide and N-ethyl neoheptanamide, using grammolar weights of 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 neoheptanoyl chloride, respectively). The same volume of diethyl ether (700 ml.) is employed as in the preparation of the N-methyl neodecanamide, the same equipment is used, and the same procedures of addition, reaction, separation, washing, 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.

4 their infrared spectrographs are shown in FIG'S. 2-4.

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'.44 1I~ ,411 I I( EXAMPLE 2 The six compounds for which manufacturing methods are described in 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 triethyl 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 mantle, a magnetic stirrer, a source of nitrogen gas with means for conveying it to below the surface of the reaction mixture, and a thermometer and thermostatic control to regulate 33 i i, _L 1 -1 i 20 the temperature of the reaction mixture, which is held at 240*C. for five hours. The reaction products are separated, washed and have ether removed from them in the same manner as described in Example 1. The products resulting have infrared spectrographs like those of the samples of corresponding products of Example 1, which are shown in FIG'S. 1-4.

EXAMPLE 3 The N-methyl neodecanamide made by the process of Example 1 was tested for cockroach repellency by dissolving one gram of it in 10 ml. of acetone and then swabbing the inside of a Dixiecup, having an internal surface area of a"o 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 S^ neodecanamide, evenly coating the cup interior at a concentrao6a15 tion of 1.0 g./m 2 Four equidistant openings, are cut in the drinking end edges of the cup so that when the cup is inverted and placed on a flat surface, it will be possible for test insects (roaches) to crawl through them and under it. An identical control cup is prepared, with the sole difference S. 20 being that the same proportion of acetone is applied to the So 002 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 So medially dividable reactangular area in a box, to which there a o are next added 100 cockroaches. The box top is transparent and the roaches cannot escape from the box. Initially the 34 21 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 attraction effected by the experimental cup because the control is essentially neutral, 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 counted. The number in the control area is the S4 percentage effectiveness of the repellent. By this test, after V« 15 two days, N-methyl neodecanamide is 100% effective against the control. After two days, when N-methyl neodecanamide (NMNDA) 1 V is compared to DEET, and to a successful cockroach repellent, ,i i' identified as MGK-874, the N-methyl neodecanamide (NMNDA) is S rated to be 9 times and 19 times as effective, respectively, as the other repellents. After five days after application I 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 Safter 14 days. However, after 21 days none of the experimental and comparative repellents is of much repellent effect so 35 22 comparisons after that time are not considered to be significant.

FIG. 5 is a graph showing comparative effectiveness (in of N-methyl neodecanamide and DEET in repelling roaches. The number of roaches hiding under the DEET treated cup is plotted for each of the indicated days after the applications of the repellents. The comparative effectiveness of the experimental compound, NMNDA, in is the number (out of 100) of roaches 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, fir at the same concentration, 1.0 The results are of the same type and order as described above for the contact repellency tests but the absolute effectivenesses 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 repellent action is more due to a vapor effect than to contact.

In the described tests results are the same whether the repellents are made by the direct condensation method, from neoalkanoic acids, or from the neoalkanoyl chlorides. Similar results are obtainable when other neoalkanamides of the invented types are employed, such as N-ethyl neodecAnamide, N-butyl 36 f neodecanamide, N-methyl neotridecanamide, N-ethyl neotridecanamide, the N-methyl- and N-ethyl- neoheptanamides, -neononanamides, neoundecanamides, 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 ,I *mixture of isobutane and cyclobutane or 60:40 solutions of Freon 12 and Freon 11 (dichloridifluoromethane and trichloromonofluoromethane, respectively) or in other pressurized solvents. Instead of applying the solution at the concentration in the tests reported earlier in this example, concentrations 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 S hold the repellent in homogeneous suspension as colloidal droplets, with its concentration usually being somewhat lower than for the organic solvent solutions, 5% 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.

37 24 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-effective too, as well as contact-effective. When S00 S floors, walls, counters, sinks, cabinets, appliances, windows, doors, rugs and carpets in the house or apartment are treated with the invented repellents, N-methyl neodecanamide, N-ethyl neodecanamide or N-methyl neotridecanamide, the o. 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, .0 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 o 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, results are usually better with higher application rates, 38 they interact with other perfume components and often strengtnen 25 EXAMPLE 4 N-methyl ntotridecanamide (NMNTDA) was made from neotridecanoyl chloride and methyl amine by the method described in Example 1 for the manufacture of N-methyl neodecanamide, using stoichiometrically adjusted proportions of the acid chloride 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 0 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 gravity, at 20°C., of 0.9117 g./cu.cm. The Nmethyl neotridecanamide resulting is purified by the method described in Example 1 and yields the infra-red spectrograph 5 of FIG. 4.

000 000 0 0 00 1 03 o oo 0 0 0 01 o 00 S00 00 0 00 00 0 0 00 00 0 0 00 0 0 00C 0 0 0 1 0 1 The N-methyl neotridecanamide made possesses a faint, pleasant 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 repellency level, whereas comparable average test results for N-methyl neodecanamide are about 11 days and 17 day-s, respectively.

When the N-ethyl neodecanamide is made, employing essentially the same.synthesis, but with ethyl amine reactant, it, too, is tested for insect repelling characteristics but is found to be significantly less effective in this respect than the N-methyl neotridecanamide.

39 4 EXAMPLE N-Methyl neodecanamide (NMNDA), dissolved at a suitable concentration, 10%, in acetone, is applied to a cotton stocking so that 1 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 socovered arm is exposed in a cage of adult mosquitoes of a type against which DEET is an effective repellent. Two such species are Aedes 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 i, five bites are received within a one-minute exposure period.

The degree of repellency of a treatment chemical or composition 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 the described test against Aedes aegypti DEET is rated 22 and NMNDA is rated 15, and when the test mosquito S is Anopheles quadrimaculatus the ratings are 29 and 36, respectively. Thus, the present N-lower alkyl neoalkanamide is about equivalent to the DEET standard in mosquito repellency, as measured by the described Agricultural Research Service 40 14, II. 27 Department of Agriculture) screening test, as employed by their Insects Affecting Man and Animals Research Laboratory at Gainesville, Florida.

In actual 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 aegypti and Anopheles quadrimaculatus when 0.3 g. is applied to a human forearm. Similar results are obtainable with other alkyl neoalkanamides, such as N-ethyl neodecanamide, N-methyl neotridecanamide, N-ethyl neotri- 9r decanamide, N-methyl neononanamide and N-ethyl neoundecanamide, S, and mixtures of two or more thereof.

lo 4 t t i t ts 1 41 28

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4 EXAMPLE 6 (Built Particulate Detergent) Component Sodium linear tridecyl benzene sulfonate Sodium tripolyphosphate Sodium carbonate Sodium bicarbonate Borax Enzyme blend (proteolytic amylolytic in powdered carrier) Sodium carboxymethylcellulose Fluoresuznt brightener N-methyl neodecanamide Water Percent 20.0 40.0 10.0 10.0 10.5 100.0 4444 444 4r4' 4 I t 4 4I 44 4 4 4I 4 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 particle sizes in the range of No's. 10 to 100, U.S. Sieve Series. Subsequently, the enzyme powder is 20 blended with the spray dried beads and the insect repellent, in liquid state, is sprayed onto the mixture, while it is S being tumbled, to form a uniform composition. N-methyl neotridecanamide can be substituted for the NMNDA, if desired, and clothes washed will be more insect repellent than control laundry.

42 i::i 29 EXMPLE 7 (Scouring Cleanser) Component Silex (finely divided silica powder) Sodium linear dodecyl benzene sulfonate N-ethyl neodecanamide Percent 97.5 100.0 It I I ii ii It it ii ji

II

II

EXAMPLE 8 (Built Liquid All-Purpose Detergent) Component Percent *Nonionic detergent Sodium linear dodecyl benzene sulfonate Sodium cumene sulfonate Sodium carbonate Sodium bicarbonate Fluorescent brightener 0.02 Dye 0.01 N-methyl neononanamide or N-methyl neodecananide Water (deionized) 84.97 1.00.0 *Condensation product of 1 mole of higher fatty alcohol mixture averaging 10 carbon atoms, with 5 moles of ethylene oxide.

'a I a 43 30 EXAMPLE 9 (Built Liquid All-Purpose Cleaner) Component Sodium linear dodecylbenzene sulfonate Sodium sulfate Natural soda ash Sodium bicarbonate Nonionic detergent Isopropyl alcohol Distilled coconut oil fatty acids Dyes (as 0.1% aqueous solutions) Perfume Softened water N-methyl neotridecanamide Percent 3.7 3.3 1.8 0.6 0.8 80.3 100.0 0 0 4 4 O4 40 o «0i 0 0 00 a 4 4 4 4 4 4 i I( 15 Condensation product of one mole of a mixture of higher fatty alcohols of 9-11 carbon atoms, with 6 moles of ethylene oxide.

The pH of the insect repellent liquid all-purpose cleaner is adjusted with either sulfuric acid or caustic soda to be 10.5 t0.2.

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.

[r i iI i t', 44 EXAMPLE (Liquid Pine Oil Cleaner) Component Percent Sodium paraffin sulfonate 6.8 Isopropanol Neodol 23-6.5 (Shell Chemical Corporation) Pine oil 10.0 N-methyl neotridecanamide 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 the above composition is used as a cleaner it leaves surfaces to which it has been applied, in 'II, concentrated or diluted form, insect repellent for periods up to three weeks.

I 14 1 4 r i k4, NLGIi EXAMPLE 11 (Carpet Cleaner) Component Sodium salt of lauricmonoethanolamide sulfosuccinate Mixed lipolytic, proteolytic and amylolytic enzymes Sodium tripolyphosphate Sodium hexanietaphosphate Sodium monophosphate Sodium bicarbonate Urea *Micro-Ceg) N-methyl neoundecananide Percent 30.0 20.0 3. 20.0 10.0 100.0 0A0 0 00 0 0 0 004 0 20 *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 (Upholsterv Cleaner) 00 Component S*Suiframin 055 Aqueous ammonia (28%) Water N-methyl neodecanamide Percent 10.0 30.0 58.5 100.0 46 mixture, and a thermometer And thermostati.c control, to regulate 33 *Linear alkylaryl sulfonic acid (Witco Chemical Corp.) Before use this upholstery cleaner is mi2xed 1:3 by volume with Stoddard solvent.

EXAMPLE 13 (Hair Shampoo)- Component Amnmoniumn monoglyceride sulfate Hydroxypropyl methyl cellulose Polyacryl amide N-methyl neodecanainide Deionized water

I

ill ii Percent 22.0 75.0 100.0 #044 4 41' 4 .441 41 44 4 44 4 44 4 44 o 4' 4 4144 o o 34~

ID

p 444 4 .4 44 4 44 op 03 4 044 20 4444 4 4 4444 44 14 44 4 4 4 EXAMPLE 14 (Skin Cream) Copoent Yellow ceresin wax Yellow beeswax Stearic acid White petrolatuin White mineral oil Waiter Borax Triethanolamine Amount (as indicated) 2.0 ounces 8.0 fluid ounces 0.3 ounce 0.5 fluid ounce The ceresin, beeswax, petrol~tump stearic acid And white mineral oil are melted together by heating to 710C.

The borax is dissolved in hiot water and the triethanolamine 47 34 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 begins to thicken there are added to it 10 grams of N-methyl neodecanamide.

EXAMPLE 15 (Body Lotion) Component Parts Glyceryl monostearate 50.0 Oleic acid 30.0 Mineral oil 15.0 Lanolin 10.0 Triethanolamine 12.0 SSodium lauryl sulfate 10.0 Preservative 10.0 15 Water (deionized) 980.0 N-ethyl neononanamide 12.0 a 4 EXAMPLE 16 (Bar Soap) Component Percent Higher fatty acid soap 88.0 N-methyl neoundecanamide Titanium dioxide 0 4 t S* Preservative (stannic chloride) 0.2 Water 9.8 100.0 80:20 tallow:coco sodium soap Instead of soap bars and cakes, soap-synthetic bars can be made by substituting sodium coco-monoglyceride sulfate for up to of the soap content of the formula. Similarly, by employing a 48

L-

35 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 and synthetic laundry bars can also be made and the content of the insect repellent will sometimes be increased in such bars, up to about EXAMPLE 17 (Repellent Spray) Component Percent I 15 *Propellant 12 45.5 S**Propellant 11 45.5 Mineral Oil N-methyl neodecanamide 100.0 i *dichlorodifluoromethane i ,20 **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.

49 L 36 EXAMPLE 18 (Powdered Repellent) Copent Clay, powdered N-methyl neodecanamide Percent 99.0 100.0 EXAMPLE '.19 (Floor Wax) 04 Comonnt Montan based ester wax Polyethylene wax Non-oxidized microcrystalline wax Tall oil fatty acids Aqueous potassium hydroxide solution 4 4 (43%) N, N-diethylaminoethanol "15 Methyl carbitol 004 N-propyl neoheptanamide Water Parts 0.2 80.3 100.0 00 @0 0 0 0 0 0 0 S00 0 0 EXAMPLE 20 (Aerosol Furniture Polish) 4' Component to, Carnauba wax tit t Beeswax Ceresin wax Silicone oil (DC 200) Stoddard solvent Sodium soap (75:25 tallow~coco) Water Parts 5.0 5.0 40.0 130.*0 3 -4 -50-1 37 A wax-silicone concentrate is made by heating the Stoddard solvent to 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 admixed 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 Parts of Propellant 12 are pressure loaded into dispensing containers after pre-loadings of the balance of the composition.

EXAMPLE 21 (Shelf. Paper) Rolls of shelf paper are sprayed on both sides 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 repellent is regulated to be 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 repellent by volatilization is inhibited by the rolling of the paper. In a modification of this example the neoalkanamide repellent is added to the paper pulp during the manufacturing process but care must be taken not to drive off the repellent during any drying operations.

51 i 38 EXAMPLE 22 (Garbage Can Insect Repellent) A 2% concentration of N-methyl neodecanamide 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 0049 I. Boric acid 98.0 N-methyl neodecanamide 100.0 000 The various products of Examples 5-23 are all effective in repelling insects, especially German cockroaches.

However, they represent only a few of the many repellent 0 0 compositions and 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.

0 4«

I

52 is found to be sign1i1canfly 4eb eAA1~..h.vr 1 than the N-methyl neotridecanamiude.

39 EXAMPLE 24 2 15 Copoent Percent p-Tertiary butyl cyclohexyl acetate 12.0 N-ethyl neodecananide 10.0 Linalool 10.0 Gteraniol 10.0 i3unzyl salicylate 10.0 Benzyl acetate 10.0 Ci trone liol Terpineol aipha-Isomethyl ionone Linalyl acetate Phanylethyl alcohol blethylcedryl ketone Ionone (alpha/beta) 1ydroxycitronellal-methyl anthranilate Schiff base Axnbreine compound (CFE No. 2 [Colgate]). 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 strengthen the perfume and make it more persistent. Simil-ar good effects &re obtainable by substituting N-methyl neodecanamide for the ethyl homologue or by employing others of the described N-lower alkyl nteoalkanamides in place thereof, or by using mixtures of such materials. Specifically, the N-methyl neodecananide harmonizes and floralizes the accord between the other perfume components and strengthens the fragrance.

t 44t 53 40 i li; i ~wrr~-- -54- EXAMPLE Component Styrallyl propionate N-ethyl neodecanamide gamma-Undecalactone Anethol Benzyl acetate Ethylmethylphenyl glycidate Benzyl formate Dimetol (Givaudan) Hydroxyethyl pyrrone in diethyl Percent 20.0 15.0 10.0 10.0 10.0 tl i Si

I

4? iir phthalate) Allylcyclohexane propionate gamma-Nonalactone Linalyl benzoate Ylang ylang extra 100.0 The components are mixed together to make a tropical fruit fragrance, suitable for use in household products, 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, juicier and less lactonic.

Instead of the N-ethyl neodecanamide there may be substituted in the above perfume formula other N-lower alkyl neoalkanamides, such as N-methyl neodecanamide, N-ethyl neoundecanamide, N-ethyl neononanamide, N-n-propyl neoheptanamide, amd N-isopropyl neotetradecanamide. While each of the mentioned neoalkanamides has a different fragrance and all are of different stabilities, 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.

I

f- i t L-r- -1 1. I MOMAr. i~ 41 ComponentEXAMPLE 26, Citronello.

Phenylethyl alcohol N-ethyl neodecanamide Geraniol Phenoxyethyl isobutyrate Linalool p-Tertiary butylcyclohexyl acetate Geranyl acetate Eugenol Phenylethyl acetate lenzyl acetate alpha/beta lonone '15 Lauric aldehyde (10% solution in diethyl phthalate) aipha-Isomethyl ionone d Dimethylbenzyl carbinyl acetate Cuaiacwood aceta..

Rose oxide R (10% solution in diethyl phthalate) 12 0 Ylang ylang (complete) Undecylenic aldehyde (10% in diethyl. phthal~te) Ddmascenone (Firmenich, solution in diethyl phthalateJ) Percent 25.0 10.*0 10.0 3.9 O00 06 0O O 0 6 0 O 09 06 0 0 0 00 O 00 00 00 O 003 O 0 0.0 00 0 Citral 0.1 10000 The above components are mixed together to form a perfuzm compound which is of a rose fragrance. In the perfume the N-ethyl neodecanamide causes the fruity ester aspect of the rose fragrance to take on a sugary, jam-like quality, while the jonones are subdued. Additionally, the perfume is strengthened and its substantivity and persistence are increased.

S

42 t 4 1 4 t r C C EXAMPLE 27 Component Percent iydroxycitronellal (synthetic) 28.0 N-methyl reodecanamide 20.0 Cyclamnen aldehyde Geranio. 20.0 Citronellol 15.0 JBrahmanol 10 (Dragoco) Phenylethyl alcohol 1loliotropine Indole (10% solution in diethyl phthalate) alpha/beta lonone giamma Nonalactone Lilial (Givaudan) Citronellyl oxyacetaldehyde lBourgeonal (Naarden)- 100.0 The perfume compound of the above formula is made by mixing of the components, and the result is a lily fragrance. The presence of the N-methyl neodecanamide sweetens and naturalizes the accord, 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$ pursistent 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 neodecananide, such as N-ethyl neodecanamide, N-butyl ncooctanamide, and N-methyl neotridecananide, will have similar effects.

56 43 EXAMPLE 28 Component Sodium linear tridecyl benzene sulfonate Sodium tripolyphosphate Sodium carbonate Sodium bicarbonate Borax Enzyme blend (proteolytic amylolytic in powdered carrier) Percent 20.0 37.0 10.0 10.0 fe 4, p4o o o4

I,

Sodium carboxymethylcellulose Fluorescent brightener Perfume (of Example 21+ formula) Water 10.5 100.0 All of the 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 compositions helps to make washed laundry washed with such detergent compositions more insect repellent than laundry washed with control products.

57 insect repellent tnereon, so suV, 0u4au=c AW M become insect repellent.

In addition to the perfumes illustrated in Examples 24-27, a wide variety of other perfume types and formulas can be made, utilizing the described N-lower alkyl neoalkanamide perfuming materials. 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 t 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.

t 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 "t repellents, are only a few of the many compositions and "e articles of manufacture within the present invention, wherein the described perfumes may be employed instead of the Nalkyl neoalkanamides per se. In such examples the described N-lower alkyl neoalkanamide(s) and the perfume(s) improve the Ii a' Ct 4

I'

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i j r 58 45 the product odor and also help to make such product insect repellent. In addition to the compositions recited in Examples 6-23 and 28, the described N-lower alkyl neoalkanamides 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 concentrations corresponding to 0.3% of N-methyl neodecanamide or 0.3% of N-ethyl neodecanamide in chlorinated powdered scouring cleansers, after two weeks of elevated temperature agingat 49 0 C. both neodecanamides exhibit excellent odor and color stability. Similar excellent odor and color stability are 0oa oo as also noted at neoalkanamide concentrations of 0.2% in a "o Go particulate phosphate-built synthetic organic detergent compo- 0 0 o a "Oo0 sitions and at 1% in toilet soap. The proportions of perfumes o a- 15 employed will normally be from 2 to 20 or 5 to 10 times the proportions of the N-lower alkyl neoalkanamides in the mention- Go oo< ed products. Generally, such products are not normally subjected 0 a o° to temperatures as high as 49°C. so the test is considered to 01 be a severe one, especially when volatile materials are being tested. At room temperatures the alkanamides are stable for 0oo, much longer periods of time.

oB o~ The invention has been described with respect to 0 0 various illustrations and embodiments thereof but is not to be limited to 'them because it is evident that one of skill in the art will be able to utilize substitutes and equivalents without departing from the invention.

59

Claims (18)

1. A detergent composition for washing hard or soft surfaces and for making them insect repellent which comprises a detersive proportion of soap or synthetic organic detergent, and an insect repelling proportion of N-alkyl neoalkanamide, wherein the alkyl is of 1 to 4 carbon atoms and the neoalkanoyl moiety is of 7 to 14 carbon atoms, said insect repelling proportion of said N-alkyl neoalkanamide being sufficient so that enough is retained on such surface, after washing with the detergent composition, to repel insects from such surface.

2. A particulate laundry detergent composition according to claim 1 comprising 1 to 35% of a synthetic organic detergent selected from the group consisting of anionic, nonionic, amphoteric, ampholytic and zwitterionic detergents, and mixtures thereof, 10 to 90% of builder(s) or such detergent(s), and 0.2 to 10% of N-lower alkyl neoalkanamide or a mixture of such N-lower alkyl neoalkanamides.

3. A particulate detergent composition according to claim 2 comprising 7 to 30% of a synthetic organic detergent selected from the group consisting of anionic and nonionic detergents, and mixtures thereof, 20 to of water soluble and/or water insoluble builaer salts for such detergent(s), 0 to 50% of water soluble filler salt and 0.5 to 5% of N-lower alkyl neoalkanamide or a mixture of such N-lower alkyl neoalkanamides wherein the number of carbon atoms in the lower alkyl(s) is/are in the range of *o 0 1 to 2.

4. A liquid detergent composition according to claim 1 wherein the number of carbon atoms in the neoalkanoyl moiety of the N-lower alkyl neoalkanamide is in the range of 9 to 11. A liquid detergent composition according to claim 4 L comprising 3 to 20% of a synthetic organic detergent cQ R selected from the group consisting of anionic and nonionic I 61 detergents, and mixtures thereof, 10 to 30% of water soluble and/or water insoluble builder salts for such detergents, 0 to 20% of water soluble filler salt, 0.5 to of N-methyl neodecanamide, and 50 to 90% of water.

6. A shampoo according to claim 1, for washing human hair and for making it repellent of insects, comprising 2 to 25% of a synthetic organic detergent selected from the group consisting of anionic, nonionic, amphoteric, ampholytic and zwitterionic detergents, and mixtures thereof, and 0.2 to 10% of N-lower alkyl neoalkanamide or a mixture of such N-lower alkyl neoalkanamides, in an aqueous medium.

7. A rug shampoo according to claim 1, for cleaning rugs and carpets and for making them repellent of insects, comprising 1 to 35% of a detergent selected from the group consisting of water soluble soap and synthetic organic detergent(s) selected from the group consisting of anionic, nonionic, amphoteric, ampholytic and zwitterionic detergents, and mixtures thereof, 0.2 to 10% of N-lower alkyl neoalkanamide or a mixture of such N-lower alkyl neoalkanamides, and 0 to 40% of builder(s) for the detergent, in a liquid medium.

8. A solid insect repellent detergent product in bar or cake form for washing persons, animals, laundry, rugs and/or had surfaces and making them repellent to insects, which comprises soap and/or synthetic organic detergent and an insect repelling proportion of N-alkyl 4 neoalkanamide, wherein the alkyl is of 1 to 18 carbon 'atoms and the neoalkanoyl moiety is of 7 to 14 carbon atoms.

9. A detergent bar according to claim 8 wherein the detersive component is selected from the group consisting of synthetic anionic, nonionic, amphoteric, ampholytic and zwitterionic detergents, and mixtures thereof, and the N-alkyl neoalkanamide is one wherein the alkyl is of 1 to S 4 carbon atoms and the neoalkanoyl moiety is of 9 to 11 4Aaro 62 carbon atoms. A soap bar accordiuy to claim 8 wherein the detersive component is a soap of a mixture of higher fatty acids of carbon atom contents in the range of 10 to 18, and the N-alkyl neoalkanamide is one wherein the alkyl is of 1 to 4 carbon atoms and the neoalkanoyl moiety is of 9 to 11 carbon atoms. 11, An insect repellent composition which comprises an insect repellent proportion of N-alkyl neoalkanamide wherein the alkyl is of 1 to 4 carbon atoms and the neoalkanoyl moiety is of 7 to 14 carbon atoms, dispersed or dissolved in a liquid medium.

12. An insect repellent composition according to claim 11 wherein the alkyl of the N-alkyl neoalkanamide is of 1 or 2 carbon atoms and the neoalkanoyl moiety thereof is of 9 to 11 carbon atoms, and the N-alkyl neoalkanamide is "dispersed in an aqueous medium at a concentration in the range of 0.2 to

13. An insect repellent composition according to claim 11 wherein the alkyl of the N-alkyl neoalkanamide is of 1 or 2 carbon atoms and the neoalkanoyl moiety thereof is of 9 o to 11 carbon atoms, and the N-alkyl neoalkanamide is So dissolved in a liquid solvent medium at a concentration in the range of 0.2 to o°o°o14. An insect repellent composition according to claim 13 wherein the N-alkyl neoalkanamide is N-methyl or N-ethyl neodecanamide, the concentration thereof in the liquid solvent medium is in the range of 0.5 to 10%, and the solvent medium is a normally gaseous hydrocarbon or halogenated hydrocarbon under sufficient pressure to be in liquid state at room temperature. 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 63 carbon atoms.

16. A process according to claim 15 wherein the alkyl of the neoalkanamide is of 1 or 2 carbon atoms and the neoalkanoyl moiety thereof is neodecanoyl.

17. A process according to claim 15 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 N-lower alkyl neoalkanamide(s), wherein the lower alkyl is of 1 to 4 carbon atoms and the neoalkanoyl moiety is of 9 to 11 carbon atoms, said insect repelling proportion of said N-lower alkyl lower neoalkanamide(s) being sufficient so that enough is retained on the washed area, location or item, after washing with the detergent composition, to repel insects from such area, location or item.

18. A process according to claim 15 wherein the N-alkyl neoalkanamide(s) application rate is in the range of 0.2 to 10 g./sq.m.

19. A perfume which comprises N-lower alkyl neoalkanamide or a mixture of a plurality of such N-lower alkyl neoalkanamides, wherein the lower alkyl is of or averages 1 to 4 carbon atoms and the neoalkanoyl moiety thereof is f of or averages 5 to 14 carbon atoms, and at least one perfume component which is of a type selected from the group consisting of essential oils, esters, ethers, aldehydes, alcohols, hydrocarbons, ketones and lactones, in which the content of such neoalkanamide(s) is in the range of 0.1 to 98%. A perfume according to claim 19 which is in liquid state, and wherein the neoalkanoyl moiety of the N-lower alkyl neoalkanamide is of 7 to 14 carbon atoms, the content of neoalkanamide(s) in the perfume is in the range of 1 to 60/o and the neoalkanamide(s) is/are in mixture ,with a plurality of perfume components of a plurality of t r 'A etr 64 the types listed in claim 19.

21. A perfume according to claim 20 wherein the lower alkyl(s) of the neoalkanamide(s) is/are of 1 to 2 carbon atoms, the neoalkanoyl moiety/moieties thereof is/are of 9 to 11 carbon atoms, and the content of neoalkanamide(s) in the perfume is in the range of 2 to

22. A perfume according to claim 21 wherein the N-lower alkyl neoalkanamide is N-methyl- and/or N-ethyl neoalkanamide and the content thereof in the perfume is in the range of 5 to

23. A perfume according to claim 21 which comprises at least 1% of each of such ester, aldehyde and alcohol classes of perfume components.

24. A perfume according to claim 22 wherein the N-lower alkyl neoalkanamide is N-ethyl neodecanamide and the balance of the perfume comprises 5 to 40% of citronellol, to 30% of geraniol and 2 to 40% of phenylethyl alcohol. A household product which is a particulate detergent composition, a toilet soap, in bar or cake form, a liquid laundry detergent composition, a detergent composition for cleaning hard surfaces, a shampoo composition for shampooing hair, an upholstery shampoo, a rug shampoo, a floor polish, a furniture polish, an insect repellent, an insecticide or a scouring cleanser, which is perfumed with 0 0.1 to 10% of a perfume according to claim 19. DATED this 22nd day of August 1990 COLGATE-PALMOLIVE COMPANY Patent Attorneys for the Applicant: F.B. RICE CO. K ;i '0*