JPS6067445A - Perfume composition and perfumed product - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides at least L or more 2-ethyl-2 as a perfume base.
- Perfume compositions containing esters of methylbutanoic acid and products perfumed with these compounds or perfume compositions containing these compounds (1) erfumed prod
-11 (21S) 1 related.

There is continued interest in the production and use of synthetic fragrances. This is because, in contrast to natural products, they always have 1i, L
This is because it is possible to manufacture products with consistent quality.

General formula % formula % (wherein R1 is alkyl having up to 8 carbon atoms, alkenyl, alfukidialkyl, cycloalkyl,
It has now been found that esters of 2-ethyl-2-methyl-butanoic acid having alkylcycloalkyl, cycloalkylalkyl or aralkyl groups are valuable aromatics.

They add a variety of desired odors (
odd'our notes, i.e., green notes.
l), fruity, mint-scented (+n
1nty), wood (u+oody), and flower (flo
rai) type odor. Ethyl esters are particularly distinguished by their natural odor (0-dour) properties. This ethyl ester is British Special R' [
Specification number 1. (No. 104,286 and J, R, Rol
and J. D. C. Wilson and W. E.) (a
J, A Il+, C11e+ by -nford
n, Soc, ? 2.2122-24 (1950
)It is described in. However, the above publications do not indicate any effectiveness of this compound as a perfume base. Regarding the upper limit of 8 carbon atoms, the applicant has, for the sake of completeness, Fragrance intensity
Esters according to the invention clearly indicate that ty) is considered insufficient, for example 2-ethyl-2-
They are prepared according to generally known esterification methods by reaction of methyl-butanoic acid or its customary derivatives, such as acid chlorides, with the corresponding alcohols.

The esters according to the invention can be used successfully in perfumery compositions or directly as scenting agents in various products. The expression "perfume composition" refers to fragrances and optionally a powdered matrix (1) dissolved in a suitable solvent if desired.
ultimate su! +5trate) mixed with adjuvants, which are used to impart a desired fragrance to the skin or to various products. The following items (fll 1 soil soap, detergent, air 7 ressurener (air rresl+ene)
r), room spray, pomander
, candles and cosmetics, such as creams, ointments, lotions (1, oilet u+a
ters), pre-shave (1) re-shave) and after-shave (afLpr-shan).
e) Lotion, talc powder, hair care
-care) composition, body deodorizer (i+ody deo
rdoran-ts) and antiperspirants (antiper
s1+1ran1. s).

Fragrances and mixtures thereof which can be used in combination with the compounds according to the invention for the production of perfume compositions are, for example, natural products such as essential oils.
oi l), absolute) (al+5olutes
), resinoids, 4jJ fat, concrete, etc., but also synthetic aromatics such as hydrocarbons, alcohols, aldehydes, gamma ton, ethers, acids, esters, acetals, ketals, nitriles, etc. Includes saturated and unsaturated compounds as well as aliphatic, carbocyclic and heterocyclic compounds.

Examples of fragrances that can be used in combination with the compounds according to the invention are delaniol, delanyl acetate, linalool 1, linalyl acetate, tetrahydrolinalool, citronellol, citronellyl acetate, dihydromyrcenol, dihydromyrcenyl acetate, tetrahydromyrcenol, terpineol, tilvinyl acetate, 7-ball, novylacetate, 2-phenylethanol, 2-phenylethyl acetate, pen')
alcohol, benzyl acetate, benzyl salicylate, styralyl acetate)
c-(・La1.+・), benzyl benzoate, amyl salicylate, dimethylbenzyl carbinol, trichloromethylphenyl carbinyl acetate-1-, pt
ert-butyl-cyclohexyl acetate, isononyl acetate, benzyl acetate (vetiver
ylacpl, ntc), vetiverol (veLive
rol), α-hexylcinnamaldehyde, 2-methyl-3-(p-tert, -butylphenyl)-propanal, 2-methyl-3-(ρ-isopropylphenyl)-propanal, 3-(ρ- tert, -7” tylphenyl)-propanal, tricyclodecenyl acetate, tricyclodecenyl propionate, 4.(4-
Hydroxy-4-methylbenyl methyl)-cyclohexa-
3-ene-carbaldehyde, 4-(4-methyl-3-
pentenyl)-cyclohex-3-enecarbaldehyde, 4-7cetoxy-3-pentyl-tetrahydropyran, 3-carboxymethyl-2-pentylcyclopencune, 2-1doheptylcyclopentamene, 3-methyl-
2-pentyl-2-cyclobentenone, 1-dodecanal, n-dodecanal, dec-9-en-1-ol, phenoxyethyl isobutyrate, phenylacetaldehyde dimethyl acetal, phenylacetaldehyde diethylacecur, geranyl nitrile, citronellyl nitrile , cedryl acet 1
ate), 3-isocamphyl-cyclohexyl-7-ol,
Cedryl methyl ether, Yinlongi 7-ol/n (is
olo-ngifolanone), obepine nitrile, obepin, heliotropin, coumarin, eugenol, vanillin, diphenyl oxide, hydroxycitronellal, ionones (1onones), methyl ionones, isomethyl ionones, irons (iro
nes), cis-hex-3-enol and its esters, indane musks,
Tetralin musks, inchroman musks, macrocyclic ketones (Inae-roCyclic, kel, oncs)
), macrolactone musk M (, n.

cro 1 actone musks), ethylene brassylate (eth-ylene brassylate)
) and aromatic nitro musks (ar-oma+ic n
1tro musks).

Auxiliaries and solvents that can be used in perfume compositions containing one or more compounds according to the invention include:
Examples include ethanol, isopropyl alcohol, diethylene glycol monoethyl ether, and diethyl hetatalate.

The amount in which the compounds according to the invention can be used in a perfume composition or perfume product can vary within wide limits;
Among others, the nature of the product in which the aromatic substance is used, fragrance ML.
The nature and amount of the ingredients in the composition and the desired aroma effect (
Depends on odour e"recL).

It is therefore possible to specify only very rough limits, but these give sufficient information to enable a person skilled in the art to independently use the compounds according to the invention. In most cases, only 0.1% by weight of 114. would already be sufficient to achieve a clearly perceptible odor effect.

On the other hand, in order to achieve a specific fragrance effect, two
It is possible to use amounts of 0% by weight or even higher amounts. Perfumed with the help of a perfume composition (1
[erfu+ned) products, these concentrations are correspondingly lower depending on the perfume composition used in the product.

The following examples merely serve to illustrate the preparation and use of the compounds according to the invention, but the invention is not limited thereto.

Production of fruit-free ethyl 2-ethyl-2-methyl-butyrate 260 g of concentrated sulfuric acid was mixed with 2-ethyl-2-methyl-butanoic acid 2GO.
(2 moles) and 386 g (8 moles) of ethanol in 15 minutes with effective stirring. During this process, the temperature rises to about 60°C. The mixture is then heated under stirring and reflux for 3 hours. The layers separate as the mixture cools to room temperature.

The top layer is diluted with 200 ml of water and then extracted with cyclohexane. The cyclohexane layer is combined with the original bilayer and the mixture is washed with sodium carbonate solution until neutral. The cyclohexane solution is then evaporated and the residue is distilled under reduced pressure. desired ethyl ester 25
8 g is obtained.

Boiling point 65°C10,3kPa; n20=1.4110;
NMR(1(', 10 MHz, δ, 111111 for TMS, solvent: CCL); 0.81(6H,
t, J=71h): 1°06(3H,s); 1.24(
31-1, t,, J=7Hz); 1°0-], Shin 4.
Hlm); 4.08 (2H, q, J=7Hz>.

The compound has a pleasant fruity and woody aroma with an aspect reminiscent of taHetes oil. Preparation of 2'-ethylhexyl 2-ethyl-2-methyl-butyrate 15.5 g of 2-ethylhexanol ( 0.12 mol),
A mixture of 1]-toluenesulfonic acid]Of)+nFI and 15 () ml of toluene is heated to reflux temperature and the water formed is distilled off by azeotropic distillation. Once the mixture has cooled to room temperature, it is washed with sodium carbonate solution until neutral. The toluene solution is then evaporated and the residue is distilled under reduced pressure. 14.5 g of the desired ester are obtained.

Boiling point 95℃ 10JkPa: n2'=L4320; NMR
:0.81(61-1,[,J=7Hz);1.05(
3H, s); 0.6-1.9 (191'', m); 3.
90(2) (,d, J = 6 Hz).

The compound has a pleasant minty odor (minty), tI
l. Has a somewhat fruity aroma.

Actual example-) The following esters were prepared as described in Example 2.

Allyl 2-ethyl-2-methyl-butyrate boiling point 90℃
/(1,3kPa:NMR:0.81(6H,L.

J=7Hz),'1.08(3H,s):1. O-1,
9 (4H, +n): 4.49 (2H, d, with fine structure, J = 7Hz); 5,0-5.4 (2H, Satoru); 5
, 6-6.1 (IH, +n).

Spicy green and floral aroma, somewhat reminiscent of medica oil (
Reminiscent of oil (e.g. oil).

Isobutyl 2-ethyl-2-methyl-butyrate boiling point'
,)O"C10,3kPa;n%'=1.4115:N
MR: 0,81(61-], t, J=7Hz); (1,
94 (61-1, (1, J = 7Hz): 1.06 (3H
,s);1. O-2゜2 (51-1, +n); 3,7
8 (2H, d, J=6Hz).

Woody and mint aroma with floral tones.

Cyclohexyl 2-ethyl-2-methyl-butyrate boiling point 5°C/0.3 kPa; n2o. =1.446
2: NMR: 0.80 (61 (, L, J = 711z);
], 04(3■1,s):1.0-2.0(14,1-
1, +++); C65 (] IHm).

Fruit scent.

2'-Methoxyethyl 2-ethyl-2-methyl-butyrate Boiling point 75°C 10.3 kPa; NMR: 0.81 (61-
1, 1,? )(z);]',06(31-1,s);1
, 0-1.9 (4H, m); 3,30 (3N, s):
3.46 (2ft, t,, J = 51-1z):
4.12 (2[-1, t, J=SHz).

Grassy and somewhat woody aroma.

Benzyl 2-ethyl-2-methyl-butyrate boiling point 11
8℃/ii, 3kPa: n glance = 1, 4.89
0; NMR: 0.77 (61-1, ll,) = 7H
zGlO? (3H,s);1. (1-], ri(4,1-
I, m); 5, +10 (21-L s);? , 0-
7.3 (5H, Broadk).

Grassy and somewhat porous aroma.

2'-Phenylethyl 2-ethyl-2-methyl-butyrate Boiling point 125°C 10,3 kPa; n p' ” 1.48
30; NMR: 0,7'3 (6t1, t, J=7
Hz);1. 01 (311, S); 1.0-1.9
(4tL m): 2.86 (2H1tl, J=7Hz)
;4.20 (2H, t, J=7Hz): 6.9-7.3
(5H, Broads).

Aromas of flowers and some fruit.

Examples” Shampoo and shower and light foam formulations (sl+o-
+uCr and 1oath foam prel]
The pine type is very suitable for
A fragrance composition of type 1) was prepared according to the following procedure.

3.15 parts by weight Bornyl acetate 100 parts by weight 2-Butyl-4,4,6-drimethyl-1
, 3-dioxane 50 parts by weight Siberian pine needle oil (sil+erian pi)
30 parts by weight 5-7 cetyl-3-isopropyl-1,1,
2,6-thitramethyl-indane 30 parts benzyl acetate 30 parts orange oil 30 parts linalyl acetate 30 parts 2,6-thitramethyl-indane 20 parts tridecanal 15 parts 4-1. ert, -Butylcyclohexyl acetate 10 parts by weight Coumarin 10 parts by weight Terpineol 10 parts by weight Thiruvinyl acetate 10 parts by weight Lavandin oil
10 parts by weight n-decanal 7 parts by weight Sibeltal NB 1 (14 (cil, ro)
verl, al NI'3 11') 4. ) * 5 overlapping parts dodecanal 5 parts by weight Styralyl acetate 1 (sl, yralyl acel, ate) 5 m view B
3 parts by weight of 3-isocamphylcyclohexanol 2 parts by weight of ionone 30 parts by weight of isoeugenol 2-4 parts of ethyl 2-ethyl-2-methyl-butyrate
l) (1 part by weight) Floral fantasy type
pe) was prepared according to the following method.

350Lily of tl+e valley 1eas
e)★20 +1 parts by weight lilac base★175 parts by weight jasmin 1ea
se) '75 parts by weight Hyacinth base (hyacinth 1ease)★ 70 parts by weight Rosewood oil
) 7 fi ffi parts dihydromircenol S 0 parts ylang-ylan oil 40 parts tricyclodecenyl acetate 40 parts 2-(hept-3-yl)-dioxolane 30 parts litho- Cubeva oil (111゜5ea-cul+eba oil) 2 (1
Intussusception ff1s methyl-pencyl-carvinyl acetate 10 overlap parts Eudel/-ol 10 parts by weight 5-7 cetyl-3-isopropyl-1,1,
2,6-titramethylindane 3 ff1ffinB 2 , 2 parts by weight of 4-dimethyl-cyclohex-3-ene-carbaldehyde 50 parts by weight of isoeugenol 1200 parts by weight of ethyl 2-ethyl-2-methyl-butyrate A perfume composition prepared is British Patent Specification No. 1゜5=1
It can be used with good results in air freshener formulations made according to No. 4,221.

★ Naarden International N.B. (Nua
rden Internal, 1onal N, V,)
Perfume base (marked by Arked).

Patent applicant Naarden International N.
Beichi

Claims (1)

[Claims] 1. Formula % Formula % (wherein R represents an alkyl, alkenyl, alkoxyalkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl or aralkyl group having at most 8 carbon atoms) ) A perfume composition or a perfumed product, characterized in that it contains one or more esters of 2-ethyl-2-methyl-butanoic acid. A perfume composition or a perfumed product according to claim 1, characterized in that it contains ethyl ester of 2,2-ethyl-2-methyl-butanoic acid. Perfume composition according to claim 1, characterized in that it contains at least 0.1% of one or more esters of 2-ethyl-2-methyl-butanoic acid as described above. 4. One or more esters of 2-ethyl-2-methyl-butanoic acid as defined in claim 1 or one of claims 1 to 3 for flavoring products.
Use of a perfume composition according to one or more of the above. 5, formula % formula % (3 (wherein R represents an alkyl, alkenyl, alkoxyalkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl or aralkyl group having at most 8 carbon atoms; (However, ethyl ester of 2-ethyl-2-methyl-butanoic acid is excluded).