SU721398A1 - Alkyl- or alkylsubstituted 2,2-dialkyl-4-pentenal ethyleneacetals as perfume - Google Patents

Description

The invention relates to new chemicals, ethelenocetals of alkyl- or alkenyl-substituted 2,2-dialkyl-4-pentals, which can be used in the perfume industry to create perfume compositions and fragrances.

It is known that alkyl- and alkenyl-substituted 2,2-dialkyl-4-pentenals are aromatic substances [1].

These aldehydes are produced under the trade names ’э eugenal’ and 'prisal ’. Their disadvantage is the relatively low chemical resistance, which limits the warranty shelf life to 3-6 months.

The aim of the invention is to expand the assortment of aromatic substances more chemically stable in comparison with the known ones.

This goal is achieved by the ethylene acetals of alkyl or alkenyl substituted 2,2-dialkyl-4-pentenals of the general formula I

where R is CH ₃ ;

R ,, - CH ₃ orsn _g sn _g CH = C (CH ₃ ) _g ,

moreover, if r ₂ - sn ₂ sn ₂ sn = = C (CH ₃ ) ₂ then Rj 7 R3 »R4 - sn ₃ ; R ₃ - MF ₃ or C ₂ H 5 , and, if

R ₃ - C ₂ H _S , then R ₍ = R ₂ - CH ₃ , R ^ - C ^ Hg.

R _zj is CH ₃ or C ₄ H ₉ , and if R ^, then R ^ _t R ₂ C1C f

R ₃ - with _g n ₆ .

The proposed ethylene acetals of aldehydes have a softer and more delicate odor and are practically not subject to oxidation. They can be used to create perfumes and fragrances with the smell of iris and fresh herbs.

The ethylene acetals of substituted dialkyl pentenals of this structure are obtained by reacting ethylene glycol and the corresponding aldehydes in the presence of acidic catalysts by azeotropic distillation of the water formed during the reaction. The yield of the target product to'80%. The structure of the obtained compounds was confirmed by the IR and PMR spectra and elemental analysis.

"1

PRI me R 1. Obtaining ethylene acetal 2,2,5,9-tetramethyl-4,8-decadienal (ethylene acetal eugenal).

A mixture of 52 parts by weight (0.25 mol) 2,2,5,9-tetramethyl-4,8-decadienal (eugenal), 23.25 parts by weight (0.375 mol) 5 ethylene glycol, 0.1 parts by weight p-toluenesulfonic acid and 100 parts by weight toluene is boiled for 2 hours with stirring in a flask equipped with a reflux condenser with a water separator, separating about 6 parts by weight of water. The resulting reaction mass is washed with a solution of sodium bicarbonate. · Then, toluene is distilled off and the residue is distilled in vacuo, selecting 98% (by GLC) eugenal ethyleneacetal (mixture of cis and trans isomers), b.p. 97-107 ° C / 5 mmHg, p ²⁰ = 1.4 7 4 3, yield 82%.

Repeated vacuum distillation results in a 100% (by GLC) ethylene acetal eugenal formula

CH; R ₂ : in the formula I r ₁ -r ₃ = r ₄ CH ₂ -CH ₂ CH = C (CH ₃ ) ₂ .

Eugenal Ethylene Acetal - a clear, colorless or slightly yellowish liquid; n ² ° = 1.4745; d ₄ ° = 0.9 261; ' MR ^; found 76.54, calculated 76.24.

IR (cm * ¹ ): 1042, 1108

1360 (CH ₂ in the cycle); 1378 (CH in the loop); 2728, 2780

2930 (CH); 2970 (CH,);

(> C = CH-).

S (O-CH-O) 3.76 t. (- O-CH-O-);

(CH ₃ ); 1.397 (-O-CH-O-);

3030, 3050

₁ H-NMR spectrum: 4.40 (O-CH ₂ -CH ₂ -O); 0.83

C / 1.94 (3 (= CH ~); 5.10 m

Sn

C, 76.19; H, 11.11. nice floral greenery.

Obtaining ethylene (-CH ₂ -CHF); 5.0 (CH = C <);1.57; 1

Found,%: C H 11.19, 11.29.

Calculated,%:

The product has a hint of smell

PRI me R 2.

acetal 27 Ethyl-2-butyl-5-methyl-4-hexenal (ethylene acetal irisal).

Work according to example 1, based on · 2-ethyl- ^| 2-butyl-5-4-hexenal (irisal) and ethylene glycol. After distillation in vacuo, 96% (by GLC) of irisal ethylene acetal is obtained with a boiling temperature of 112 ° C / / 7 mmHg, n ²⁰ = 1.4 6 8 0.

Repeated vacuum distillation results in a 100% (by GLC) ethylene acetal irisal formula

In the formula IR ₍ = R - CH; R _g - C _g H ₆ ;

- From „N _d .

Irisale Ethylene Acetal is a clear, colorless or slightly yellowish liquid; n ^g _in ° '= 1.4682; d ^ = 0.9266, MR ₀ : found 72.03, calculated 72.08.

IR spectrum (cm ' ¹ ): 1040, 1110'-O-CH-O-); 1358 (CH _g per cycle); 1378 \ CH ₃ ); 1400 (CH in the cycle); 2932 (CH ₂ ); 2960 (CH ₃ ); 3050 (> C = NW).

1 H-NMR spectrum: 4.50 S (O-CH-O); 3.79 t (0-CH ₂ -CH ₂ -0); ' 1.99 (CH ₂ -CH =); 5.11t (CH = C); 1.57, 1.6 bt [(CH) C =].

Found,%: C 74.87, 74.97;

H, 11.66; 11.70.

Calculated,%: C 75.00; H, 11.66.

The product has a greasy tint of iris,

Example 3, Preparation of 2,2,5-trimethyl-4-hexenal (grass) ethylene acetal - ethylene travel.

They work according to example 1, starting from 2,2,5-trimethyl ~ 4-hexenal (ethylenetraveal) and ethylene glycol. After distillation in vacuo receive 98% (by GLC) ethylenetraveal with so Kip. 50 ° C / 4 mmHg, PD ° = 1.4551,

Repeated vacuum partitioning results in a 100% (by GLC) ethylenetraveal formula

In the formula, IR ₄ = R ₂ = R _g = R ₄ - CH ₃ .

Ethylene Traveal - a clear liquid, colorless or slightly yellowish; n ²⁰ = 1.4560, d ₄ ° = 0.9298 / MR ': found 53.78, calculated 53.55.

IR spectrum (cm ¹ ): 1042, 1108 (—O — CH — O—); 1360 (CH ₂ in the cycle); (CH ₃ ); 1397 (CH in the loop); 2930 2972 (CH ₃ ); 3032, 3052 (> C = CH)

1 H-NMR spectrum: 4.40 S (O-CH-O); Si

1378 (CH ₂ );

:, 94d (CH ₂ -CH =); 5.10t (CH = C <);

1.57, 1.68 t [(CH ₃ ) ₂ C =).

Found,%: C 71.61, 71.59;

H, 10.68; 10.93.

Calculated,%: C 71.73; H, 10.86. The product has an intense smell of grass and fresh herbs.

Claims (3)

(54) ETHYLECHETTALS OF ALKYL OR ALKENYL-SUBSTITUTE 2,2-DIALKYL-4-PECHTENAL AS DULE-WITHOUT SUBSTANCES . A mixture of 52 wt.h. (0.25 mol) 2,2,5,9-tetramethyl-4,8-decadienal (egenal), 23.25 parts by weight (O, 375 mol) ethylene glycol, 0.1 weight.h. p-toluensulfonate and 100 weight.h. toluene is boiled for 2 hours with stirring in a flask equipped with a reverse fridge with a water separator, section about 6 parts by weight. water. The resulting reaction mass is washed with sodium bicarbonate solution. Then toluene is distilled off and the residue is distilled in a vacuum. 98% (by GLC) ethylene chain ethenal (mixture of cis- and trans-isomero bp. 97-107 ° C / 5 mm Hg, 4743, yield 82%. Repeated vacuum distillation yields 100% ethylene acetal (by GLC) egenal of the formula: In formula I. - CH; R CH2 – CH CH • CH (CH3) 2 Ethylene acetal egenal - transparent colorless or slightly yellowish liquid; pc ° 1.4745; 0.92 found 76.54, calculated 76.2 IR spectrum (cm): 1042, 1108. (- 0-CH-0-); 1360 (SP in the cycle); 137 (CH "); 1.397 (CH in c glue); 2728, 278 (-0-CH-0-); 2930 (CH); 2970 (CH); 3030, 3050 (). PMR spectrum: 4.40 S (O-CH-0) ;. 3.7b (O-CHg-CH-O); 0.83 S (); 5.0 m (CH-); 5.10 m (); 1.57; 1.64 m (CH3) C. ,%: С 76,25; 76,32; H 11,19, 11,29. Calculated,%: С 76,19; H 11,11. The product has a pleasant floral smell with a touch of green. 2. Preparation of 2-ethyl-2-butyl-5-methyl-4-hexenal ethylene acetal (ethylene acetal trisodium). The operation is carried out according to Example 1, starting from 2-ethyl-2-butyl-5-4-hexenal (toffee and ethylene glycol. After distillation in vacuo, 96% (by GLC) ethylene acetal toffee with boiling point / 7 mm Hg are obtained. Art., 1.4680. Repeated vacuum distillation yields 100% (according to GLC, ethylene acetal orrisal formula, CrH5 / - h -. I ScN3 Formula IR, R2 - CHg; R - -. Ethylene acetate orrisal - prozracha colorless or slightly yellow liquid; 1.4682; d 0.9266, Rpg found 72.03, calculated 72.08. IR spectrum (): 1040, 1110-U-CH-O-), 1358 (СНе in the cycle); 1378 vCHj); 1400 (CH in the cycle); 2932 (CH); 960 (CHj); 3050 (). HMR spectrum: 4.50 S (O-CH-O); 3, 79t (); 1.99 (CH2-CH); 5.11 t (); 1.57, 1.66 t (CH,) C. Found,%: C 74.87, 74.97; 11.66, 11.70. Calculated,%: C 75.00; H 11.66. The product has the smell of toffee with a fat tint. PRI m, e r 3. Preparation of ethylene acetal 2,2,5-trimethyl-4-hexenal (herbal) - ethylene etheveal. Work as in example 1, based on 2,2,5-trimethyl-4-hexenal (ethylene traveal) and ethylene glycol. After distillation in vacuo, 98% (by GLC) of ethylene traveal are obtained with a bp. 50 ° C / 4 mmHg, n | 1,4551. Repeated vacuum septum results in a 100% (by GLC) ethylene-traveal formula. In formula I - CH. Ethylene traveal is a clear liquid, colorless or slightly yellowish; 1.4560, 0.9298,. Found 53.78, calculated 53.55. J-spectrum (): 1042, 1108 (-0-CH-0-); 1360 (CH, in the cycle); 1378 (CH3); 1397 (CH in the cycle); 2930 (CH); 2972 (CH, 3032, 3052 (). PMR spectrum: 4.40 S (O-CH-O); 3.76m (O-CH-CHa-C); 0.83 S /;, 94d (CH2- CH); 5.10m (); 1.57, 1.68m (CH3) g C. Found,%: C 71.61, 71.59; H 10.68, 10.93. Calculated,%: C 71 , 73; H 10.86. The product has an intense smell of grass and fresh greens. Claims of the Invention Ethylene acetals are alkyl- or alkenyl-substituted 2,2-dialkyl-4-peitenals of the general formula - B. O (1Hg where R. Rg Rj 5 7213986 CH, ; R - CH or Cj, Hg, and, if CH, or CH4CHgCH C (CH3) g, R -, then R, R - CHj, and, if Rg - CHgCHgCH Rj -, as dumis 0 (04) 2, then R, R, R substances. CHj; sources of information, CHj or CjHg, moreover, if5 taken into account in the examination of Rj - CjHg, then - CHg, 1. USSR Copyright Certificate 4 355147, class C 07 C 47/20, 1965,