DE2201365A1 - New alpha-methyl butyric acid ester - Google Patents

Description

Or. Ing.A. Yonder Werft \ 2, j _on 1972

PATENT APPLICATION II

• 6510/55

L. Givaüdan & Qe Societe Anonyme, Vernier-Geneve (Switzerland)

New α-methyl butyric acid ester

. ' The invention relates to a new compound, namely 3-ethyl-1-pentene -> - yl-an] ethyl butyrate of the formula

a process for its production and its use as a fragrance in the perfume industry.

The compound of the formula I can be obtained according to the invention by
a) 3-Aethyl-1-penten - ^ - ol with α-methylbutyric acid

esterified, or that one

Hen / 11/29/71 209837/1217 oriqi _NAL inspected

b) 3-ethyl-1-pentin-3-yl-a-methylbutyrate partially hydrogenated.

The esterification according to process variant a) can be carried out by the methods known per se for the esterification of tertiary alcohols be made. The acid ponenta is preferred in the form of a functional derivative such as acid chloride or anhydride. One can use this derivative directly, like e.g. in the case of the anhydride, with the alcohol, or, as in the case of the chloride, with an alkali metal salt, such as the sodium or React the potassium salt of the alcohol. One can in a solvent such as benzene; Toluene, cyclohexane etc., preferably in benzene, and work at elevated temperatures, e.g. at the reflux temperature of the reaction equipment.

The reaction product can by conventional methods from the Reaction mixture can be isolated, e.g. by taking up the latter in ether, washing this extract and distillation.

The partial hydrogenation of 3-ethyl-1-pentin-3-yl-α-methylbutyrate according to process variant b) can also be carried out by known methods. One works e.g. in the presence of a selective hydrogenation catalyst, preferably an approximately 5 ^ palladium-calcium carbonate catalyst, whose activity has been reduced by treatment with a lead salt solution and, if desired, with quinoline ("Lindlar catalyst") [HeIv. Chim. Acta 22, 446 (1952)]. The hydrogenation can be used in the absence or presence of a solvent, e.g. an inert solvent such as ligroin or petroleum ether, take place at room temperature and atmospheric pressure. Working up is best done by filtering off the catalyst, distillation of the solvent and fractionation of the residue.

ORIGINAL INSPECTED

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The jJ-Aethyl-l-penteri ■ - / ■■ '■ - - .. j .; '.'; method variant b) used, ο> -Aev '. · / methylbutyrate (IIl) can be used according to ochoj; ia /;

Scheme A

Ver

Ill

According to this scheme v / ird for the purpose of producing the unsaturated Alcohol IV. Diethyl ketone with acetylene according to methods known per se, e.g. in the presence of an alkali metal such as lithium or sodium, ammonia and a catalyst such as ferric chloride, condensed. The received Alcohol IV can then be partially hydrogenated to alcohol II become, e.g. 3. using Lindlar catalyst.

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For the preparation of the butyrate III is according to the above scheme of acetylenic. unsaturated alcohol IV is esterified with pi-methylbutt acid. The esterification can in itself known methods of esterifying tertiary acetylenically unsaturated alcohols can be carried out, e.g. by using the Alcohol with a functional derivative of the acid component, how the chloride or anhydride converts.

The ester I according to the invention is distinguished by special features Fragrance properties. From special perfume tables Interest is a product which, in addition to the pure ester I, 10 to 10, preferably 10 ^ to 10 parts by weight Contains J-ethyl-i-penten-J-oil (II), a mixture of this type is obtained when the ester I is prepared according to process variant a) and the reaction product which the Contains compound II as a by-product, does not purify carefully. This product is characterized by a pronounced green, spicy, $ n Tagete3 oil remember odor.

The ester I and the above-mentioned mixture with compound II can be used in the perfumery industry for the production of perfumes and perfumed products, for example for perfuming soaps, solid and liquid detergents, aerosols, due to their advantageous odor, which is particularly noticeable in the top note , cosmetic products of all kinds, such as toilet water, ointments, facial milk, make-up, lipsticks, bath salts and oils. The content of the fragrance according to the invention in the perfumes or the perfumed products can be

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lie within wide limits, for example between about l $ ₀ (detergents) and about 20% (alcoholic solutions). In perfume bases or concentrates, it can of course also be over 20%.

The fragrance according to the invention can be fragrance compositions with the most varied of notes, but advantageously fragrance compositions with woody, "chypre" or flowery ones Notes are incorporated. Flowery compositions gain strength and a more pronounced top note and also the other of the compositions listed are modified in an advantageous manner by adding the ester according to the invention.

Examples of fragrance compositions (concentrates) are the following:

1. Lily of the valley concentrate compound I + traces of alcohol II phenylacetaldehyde dimethylacetal sandalwood essence

Rhodinol 70 (rhodinol-citronellol mixture, 7OYes containing rhodinol) linalyl cinnamic acid ester Phenylethyl alcohol extra α-hexyl-cinnamaldehyde Hydroxyeitronellal

Parts by weight 20 10 70

100 100

300

500

2000

· Lilac k on ζ e η tr at compound I + traces of alcohol II anisaldehyde ex anethole benzyl acetate phenylethyl alcohol extra lilyl alcohol for par i'üi'iiü tische purposes terpineol

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Parts by weight

100

150

200

290

__? f) 0

1000

"Chypre"

Chypre " - Concentrate Gev; lch t place

Compound I + traces of alcohol II 10

Methylphenylcarbinylacetate 10

Lauric aldehyde 10fo 10

n-Undecylaldehyde ICfS, 20

Benzyl acetate '30

Sandalwood oil 40

Tree moss abs. 50 $ 50

Coumarin crystallizes 50

Ketone musk 50

Patchouli Essence 60

Citronellol extra 60

a-phenylethyl alcohol extra 60

α-hexyl cinnamon alcohol 60

Vetivenyl acetate 80

Hydroxycitronellal 80

Methyl jonon. 80

Benzyl salicylate 100

Bergamot Essence 150

1000

The combination used in the previous examples

of compound I with compound II provides the reaction product according to synthesis example 1 below.

In the examples below are the temperatures given in degrees Celsius.

209837/1 21 7

■ -20138 λ

52.8 g sodium hydrio ■ >',:..'<uv; - ■■■■ .- ■ ■■ . .. '..- ■; -, r'enge and 1 liter of anhydrous Ε ·: ·. \ .- τ. "■. ---. Λ. ·: ■ ·. - .. '.' :.:; ': - ο T ^ b ¹ S "gassing in a round flask, - ■ r.: ν ■' ■ '. -ν -. " ..:.:.: ..: .. ^ _z ..:> ?:;; l ·;,! 'funnel and cooler: ■■.":'a'.ol".. . :>: '..' ■ .. '■: ■ .; S ⁱ ::: -! H Ic-L, given. For rooms ;; · ■;' .: ■ w i-. "- '■ ■ ; : - ::.,; ':, - wise Il4.2 g 3-ethyl-1-pe:; V.;: ■■ j-cl. ■■ ■ /, '.' ■.:. '■ "^?". ^ AV ~ V:. mixture 4 hours on the refe ^ -, i> u .. - \, ".. ■ - .. r" ^: " ^7. ~: jj:: 120.6 g a-Mothylbutte ^ acid ·.:!:" . ^1st :: ° iö 1: '.: ■ - - - ^:. ■■■■'"." ..: "- interval from 0-5 ° Z '^ ^ nd sol: - i-ie::" .. - ..-. ■. '[.-.' .. \ "'..' ■ '::' ■: .-

Increase to 10 ° for 15 minutes, f -'- in g :. .-: ■ ;:: - _; -: '■■ "- ■ -: C · *' ■! 'T.-j je .. ■ on ice, takes up in ether and was. ■'."; · .: "Ι '^ ί, / ΐΒ ^ ;;; :: Extracts with a 3? 3-igen bi carbon a"' ..i '' -. ^.; ".". · .: i :: t-raui '"; it ^ and dry the organic phase mj / wa;: ■: ■ .sr: Γγeit. ¹ :; Na ^ riu.; ..: The solvent is evaporated off and e ' stops: : 22 "g Echrr -:.: A fractional distillation of this ¥ x: ur ~"' .cL product «?? .-

! 100 g olfactory valuable 3-ethyl - ■■ ^ c "s - '''-' yl ~ ^ix-Ee: r; '.

butyrate with a boiling point of 87> 5 ~ 88.5 ^Ο Α ^ ^ Eq; _f n ^ '= li ^ 33> lj!

That used as the starting material ^ T-ftethyl-l-pentir: > -ol can be obtained as follows;:, become;

2.5 liters of liquid ammonia combined with ".o iron-III-nitrate in a Rundicolben?" with Hührer-j 'dropping funnel, Acetyleneinloitungsrchr and? aekflussrühre ^:! provided with dry ice-isopropahol cooling coil. Over a period of 90 minutes: 84 g of lithium are then added in small pieces. After? 0 minutes, the reaction mixture turns gray. Acetylene is passed in for 7 hours, which has previously been passed through a glass spiral cooled with dry ice to dry it with sulfuric acid and calcium chloride and then to remove traces of acetone; or el ·.-η was. After standing for 12 hours, add another ri., 5 liters of liquid ammonia to d'-r: flask ¹ YYes; jejt ^ t viiederu; · acetylene a. To

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Another hour you start with the addition of 1.11 kg Diethyl ketone, which extends over a total of 5 hours. The mixture is then left on 2 hours and then add 75 g of dry ammonium chloride in small pieces. After 12 hours, it is added with cooling Add 1 liter of a saturated ammonium chloride solution to the reaction mixture, then water, and then extract it with ether. the The essential extracts are washed with water, with a 10% tartrate solution and again with water. One dries the organic phase using anhydrous sodium sulfate and the solvent is evaporated. 1.46 kg of crude product are obtained, its

Distillation yielded 762 g of 3-ethyl-1-pentyn-3-ol. Boiling point 136 °, n ^ ° = 1.4378-1.4 ^ 82.

112 g of 3-ethyl-1-pentyn-3-ol are dissolved in 100 ml of methanol hydrogenated in the presence of the Lindlar catalyst. After admission the theoretical amount of hydrogen is filtered off from the catalyst and the methanolic solution is concentrated. Man receives 151 g of crude 3-ethyl-1-penten-3-ol, its distillation

PO yields 89.1 g of pure product with a boiling point of 74 ° / ö5 mm Hg, η = 1.4372.

Example 2

39.2 g (0.2 mol) of 3-ethyl-1-pentin-3-yl-oc-methylbutyrate are hydrogenated in the presence of 3 g of Lindlar catalyst at 20 ° under atmospheric pressure. After taking the theoretical Amount of hydrogen (5000 ml), the hydrogenation is interrupted. The catalyst is filtered off and the reaction product distilled. 27.7 g (70% yield) of 3-ethyl-1-penten-3-yl-a-methylbutyrate are obtained.

The 3-ethyl-1-pentin-3-yl-a-methylbutyrate used as starting material can be obtained as follows:

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In a four-necked flask equipped with a condenser, dropping funnel, thermometer and stirrer, 56 g (0.5 mol) of 3-ethyl-1-pentyn-3-ol are added dropwise at 20 ° to 102 g (0.55 mol) of a-methylbutyric anhydride (containing 1 g of orthophosphoric acid). The temperature is then held at 60 ° for three hours. The reaction mixture is poured onto ice; it is then extracted with pentane. The organic layer is washed with water, with a saturated sodium carbonate solution, and again with water. After drying and evaporation of the solvent, 13 ² ^ g of crude product are obtained which is distilled under vacuum. One gets so 79 * ^ S 3-ethyl-lpentin-3-yl-a-rnethylbutyrat (81 $ yield), bp 93-9 ^J f ° / 15 mm Hg. ngo = 1.4350.

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Claims (21)

Claims l) Process for the preparation of 3-ethyl-1-penten-3-yld-methylbutyrate, characterized in that one a) 3-ethyl-1-penten-3-ol esterified with o (-liethylbutyric acid, or that one b) 3-ethyl-1-pentin-3-yl - «(- ethylbutyrate partially hydrogenated. 2. Process for improving the odor properties of fragrance compositions, characterized in that nan these compositions 3-ethyl-l-penten- "3-yl - ^ -: aethyroutyrat incorporated. 3. The method according to claim 2, characterized in that a fragrance composition 3-ethyl-1-penten-3-yl - «'tmethylbutyrat Incorporated with traces of 3-ethyl-1-penten-3-ol. 4. The method according to claim 3, characterized in that that the weight ratio of the traces of 3-ethyl-1-penten-3-ol -2 -5 to 3-ethyl-1-penten-3-yl - «<- ethyl butyrate 10 to 10 to 1 amounts to. 5. The method according to claim 4, characterized in that the weight ratio of the traces 3-ethyl-1-penten-3-ol to 3-cheats. to 3-ethyl-1-penten-3-yl ~ o ~ -ethylbutyrate 10 to 10 to 1 6. Process for the production of smell of fkoiaposit ionen, characterized by dr.üü nan 3-ethyl-1-penten-3-yl- <H- ^ ethylbutyrate with odoriferous substances which are per se customary in such compositions and / or carrier material! 209837/1217 7. The method according to claim 6, characterized in that that 3-ethyl-1-penten-3-yl-o (-raetbyruutyrat and traces of 3-Aethyl-1-penten-3-ol with per se in such compositions common fragrances and / or carrier materials mixed, 8. The method according to claim 7, characterized in that that the weight ratio of the traces of 3-ethyl-1-penten-3-ol to 3-ethyl-1-penten-3-yl-ef-diethylbutyrate is 10 to 10 amounts to. 9. The method according to claim 0, characterized in that the weight ratio of the traces of 3-ethyl-1-penten-3-ol ^ p a to 3-ethyl-1-penten-3-yl-oH! iethylbutyrat 10 to 10 amounts to. 10. Fragrance composition, characterized by a Content of 3-ethyl-1-1-penten-3-yl-c <-2iethylbutyrate. 11. Fragrance composition, characterized by a content of 3-ethyl-1-penten-3-yl-c <-uiethylbutyrat with traces of 3-ethyl-l ~ penten-3-ol. 12. fragrance composition according to claim 11, characterized in that that the weight ratio of the traces 3-ethyl-l- _2 penten-3-ol to 3-ethyl-1-penten-3-yl ^ -inethylbutyrate 10 bis 10 to 1. 13. Fragrance composition according to claim 12, characterized in that clc.3S the weight loss of the traces of 3-ethyl-l-penten-3-ol to 3-ethyl-1-penten-3-yl-cC-i: iethylbutyrate 10 bis 10 ~ ^ to 1 equals. 14. Use of 3-ethyl-1-penten-3-yl-cf-methylbutyrate as a fragrance for the division of perfumes \ md jpaffJiaierton 209837/1217 Products. 15. The use of J-ethyl-l-penten-S-yl-ef-methylbutyrate with traces of 3-ethyl-l-penten-3-ol as a perfuming ingredient for the preparation of perfumes and perfumed products before _#. 16. Use of 3-ethyl-1-penten-3-yl-o (-inethylbut7rate with 1 to 0 _r 001 ^> 3-ethyl-1-penten-3-ol as a fragrance substance for the production of perfumes and perfumed products. 17. Use of 3-ethyl-1-penten-3-yl-aqueous butyrate with 0.1 to 0.01 # 3-ethyl-1-penten-3-ol as a fragrance for the preparation of perfumes and perfumed products. 209837/1217 18. 3-Ethyl-1-pent-en-3-yl-tf-diethyl butyrate. 19. 3-Aethyl-1-penten-3-yl-c <-Eiethylbutyrat with traces of 3-A ethy1-1-penten-3-ol. 20. 3 - /. Ethy 1-1-penten-3-yl-vi-ynethyl butyrate with 1 to 0.001 # 3-ethyl-1-penten-3-ol. 21. ^ -AGthyl-1-penten ^ -yl - ^ - methylbutyrate with 0.1 to 0.01 $ 3-ethyl-1-penten-3-ol. 209837/1217