PL243564B1 - Application of 5-phenyl-3-methyl-2-cyclohexenone - Google Patents

Abstract

The subject of the invention is the use of 5-phenyl-3-methyl-2-cyclohexenone for the production of fragrance compositions and as a component of perfume compositions. The subject of the invention is also a fragrance composition containing 5-phenyl-3-methyl-2-cyclohexenone as a substance imparting fragrance, in an amount from 1.0 to 3.0% by weight. in relation to the weight of the composition and solvents, fixing agents and other auxiliary agents.

Description

Description of the invention

The subject of the invention is 5-phenyl-3-methyl-2-cyclohexenone and its use as a fragrance and a component of a fragrance composition.

Ketones constitute a large group of compounds characterized by a variety of odors. The intensity of the odor of ketones, like other compounds, weakens as their molar mass increases. Ketones containing more than 18 carbon atoms in the molecule are generally odorless. Of the cyclic ketones, the most interesting in terms of smell are the alkyl derivatives of cyclopentanone and cyclohexanone. Cyclopentanone and cyclohexanone have an almond-mint scent. The introduction of a methyl group into the ring of these ketones modifies the odor, so 2-methylcyclohexanone has a mint-almond odor, 3-methylcyclohexanone has a mint-camphor odor, and 2,2,6-trimethylcyclohexanone has a sharp, thujone odor with a slight honey note.

Derivatives of cyclopentenones, e.g. jasmon - 3-methyl-2-(pent-2-enyl)-cyclopent-2-en-1-one and isojasmon - 3-methyl-2-pentylcyclopentone, are valuable in perfumery, with a beautiful, lasting scent of jasmine. -2-en-1-on.

Odorous ketones are also found among cyclohexenone derivatives, e.g. 3-methyl-2-cyclohexenone has a strong nutty-caramel odor. The presence of a larger number and larger alkyl substituents in the cyclohexene ring affects the smell of the ketone, often giving it a herbal, woody note. Examples include: isophorone - 3,5,5-trimethyl-2-cyclohexenone with a camphor-mint scent with a green-floral note, 4-isopropyl-2-cyclohexenone with a sharp woody-caraway scent, 3-methyl-5-propyl- 2-cyclohexenone with a warm, spicy-woody scent and megastigmadienone - 3-(but-2-enyl)-2,4,4-trimethyl-2-cyclohexenone with a beautiful, lasting floral-fruity scent with a hint of tobacco.

The smell of cyclic ketones depends strongly on the size of the ring. Rings containing 15-17 carbon atoms, both saturated and unsaturated, cycketones (so-called macrocyclic ketones) are characterized by a musky scent that is exceptionally valuable in perfumery. In this group, civetone - cycloheptadec-9-en-1-one and muscone - 3-methylcyclo-pentadecanone are of particular importance. The muscone analogue is: 14-methylcyclopentadec-5-en-1-one, cyclopentadecanone and cycloheptadecanone. These are natural fragrance compounds of animal origin, they can be obtained from natural sources, but their synthetic substitutes are also used, which are identical in chemical and sensory terms.

Macrocyclic ketones, apart from a specific musky scent and an animal, slightly fecal note, perfectly preserve, strengthen and "bouquet" the scent of the perfume composition.

Scented ketones are also present among terpenoids. A monocyclic terpene ketone, namely 5-isopropenyl-2-methyl-2-cyclohexenone carvone (p-mentha-6,8-dien-2-one), with a penetrating, refreshing caraway scent, enjoys great interest, not only in perfumery. , with spicy and herbal notes and menthone - 2-isopropyl-5-methylcyclohexanone (p-menthan-3-one), with a fresh green-mint scent.

This group of ketones also includes bicyclic monoterpenoids, such as camphor - 2-bornanone with a camphor-like scent with spicy and exotic notes and fenchone - 1,3,3-trimethyl-2-norbornanone with a camphor-like scent.

State of the art

In the fragrance industry, there is constant interest in developing new fragrances that allow the creation of new fragrance oils that are used in perfumes and other products requiring a specific scent, such as cosmetics, detergents, etc. There is a constant search for new, surprising fragrance compositions that are durable and unchanging. odor during storage of the composition and safe for health. Fragrances containing cyclic ketones are known in the art.

US 3,962,148 discloses the use of 4,4,6-trimethyl-2-cyclohexenone as a deodorant and especially as a valuable ingredient for the production of substitutes for certain natural oils. 4,4,6-Trimethyl-2-cyclohexenone has a warm, herbal, minty, camphorous scent, especially useful in adding accents to a fragrance composition. It can be a valuable ingredient in perfume compositions.

EP 2,687,586 discloses the use of certain cyclohexenones as agents for further enhancing the olfactory sensation and aroma and/or flavor compositions. Single compounds or their mixtures, preferably selected ones, may be used to enhance the odor properties

PL 243564 Β1 from the group consisting of 2,3,4,5-tetramethylcyclohex-2-en-1-one and 3-ethyl-5-isopropyl-2-methylcyclohex-2-en-1-one. The fragrance and/or flavor composition according to the invention may be incorporated into flavored products, in particular nutritional, oral care or perfume preparations. Such products routinely contain ingredients that perform functions other than creating flavor or fragrance (e.g. dyes) and/or are already a ready-made commercial product (e.g. perfume oil).

However, US9975838 discloses a simple, inexpensive and reliable new method for the synthesis of cyclohexenone and cyclohexenol compounds, wherein the mentioned compounds can be used in particular in the perfume, cosmetics and detergent industries, and these compounds have specific odors and odor persistence properties. The method according to the invention consists in the condensation of a ketone with α-methylene aldehyde in order to obtain cyclohexenone compounds of formula (I), (II) or (III) in a domino reaction.

Moreover, US 7,569,733 discloses a compound of formula (VII) 6-methyl-4-(2',2 ^, ,3 ^, -trimethyl-3'- cyclopenten-1'-yl)-2-cyclohexen-1-ol, a substance a fragrance or fragrance composition containing such a compound and a perfumed or flavored product containing such a compound. The invention also relates to the use of a compound of formula (VII) as a fragrance and/or for improving the binding of a fragrance or fragrance composition. Furthermore, the invention relates to a method for preparing a compound of formula (VII), a method for preparing a precursor of a compound of formula (VII) and the precursor itself. Also relates to a method of producing, enhancing or modifying the sandalwood fragrance in the mixture. From the above review, it is known that in the state of the art there are known fragrance compounds from the group of cyclic ketones or their derivatives, which are used in industry. However, due to the need for new fragrances that will have better aromatizing properties or will provide longer-lasting fragrance compositions, there is a constant need for further research on further compounds from the group of cyclic ketones.

The inventors found that 5-phenyl-3-methyl-2-cyclohexenone has odorous properties. So far, this compound has not been characterized in the literature regarding its odor.

The subject of the invention is the use of 5-phenyl-3-methyl-2-cyclohexenone of formula 1 for the production of fragrance compositions, preferably as a component of perfume compositions.

The invention also provides a fragrance composition which contains 5-phenyl-3-methyl-2-cyclohexenone of formula 1 as a fragrance substance, in an amount from 1.0 to 3.0% by weight. in relation to the weight of the composition and solvents, fixing agents and other auxiliary agents.

The invention concerns the use of 5-phenyl-3-methyl-2-cyclohexenone of formula 1 for the production of fragrance compositions.

Pattern 1.

-phenyl-3-methyl-2-cyclohexenone

The ketone according to the invention is characterized by a pleasant, floral and fruity smell with a sweet and sour note of kiwi and a threshold concentration of 100 ppm.

This ketone can be used as a component of the middle note of a perfume composition. The invention also includes a fragrance composition containing 5-phenyl-3-methyl-2-cyclohexenone as a fragrance substance in an amount from 1.0 to 3.0% by weight relative to the weight of the composition. The composition may additionally include solvents, fixatives and other ingredients appropriate to the composition of the product for which the composition is intended.

Example 1

The synthesis of 5-phenyl-3-methyl-2-cyclohexenone was carried out in two stages [R. N. Lacey, J. Chem. Soc. (1960) 1625]. In the first stage, 6-acetyl-5-phenyl-3-methyl-2-cyclohexenone was obtained in the condensation reaction of acetylacetone with benzylideneacetone in the presence of sodium methoxide, and in the second stage, the obtained product was deacetylated in an aqueous sodium hydroxide solution.

In the first stage, 30 ^cm3 of anhydrous methanol and 2.0 g of metallic sodium cut into slices were poured into a round-bottom flask equipped with a thermometer, a Dean-Stark cap and a reflux condenser. After the metal had reacted, a mixture containing 152.0 g (1.518 mol) of acetylacetone and 130.0 g (0.889 mol) of benzylideneacetone was poured into the flask in one portion. The mixture was heated to reflux, collecting volatile products in the cap, until the temperature in the flask reached 182°C (1.5 hours). After cooling the contents of the flask to room temperature, diethyl ether (150 cm ³ ) was added and transferred to a separating funnel with a capacity of 1 dm ³ , then washed with a 10% sulfuric acid solution (100 cm ³ ) and then with two portions of water (100 cm ³ each) . The separated organic phase was dried over anhydrous magnesium sulfate. The extract was evaporated under reduced pressure (evaporator) to obtain a crude, liquid product in the form of a light brown liquid weighing 238.5 g. The product was distilled under reduced pressure (water pump), collecting the main fraction in the temperature range of 190-210°C/20 hPa. The obtained main fraction was subjected to repeated distillation under reduced pressure (oil pump), separating the product in the form of a light yellow, viscous liquid with a boiling point of 146-150°C / 0.27 hPa and a mass of 145.7 g, yield 71.8%.

In the second stage of the synthesis, 6-acetyl-5-phenyl-3-methyl-2-cyclohexenone purified as above and a sodium hydroxide solution (80 g of NaOH in 600 cm ³ of water) were placed in a round-bottomed flask with a capacity of 1 dm ³ equipped with a reflux condenser and heated to boiling for 30 minutes. After cooling, the post-reaction mixture was transferred to a separatory funnel with a capacity of 1 dm ³ and extracted three times with diethyl ether, each in 50 cm ³ portions. The ether extracts were combined, washed with a 10% sulfuric acid solution (100 cm ³ ) and twice with water in 100 cm ³ portions with the addition of a few drops of acetic acid to remove the emerging emulsions. The organic phase was dried with anhydrous magnesium sulfate. The dried extract was evaporated under reduced pressure (evaporator) to obtain a light brown, viscous liquid. The crude product was subjected to fractional distillation under reduced pressure (water pump), obtaining 5-phenyl-3-methyl-2-cyclohexenone as a slightly yellowish, quite viscous liquid with a boiling point of 182-3°C / 19 hPa (exp), mp. 179-181°C / 16 hPa (lit.) [J. Org. Chem., 13 (1948) 31] with a mass of 103.1 g (86.8%). The final yield is 62.3% (after two steps). After three days of storage at room temperature, the distillate solidifies, melting point 35-6°C (exp), 36-7°C (lit.) [J. American Chem. Soc., 75 (1953) 2635]. As a result of further purification of the product by crystallization from methanol with the addition of activated carbon, it was obtained in the form of a colorless solid. Crystallization efficiency approximately 70%.

The obtained 5-phenyl-3-methyl-2-cyclohexenone has a pleasant, floral and fruity smell with a sweet and sour kiwi note. There were no changes in its physicochemical or odor properties within 6 months from the date of its synthesis.

Example 2 Fragrance composition containing 5-phenyl-3-methyl-2-cyclohexenone - bergamot oil 20% by weight - grapefruit oil 20% by weight - lemon oil 15% by weight - lavender oil 10% by weight - geraniol 10% by weight - linalool 5% by weight - sage absolute 5% by weight - MuskT synthetic musk 5% by weight - nerol 3% by weight - 5-phenyl-3-methyl-2-cyclohexenone 3% by weight - citral 2% by weight - terpinyl acetate 2% by weight Together 100% by weight The composition has a fruity and floral scent

PL 243564 Β1

Claims (3)

Patent claims 1. Use of 5-phenyl-3-methyl-2-cyclohexenone of formula 1 (formula 1) for the production of fragrance compositions. 2. Use according to claim 1, characterized in that 5-phenyl-3-methyl-2-cyclohexenone is used as an ingredient of perfume compositions. 3. A fragrance composition characterized by containing 5-phenyl-3-methyl-2-cyclohexenone of formula 1 as defined in claim. 1 As a fragrance, in an amount from 1.0 to 3.0% by weight. in relation to the weight of the composition and solvents, fixing agents and other auxiliary agents.