Novel aldehydes and nitriles, obtained from isophorone, and application thereof in perfumery

FIELD: chemistry.

SUBSTANCE: invention relates to novel compounds of formula (I), which can be applied as an aromatic compound or a smell-masking agent. In formula (I) R stands for a hydrogen atom, C1-C6 alkyl, C2-C6 alkenyl or =CH2; Z stands for CN or CHO; and there is not more than one dashed bond. The following conditions must be observed: if Z stands for CHO and there is one of the dashed bonds, R does not stand for a hydrogen atom, and if there is a dashed bond between carbons Ca and Cb, R does not stand for a group = CH2. The invention also relates to a method of obtaining a formula (I) compound, its application as the aromatic compound or the smell-masking agent, and a perfumery composition.

EFFECT: increased activity of the composition application.

10 cl, 1 tbl, 10 ex

 

The present invention relates to new aldehydes and NITRILES derived from isophorone with special fragrance, as well as to the use of these compounds in perfumery.

The term "perfume" is used in this description to refer only to perfume in the traditional sense of the term, but also to cover other areas where the smell of food is important. We can talk about perfume compositions in the usual sense of the word, such as perfume bases or concentrates, colognes, toilet water, perfumes and similar products; compositions for local application - in particular, the cosmetic compositions such as creams for face and body, talc powder, oil for hair, shampoo, hair lotions, salts and oils for baths, shower gels and bath soap, toilet soap, antiperspirants and deodorants for body lotions and shaving creams, Soaps, creams, toothpastes, rinsing the mouth, lipstick and similar products; and tools for cleaning the house, such as softeners, detergents, cleansers, deodorants for rooms and similar products.

The terms "aromatic substance", "fragrant", "odorous" used in the description interchangeably with respect to any organoleptic compounds that stimulate pleasant olfactory sensations.

By the expression "mask" or "mask" refers to reducing or eliminating the perception of a bad smell or bad taste, the generated one or more molecules comprising the composition of the product.

Numerous derivatives of cyclopentane type, in particular compounds, including the skeleton campolina, or Cyclopentanone described in the literature due to their interesting olfactive properties. For example, in patent applications US 5073538, EP 0146859, US 4477683 and Bruns et al. (Bruns, K.; Weber, U.;Development in food science,1998, 18 (F&F), 767-776) described derivatives 2,4,4-trimethylcyclopentanone, some of which are of interest for use in the perfume industry. In addition, the literature describes very little of compounds of the type of NITRILES or aldehydes derived 2,4,4-trimethylcyclopentanone (US 3931143, US 4477683 and Wheler O. H.; De Rodriguez E. G.;J. Org.Chem.,1964, 29(3), 718-721), and in none of these documents do not describe their olfactive properties.

In General, in the perfume industry there is a continuing need for new molecules of odoriferous substances, in order to expand the range of music offered by the perfumers to create their products. In addition, this need increases as the perfume industry is facing tougher international regulations, as well as awareness of environmental problems and with increasing demands from consumers. Thus, the purpose of the present invention is to provide new and sweet/what do odorous compounds.

The present invention relates to new aldehydes and NITRILES derived from isophorone. The advantage of these compounds is that they receive reliable and inexpensive.

Thus, the present invention relates to compounds of General formula (I) below:

in which:

R denotes a hydrogen atom, a C1-C6alkyl, C2-C6alkenyl or =CH2;

Z represents CN or CHO; and

there is no more than one of the dashed relations;

provided that:

if Z denotes the SNO and has one of the dashed relations, then R does not denote a hydrogen atom, and

if there is a dashed bond between carbon Ca and Cb, then R does not denote the group =CH2.

The term "C1-C6alkyl" in the context of the present invention involve any monovalent radical derived from a saturated carbon chain, either linear or branched, containing 1 to 6 carbon atoms, in particular methyl, ethyl,npropyl, ISO-propyl,nbutyl, ISO-butyl, tert-butyl, pentyl and hexyl. The preferred alkilani are methyl, ethyl,n-propyl, ISO-propyl,nbutyl, ISO-butyl,npencil.

The term "C2-C6alkenyl" in the context of the present invention involve any monovalent organic radical which is derived the carbon chain, linear or branched, containing from 2 to 6 carbon atoms that includes at least one double bond, in particular ethynyl,npropenyl, ISO-propenyl,n-butenyl, ISO-butenyl, tert-butenyl,npentenyl andnhexenyl. The preferred alkenylamine are ethynyl,npropenyl, ISO-propenyl,n-butenyl, ISO-butenyl, andnpentenyl.

The present invention also relates to stereoisomers of formula (I), in particular to diastereoisomerism formula (I), and mixtures of these isomers in any ratio.

In particular, the present invention relates to compounds of General formula (Ia):

in which:

R denotes a hydrogen atom, a C1-C6alkyl, C2-C6alkenyl or =CH2;

Z represents CN or CHO;

the compounds of General formula (Ib) and (Ic):

in which:

R denotes a hydrogen atom, a C1-C6alkyl, C2-C6alkenyl or =CH2;

Z denotes a group CN or CHO; and

provided that, if Z denotes the SSS, then R is not a hydrogen atom;

the compounds of formula (Ib) and (Ic), as well as to compounds of General formula (Id):

in which:

R denotes a hydrogen atom, a C1-C6alkyl or C2-C6alkenyl;

Z represents CN or CHO; and

if what if Z denotes SNO, then R is not a hydrogen atom.

According to the first form of the present invention relates to compounds of General formula (I'):

in which:

R denotes a hydrogen atom, a C1-C6alkyl, C2-C6alkenyl or =CH2; preferably R represents a hydrogen atom, alkyl With1-C6or =CH2; more preferably R represents a hydrogen atom, methyl, ethyl,n-propyl, ISO-propyl or =CH2; still more preferably R represents a hydrogen atom, methyl or =CH2; and there is at most one dotted ties;

provided that when the dotted bonds between carbons CA and Cb, R is the group =CH2.

Particularly interesting compounds of formula (I') are compounds (1) to(6), are presented in table 1.

The first variant implementation of this option relates to compounds of formula (Ia'):

in which:

R denotes a hydrogen atom, a C1-C6alkyl, C2-C6alkenyl or =CH2; preferably R represents a hydrogen atom, a C1-C6alkyl or =CH2; more preferably R represents a hydrogen atom, methyl, ethyl,n-propyl, ISO-propyl or =CH2; still more preferably R represents a hydrogen atom, metelli =CH 2.

The second option relates to compounds of formula (Ib'):

in which:

R denotes a hydrogen atom, a C1-C6alkyl, C2-C6alkenyl or =CH2; preferably R represents a hydrogen atom, a C1-C6alkyl or =CH2; more preferably R represents a hydrogen atom, methyl, ethyl,n-propyl, ISO-propyl or =CH2; still more preferably R represents a hydrogen atom, methyl or =CH2.

The third variant of this form of implementation relates to compounds of formula (Ic'):

in which:

R denotes a hydrogen atom, a C1-C6alkyl, C2-C6alkenyl or =CH2; preferably R represents a hydrogen atom, a C1-C6alkyl or =CH2; more preferably R represents a hydrogen atom, methyl, ethyl,n-propyl, ISO-propyl or =CH2; still more preferably R represents a hydrogen atom, methyl or =CH2.

Finally, the last option of this form of implementation relates to compounds of formula (Id'):

in which:

R denotes a hydrogen atom, a C1-C6alkyl or C2-C6alkenyl; preferably R represents a hydrogen atom or a C1-C6alkyl; more preferably R represents a hydrogen atom, IU the sludge, ethyl,n-propyl or ISO-propyl; still more preferably R represents a hydrogen atom or methyl.

According to the second form of implementation of the present invention relates also to compounds of General formula (I):

in which:

R denotes a hydrogen atom, a C1-C6alkyl, C2-C6alkenyl or =CH2; preferably R represents a hydrogen atom, a C1-C6alkyl or =CH2; more preferably R represents a hydrogen atom, methyl, ethyl,n-propyl, ISO-propyl or =CH2; still more preferably R represents a hydrogen atom, methyl or =CH2and there is at most one dotted ties;

provided that when one of the dashed relations, then R is not a hydrogen atom, and

if there is a dashed bond between carbon CA and Cb, then R is not a group =CH2.

Particularly interesting compounds of formula (I) are the compounds (7)-(9) are presented in table 1.

The first version of this form of implementation relates to compounds of formula (Ia”):

in which:

R denotes a hydrogen atom, a C1-C6alkyl, C2-C6alkenyl or =CH2; preferably R represents a hydrogen atom, a C1-C6alkyl or =CH2; more preferably R appears the t hydrogen atom, methyl, ethyl,n-propyl, ISO-propyl or =CH2; still more preferably R represents a hydrogen atom, methyl or =CH2.

The second option relates to compounds of formula (Ib”):

in which:

R denotes a1-C6alkyl, C2-C6alkenyl or =CH2; preferably R represents C1-C6alkyl or =CH2; more preferably R represents methyl, ethyl,n-propyl, ISO-propyl or =CH2; still more preferably R represents methyl or =CH2.

The third option this option implementation relates also to compounds of formula (Ic”):

in which:

R denotes a1-C6alkyl, C2-C6alkenyl or =CH2; preferably R represents C1-C6alkyl or =CH2; more preferably R represents methyl, ethyl,n-propyl, ISO-propyl or =CH2; still more preferably R represents methyl or =CH2.

Finally, the last option of this form of implementation relates to compounds of formula (Id):

in which:

R denotes a1-C6alkyl or C2-C6alkenyl; preferably R represents C1-C6alkyl; more preferably R represents methyl, ethyl,n-propyl or isopropyl; even more preferably R represents methyl.

More specifically, the invention relates to compounds of formula (I) shown in table 1.

The invention includes all enantiomers and diastereoisomeric compounds of formula (I), individually or in the form of a mixture. The presence in the structure of the compounds of formula (I) centers of asymmetry leads to the existence of the enantiomeric forms of each of these compounds. The invention includes compounds represented by the General formula (I), in the form of mixtures of enantiomers in various ratios, in particular racemic mixture. The invention also includes compounds of formula (I) in the form of only one enantiomer. Obtaining mixtures of enantiomers or optically pure forms carried out by methods known to the expert, using, for example, optically enriched or optically pure starting materials.

The advantage of the compounds of formula (I) is that the way of obtaining reliable and inexpensive. Thus, the compounds of formula (I) can be obtained from isophorone.

The present invention relates also to a method for obtaining compounds of formula (I), including the state, which consists in the interaction of the compounds of formula (A):

with diethylphosphonoacetate formula RCH(CN)PO(OC2H5)2in which R is oznachaet a hydrogen atom, With1-C6alkyl or C2-C6alkenyl; preferably R represents a hydrogen atom or a C1-C6alkyl; more preferably R represents a hydrogen atom, methyl, ethyl,n-propyl or ISO-propyl; still more preferably R represents a hydrogen atom or methyl; or alkylsulfates formula NCCH2COOR' in which R' denotes a1-C4alkyl; preferably R' denotes methyl.

In the first stage receive epoxide of isophorone isophorone by epoxidation by Weitz-Scheffer. Rearrangement of the epoxide of isophorone in the acidic environment allows you to get 2,4,4-trimethylcyclopentanone (A).

According to the first variant implementation of the compounds of formula (Ia') and (Id') are obtained according to scheme 1:

Under the action of diethylphosphonoacetate formula RCH(CN)PO(OC2H5)2in which R has the above values, Cyclopentanone of formula (A) obtain the compounds of formula (Id'). This reaction is mainly carried out in the presence of a base, such as an organolithium compound, preferably utility (BuLi) in apolar solvent, such as tetrahydrofuran. Hydrogenation of compounds of formula (Id') allows to obtain the compounds of formula (Ia'), in which R cannot denote =CH2. Hydrogenation OS is p in terms well known to the expert, for example in an autoclave in an atmosphere of hydrogen in the presence of catalyst (5% palladium on coal.

According to the second form of implementation of the compounds of formula (Ib') and (Ic') and compound (5) and (6) are obtained by following scheme 2:

In the first stage, Cyclopentanone of formula (A) condense with alkylsulfates formula NCCH2COOR' in which R' denotes a1-C4alkyl, preferably methyl, with the formation of the compounds of formula (In). The condensation reaction is carried out, for example, in the presence of acetic acid (Asón) and ammonium acetate (AcONH4) in an aprotic apolar solvent, such as cyclohexane, at the boiling point under reflux.

Then according to the first variant connection (In) direct the decarboxylation, with optional subsequent hydrogenation and/or alkylation of compounds of formula (Ia'), (Ib') or (Ic'). The decarboxylation reaction carried out mainly in the presence of alkali metal halide such as lithium chloride, in a polar solvent such as N-organic. The hydrogenation is carried out in conditions well known to the expert, for example in an autoclave in an atmosphere of hydrogen in the presence of catalyst (5% palladium on coal. The alkylation can be carried out through the Yu alkylating agent, selected from allylbromide, alkylated or alkylchloride, and bases, such as, for example, diisopropylamide lithium ortert-butyl potassium. A suitable solvent for this reaction can serve as an apolar solvent, such as tetrahydrofuran or polar aprotic solvent, such as dimethylformamide.

According to the second variant restore the connection of the formula (V) with subsequent de-hydration and, optionally, hydrogenation and receive connections (5) and (6). The recovery is mainly carried out using a hydride such as NaBH4. The hydrogenation reaction carried out under conditions well known to the expert, for example in an autoclave in an atmosphere of hydrogen in the presence of catalyst (5% palladium on coal.

As a rule, the compounds of formula (I) receive a recovery under moderate conditions corresponding nitrile functional groups of compounds of formula (I') to aldehyde functional groups. This recovery can be accomplished, for example, in the presence of hydride diisobutylaluminum (Dibal) in an apolar solvent such as toluene.

In connection with their fragrant properties of the compounds of formula (I) find a wide variety of applications, particularly in perfumery and unlimited in cosmetics, as well as tools for cleaning.

Thus, the invention from OSISA well as the application, at least one of the compounds of formula (I) according to the invention as a fragrant agent or compound, as agent for masking the smell of, or as agent, neutralizing odor, individually or in the form of a mixture with one or more other aromatic compounds known to the expert that the expert chooses depending on the desired effect. Additional or more aromatic agents can be compounds of the formula (I) or other aromatic agents, known to specialists.

For these same reasons, the invention relates also to method of flavoring base product, including the addition compounds according to the invention to the base product. The connection according to the invention can be added individually or in a mixture with one or more other aromatic compounds known to the expert that the expert chooses depending on the desired effect. Additional or more aromatic agents can be compounds of the formula (I) or other means fragrant, well-known specialist. The base product can be, in particular, perfume, in particular perfume or perfume concentrate, eau de Cologne, toilet water or perfume; cosmetic composition, in particular a cream for the face and for the ate, talc powder, hair oil or body, shampoo, hair lotion, bath salt, bath oil, shower gel, bath gel, soap, antiperspirant, body, deodorant, body lotions, shaving cream, shaving soap, cream, toothpaste, mouthwash for oral or lipstick; or means for cleaning the house, in particular emollient, detergent, detergent or deodorant for indoor use.

The invention relates also to compositions comprising a base product and an effective amount of one or more compounds of the formula (I) according to the invention.

We can talk about fragrant compositions per se, or composition, in which the fragrant agent is used to mask or neutralize certain smells.

The base product is easily selected by a specialist depending on the specific composition and, therefore, from the set of usage, for which normal components, such as solvent(s) and/or additive(s), is well known.

An effective amount of compounds of formula (I) according to the invention introduced into the composition depends on the nature of the composition, the desired smell and the nature of other odorous or not compounds, optionally present in the composition, and can easily be determined by a specialist, knowing that it varies widely is m the range from 0.1 to 99 wt.%, more specifically from 0.1 to 50 wt.%, in particular from 0.1 to 30 wt.%.

The compounds of formula (I) according to the invention can be used as such or can be introduced or supported on an inert carrier material or the carrier may contain other active ingredients of the final composition. Can be used a variety of materials-storage media including, for example, polar solvents, oils, fatty substances, finely ground solid products, cyclodextrins, maltodextrins, gums, resins and any other carrier material, known for such compositions.

Thus, the invention relates also to the use of compounds of formula (I) for the preparation of fragrant compositions or create a scented product, designed for applications described above, in particular, in perfumery, cosmetics, for example for the preparation of shampoos or Soaps, and to create products for home cleaning, such as softeners or detergents.

The invention relates, more specifically, to perfume compositions, in particular perfume or perfume concentrate, the eau de Cologne, toilet water, or spirits, including at least one compound of formula (I) or composition comprising at least one compound of formula (I).

In particular, the invention relates to the cosmetic is in transition composition, for example, such as cream for face and for body, talc powder, hair oil or body, shampoo, hair lotion, bath salt, bath oil, shower gel, bath gel, soap, antiperspirant, body, deodorant, body lotions, shaving cream, shaving soap, cream, toothpaste, mouthwash for mouth, lipstick comprising at least one compound of formula (I) or at least one composition comprising, at least one compound of formula (I). Another object of the invention is a method for the cosmetic treatment or cosmetic care with a preventive or other purposes, use at least one compound of formula (I) or at least one composition comprising at least one compound of formula (I).

The invention also relates to means for cleaning the house, in particular, to soft, detergent, cleaning tool, deodorant premises, including at least one compound of formula (I).

Compounds according to the invention can be used individually or in combination, as such, or may be introduced or supported on an inert carrier material or the carrier may contain other active ingredients in the final composition. Can be used a variety of media materials, including, e.g. the, polar solvents, oils, fatty substances, finely ground solid products, cyclodextrins, maltodextrins, gums, resins and any other carrier material, known for such compositions.

The following examples better illustrate the different ways of obtaining new compounds according to the invention and their application and their interest. These examples are presented only for illustrative purposes and may not be considered as limiting the scope of invention.

Example 1: Obtain 2-(2,4,4-trimethylcyclohex-1-enyl)acetonitrile (1) and 2-(3,3,5-trimethylcyclohexane-1-enyl)acetonitrile (2)

Placed in the vessel Cyclopentanone And 1.5 EQ. medicinehat.ca, 1 EQ. acetic acid and 10 molar % of ammonium acetate in cyclohexane. The reaction medium is refluxed to remove water formed by the apparatus type Dean-stark. After boiling during the night conversion And reaches a satisfactory value (>90%) and then give the reaction medium to return to room temperature. Washed with sodium bicarbonate solution, then with salt water. After drying over magnesium sulfate, filtered through paper and the solvent is evaporated, the crude product is distilled under reduced pressure.

T Kip.=80°C/0.3 Torr

Methyl-2-cyano-2-(2,4,4-trimethylcyclopentanone)acetate In place in a vessel with 2 ek is. lithium chloride in a mixture of 98:2 NMP (N-methylpyrrolidone) and water. Stirred at 150°C. After 3 hours the reaction medium is cooled to room temperature, then poured into 1% aqueous HCl. Stirred for a few minutes, then extracted twice with MTBE (methyl-tert-butyl ether). The combined organic layers washed with sodium bicarbonate solution, then with salt water. After drying over magnesium sulfate, filtered through paper and the solvent is evaporated, the crude product is distilled under reduced pressure. Get a mixture of 70:30 2-(2,4,4-trimethylcyclohex-1-enyl)acetonitrile and 2-(3,3,5-trimethylcyclohexane-1-enyl)acetonitrile.

BP.=78-82°C/6 Torr

Olfactive description: the aroma is spicy with notes of cumin, wood, citrus, strong

Major isomer:

1H-NMR (200 MHz, CDCl3): δ (M. D.) a 1.08 (s, 6N), and 1.63 (s, 3H), of 2.15 (s, 2H), 2,25 (s, 2H), is 3.08 (s, 2H).

13C-NMR (50 MHz, CDCl3): δ (M. D.) 17,43, 19,82, 30,07, 30,19, 50,99, 53,84, 121,95, 136,53, 136,54.

MS [e/m (%)]: 149 (M+, 45), 135 (10), 134 (100), 109 (43), 108 (15), 107 (27), 94 (21), 93 (66), 91 (26), 79(22), 77(18), 67 (16), 41 (14), 39 (13).

Minor isomer:

1H-NMR (200 MHz, CDCl3): δ (M. D.) 1,02 of-1.04 (m, 3H), of 1.08 (s, 6H), of 1.10-1.20 (m, 2H), 1,95-2,05 (m, 1H), 3,01 (s, 2H), 5.56mm (s, 1H).

13C-NMR (50 MHz, CDCl3): δ (M. D.) 14,40, 18,22, 28,52, 36,70, 40,77, 48,92, 118,08, 134,15, 139,95.

MC [e/m (%)]: 149 (M+, 53), 148 (22), 135 (11), 134 (94), 122 (10), 120 (12), 109 (26), 108 (35), 107 (48), 106 (22), 94 (38), 93 (48), 92 (15), 91 (27), 83 (100), 0 (19), 79 (27), 77 (23), 69 (37), 67 (21), 66 (30), 65 (22), 56 (20), 55 (33), 54 (10), 53 (15), 51 (11), 43 (10), 41 (41), 39 (31).

IR (film, cm-1): 759w, 840w, 931w, 1070w, 1159w, 1241w, 1315w, m, m, m, m, m, m, s.

Example 2: Obtain 2-(2,4,4-trimethylcyclopentanone)acetonitrile (3)

In an inert atmosphere put 1.1 EQ. diethylphosphonoacetate in THF (tetrahydrofuran). To this product are added dropwise at a temperature of about 10°With 1.1 EQ. solution of utility in hexane. Then stirred for one hour at room temperature and then added dropwise at a temperature of about 10°With 1 EQ. of Cyclopentanone A. the Reaction medium is stirred for several hours at room temperature, then poured into 10% HCl solution. The aqueous layer was extracted three times with MTBE. The combined organic layers washed with sodium bicarbonate solution, then with salt water. After drying over magnesium sulfate, filtered through paper and the solvent is evaporated, the crude product is distilled under reduced pressure. Get a mixture of 75:25TRANSandCISisomers of 2-(2,4,4-trimethylcyclopentanone)acetonitrile.

BP.=85°C/6 Torr

Olfactive description: the aroma of fresh citrus with a hint of citrus fruit, green, strong

Major isomer:

1H-NMR (200 MHz, CDCl3): δ (M. D.) 0,99 (s, 3H), of 1.12 (s, 6H), 1,20-of 1.32 (m, 2H), 1,72-of 1.95 (m, 1H), 2,23-2,61 (m, 1H), was 2.76-2.82 from (m, 1H), 5,12 (s, 1H).

13C-NMR (50 MHz, CDCl3): δ (M. D.) 18,88, 28,01, 29,37, 37,84, 39,22, 48,59, 49,41, 91,17, 117,93, 178,84.

MC [e/m (%)]: 149 (M+, 47), 148 (21), 135 (11), 134 (90), 122 (11), 120 (12), 109 (22), 108 (34), 107 (42), 106 (18), 95 (10), 94 (35), 93 (49), 92 (15), 91 (22), 84 (10), 83 (100), 81 (15), 80 (19), 79 (26), 78 (10), 77 (20), 69 (33), 67 (19), 66 (29), 65 (21), 56 (22), 55 (35), 53 (15), 51 (11), 43 (10), 41 (40), 39 (30).

Minor isomer:

1H-NMR (200 MHz, CDCl3): δ (M. D.) to 0.89 (s, 3H), 1.14 in (s, 6H), 1,20-of 1.32 (m, 2H), 1,72-of 1.95 (m, 1H), 2,23-2,61 (m, 1H), was 2.76-2.82 from (m, 1H), 5,24 (s, 1H).

13C-NMR (50 MHz, CDCl3): δ (M. D.) 19,93, 27,24, 28,88, 38,06, 38,58, 49,63, 50,18, 91,50, 117,93, 178,84.

MC [e/m (%)]: 149 (M+, 12), 135 (10), 134 (100), 109 (17), 107 (11), 94 (20), 93 (82), 91 (21), 79 (20), 77 (14), 41 (12).

IR (film, cm-1): 770w, m, s, 880w, 996w, 1268w, 1320w, m, m, m, s, s, s, m, s.

Example 3: Obtain 2-(2,4,4-trimethylcyclopentanone)acetonitrile (4)

A solution containing 1 equivalent mixture of compounds 1 and 2 obtained in example 1 in toluene and 5 wt.% 5% palladium on coal placed in an autoclave under a hydrogen pressure of 20 bar and at a temperature of 40°C. At the end of the reaction, the autoclave is rinsed with nitrogen and the solution is filtered through celite. The filtrate is concentrated. The obtained crude product in the form of two diastereoisomers in the ratio of 70:30 purified by distillation.

T Kip.=80°C/6 Torr

Olfactive description: the scent of green, fresh with a hint of zest, strong

Major isomer:

1H-NMR (200 MHz, CDCl3): δ (M. D.) 0,92-1,08 (m, 3H), 1.04 million (s, 6H), 1,15-of 1.42 (m, 2H), 1.60-to 1,87 (who, 3H), 2,23 is 2.44 (m, 3H).

13C-NMR (50 MHz, CDCl3): δ (M. D.) 18,82, 21,33, 31,54, 37,09, 39,94, 43,66, 47,86, 50,59, 119,42.

MC [e/m (%)]: 151 (M+, 0,3), 136 (39), 119 (20), 111 (21), 108 (16), 96 (13), 95 (100), 83 (67), 82 (26), 69 (30), 67 (18), 56 (11), 55 (25), 41 (28), 39 (14).

Minor isomer:

1H-NMR (200 MHz, CDCl3): δ (M. D.) 0,92-1,08 (m, 3H), 1.04 million (s, 6H), 1,15-of 1.42 (m, 2H), 1.60-to to 1.87 (m, 3H), 2,23 is 2.44 (m, 3H).

13C-NMR (50 MHz, CDCl3): δ (M. D.) 16,16, 19,29, 30,43, 35,47, 37,09, 39,04, 46,71, 49,42, 120,36.

1H-NMR (200 MHz, CDCl3): (M. D.) 0,92-1,08 (m, 3H), 1.04 million (s, 6H), 1,15-of 1.42 (m, 2H), 1.60-to to 1.87 (m, 3H), 2,23 is 2.44 (m, 3H).

13C-NMR (50 MHz, CDCl3): (M. D.) 18,82, 21,33, 31,54, 37,09, 39,94, 43,66, 47,86, 50,59, 119,42.

MS [e/m (%)]: 151 (M+, 0,3), 136 (39), 119 (20), 111 (21), 108 (16), 96 (13), 95 (100), 83 (67), 82 (26), 69 (30), 67 (18), 56 (11), 55 (25), 41 (28), 39 (14).

1H-NMR (200 MHz, CDCl3): (M. D.) 0,92-1,08 (m, 3H), 1.04 million (s, 6H), 1,15-of 1.42 (m, 2H), 1.60-to to 1.87 (m, 3H), 2,23 is 2.44 (m, 3H). δ (M. D.) 16,16, 19,29, 30,43, 35,47, 37,09, 39,04, 46,71, 49,42, 120,36.

MC [e/m (%)]: 151 (M+, 0,2), 136 (25), 119 (13), 111 (29), 109 (10), 108 (20), 96 (27), 95 (100), 94 (11), 84 (16), 83 (69), 82 (31), 81 (11), 69 (52), 68 (10), 67 (20), 56 (24), 55 (29), 53 (11), 41 (34), 39 (17).

IR (film, cm-1): 931w, 1064w, 1316w, m, m, 14124, m, m, m, s, s.

Example 4: Obtain 2-(2,4,4-trimethylcyclopentanone)Acrylonitrile (5)

1.1 EQ. sodium borohydride is placed in an inert atmosphere in ethanol at 10°C. To this mixture is added dropwise methyl-2-cyano-2-(2,4,4-trimethylcyclopentanone)acetate Century Reaction medium is stirred overnight at room temperature, then neutralized AC the tone. The mixture is then poured into cold 10% HCl solution. Extracted the aqueous layer twice with MTBE. The combined organic fractions washed with sodium bicarbonate solution, then brine. After drying over magnesium sulfate, filtered through paper and the solvent is evaporated, get 3-hydroxy-2-(2,4,4-trimethylcyclopentanone)propanenitrile in the form of four diastereoisomers in the ratio 11:13:23:53.

3-hydroxy-2-(2,4,4-trimethylcyclopentanone)propanenitrile placed in an inert atmosphere in dichloromethane at 10°C. To this mixture of 2.2 EQ. DBU (diazabicyclo[5.4.0]undec-7-ene) and a few crystals of DMAP (4-dimethylaminopyridine), then added dropwise with 1.2 EQ. triperoxonane anhydride. The reaction medium is stirred overnight at room temperature, then poured into water. The aqueous layer was extracted once with dichloromethane. The combined organic fractions washed with water. After drying over magnesium sulfate, filtered through paper and the solvent is evaporated, the crude product is obtained in the form of two diastereoisomers in the ratio of 70:30, purified by distillation under reduced pressure.

BP.=35°C/of 0.3 Torr

Olfactive description: the scent of green, fruity with notes of peach skin, honey.

Major isomer:

1H-NMR (200 MHz, CDC13): δ (M. D.) of 0.85 (d, J=7.2 Hz, 3H), 0,96 was 1.06 (m, 6H), 1,10-1,1 (m, 2H), 1,64 of-1.83 (m, 4H), 2,17-2,48 (m, 1H), 2,55-of 2.64 (m, 1H).

13C-NMR (50 MHz, CDCl3): δ (M. D.) 18,94, 31,70, 40,84, 42,07, 46,98, 48,61, 49,20, 50,39, 203,41.

MC [e/m (%)]: 163 (M+, 1), 148 (21), 121 (10), 120 (12), 107 (10), 106 (40), 84 (100), 83 (15), 79 (21), 77 (13), 55 (16), 41 (21), 39 (13).

Minor isomer:

1H-NMR (200 MHz, CDCl3): δ (M. D.) of 0.85 (d, J=7.2 Hz, 3H), 0,96 was 1.06 (m, 6H), 1,10-1,17 (m, 2H), 1,64 of-1.83 (m, 4H), 2,17-2,48 (m, 1H), 2,55-of 2.64 (m, 1H).

13C-NMR (50 MHz, CDCl3): δ (M. D.) 16,94, 30,64, 35,64, 36,46, 46,12, 48,51, 49,67, 50,65, 203,41.

MC [e/m (%)]: 163 (M+, 0,4), 148 (12), 106 (29), 84 (100), 79 (17), 77 (11), 69 (46), 55 (11), 41 (18), 39 (11).

IR (film, cm-1): 841w, s, 1078w, 1195w, 1294w, m, m, 1407w, m, m, m, m, s.

Example 5: Obtain 2-(2,4,4-trimethylcyclopentanone)propanenitrile (6)

A solution containing 1 equivalent of 2-(2,4,4-trimethylcyclopentanone)Acrylonitrile, 5 in toluene and 5 wt.% 5% palladium on coal, placed in an autoclave under a hydrogen pressure of 20 bar and at a temperature of 40°C. At the end of the reaction, the autoclave is rinsed with nitrogen and the solution is filtered through celite. The filtrate is concentrated. The crude product is obtained in the form of four diastereoisomers in the ratio 8:18:22:52, purified by distillation.

BP.=46°C/0,7 Torr

Olfactive description: the scent of green, sharp, with a hint of sage, woody.

4 Overlapping isomer:

1H-NMR (200 MHz, CDCl3): δ (M. D.) 0,91-of 1.03 (m, 6H), 1,09-1,11 (m, 3H), 1,31-of 1.92 (m, 2H), 1,25-of 1.39 (m, 3H), 1,72-of 1.74 (m, 1H), 2.21 are 2,43 (m, 1H), 2,59-2,84 (m, 1H).

13C-NMR and 50 MHz, CDCl3major isomer (52%)): δ (M. D.) 16,51, 20,91, 28,73, 30,88, 30,99, 35,95, 38,42, 46,23, 49,64, 50,78, 123,32.

MC [e/m (%)] isomer in the amount of 52%: 165 (M+, 1), 150 (49), 133 (32), 111 (65), 109 (10), 96 (19), 95 (100), 83 (54), 81 (14), 69 (69), 67 (14), 56 (11), 55 (43), 53 (11), 41 (32), 39 (14).

MC [e/m (%)] isomer in the amount of 22%: 165 (M+, 0,4), 150 (57), 133 (26), 111 (33), 96 (14), 95 (100), 83 (68), 81 (11), 69 (47), 67 (12), 55 (34), 41 (25), 39 (12).

MC [e/m (%)] isomer in the amount of 18%: 165 (M+, 0,3), 150 (31), 133 (17), 122 (11), 111 (84), 110 (17), 109 (19), 96 (19), 95 (83), 94 (11), 84 (29), 83 (54), 82 (13), 81 (15), 69 (100), 67 (17), 56 (18), 55 (49), 53 (13), 41 (40), 39 (17).

MC [e/m (%)] isomer in the amount of 8%: 165 (M+, 0,1), 150 (29), 133 (19), 111 (87), 110 (16), 109 (18), 96 (15), 95 (83), 94 (14), 84 (32), 83 (56), 82 (13), 81 (17), 69 (100), 67 (15), 56 (15), 55 (49), 53 (11), 41 (38), 39 (16).

IR (film, cm-1): 979w, 1103w, 1197w, 1319w, m, m, m, m, m, s.

Example 6: Obtain 2-(2,4,4-trimethylcyclopentanone)acetaldehyde (7)

2-(2,4,4-trimethylcyclopentanone)acetonitrile 4 is placed in an inert atmosphere in toluene at a temperature of 10°C. To this mixture is added dropwise with 1.2 EQ. Dibal-H (hydride diisobutylaluminum). The reaction medium is stirred for several hours at room temperature, then poured into a mixture of 20:40:40 acetic acid, water and ice. The aqueous layer was extracted once with toluene. The combined organic layers washed with sodium bicarbonate solution, then with salt water. After drying over magnesium sulfate, filtered through paper and the solvent is evaporated, the crude product is obtained in the form of two is diastereoisomers in the ratio of 70:30, purify by distillation under reduced pressure.

BP.=50°C/of 0.3 Torr

Olfactive description: the aroma of a pronounced green, citrus, spicy, with a hint of cumin, very strong.

Major isomer:

1H-NMR (200 MHz, CDCl3): δ (M. D.) 1,05 (2D, J=7,0 Hz and J=6.8 Hz, 6H), 1,57-of 1.64 (m, 2H), 1,94-to 1.98 (m, 1H), 2,28 to 2.35 (m, 1H), 2,52-a 2.71 (m, 2H), 7,14-7,28 (m, 5H), 9,65 (s, 1H).

13C-NMR (50 MHz, CDCl3): δ (M. D.) 10,26, 17,71, 33,71, 33,91, 35,43, 51,88, 126,27, 128,71 (2C), 128,81 (2C), 142,49, 205,95.

MC [e/m (%)]: 154 (M+, 2), 110 (35), 95 (100), 69 (21), 55 (17), 41 (17).

Minor isomer:

1H-NMR (200 MHz, CDCl3): δ (M. D.) 0,89 (2D, J=7,0 Hz and J=6.8 Hz, 6H), 1,57-of 1.64 (m, 2H), 1,94-to 1.98 (m, 1H), 2,28 to 2.35 (m, 1H), 2,52-a 2.71 (m, 2H), 7,14-7,28 (m, 5H), for 9.64 (s, 1H).

13C-NMR (50 MHz, CDCl3): δ (M. D.) 8,57, 15,78, 32,59, 34,02, 36,97, 50,93, 126,27, 128,71 (2C), 128,81 (2C), 142,49, 205,95.

MC [e/m (%)]: 154 (M+, 0,5), 110 (36), 109 (13), 95 (100), 83 (11), 69 (33), 55 (21), 41 (22).

IR (film, cm-1): S, m, m, m, 1603w, s, 2704w, m, m, m, m, 3062.

Example 7: Obtain 2-(2,4,4-trimethylcyclopentanone)acrylaldehyde (8)

2-(2,4,4-trimethylcyclopentanone)Acrylonitrile 5 is placed in an inert atmosphere in toluene at a temperature of 10°C. To this product is added dropwise with 1.2 EQ. Dibal-H (hydride diisobutylaluminum). The reaction medium is stirred for several hours at room temperature, then poured into a mixture of 20:40:40 acetic acid, water and ice. The aqueous layer was extracted once with toluene. The combined organic layers is raybaut solution of sodium bicarbonate, then salt water. After drying over magnesium sulfate, filtered through paper and the solvent is evaporated, the crude product is obtained in the form of two diastereoisomers in the ratio of 70:30, distilled under reduced pressure.

BP.=40°C/of 0.3 Torr

Olfactive description: the scent of green, citrus, woody, strong.

Major isomer:

1H-NMR (200 MHz, CDCl3): δ (M. D.) to 0.88 (d, J=6.4 Hz, 3H), 1.05 of (2s, 6H), to 1.22 to 1.34 (m, 2H), 1.60-to to 1.87 (m, 2H), 2,04-2,17 (m, 1H), 2.57 m-to 2.67 (m, 1H), 6,01 and 6,28 (2s, 2H), by 9.56 (s, 1H).

13C-NMR (50 MHz, CDCl3): δ (M. D.) 18,61, 31,78, 37,28, 39,56, 45,53, 49,06, 50,60, 133,39, 153,26, 195,50.

MC [e/m (%)]: 166 (M+, 35), 151 (89), 137 (30), 133 (43), 124 (17), 123 (60), 110 (26), 109 (100), 108 (21), 107 (21), 105 (20), 96 (12), 95 (88), 93 (25), 91 (24), 84 (29), 83 (39), 82 (11), 81 (58), 79 (32), 77 (22), 70 (12), 69 (57), 68 (11), 67 (39), 65 (11), 56 (10), 55 (42), 53 (27), 43 (16), 41 (58), 39 (31).

Minor isomer:

1H-NMR (200 MHz, CDCl3): δ (M. D.) a 0.59 (d, J=7.2 Hz, 3H), 1.05 of (2s, 6H), to 1.22 to 1.34 (m, 2H), 1.60-to to 1.87 (m, 2H), 2,04-2,17 (m, 1H), 2.57 m-to 2.67 (m, 1H), 6,07, and of 6.20 (2s, 2H), by 9.56 (s, 1H).

13C-NMR (50 MHz, CDCl3): δ (M. D.) 18,13, 31,54, 34,56, 37,28, 40,47, 43,24, 49,74, 134,33, 151,82, 195,50.

MC [e/m (%)]: 166 (M+, 25), 151 (66), 137 (27), 133 (29), 124 (14), 123 (44), 110 (20), 109 (100), 108 (18), 107 (17), 105 (14), 95 (68), 93 (20), 91 (22), 84 (72), 83 (39), 82 (10), 81 (57), 79 (29), 70 (11), 69 (86), 67 (32), 65 (10), 56 (12), 55 (39), 53 (23), 43 (13), 41 (57), 39 (29).

IR (film, cm-1): 895w, m, 1190w, 1242w, 1364w, 1376w, m, 1623w, s, 2696w, m, m.

Example 8: Obtain 2-(2,4,4-trimethylcyclopentanone)propanimidamide (9)

2-(2,4,4-trimethyltin opentel)propanenitrile 6 is placed in an inert atmosphere in toluene at 10°C. To this product is added dropwise with 1.2 EQ. Dibal (hydride diisobutylaluminum). The reaction medium is stirred for several hours at room temperature, then poured into a mixture of 20:40:40 acetic acid, water and ice. The aqueous layer was extracted once with toluene. The combined organic layers washed with sodium bicarbonate solution, then with salt water. After drying over magnesium sulfate, filtered through paper and the solvent is evaporated, the crude product is obtained in the form of three diastereoisomers defined by CPG, in the ratio 73:16:11, distilled under reduced pressure.

BP.=40°C/of 0.4 Torr

Olfactive description: the aroma is woody, dry, green, citrus, fresh.

3 Overlapping isomer:

1H-NMR (200 MHz, CDCl3): δ (M. D.) 0,95-1,03 (c overlapped, 6H), 1,07-1,11 (d overlapped, 3H), 1,17-of 1.32 (m, 2H), of 1.40-1.50 (m, 1H), 1,62-1,71 (m, 1H), 1,81-2.05 and 2,20-2,23 (2m, 2H), 2,35-2,48 (m, IH), for 9.64 and 9,70 (2s, 1H).

13C-NMR (50 MHz, CDCl3the isomer in the amount of 73%): δ (M. D.) 9,43, 19,34, 31,21, 31,40, 37,0, 37,40, 45,90, 47,10, 48,65, 50,46, 205,88.

MC [e/m (%) isomer in the amount of 73%]: 168 (M+, 1), 111 (14), 110 (49), 95 (100), 83 (26), 69 (30), 58 (10), 55 (27), 41 (17).

MC [e/m (%), isomer 16%]: 168 (M+, 0,1), 111 (19), 110 (71), 97 (13), 95 (100), 83 (40), 69 (52), 67 (10), 58 (11), 55 (42), 43 (11), 41 (24).

MC [e/m (%), isomer at 10%]: 168 (M+, 1), 111 (20), 110 (37), 109 (12), 95 (100), 83 (79), 82 (15), 69 (45), 67 (13), 58 (33), 55 (45), 43 (12), 41 (27), 39 (10).

MC [e/m (%)]: 190 (M+, 18), 132 (11), 131 (39), 117 (33) 105 (16), 104 (33), 92 (25), 91 (100), 85 (31), 65 (14).

IR (film, cm-1): 840w, 885w, 920w, 971w, 1365w, 1377w, m, s, 2700w, m, m, m.

Example 9: Fragrance composition containing the compound 5

Chord candy type with lemon note was obtained using the following ingredients:

IngredientsChord AndChord
THYMOL 10% in DPG55
LABIENOXIME 10% in DPG55
CITRONELLYL ACETATE1010
ALCOHOL C911
EXILARCHY ALDEHYDE5050
ALDEHYDE C855
ALDEHYDE C922
BETA-PINENE5050
CITRONELLOL 98% 1010
GALAXOLIDE SANS DANS PE MIP100100
M. C. P. HYDRATED NATURAL11
TRIPEL22
ETHYL MALTOL22
VERTENEX No. 23030
CITRON ESS Italy SS CITRATE300300
LEMONY3030
DPG397297
Connection 50100

Rating: Additive compound 5 gave more intensity this lemon note, which greatly strengthened "lemon" and "nitrile" notes. The connection has created a refined flavor and stressed note ethyl-maltol in the composition. The same effect was observed when using compounds in alcoholic beverages and shampoos.

PR is measures 10 : Fragrance composition containing the compound 5

Chord flavor of the type of green peach was achieved using the following ingredients:

INGREDIENTSCHORD ANDCHORD
SUBSTANCE X24242 1% in DPG2020
MELONAL M11
BUCHU FEUILLE SS11
The ethyl ACETATE8080
ETHYLACETOACETATE5050
PHENETHYL ALCOHOL5050
BENZOIC ALDEHYDE55
ALDEHYDE C144040
ALDEHYDE C192020
DELTA DODECALACTONE 1010
DAMASCENE11
DELTA-DECALACTONE1515
GAMMA DODECALACTONE1010
GAMMA-DECALACTONE8080
GAMMA VALEROLACTONE1515
CIS-3-HEXENOL8080
ALPHA IONON44
CIS-JASMIN44
LINALOOL150150
MUSC T150150
CIS-3-HEXANICOTINATE8080
NECTARY1515
DPG109109
Connection 5060

Rating: Additive compounds 5 significantly increased the intensity of the aroma, it was enriched with green notes. Several members of the group of experts expressed the same opinion: they prefer the song with the connection 5. The aroma of this composition could be felt when it is used in shampoo.

1. The compound of formula (I):
,
in which
R denotes a hydrogen atom, a C1-C6alkyl, C2-C6alkenyl or =CH2;
Z represents CN or CHO; and
there is no more than one of the dotted ties;
provided that:
if Z denotes the SNO and has one of the dotted ties, R does not denote a hydrogen atom, and
if there is a dashed bond between carbon Ca and Cb, then R does not denote the group =CH2.

2. Connection on p. 1, having the General formula (I'):
,
in which
R denotes a hydrogen atom, a C1-C6alkyl, C2-C6alkenyl or =CH2;
there is no more than one of the dotted ties;
provided that:
in the presence of the dotted bonds between carbons Ca and Cb R is not the group =CH2.

3. Connection on p. 2, in which R train is achet a hydrogen atom, or methyl, or =CH2.

4. Connection on p. 1, having the General formula (I”):
,
in which
R denotes a hydrogen atom, a C1-C6alkyl, C2-C6alkenyl or =CH2;
there is no more than one of the dotted ties;
provided that:
if one of the dashed links R is not a hydrogen atom, and
in the presence of the dotted bonds between carbons Ca and Cb R is not the group =CH2.

5. Connection on p. 4, in which R denotes a hydrogen atom, methyl or =CH2.

6. The method of obtaining the compounds of formula (I), characterized in that the said method comprises the stage of interaction of the compounds of formula (A):

with diethylphosphonoacetate formula RCH(CN)PO(OC2H5)2in which R denotes a hydrogen atom, a C1-C6alkyl or C2-C6alkenyl; or
with alkylsulfates formula NCCH2COOR' in which R' denotes a1-C4alkyl.

7. The use of compounds according to any one of paragraphs.1-5 as a fragrant compound or agent.

8. The use of compounds according to any one of paragraphs.1-5 as agent for masking the smell.

9. The use according to any one of paragraphs.7 and 8, in which the compound according to any one of paragraphs.1-5 is present in combination with at least one other aromatic or parfumer the m component, and/or at least one solvent and/or at least one additive.

10. Fragrance composition, characterized in that it contains a compound according to any one of paragraphs.1-5.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to campholene derivatives of general formula (I), a fragrant or aromatic flavouring composition and use thereof in perfumery to obtain perfumed bases and concentrates, as aromatic agents for producing flavouring compositions or products, as agents which mask smell and/or taste, including in a combination with other perfumery or aromatic ingredients, solvents and additives. In general formula (I) , R1, R2, R3, R4 and R5 each independently denote a hydrogen atom or a linear or branched C1-C5 alkyl or C2-C5 alkenyl group, - Y denotes CN, C(O)R6 or a CR6(ORα)(ORβ) group, where R6 denotes a hydrogen atom or a linear or branched C1-C5 alkyl or C2-C5 alkenyl group, and Rα and Rβ simultaneously denote a linear or branched C1, C2, C3, C4 or C5 alkyl or C2, C3, C4 or C5 alkenyl group, the - 5-member ring is saturated or contains a double bond between C3' and C4' in formula (I), and the side chain, if necessary, contains a double bond between C1 and C2 and/or between C3 and C4, under the condition that said derivative is not 3-methyl-6-(2,2,3-trimethyl-cyclopent-3-enyl)-hex-4-enal.

EFFECT: use of campholene derivatives to obtain perfumed bases and concentrates.

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FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing (-)-beta-elemenal, use of (-)-beta-elemenal as an antitumour agent, as well as to a pharmaceutical composition and a medicinal agent based on said compound. The method involves reaction of a mixture of isomeric beta-elemenols (2:1) with c MnO2, activated in a vacuum at 150°C as a catalyst. The initial mixture of isomeric beta-elemenols (2:1) is obtained by reacting a mixture of diastereomeric epoxides (2:1) with diisopropylamine in the presence of n-BuLi.

EFFECT: higher efficiency.

4 cl, 21 tbl, 9 dwg, 36 ex

FIELD: chemistry.

SUBSTANCE: method involves Wittig olefination of the 6E-isomer of 2E-2,6-dimethyl-8-triphenylsilyloxyocta-2,6-dien-4-yn-1-al (synthon C10)ylid, generated in situ from β-cyclogeranyltriphenyl phosphonium halide, removal of triphenylsilyl protection in the obtained silylated 13E-isomer of 11,12-didehydroretinol. After removal triphenylsilyl protection, the obtained 13E-isomer of 11,12-didehydroretinol is oxidised to 11,12-didehydroaldehyde using MnO2 without extracting the semi-product separately and further purification procedures, and stereo-specific reduction of the triple bond in 11,12-didehydroaldehyde is then carried out in via hydrogenation on a Lindlar catalyst to obtain the desired 11-cis-retinal isomer, where generation of ylide from β-cyclogeranyltriphenyl phosphonium halide is carried out under the following conditions: a) NaH in tetrahydrofuran at 0-5°C, b) anhydrous K2CO3 in dichloromethane, in the presence of interphase transfer catalysts - quaternary ammonium salts at 20-25°C, or c) 1,2-epoxybutane in dichloromethane at 50-60°C.

EFFECT: obtaining medicinal agents for preventing or therapy of severe pathologies of the human optical system.

2 cl, 1 dwg, 1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method for synthesis of campholene aldehyde which is widely used in perfumery and household chemicals. The method involves conversion of α-pinene epoxide in a supercritical complex solvent consisting of a mixture of carbon dioxide, propanol-2 and water at temperature of 160-240°C and pressure of 130-220 atm. As a rule, the conversion reaction is carried out in a supercritical solvent with molar ratio water/α-pinene epoxide equal to 5-7.9.

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2 cl, 1 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to campholene derivatives of general formula (I), a fragrant or aromatic flavouring composition and use thereof in perfumery to obtain perfumed bases and concentrates, as aromatic agents for producing flavouring compositions or products, as agents which mask smell and/or taste, including in a combination with other perfumery or aromatic ingredients, solvents and additives. In general formula (I) , R1, R2, R3, R4 and R5 each independently denote a hydrogen atom or a linear or branched C1-C5 alkyl or C2-C5 alkenyl group, - Y denotes CN, C(O)R6 or a CR6(ORα)(ORβ) group, where R6 denotes a hydrogen atom or a linear or branched C1-C5 alkyl or C2-C5 alkenyl group, and Rα and Rβ simultaneously denote a linear or branched C1, C2, C3, C4 or C5 alkyl or C2, C3, C4 or C5 alkenyl group, the - 5-member ring is saturated or contains a double bond between C3' and C4' in formula (I), and the side chain, if necessary, contains a double bond between C1 and C2 and/or between C3 and C4, under the condition that said derivative is not 3-methyl-6-(2,2,3-trimethyl-cyclopent-3-enyl)-hex-4-enal.

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The invention relates to the chemistry of adamantane derivatives, and in particular to a new method of obtaining-adamantylidene aldehydes of General formula

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FIELD: chemistry.

SUBSTANCE: invention relates to a method for producing 2-(2-hydroxy)adamantylalkyl(aryl)ketones of general formula: , which are intermediate products during synthesis of possibly biologically active substances. The method involves reaction of adamantanone cyanohydrin with Grignard reagents selected from: ethylmagnesium bromide, benzylmagnesium chloride, alkylmagnesium chloride, in a medium of anhydrous diethyl ether or tetrahydrofuran in molar ratio of reagents equal to 1:2, respectively, at temperature 30-45°C for 2-3 hours, with subsequent treatment of the reaction product with water and acetic acid and extraction of the end product.

EFFECT: high output of end products.

3 ex

The invention relates to the synthesis of adamantane derivatives, and in particular to a method for producing 1-adamantylamine, which can be used as intermediate for the synthesis of functional adamantanes, as well as biologically active substances

FIELD: chemistry.

SUBSTANCE: invention relates to campholene derivatives of general formula (I), a fragrant or aromatic flavouring composition and use thereof in perfumery to obtain perfumed bases and concentrates, as aromatic agents for producing flavouring compositions or products, as agents which mask smell and/or taste, including in a combination with other perfumery or aromatic ingredients, solvents and additives. In general formula (I) , R1, R2, R3, R4 and R5 each independently denote a hydrogen atom or a linear or branched C1-C5 alkyl or C2-C5 alkenyl group, - Y denotes CN, C(O)R6 or a CR6(ORα)(ORβ) group, where R6 denotes a hydrogen atom or a linear or branched C1-C5 alkyl or C2-C5 alkenyl group, and Rα and Rβ simultaneously denote a linear or branched C1, C2, C3, C4 or C5 alkyl or C2, C3, C4 or C5 alkenyl group, the - 5-member ring is saturated or contains a double bond between C3' and C4' in formula (I), and the side chain, if necessary, contains a double bond between C1 and C2 and/or between C3 and C4, under the condition that said derivative is not 3-methyl-6-(2,2,3-trimethyl-cyclopent-3-enyl)-hex-4-enal.

EFFECT: use of campholene derivatives to obtain perfumed bases and concentrates.

10 cl, 1 tbl, 2 dwg, 20 ex

FIELD: chemistry.

SUBSTANCE: present invention represents nitrile compound of formula (I) where R represents halogen, C1-C11-alkyl optionally substituted with, one or more halogen atoms, C2-C6-alkenyl optionally substituted with, one or more halogen atoms, C2-C6-alkinyl optionally substituted with, one or more halogen atoms, C3-C7-cycloalkyl optionally substituted with, one or more halogen atoms or (C3-C7-cycloalkyl optionally substituted with, one or more halogen atoms) C1-C4-alkyl, applied for insect and mite control both as pesticide composition, and itself.

EFFECT: high efficiency of the present compound.

12 cl, 180 ex, 4 tbl, 6 dwg

FIELD: organic chemistry, insecticides.

SUBSTANCE: invention relates to novel 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl-2,2-dimethyl-3-(2-cyano-3-hydrocarbyloxy-3-oxo-1-propenyl)cyclopropane carboxylates of the formula (1): wherein G means (C1-C4)-alkyl or (C3-C4)-alkenyl, and to a composition used for control of pest-insects comprising the effective amount of 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl-2,2-dimethyl-3-(2-cyano-3-hydrocarbyloxy-3-oxo-1-propenyl)cyclopropane carboxylate of the formula (1). Also, invention relates to a method for control of pest-insects involving applying the effective amount of 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl-2,2-dimethyl-3-(2-cyano-3-hydrocarbyloxy-3-oxo-1-propenyl)cyclopropane carboxylate of the formula (1) on pest-insects or in their residence medium.

EFFECT: valuable properties of compounds.

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The invention relates to the chemistry of adamantane derivatives, and in particular to a new method of obtaining adamantylidene NITRILES of General formula

where R1=H: R2=H, CH3WITH2H5, (CH3)2CH2WITH6H5WITH10H5C5H10N, C5H10NCH2, (CH2)3JV; R1=CH3: R2=CH3,

which are important intermediates in the synthesis of some biologically active substances

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing 4-[2-chloro-1-formyl-2-R-vinyl]-5-nitrophthalonitriles of said general formula where R denotes C6H5, or 4-OCH3C6H4, or 4-CH3C6H4, or 2-thienyl, which can be used as precursors in synthesis of biologically active substances, phthalocyanines and hexazocyclanes. The disclosed method includes use of substituted 4-nitro-5-(2-oxoethyl)phthalonitriles and phosphorus oxychloride POCl3 as starting reagents. Reaction of said reagents takes place at 90-110°C and molar ratio 1:2-3, respectively, for 2.5-5 hours in dimethylformamide solution. The reaction mass is then cooled and poured into cold 5-20% sodium bicarbonate solution. The crystalline precipitate is filtered, recrystallised from an alcohol and dried on air.

EFFECT: high degree of purity of the compound.

1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the field of organic chemistry, namely to a method of obtaining 2-cyano-3-arylacrylic acids of general formula given below, which can be applied as a regulator of plant growth, synthesis of medications, fungicides and pesticides. The method consists in boiling respective 2-arylidenemalononitriles in a medium of diluted nitric acid with a ratio nitric acid (65%): water as 5:3 (by volume) in the presence of catalytic amounts of potassium permanganate for 4-6 hours. The obtained sediment is washed with water, the target product is separated by re-crystallisation from water. In the said general formula Ar represents C6H5 (a), 2-ClC6H4 (b) and 3-ClC6H4 (c).

EFFECT: claimed method makes it possible to obtain 2-cyano-3-arylacrylic acids with good output, with the simultaneous reduction of harmful wastes and elimination of organic solvents from the process.

3 ex

FIELD: chemistry.

SUBSTANCE: method of producing di(4-cyanophenyl)bromomethane can be used as an intermediate product in synthesis of medicinal agents, particularly anticancer drug letrozole. The disclosed method of producing di(4-cyanophenyl)bromomethane includes bromation of di(4-cyanophenyl)methane with bromosuccinimide in an inert solvent in the presence of benzoyl peroxide while heating. The reaction is carried out with an excess of 0.2-0.3 mol bromosuccinimide at 105-115°C.

EFFECT: method increases output and purity of the product.

2 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: method consists in an interaction of α-aminonitrile with amines with heating. As α-aminonitrile, 2-amino-2-cyanoadamantane is used, and as amines - cyclohexylamine, 3-aminopropanol and morpholine. The process is carried out in the presence of potassium carbonate at 80-100°C.

EFFECT: method makes it possible to increase the output of 2-amino-2-cyanoadamantane derivatives.

3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a novel method of obtaining 2-amino-2-cyanoadamantane derivatives of the given general formula , which can be applied as semi-products in a synthesis of biologically active amino acids, diamines and heterocyclic compounds. The claimed method consists in a reaction of adamantanone-2 with amines and a cyanogroup carrier in heating in the presence of potassium carbonate. As amines used are cyclohexylamine, 2-aminoethanol, aniline, piperidine, morpholine or piperazine, and as the cyanogroup carrier used is acetone cyanohydrin or 2-amino isobutyronitrile. The process is carried out in one stage for 1.5-2 h at 80-100°C. In the given general formula R=H, , -CH2CH2OH, C6H5, R-R1=-(CH2)5-, -CH2CH2OCH2CH2-, -CH2CH2NHCH2CH2-.

EFFECT: method makes it possible to obtain derivatives of 2-amino-2-cyanoadamantane of the said general formula with the high output.

8 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a novel method of obtaining 2-amino-2-cyanoadamantane derivatives of the given general formula , which can be applied as semi-products in a synthesis of biologically active amino acids, diamines and heterocyclic compounds. The method consists in a reaction of adamantanone-2 with derivatives of amines in the presence of potassium carbonate with heating. As amine derivatives used are aminonitriles from the group 2-N-cyclohexylamino-2-cyanopropane, 2-N-piperidino-2-cyanopropane, 2-N-benzylamino-2-cyanopropane with a molar ratio adamantanone-2:aminonitrile, equal to 1:1.2-1.5, and a temperature of 80-100°C. The process takes place in one stage for 60-70 min.

EFFECT: method makes it possible to obtain derivatives of 2-amino-2-cyanoadamantane of the given general formula with the high output.

3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing norbornane derivatives of general formula , where R1=H, R2=CN; or R1R2=CH2-CH2-CH2-, which can be used in organic synthesis as semi-products, e.g. for synthesis of adamantane. The method involves hydrogenating a norbornene derivative with hydrogen gas at atmospheric pressure on a catalyst. The norbornene derivative used is dicyclopentadiene or 2-cyanonorbornene-5, and the catalyst used is nickel nanoparticles, obtained by reducing nickel (II) chloride with sodium borohydride in an isopropanol medium in situ. The process is carried out in an isopropanol medium at temperature of 40-50°C for 6-8 hours, followed by separation of the end product.

EFFECT: method simplifies production of compounds of said general formula.

2 ex

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