MXPA98008318A - Perfume compositions containing macrocic - Google Patents

Abstract

The present invention relates to perfume compositions, which contain macrocycles, namely compounds of 15 to 17 members of formula (I), in which, the dotted line means an optional additional bond, X and Y mean methylene or C2 polymethylene. -12, optionally substituted with an additional methyl group, and A means hydrogen or methyl in the case of the unsaturated compound and methyl in the case of the unsaturated compound, and methyl in the case of the saturated compounds, with the proviso that the unsaturated compounds they are present in more than 80% in the cis form when A means hydrogen and are present in more than 50% in the cis form when A means methyl, with the exception of Z-oxaciclopentadec-6-en-2-one (ring of 15 members), Z-oxacycloheptadec-8-en-2-one (17-membered ring) and Z-oxacycloheptadec-11-en-2-one (17-membered ring), a process for the manufacture of Formula I and the use of the compounds of formula I like perfumes or odorant

Description

i »" PERFUME COMPOSITIONS CONTAINING MACROCICLES DESCRIPTION OF THE INVENTION The invention relates to compositions of 5 perfumes or odorants containing mareocycles, namely composed of 15 to 17 members of formula Wherein, the dotted line means an optional additional bond, X and Y mean methylene or polyethylene of C2-12, optionally substituted with an additional methyl group, and A means hydrogen or methyl in the case of the unsaturated compound and methyl in the case of the saturated compounds, with the proviso that the unsaturated compounds are present in more than 80% in the cis form when A means hydrogen and are present in more than 50% in the cis form when A means methyl. with the exception of Z-oxaciclopentadec-ß-en-2-one (ring of 15 members), Z-oxacicloheptadec-8-en-2-one (ring of 17 members) and Z-oxacicloheptadec-ll-en-2-one (ring of 17 members), and a procedure for the manufacture of the compounds of formula I. REF. 28474 The compounds of formula I or mixtures of the compounds of formula I are partially novel and partially known. The compounds I 'or the mixtures defined as I' with the substituents previously defined for formula I are novel with the exception of Z-oxacyclopentadec-3- (or 6- or 13-) en-2-one, Z-oxacyclohexadec -3- (or 6-, 11-, 12- or 13) en-2-one and Z-oxacicloheptadec-8- (or 10-, 11-, 12-, 13- or 15-) en-2-one . The compounds I and I 'thus encompass the corresponding oxacyclopenta (or -hexa or -hepta) decen-2-ones and the corresponding decan-2-ones. It is intended that Formula I include all possible isomers. Thus, in the case of the saturated and unsaturated compounds, racemates and optically active compounds, ie, the R and S forms, are included. In the case of unsaturated compounds, the cis / trans ratio is that according to the above definition. In addition, diastereoisomeric forms which are related to a multiple methyl substitution are also possible. In 1927, Kerschbau isolated an ambretide (Z-oxacicloheptadec-8-en-2-one) from ragweed seed oil (musk seed oil) (Ber 60,902, 1927) Maurer, isolated Z-oxaciclopentadec-β -in-2-one of the same oil (B. Maurer, A. Grieder, Helv. Chim. Acta, 60, 1155, (1977) .The IFF company has protected the synthesis of E-oxacicloheptadec-10-en-2 -one in a patent (USP 4 064 144) Mookherjee has described the synthesis of a mixture of oxacicloheptadec-8-en-2-one, oxacicloheptadec-9-en-2-one, oxacicloheptadec-10-en-2-one and oxacicloheptadec-11-en-2-one, with the third compound, being present in 80% in the aforementioned mixture.No stereochemistry of the compounds occurs (BD Mookherjee, R. Trenkle, RR Patel, J Org. Chem. 37, 24, 3846, (1972).) Since the aforementioned synthesis is the pyrolysis of an ester, the selective formation of a cis-olefin would not be expected (see in this respect, Houben-Weyl, volume V / lb, 105, 1 972) Firmenich has protected a mixture of E-oxacyclohexadec-12-en-2-one and E-oxacyclohexadec-13-en-2-one mainly, with the Z isomers being present only in a small percentage (EP 0 424 787 ). The company IFF has protected the use of oxacyclohexadec-ll-en-2-one (USP 4 541 950), but the cis / trans ratio of the product obtained is not given. Since, however, the product was obtained by metathesis, it is in doubt whether the trans content is greater than the cis content. see in this regard A. Fürstner, K. Lange ann, J. Org.

Chem. 61, 3942, 1996.

The French company Mane et Fils in F-06620 Bar s / Loup sells a compound under the name cis-iso-ambretolida. This is Z-oxacicloheptadec-ll-en-2-one (Parfums, Cosmétiques, Actualiées, No 128, avril / mai 63, 1996). C. Collaud (Helv. Chim. Acta 25, 965, 1942) describes the production of a mixture of oxacicloheptadec-6-en-2-one and oxacicloheptadec-7-en-2-one, without giving the stereochemistry of the products. Since the aforementioned synthesis is, furthermore, a pyrolysis of an ester, the selective formation of a cis olefin could not be expected. In addition to the extremely low threshold values, the compounds I have a very good adhesion. All have intense musk notes, which are also often accompanied by powder, fruity, floral side notes. The compounds also have notes, similar to amber, that smell like the seeds of abelmosco. Z-13-methyl-oxaciclopentadec-10-en-2-one has an especially fine perfuming effect with a dominant musk note. The note of musk is rounded by a powdery, fruity component. Preferred compounds according to the invention are those set forth hereinafter -Z-13-Methyl-oxacyclopentadec-10-en-2-one: This compound is characterized by a very low threshold value. The value of the olfactometric threshold is 0.578 ng / 1.

The threshold value GC is 0.1 ng / 1. This gives an "odor value" of 18038 [see N. Neuner-Jehle, F. Etzweiler, in Perfumes: Art Science and Technology, Edited by P. M. Müller, D. Lamparsky]. This is the highest "smell value" that has been known for a macrocyclic musk. For example, him Musk Rl (1, 7-dioxa-cycloheptadecan-8-one) has a threshold value of 0.33 ng / 1; a vapor pressure of 3.24 μg / 1 and an "odor value" of 3074. The tibetolide has a threshold value of 2.16 ng / 1, a vapor pressure of 6.64 μg / 1 and an "odor value" of 3074. All macrocyclic musk perfumes have even lower values: Z-13-methyl-oxaciclopentadec-10-en-2-one is distinguished by a powder odor similar to musk, similar to lactone, fruity; -Z- Oxacicloheptadec-12-en-2-one: Odor similar to that of tibetolide, strong, after the seeds of abelmosco; -Z-oxaciclohexadec-5-en-2-one: Smell similar to musk, powdery, lactonic; -Z-oxaciclohepadec-9-en-2-one: The compounds have never been produced with the purity achieved here, the spectral data and olfactory properties were not known, strong nitroalmice note, with an impact lactonic acid, woody, animal; -Z-oxacicloheptadec-10-en-2-one: The compound has a smell similar to that of musk, after ambretolida, after seeds of abelmosco, powdery, frutal, green; -10-methyl-oxaciclopentadecan-2-one: The compound has an odor similar to that of the nitroalmix, dusty, lactonic, woody, earthy; -8-methyl-oxaciclopentadecan-2-one:. The compound has a smell similar to that of the nitro-alcohol, dusty, similar to that of amber, fruity; -9, 13-dimethyloxacyclopentadecan-2-one: The compound has a smell similar to that of musk, fruity, powdery, floral, similar to that of lactone; -oxacicloheptadec-7-en-2-one: Fruity, musk-like odor, floral, similar to that of abelmosco seeds; -Z-oxacicloheptadec-13-en-2-one: Very desirable odor, similar to that of the musk, powdery, lactonic, floral ketone; -7-methyl-oxaciclohexadecan-2-one: The compound has a smell similar to that of musk, floral, fruity, powdery, similar to that of lactone. -8, 15-dimethyl-oxaciclopent-7-en-2-one: Nitroalmizcle, powdery, animal; -15-methyl-oxacyclohepadec-12-en-2-one: The compound is distinguished by an odor similar to that of musk, woody, animal, earthy sweet, fruity. The acrocycles I can be used in a general manner in the same way as known musk perfumes. In this way, they harmonize with a large number of natural and also synthetic products, which are often used in perfume compositions. In particular, in the base note, the base note. they produce interesting effects in combination with woody and amber chords, patchouli oil perfumes, as well as cedar wood and sandalwood. The moderate floral notes confer elegance and radiance to the compounds. Some examples of the kinds of substances that harmonize well are: -Natural products, such as absolute tree moss, geranium oil, absolute jasmine, patchouli oil, rose oil, sandalwood oil, vetiver oil and oil of ylang-ylang, etc, -alcohols, such as citronellol, Ebanol®, geraniol, linalool, phenylethyl alcohol and Sandalore®, etc., -aldehydes and ketones, such as Florozone® (3- (4-ethylphenyl) -2 , 2-dimethyl-propional), hydroxycitronellal, Iso-E-Super® (1,2,3,4, 5, 6, 7, 8-octahydro-2, 3, 8, 8-tetramethyl-2-octanaphthalene), Isoraldein®, altol, methyl edril ketone, methylionone and vanillin, etc; -ethers and acetals, such as ambrox, geranyl methyl ether, rose oxide and Spirambrene® (2 ', 2', 3, 7, 7-pentamethyl-spiro [bicyclo [4.1.0] heptan-2, 5 '- [ 1, 3] dioxane]), etc; -teters and lactones, such as Berryflor®,? ecalactone and? -undecalactone, etc. Its versatility allows a wide use of macrocycles or formula I not only in oriental sweet creations, but also in olfactory directions of "fougére", "chypre" and "floral". By virtue of the low threshold values and the good adhesion, the composition for cosmetic products, washing agents and similar mass produced products, are also contemplated in the addition to luxurious perfumes. The compounds of formula I can be used within broad limits, which can be extended in the compositions, for example, from about 0.1% by weight (detergents) to about 40% by weight (alcoholic solutions), without these values being, however, limiting values, since the experienced perfumer can also produce effects with even lower concentrations or can synthesize novel complexes with even greater amounts. Preferred concentrations range from about 3% to about 20%. The compositions manufactured with the compounds or formula I can be used for all types of perfumed consumer products (eau de Cologne, toilet water, extracts, lotions, creams, shampoos, soaps, balsams, powders, deodorants, detergents, etc.) . The compounds of formula I can therefore be used for the production of compositions and, as will be apparent from the above recollection, a wide range of perfumes and mixtures of known perfumes can be employed. In the production of such perfuming compositions or perfume mixture set forth above, a method known to a perfumer may be used, such as, for example, that of WA Poucher, Perfumes, Cosmetics, Soaps, 2nd vol., 7th edition, Chapman and Hall, London 1974. The process for manufacturing the compounds of formula I or mixtures thereof comprises lactonizing a compound of the formula wherein, A, X and Y have the above meaning and represent OH, alkanoate, for example, acetate, or a leaving group, such as mesylate, tosylate, I, Br, Cl etc., in a manner known per se , namely at elevated temperature and under basic conditions, and, if desired, hydrogenation of the unsaturated formula I compound thus obtained. The compounds of formula II can be obtained by subjecting a compound of the formula Br to a Wittig reaction with a compound of the formula The lactonization of a compound of formula II to a compound or formula II can be carried out, for example, according to the Collaud method (BP No. 490 044, January 4, 1937, C. Collaud, Helv. Chim. Acta, 965 , 1942). Here, the preparation of the 2, 3-dihydroxy-propyl ester of? -hydroxycarboxylic acid is first effected by the treatment of the corresponding sodium salt of the? -hydroxycarboxylic acid or the formula II with chloropropane-1,2-diol, followed by by internal transesterification in the presence of a methanolate, especially sodium methanolate. The resulting monomer is distilled from the reaction mixture in the presence of a high-boiling solvent or introducing an agent, for example glycerol. A second possibility for the lactonization of a compound of formula II to a compound of formula I is that described, for example, in Patent CH 344 712. The? -hydroxycarboxylic acid is heated at high temperature in the presence of a base (KOH) , NaOH, etc.) and glycerol, obtaining a polyester. Subsequently, an internal transesterification is carried out in the presence of sodium methylate. The resulting monomer is distilled from the reactor in a high boiling point solvent, for example glycerol. When W means I, Br or Cl, the lactonization of a compound of formula II to formula I can also be carried out according to the method of Mandolini et al. (G. Galli, G. Giannelli, G. Illuminati, L. Mandolini, J. Org. Chem., Vol. 44, No. 8, 1258, 1979). Here, the β-bromoalkanoate of formula II is added dropwise to a suspension of potassium carbonate in dimethyl sulfoxide with good agitation. The use of those known methods, however, is not suitable by itself for the manufacture of perfumes, since the sulfur notes are difficult to remove from the product. It has now been found that dimethyl sulfoxide can be replaced, surprisingly, with a sulfur-free solvent, especially N-methylpyrrolidone, and that in this way it can be an olfactoryly perfect product. The hydrogenation of an unsaturated compound of formula I can be carried out according to methods known per se, namely catalytically. Suitable catalysts are Pd on carbon or on potassium carbonate, Pt or Raney nickel, etc. This is carried out in a conventional manner in a solvent, such as an alkanol, for example methanol, ethanol etc., in ethyl acetate or acetic acid, etc. The suitable temperature range extends from about room temperature to about 100 ° C. The hydrogenation can be carried out under normal pressure or under elevated pressure. Thus, for example, a pressure of up to about 60 atm is possible. or even superior. The preparation of the compounds of formula II can be carried out according to the methods known per se by the Wittig reaction. Accordingly, a phosphonic salt of formula III is conveniently treated first with (about 2 equivalents) of a strong base to give an ylide. For example, potassium t-butylate, potassium t-amylate, methylthio, butyllithium, phenyllithium, potassium hydride, sodium hydride, hexamethyldisilazane (as the potassium or sodium salt), lithium diisopropylamide, etc., can be used. example, as bases. Preferably, an aprotic solvent such as diethyl ether, tetrahydrofuran, benzene, toluene, hexane, dimethylformamide, HMPA (hexametalphosphoric acid triamide), etc., is used as the medium for further reaction with a compound of formula IV. The temperatures are not critical, and the convenient temperature range can be wide (from about -78 to about 100 ° C). The Wittig reaction has been used sporadically for the synthesis of the precursors of macrocyclic compounds (Nicolaou et al., J. Org. Chem. 44, 4011, 1979). Büchi and Wuest (Helv. Chim. Acta, 62, 2661, 1979) have used the Horner-Emmons condensation which includes a Wittig reaction for the synthesis of the cyclic ketones of C? F, exaltone and muscone. However, the usefulness of the synthesis of macrocyclic lactones, in addition to several ring sizes, also with double bonds in various positions, was unknown until now. The process according to the invention allows for the first time the manufacture of substituted or unsubstituted macrocyclic lactones with ring sizes of 15, 16, 17 members, having optional double bond, which are mainly present in the cis form.

Example 1 100 g (0.846 mol) of 3-methyl-l, 5-pentanediol, 108 ml of ethyl acetate and 21 g of Amberlyst® dissolved in 420 ml of toluene were heated to 94 ° C at reflux temperature for 3 hours. The mixture was then cooled, filtered over Celite and concentrated on a rotary evaporator. 104.5 g of crude product were obtained as a mixture of 3-methyl-l, 5-pentanediol (25%), 3-methyl-l, 5-pentanediol monoacetate (50%) and 3-methyl-1,5-diacetate. -pentandiol (25%).

Example 2 189 g of crude product (from the preceding example) and 9 g (76 moles) of potassium bromide were placed in 377 ml of methylene chloride and treated at -10 ° C with 1.18 g (7.55 mmoles) of radical 2 , 6,6-tetramethylpiperidin-1-oxyl. 780 ml of a 12-15 percent hypochlorite solution (adjusted to pH 9 with NaHCO3 19 g / 1) was added by dripping at 0-5 ° C within 50 minutes. 40 minutes later, the temperature rose to 18 ° C despite cooling. The mixture was stirred at 2-8 ° C for 1 hour. Subsequently, an additional 195 ml of hypochlorite solution was added at 12-15 percent (adjusted to pH 9 with NaHCO3 19 g / 1) by dripping at 0-5 ° C within 15 minutes. The mixture was stirred for 30 minutes, with the temperature rising to 10 ° C. An additional 195 ml of hypochlorite solution at 12-15 percent (adjusted to pH 9 with NaHCO 19 g / 1) was added per drip within 10 minutes, with the temperature rising to 6 ° C. The mixture was stirred at 0-5 ° C for 1 hour and an additional 30 minutes. The reaction mixture was poured into water and extracted twice with methylene chloride. The organic phase was washed (negative peroxide test) with 2N HCl + 5 g of Kl and with water + 9 g of Na? S203'5H20. Subsequently, it was dried over Na2SO4 and concentrated. 177 g of crude product were obtained. This crude product was distilled and gave 114 g of product (eg 75-76 ° C, 0.2 bar) (content of ~ 70% 3-methyl-5-oxopentanol acetate according to tH-NMR).

Example 3 156 g (0.312 mol) of (8-carboxyoctyl) -triphenylphosphonium bromide were sprayed and placed in 330 ml of tetrahydrofuran. After stirring for 10 minutes, the mixture was cooled to -20 ° C and quickly treated with 69.9 g. (0.622 mol) of potassium t-butylate in 90 ml of tetrahydrofuran. The temperature rose to 6 ° C and the reaction mixture turned dark red. It was diluted with 50 ml of tetrahydrofuran and stirred at 5-10 ° C for 1 hour. It was then cooled to -20 ° C and treated with 70 g (0.30 ml, 70%) of 3-methyl-5-oxopentanoyl acetate in 50 ml of tetrahydrofuran. Therefore, the temperature was raised to 15 ° C. The mixture was stirred at -10 ° C to -8 ° C for 1 hour and subsequently at room temperature for 1 hour. It was heated to 35 ° C and stirred for an additional 30 minutes. The reaction mixture was poured into water, adjusted to pH 12 with 2N NaOH and extracted twice with ether. The organic phase was washed with 2N NaOH and the aqueous phase was acidified with 85 percent orthophosphoric acid and extracted twice with ether. The organic phase was washed with saturated sodium chloride solution, dried over sodium sulfate and concentrated. 106 g of crude product were obtained, which was purified by chromatography. The impurities (~ 36 g) were mainly triphenylphosphine oxide. The product consisted of a mixture of 9Z-14-acetoxy-12-methyltetra-dec-9-enoic acid and 9Z-14-hydroxy-12-methyltetradec-9-enoic acid in a ratio of 2: 1. The spectrum of 9Z-14-hydroxy-12-methyltetradec-9-enoic acid is Z / E = 94/6. IR (film): 3336; 3005; 2928; 2855; 1711; 1458; 1246; 1057. XH-NMR (CDC13, 200 MHz) 5.4 (2H) m; 3.7 (2H) m; 2.32 (2H) t J = 7 Hz; 0.9 (3H) d J = 6.2.

ES 238 (2); 150 (4); 136 (5); 109 (16); 95 (32); 81 (100); 67 (48); 55 (76); 41 (48).

Example 4 Apparatus: 350 ml 3-nozzle sulfonation flask, special top (see Figure 1), reflux condenser, thermostat, 2 cooling traps, HV pump with vacuum maintained constantly.

In the figure each reference number means: 1. Connection to the condenser by reflection, 2. Carrier medium + monomer, 3. Product, 4 and 9. Cooling water connection; 5. Double wall, 6 and 7. Drain valve, 8. Insulated cavity, 10. Vertical tube and 11. Connection to the distillation flask. 53. 5 g of the raw product (~ 65 percent) of the Example, 230 ml of glycerol and 1 g of potassium hydroxide (85 percent) in 1 ml of water were placed in a 350 ml sulfonation flask having an upper distillation piece. The resulting water, acetic acid and 4-5 ml of glycerol were distilled in high vacuum. After this, the upper distillation piece was removed and the flask was equipped with the special upper part described. This was filled with 150 ml of glycerol. The mixture was allowed to cool and 1 g of sodium methylate was added. The methanol formed was removed in vacuo. The mixture was heated to 170-180 ° C under reflux (initial internal temperature of 155 ° C) at high vacuum. (3-4 mbar) for 18 hours. After this time, a 15 mm thick layer of lactone was formed on the special top piece. It was allowed to cool, 1 g of sodium methylate was added and the methanol formed was distilled in vacuo. After distilling for 42 hours, the addition was repeated. After a total of 66 hours at reflux, it was allowed to cool. The contents of the upper part were divided with water and extracted four times with ether. The organic phase was washed with water, dried over sodium sulfate and concentrated. 28 g of crude product were obtained, which was distilled (diffusion pump) on a Widmer column. 20 g (69%) of 13-methyloxacyclopentadec-10-en-2-one, Z / E = 94/6, were obtained. IR (movie): 3008; 2927; 2857; 1734; 1459; 1378; 1245; 1180; 1146; 1055. XH-NMR (CDC13, 200 MHz) 5.45 (2H) m; 4.2 (2H); 0.95 (3H) d J = 6.2 Hz. 13 C-NMR (CDC13) 173.9 (s); 131.3 (d); 127.8 (d); 61.9 (t); 36.2 (t); 34.0 (t); 33.9 (t); 31.2 (d); 27.62 (t); 27.60 (t); 27.1 (t); 26.8 (t); 25.6 (t); 24.8 (t) 18.6 (9). ES 238 (2); 196 (2); 150 (5); 136 (5); 123 (5); 109 (14); 95 (30); 81 (100); 67 (49); 55 (53); 41 (48); 27 (15). Smell: similar to musk, oily, fruity, powdery, similar to lactone.

Example 5 527 g (1 mol) of 10-carboxidecyltriphenylphosphonium bromide was suspended in 1.4 1 of tetrahydrofuran. 248 g (2.2 mol) of potassium t-butylate dissolved in 1 1 of tetrahydrofuran were added at 0 °. After stirring at 5 ° C for 30 minutes, 120 g (1.18 mol) of tetrahydropyran-2-ol were added at 0-10 ° C. The reaction mixture was stirred at room temperature for 90 minutes, poured into water and extracted with t-butyl methyl ether. The aqueous phase was adjusted to pH 2 with 4N sulfuric acid and extracted with t-butyl methyl ether. 274 g of crude product were obtained. For the purification of the crude product mentioned above, 552 g were esterified with 700 ml of methanol and 10 ml of sulfuric acid as catalyst (3 hours, at reflux temperature). After working in the usual way they were obtained 620 g of crude ester, which were distilled. They were obtained 301 g (53%) of 16-hydroxyhexadec-ll-enoate methyl, Z / E = 94/6. Example 6 240 g (0.84 mol) of methyl Z-16-hydroxyhexadec-11-enoate and 50 g of potassium hydroxide were dissolved in 500 ml of methanol in a 3 liter flask. The mixture was heated to reflux temperature for 2 hours. Then the methanol was diluted and added 800 ml of glycerol to the residue. 250 ml of glycerol (150 ° C, 3 mmHg) was distilled. 160 g (1.45 mol) of 3-chloropropan-1,2-diol were added slowly at 150 ° C and the mixture was stirred at this temperature for 1 hour. Next, 200 ml of a mixture of 3-chloropropan-1,2-diol and glycerol (120-148 ° C 3 mmHg, internal temperature 160-170 ° C) were distilled. The mixture was cooled to 60 ° C and treated at this temperature with 25 ml of 5.4M ethanolic sodium methanolate solution. The mixture was distilled (3 mmHg, 180-200 ° C) and the glycerol was continuously replaced. After distilling 950 ml of a two-phase mixture, the residue was extracted with hexane. After distillation, 167 g (78%) of 12Z-oxacycloheptadec-12-en-2-one, Z / E = 91/9, were obtained. IR (film) 2928; 2857; 1736; 1461; 1245; 1174. 1 H-NMR (CDC13, 200 MHz) 5.35 (2H) m; 4.1 (2H) t J = 6. 5 Hz); 2.32 (2H) t J = 7.5 Hz. 13 C-NMR (CDC13) 173.35 (s); 130.04 (d); 129.06 (d); 63.83 (t); 34.09 (t); 28.43 (t); 28.27 (t); 28.15 (t); 27.34 (t); 27.10 (t); 26.85 (t); 26.85 (t; 26.08 (tj; 5.63 (t); 24.41 (t). ES: 252 (s); 224 (5); 195 (6); 164 (7); 150 (8); 135 (24); 123 (12); 107 (26); 96 (47); 82 (97); 67 (100); 55 (60); 41 (53); 29 (8). Smell: similar to musk, then similar to of the abelmosco, Musk 174 and tibetolida.

Example 7 The procedure was carried out analogously to that of Example 3. 27.4 g of (3-carboxypropyl) triphenylphosphonium bromide (63.8 mmol) in 100 ml of THF were placed and treated with 17.2 g (153 mmol) of potassium t-butylate in 25 ml of THF. 28.5 g (60%, 69 mmol) of 11-bromoundecanal was added to this mixture. After the usual work, 20 g of crude product were obtained and after chromatography, 14 g (66%) of crude 9Z-15-bromopentadec-4-enoic acid, Z / E = 91/9, were obtained. IR (liquid): 3008; 2926; 2854; 1711; 7436; 1281; 1252; 1211. H-NMR (CDC13) 5.4 (2H) m; 3.4 (2H) t J = 7 Hz; 2.4 (4H) m. ES 300 (2); 258 (9); 238 (35); 150 (17); 137 (25); 123 (32); 110 (38); 96 (88); 82 (91); 69 (98); 55 (100); 41 (86); 29 (32).

Example 8 17 g of potassium carbonate were placed under a nitrogen atmosphere and suspended in 200 ml of N-methylpyrrolidone. A solution of 13 g was added dropwise (41 moles) of Z-15-bromopentadec-4-enoic in 120 ml of N-methylpyrrolidone using a fine dosing dropping funnel for 7 hours, while stirring at 110-115 ° C. The mixture was stirred for 1 hour, while cooling slowly. The reaction mixture was poured into water, extracted with ether, washed with water and saturated sodium chloride solution, dried over sodium sulfate and concentrated. The crude product (9.7 g) was subjected to chromatography and distilled in a bulb tube. 5.8 g (60%) of Z-oxacyclohexadec-5-en-2-one, Z / E = 91/9, were obtained. IR (film) 3008; 2928; 2857; 1737; 1459; 1350; 1254; 1166; 1041.-NMR (CDC13, 200 MHz) 5.41 (2H) m; 4.15 (2H) t J = 6.2. 13 C-NMR (CDC 1. 172.9 (s); 131.15 (d); 127.6 (d); 64. 15 (t); 35.25 (t); 27.52 (t); 27.47 (t); 27.16 (t); 27.10 (t); 26.95 (t); 26.64 (t); 26.60 (t); 25.58 (t); 24.48 (t); 23.54 (t). ES 238 (5); 220 (2); 178 (3); 163 (2); 149 (7); 135 (9); 126 (14); 112 (22); 96 (69); 82 (90); 67. (100); 55 (94); 41 (85). Smell: similar to musk, oily, powdery, similar to lactone.

Example 9 The procedure was carried out analogously to that of Example 3. 48.5 g (0.1 mol) of (7-carboxyheptyl) triphenylphosphonium bromide were suspended in 150 ml of tetrahydrofuran. After the addition of 24.7 g (0.22 mol) of potassium t-butylate in 50 ml of tetrahydrofuran, 26.4 g (0.12 mol) of 8-bromooctanal were added dropwise. After the usual work, 35.4 g of crude 8Z-16-bromohexadec-8-enoic acid, Z / E = 93/6 were obtained. IR: 3004; 2928; 2855; 1709; 1438; 1160; 1121. XH-NMR (CDC13) 5.35 (2H) m; 3.4 (2H) t J = 6.25; 2.35 (2H) t J = 7.5.

Example 10 The procedure was carried out analogously to Example 8. 41.5 g of potassium carbonate were placed in 400 ml of N-methylpyrrolidone and treated with a solution of 34 g (0.1 mol) of 8Z-16-bromohexadec- acid. 8-enoic in N-methylpyrrolidone. After the usual work, 8 g of crude product were obtained. After chromatography and distillation in a bulb tube, 11.2 g (44%) of 2-oxacycloheptadec-9-en-2-one, Z / E = 93/6, were isolated. IR (film): 3003; 2929; 2856; 1735; 1461; 1346; 1247; 1182; 1076. X H-NMR (CDCl 3/200 Mhz) 5.39 (2 H) m; 4.12 (2H) t J = 5.5 Hz; 2.33 (2H) t J = 7.5. 13 C-NMR (CDCl.-,) 173.8 (s) 130.0 (d); 129.8 (d); 64.0 (t); 34.6 (t); 29.1 (t); 28.7 (t); 28.3 (t); 28.0 (t); 27.95 (t); 27.86 (t); 27.83 (t); 26.3 (t); 26.1 (t); 25.9 (t); 24.9 (t).

Smell: similar to that of intense musk, similar to that of lactone, after nitroalmizcle, musk of abelmosco and ambretona (limonen aldehido), woody, animal.

Example 11 The procedure was carried out analogously to Example 3. 97 g (0.2 mol) of (7-carboxyheptyl) -triphenylphosphonium bromide were dissolved in 500 ml of tetrahydrofuran. Then 45 g (0.4 mol) of potassium t-butylate (0.4 mol) in 200 ml of tetrahydrofuran were added. Subsequently, 26 g (0.2 mol) of 7-hydroxy-heptan-2-one was added. After the usual work, 49 g of crude product were obtained. After chromatographic purification, 27.6 g (60%) of crude 14-hydroxy-9-methyltetradec-8-enoic acid, Z / E =, 80/20 were isolated. XH-NMR (CDCI3 200 MHz) 5.1 (1H) 6 J = 6.5 Hz; 3.65 (2H) t J = 6.25 Hz; 2.3 (2H) t = 7.5 Hz.

Example 12 The procedure was carried out analogously to Example 4. 24.5 g (95.5 mol) of crude 14-hydroxy-9-methyltetradec-8-enoic acid (Z / E = 80/20) were placed in 50 ml of glycerol and treated with 0.54 g of potassium hydroxide (50 percent). The resulting water was distilled.

After which, the upper distillation piece was removed and the special upper part (see Figure) was fitted and filled with glycerol. After the addition of 1 g of sodium methylate, the mixture was heated to 152 ° C, 6 mbar. 24 hours later, the addition of 1 g of MeONa was carried out again. After 48 hours of extraction of the content of the special upper part, 19 g of crude product were obtained. 19 g (82%) were obtained by chromatography of 10-methyloxacyclopentadec-9-en-2-one, Z / E = 80/20. IR: (film) 2930; 2857; 1735; 1459; 1382; 1251; 1161; 1085. XH-NMR (CDC13 200 MHz) 5.03 (lH) m; 4.15 (2H) t J = 5.6 Hz (Z-isomer) 4.11 (2H) t J = 6.5 (E-isomer) 2.35 (2H) m. ES 238 (3); 210 (2); 149 (3); 135 (3); 123 (13); 109 (26); 95 (53); 81 (88); 67 (89); 55 (90); 41 (100). 13 C-NMR (CDCl 3) 173.8 (s); 134.8 (s); 126.2 (d); 64. 4 (t); 34.3 (t); 31.3 (t); 28.5 (t); 28.3 (t); 27.5 (t); 26.9 (t); 26.6 (t); 26.1 (t); 25.5 (t); 24.8 (t); isomer Z. 13 C-NMR (CDCl 3) 173.7 (s); 133.9 (s); 126.0 (d); 63. 5 (t); 38.8 (t); 33.4 (t); 28.9 (t); 28.4 (t); 27.1 (t); 26.8 (t); 25.5 (t); 24.4 (t); 23.9 (t); isomer E. Smell: similar to musk, powdery, slightly fruity, waxy.

Example 13 1.14 g of 10 percent palladium on, char to 13.5 g (57 moles) of 10-methyloxacyclopentadec-9-en-2-one in 60 ml of ethanol were added and the mixture was subsequently hydrogenated under normal pressure for 6.5 hours. It was then filtered by suction over Celite and the solution was concentrated, subjected to chromatography and distilled in a bulb tube. 8.4 g (62%) of 10-methyloxacyclopentadecan-2-one were obtained. IR (film) 2928; 2859; 1735; 1459; 1377; 1343; 1247; 1113; 1047. XH-FMN (CDC13 200 MHz) 4.14 (2H) m; 2.35 (2H) m; 0.86 (3H) d J = 7 Hz. ES 240 (0.8); 169 (4); 151 (10); 141 (11); 135 (7); 123 (8); 112 (19); 97 (69); 83 (31); 69 (54); 55 (100); 41 (81); 29 (33). Smell: similar to musk, similar to lactone, woody, nitroalmizcle, dusty, earthy.

Example 14 The procedure was carried out analogously to Example 3. 45.7 g (0.1 mol) of (5-carboxypentyl) triphenylphosphonium bromide were placed in 200 ml of tetrahydrofuran and 25 g (0.22 mol) were added dropwise at 0 ° C. ) of potassium t-butylate in 100 1 of tetrahydrofuran. Then, 15.8 g (0.1 mol) of 9-hydroxy-2-nonanone was added. After stirring for 30 minutes and in a usual manner, 28.5 g of crude 14-hydroxy-7-methyltetradec-6-enoic acid were obtained.

Example 15 138.5 g of crude 14-hydroxy-7-methyltetradec-6-enoic acid, prepared according to the preceding Example, were dissolved in 400 ml of methanol, treated with 3 ml of sulfuric acid and heated at reflux temperature for 1 hour. After the usual work and distillation 93 g (90%) of methyl 14-hydroxy-7-methyltetradec-6-enoate, Z / E = 60/40. IR (film) 3380; 2930; 2856; 1742; 1437; 1173; 1059. H-NMR (CDC13, 200 MHz) 5.1 (1H) t J = 7 Hz; 3.68 (3H) 5; 3.65 (2H) t J = 6.25 Hz; 2.31 (2H) t J = 7.5. ES: 270 (1); 220 (2); 171 (7, 8); 138 (16); 123 (31); 109 (19); 95 (61); 81 (87); 67 (65); 55 (100); 41 (63); 29 (19).

EXAMPLE 16 84.5g (0.31 moles) of methyl 14-hydroxy-7-methyl-tetradec-6-enoate, 21 g of 86 percent potassium hydroxide in 220 ml of methanol, 72 g of chloropropan-1 were mixed. 2-diol and 9 ml of 5.4 M methanolic sodium methylate solution analogously to that of Example 6. The product was distilled (bp 114 ° C) under high vacuum (0.1 Torr) and subsequently subjected to chromatography. 29 g (38%) of 8-methyloxa-cyclopentadec-7-en-2-one, Z / E = 60/40, were obtained. IR (film) 2931; 2858; 1736; 1459; 1234; 1153; 1058. H-NMR (CDC13 200 MHz) 5.06-5.22 (1H); 4.05-4.2 (2H); 2.22-2.4 (2H) m. 13 C-NMR (CDC13) 173.6 (s); 173.5 (s); 135.8 (s), 134. 9 (s); 125.1 (d); 124.3 (d); 63.6 (t); 63.5 (t); 38.5 (t); 35.1 (t); 33.9 (t); 29.8 (t); 29.5 (t); 28.8 (t); 28.1 (t); 27.63 (t); 27.62 (t); 27.36 (t); 27.2 (t); 26.8 (t); 26.5 (t); 26.0 (t); 25.93 (t); 25.8 (t); 25.1 (t); 24.7 (t); 24.5 (t); 23.2 (9); 15.4 (9). Smell: weak after musk.

Example 17 25 g (0.10 mol) of Z-8-methyloxacyclopentadec-7-en-2-one were dissolved in 150 ml of methanol and hydrogenated (1.5 hours) with 2 g of 5% palladium on carbon with a overpressure of 100 mbar, Then the mixture was filtered over Celite, and the solution was concentrated, distilled in a bulb tube and subjected to chromatography. 20 g (83%) of d-methyloxacyclopentadecan-1-one were obtained.

IR (CDCl 3) 2930; 2859; 1736; 1460; 1246; 1167. XH-NMR (CDCl 3 200 MHz) 4.3-4.0 (2H) m; 2.5-2.2 (2H) m; 0.85 (3H) d J = 7.0 Hz. 13 C-NMR (CDCl 3) 173.9 (s); 63.8 (t); 34.9 (t); 33.9 (t); 32.2 (t); 30.5 (d); 28.4 (t); 28.2 (t); 26.9 (t); 26.2 (t); 24.8 (t); 24.8 (t); 24.5 (t); 23.3 (t); 20.8 (c). ES 240 (1); 138 (12); 125 (15); 110 (11); 97 (21); 83 (35); 69 (57); 55 (100); 41 (84); 27 (39), Odor: musk, then musk of abelmosco and ambretolida, powdery, floral, nitroalmizcle, similar to amber, fruity.

Example 18 The procedure was carried out in a manner analogous to that of Example 3, 95 g (0.2 mol) of (6-carboxyhexyl) triphenylphosphonium bromide in 600 ml of tetrahydrofuran were added to 48 g (0.42 mol) of potassium t-butylate in 200 ml of tetrahydrofuran. Subsequently, 29 g (0.18 mol) of 8-hydroxy-6-methyl-2-octanone was added. After working and chromatographing, 26 g (48%) of 14-hydroxy-8,12-dimethyltetradec-7-enoic acid, Z / E = 58/42, was obtained. IR (film) 2930; 2857; 1710; 1461; 1202; 1062. XH-NMR (CDC13, 200 MHz) 5.1 (1H) t J = 7.5; 3.7 (2H) m; 2.33 (2H) t J = 7 Hz; 0.9 (3H) d J = 6.3.

ES 270 (2); 252 (7); 137 (15); 123 (77); 109 (26); 95 (62); 81 (100); 69 (55); 55 (88); 41 (55); 29 (19).

Example 19 24.5 g (0.09 mol) of 14-hydroxy-8,12-dimethyltetradec-7-enoic acid were dissolved in 50 ml of methanol and treated with phenolphthalein. 6 g of 85 percent potassium hydroxide were dissolved in 50 ml of methanol and titrated until a color change was taken. Subsequently, the methanol was distilled and 80 ml of glycerol was added. 30 ml of it were distilled. Subsequently, 20 g (0.18 mol) of chloropropan-1,2-diol were added at 130 ° C and the mixture was stirred at 130 ° C for 1 hour. Excess chloropropan-1,2-diol was distilled off and treated at 70 ° C with 4 ml of methanolic solution of 5.4 M sodium methylate. It was heated at reflux temperature for 48 hours with the special top (see FIG. ). The product-glycerol mixture was poured into 1 liter of water and extracted three times with hexane. The organic phase was washed with saturated potassium bicarbonate solution, dried, concentrated and distilled in a bulb tube under high vacuum. There were obtained 19 g (83%) of 9, 13-dimethyloxacyclopent-8-en-2-one, Z / E = 58/42. IR (film) 2928; 2858; 1734; 1457; 1378; 1249; 1152; 1068 X H-NMR (CDCl 3, 200 MHz) 5.1 (1 H) m; 4.3-3.92 (2H) m; 2.31 (2H) t J = 6.5 Hz; 0.9 (3H) t J = 6 Hz. 13 C-NMR (CDCl 3) 174.1 (s); 174.0 (s); 134.9 (s); 134.2 (s); 125.7 (d); 125.6 (d); 62.5 (t); 62.1 (t); 38.5 (t); 37.0 (t); 35.9 (t); 34.38 (t); 34.35 (t); 34.2 (t); 33.6 (t); 30.1 (t); 29.8 (d); 29.4 (d); 28.8 (t); 28.5 (t); 27.9 (t); 27.3 (t); 27.2 (t); 26.9 (t); 25.2Ü (t); 24.8 (t); 24.5 (t); 23.1 (t); 22.9 (c); 19.5 (c); 18.6 (c); 15.2 (c). ES 252 (11); 245 (45); 137 (15); 123 (93); 108 (29); 95 (60); 81 (100); 67 (53); 55 (79); 41 (59); 29 (23). Smell: similar to musk, fruity, powdery, similar to lactone, earthy, good adhesion.

Example 20 9 g (0.035 mol) of 9,13-dimethyloxacyclopent-8-en-2-one were dissolved in 100 ml of ethyl acetate, 1 g of 5% palladium on activated charcoal was added and the mixture was hydrogenated under normal pressure. This was then filtered over Celite, concentrated and distilled in a bulb tube. 9 g (99%) of 9,13-dimethyloxacyclopentan-2-one were obtained. IR (film) 2928; 2859; 1736; 1459; 1378; 1245; 1156; 1116; 1056, XH-NMR (CDCl 3) 4.4-3.92 (2H); 2.5-2.2 (2H). 13 C-NMR 174.1 (s); 174.0 (s); 62.19 (t); 62.15 (t); 36. 5 (t); 35.9 (t); 35.27 (t); 35.26 (t); 34.9 (t); 33.9 (t); 33.8 (t); 33.4 (t); 33.2 (t); 30.6 (d); 29.4 (d); 27.8 (t); 27.4 (d); 27.32 (d); 27.31 (t); 26.7 (t); 26.5 (t); 25.0 (t); 24.7 (t); 24.5 (t); 22.7 (t); 22.2 (t); 20.5 (c); 20.3 (c); 19. 6c); 19.1 (c). ES 245 (45); 170 (30); 152 (35); 140 (55); 125 (47); 111 (33); 97 (62); 83 (66); 69 (87); 55 (100); 41 (85); 29 (43). Smell: similar to musk, fruity, powdery, floral, lactonic, earthy, oily.

Example 21 The procedure was carried out analogously to that of Example 3. 60 g (0.13 mol) of (5-carboxypentyl) triphenylphosphonium bromide were suspended in 250 ml of tetrahydrofuran. Then 30 g (0.26 mol) of potassium t-butylate in 20 ml of tetrahydrofuran were added. Subsequently, 26 g (0/11 moles) of 10-bromodecanal were added. After the usual work, 28 g (65%) of crude 6Z-16-bromohexadec-6-enoic acid, Z / E = 93/7, were obtained. IR (film) 2927; 2854; 1709; 1438; 1162; 1121; 723 1 H-NMR (CDCl 3 200 MHz) 5.36 (2H) m; 3.4 (2H) t J = 6.3 Hz; 2.4 t J = 7.5 Hz. ES 252 (15); 183 (9); 152 (14); 137 (11); 123 (15); 110 (17); 96 (39); 81 (51); 69 (66); 55 (100); 41 (70).

Example 22 The procedure was carried out analogously to Example 8. 25 g of potassium carbonate was suspended in 300 ml of N-methyl pyrrolidone. 30 g (0.09 mol) of crude 6Z-16-bromohexadec-6-enoic acid in 200 ml of N-methyl-pyrrolidone was added dropwise while stirring at 110-115 ° C within 10 hours. After the usual work, 18 g of the crude product were obtained and after chromatography 12 g (53%) of Z-oxacicloheptadec-7-en-2-one, Z / E = 93/7, were obtained. IR: (film) 3002; 2928; 2856; 1735; 1461; 1233; 1147. XH-NMR (CDC13 200 MHz) 5.32 (2H); 4.12 (2H) t J = 5.5 Hz; 2.31 (2H) t J = 7.5 Hz. 13 C-NMR (CDCl 3) 173.4 (s); 130.3 (d); 129.4 (d); 64.4 (t); 34.8 (t); 29.0 (t); 28.5 (t); 28.2 (t); 27.9 (t); 27.6 (t); 27.3 (t); 27.2 (t); 26.8 (t); 26.0 (t); 25.8 (t); 24.7 (t). ES 252 (2); 109 (11); 95 (29); 81 (53); 67 (69); 55 (74); 41 (100); 27 (53).

Smell: seeds of abelmosco, fruity, similar to musk, fatty, floral.

Example 23 The procedure was carried out analogously to Example 3. 130 g (0.24 mol) of (11-carboxyundecyl) triphenylphosphonium bromide in 800 ml of tetrahydrofuran were placed. 58 g (0.51 mol) of potassium t-butylate in 200 ml of tetrahydrofuran were added and then 28 g (0.26 mol) of 4-chlorobutanil were added. After the usual work, 60 g (86%) of crude 12Z-16-chlorohexadec-12-enoic acid, Z / E = 97/3 was obtained. IR (film) 3005; 2926; 2854; 1709; 1438; 1285; 1167; 723; 694. XH-NMR (CDC13 200 MHz) 5.5 - 5.2 (2H) m; 3.51 (2H) t J = 6.5; 2.32 (2H) t J = 7.5 Hz. ES 252 (9); 123 (11); 109 (19); 95 (45); 81 (92); 68 (100); 55 (100); 41 (82); 29 (19).

Example 24 The procedure was carried out analogously to Example 8. 45 g of potassium carbonate were placed in 700 ml of N-methylpyrrolidone. A solution of 57.6 g (0.2 mol) of 16-chlorohexadec-12-enoic acid in 300 ml of N-methylpyrrolidone was added dropwise at 100-110 ° C within 5 hours. After working and chromatography, 28 g (55%) of 13Z-oxaciclohept-13-en-2-one, Z / E = 97/3 were obtained. IR (film) 3004; 2928; 2856; 1737; 1459; 1343; 1248; 1169. XH-NMR 5.45-5.27 (2H) m; 4.12 (2H) t; 2.34 (3H) t. 13 C-NMR 173.7 (s); 130.9 (d); 128.4 (d); 63.6 (t); 34.1 (t); 28.8 (t); 27.8 (t); 27.5 (t); 27.5 (t); 27.2 (t); 27.1 (t); 26.8 (t); 26.7 (t); 26.1 (t); 24.6 (t); 23.8 (t). ES: 252 (1); 109 (9); 95 (27); 81 (67); 67 (100) and 55 (70); 41 (88); 27 (23). Smell: similar to musk, then musk ketone, powdery, less fruity than ambretolida, similar to the abelmosco, lactonic, oily, floral.

Example 25 The procedure was carried out analogously to Example 3. 164.6 g (0.37 mol) of bromide (4-carboxybutyl) triphenylphosphonium were suspended in 700 ml of tetrahydrofuran. 101 g (0.9 mol) of potassium t-butylate in 150 ml of tetrahydrofuran were added and then 68 g were added. (0.36 mol) of ll-hydroxy-2-undecanone in 50 ml of tetrahydrofuran. After the usual work, 98 g of crude 5Z-6-methylpentadec-5-enoic acid were obtained.

EXAMPLE 26 98 g of crude 6-methylpentadec-5-enoic acid (from the preceding Example) were dissolved in 305 ml of methanol, treated with 2 ml of sulfuric acid and heated at reflux temperature for 2 hours. Then, the mixture was poured into water, made basic with saturated potassium bicarbonate solution, extracted twice with t-butyl methyl ether, concentrated and distilled in high vacuum (0.1 Torr, 162-170 ° C. ). 75 g (85%) of methyl 6-methylpentadec-5-enoate Z / E = 56/46 were obtained. IR (film) 3365; 2928; 2855; 1741; 1437; 1369. XH-NMR (CDC13) 5.1 (1H) t J = 7.5 Hz; 3.65 (3H) s; 3. 62 (2H) t J = 6.25 Hz; 2.3 (2H) t J = 7.5 Hz. ES 284 (2); 201 (2); 173 (6); 151 (8); 137 (23); 124 (26); 109 (31); 95 (77); 82 (91); 67 (79); 55 (100); 41 (76); 27 (26).

Example 27 The procedure was carried out analogously to Example 6. 87 g (0.3 mol) of methyl 5Z-6-methylpentadec-5-enoate and 19.5 g of 86% potassium hydroxide in 200 ml of methanol were dissolved. . 66 g of 3-chloropropan-1,2-diol and 200 ml of glycerol were added, as well as 5 ml of methanolic solution of sodium methylate 5.4M. After working in the usual manner, the product was distilled in a high vacuum on a Vigreux column. 59 g (78%) of 7-methyloxacyclohexadec-6-en-2-one, Z / E = 56/46, were obtained. IR (film) 2928; 2856; 1737; 1456; 1309; 1241; 1153. XH-NMR (CDC13 200 MHz) 5.1 (1H) m; 4.15 (2H) m; 2.32 (2H). 13 C-NMR 173.7 (s); 173.5 (s); 136.0 (s); 135.5 (s); 124.4 (d); 124.2 (d); 64.8 (t); 64.0 (t); 38.9 (t); 34.3 (t); 32.5 (t); 30.4 (t); 28.2 (t); 27.67 (t); 27.66 (t); 27.34 (t); 27.31 (t); 27.29 (t); 27.23 (t); 26.84 (t); 26.79 (t); 26.72 (t); 26.69 (t); 26.2 (t); 25.9 (t); 25.8 (t); 25.7 (t); 25.5 (t); 24.3 (t); 22.8 (c); 14.9 (c). ES 252 (13); 210 (12); 151 (13); 140 (15); 124 (22); 110 (33); 95 (100); 81 (90); 67 (66); 55 (85); 41 (68); 29 (21). Smell: similar to musk, fruity, green.

Example 28 28 g (0.11 mol) of 7-methyloxacyclohexadec-6-en-2-one were dissolved in 200 ml of ethyl acetate and hydrogenated in the presence of 2 g of 5% palladium on carbon under 150 mbar of hydrogen. The mixture was filtered over Celite, concentrated and distilled in a bulb tube. 26 g (92%) of 7-methyloxacyclohexadecane-2-one were obtained. IR (film) 2929; 2858; 2858; 1737; 1461; 1377; 1237; 1167; 1111. XH-NMR (CDC13 200 MHz) 4.3-4.1 (2H) m; 2.33 (2H) m; 0.86 (3H) d J = 6.5 Hz. 13 C-NMR (CDCl 3) 173.8 (s); 63.7 (t); 35.39 (t); 34.49 (t); 33.31 (t); 30.49 (d); 28.23 (t); 27.07 (t); 26.77 (t); 26.16 (t); 26.06 (t); 26.01 (t); 25.38 (t); 25.02 (t); 24.07 (t); 20.57 (c). ES 254 (0.4); 210 (4); 137 (6); 124 (41); 111 (32); 97 (42); 83 (67); 69 (72); 55 (100); 41 (63); 29 (17). Smell: similar to musk, floral, fruity, lactonic, powdery.

EXAMPLE 29 The procedure was carried out analogously to Example 3. 100 g (0.2 mol) of (8-carboxyoctyl) triphenylphosphonium bromide were placed in 500 ml of tetrahydrofuran and treated with 47 g (0.42 mol) of t potassium-butylate in 300 ml of tetrahydrofuran and then 33 g (0.17 mol) of 7-bromoheptanal. After the usual work and chromatography, 49 g (74%) of 9Z-16-bromo-hexadec-9-enoic acid, Z / E = 98/2 was obtained. IR (film) 3004; 2928; 2854; 1709; 1463; 1285; 937. XH-NMR (CDCl, 200 MHz) 5.35 (2H) m; 3.4 (2H) t J = 6. 5 Hz; 2.35 (2H) t J = 7.5 Hz. ES 232 (0.39); 316 (3); 272 (7.8); 252 (49); 234 (6); 182 (5); 164 (10); 150 (17); 137 (24); 123 (29); 110 (33); 96 (57); 83 (68); 69 (96); 55 (100); 41 (96); 29 (35).

Example 30 The procedure was carried out analogously to Example 8. 40 g (0.29 mol) of potassium carbonate in finely pulverized form were suspended in 600 mg of N-methylpyrrolidone. 49 g (0.147 mol) of Z-16-bromohexadec-9-ene-acid in 300 ml of N-methylpyrrolidone were added dropwise within 6 hours. A standard work was done; distillation in a bulb tube and recrystallization gave 19 g (51%) of lOZ-oxacycloheptadec-10-en-2-one, Z / E = 98/2. IR (film) 3002; 2929; 2856; 1736; 1460; 1343; 1242; 1177; 1059; 722. XH-NMR (CDC13, 200 MHz) 5.36 (2H); 4.15 (2H) t J = 5.5 Hz; 2.34 (2H) t J = 6.5 Hz. 13 C-NMR (CDCl 3) 173.61 (s); 130.12 (d); 129.88 (d); 64.11 (t); 34.51 (t); 29.05 (t); 28.46 (t); 28.32 (t); 27.98 (t); 27.68 (t); 27.57 (t); 26.31 (t); 25.77 (t); 25.64 (t); 25.00 (t). ES 284 (2); 201 (2); 173 (6); 151 (8); 137 (23); 124 (26); 109 (31); 95 (77); 82 (91); 67 (79); 55 (100); 41 (76); 27 (26). Smell: similar to that of musk, then musk of abelmosco and ambretolida, dusty, strong, fruity, green, earthy, mossy.

Example 31 The procedure was carried out analogously to Example 3. 94 g (0.2 mol) of (6-carboxyhexyl) triphenylphosphonium bromide were suspended in 500 ml of tetrahydrofuran. 47 g (0.42 mole) of potassium t-butylate in 200 ml of tramprofuran were added, followed by 50 g (0.22 mole) of 9-bromononanal. After working and chromatographing, 52 g (78%) of 7Z-16-bromo-hexadec-7-enoic acid, Z / E = 90/10 was obtained. IR (film) 3004; 2927; 2854; 1709; 1462; 1277; 1239; 939. XH-NMR (CDCl 3, 200 MHz) 5.36 (2H) m; 3.4 (2H) t J = 7 Hz; 2.35 (2H) t J = 7.5 Hz.

ES 252 (13); 150 (7); 123 (13); 110 (18); 96 (36); 83 (43); 69 (60); 55 (100); 41 (67); 29 (20).

Example 32 The procedure was carried out analogously to Example 8. 41 g of potassium carbonate were suspended in 600 ml of N-methylpyrrolidone. A solution of 51 g (0.15 mol) of Z-16-bromohexadec-7-enoic acid in 400 ml of N-methylpyrrolidone was added dropwise at 90 ° C within 8 hours. After working in a usual manner and subjecting to chromatography, 30 g (77%) of 8Z-oxacicloheptadec-8-en-2-one, Z / E = 90/10, were obtained. IR (film) 3000; 2927; 2855; 1736; 1460; 1385; 1257; 1184; 1069. XH-NMR (CDC13, 200 MHz) 5.3 (2H) m; 4.13 (2H) t J = 6 Hz; 2.32 (2H) t J = 7 Hz. 13 C-NMR (CDCl 3) 173.71 (s); 130.04 (d); 129.88 (d); 63.51 (t); 34.37 (t); 29.29 (t); 28.66 (t); 28.58 (t); 28.38 (t); 28.32 (t); 28.22 (t); 27.51 (t); 26.81 (t); 26.66 (t); 25.19 (t); 25.13 (t). ES 252 (4); 149 (8); 137 (8.6); 123 (13); 109 (23); 96 (62); 81 (100); 67 (97); 54 (64).

Smell: similar to musk, dry, then oil of abelmosco seed, dusty, floral, fruity, similar to lactone, animalic.

EXAMPLE 33 The procedure was carried out analogously to Example 3. 325 g (0.7 mol) of (5-carboxypentyl) triphenylphosphonium bromide were dissolved in 1500 ml of tetrahydrofuran. After the addition of 180 g (1.6 mol) of potassium t-butylate in 700 ml of tetrahydrofuran, the mixture was treated with 175 g (0.71 mol) of 9-hydroxy-2-decanone (purity of 70%). After the usual work, they were obtained 186 g of crude 14-hydroxy-7-methyl-pentadec-6-enoic acid. This product was dissolved in 400 ml of methanol and, after the addition of 5 ml of concentrated sulfuric acid, was heated to reflux for 2 hours, After working, distilling in a bulb tube and subjecting to chromatography, 102 g were obtained. (50%) of methyl 14-hydroxy-7-methyl-pentadec-6-enoate, IR (film) 3419; 2929; 2856; 1741; 1437; 1374; 1201; 1172. XH-NMR (CDC13, 200 MHz) 5.1 (1H) t J = 7.5 Hz; 3.8 (2H) m; 3.68 (3H) s; 2.3 (2H) t J = 7.5Hz; 1.19 (3H) d J = 6.3 Hz.

ES 284 (3); 266 (4); 168 (2); 149 (10); 137 (28); 123 (14); 108 (35); 95 (74); 81 (100); 67 (57); 55 (78); 41 (41); 29 (11).

EXAMPLE 34 The procedure was carried out analogously to that of Example 19. 105 g (0.37 mol) of methyl 14-hydroxy-7-methylpentadec-6-enoate and 26 g (0.388 mol) of potassium hydroxide were dissolved at 86 ° C. one hundred in 200 ml of methanol and treated with 90 g (0.8 mol) of 3-chloropropan-1,2-diol in 300 ml of glycerol, as well as 15 ml of methanolic solution of 30 percent potassium methylate. After the addition of the methylate solution, the upper distillation piece was replaced by the special top (see Figure 1) and heated under reflux at 180 ° C under 2-4 mbar for 4 hours. After extraction, 69.5 g (74%) of 8,15-dimethyloxacyclopent-7-en-2-one, Z / E = 6/4, were obtained. IR (film) 2920; 2857; 1731; 1459; 1376; 1237; 1130; 1056. XH-NMR (CDCl., 200 MHz) 5.11 (1H) m; 4.94 (1H); 1.56 (3H) 5; 1.21 (3H) d J = 6.25 Hz. 13 C-NMR (CDCl 3) 173.44 (s); 173.24 (s); 135.98 (s); 134.85 (s); 125.29 (d); 124.41 (d); 70.27 (d); 70.16 (d); 38.32 (t); 35.73 (t); 35.58 (t); 34.71 (t); 34.26 (t); 29.74 (t); 29.55 (t); 28.89 (t); 27.80 (t); 27. 69 (t); 27.46 (t); 27.34 (t); 26.88 (t); 25.95 (t); 25.74 (t); 25.11 (t); 24.98 (t); 24.44 (t); 23.98 (t) 23.26 (c); 20.53 (c); 19.61 (c); 15.40 (c). ES 252 (4); 154 (15); 137 (15); 121 (7); 107 (30); 95 (88); 81 (100); 67 (73); 55 (93); 41 (80); 29 (26). Smell: similar to musk, dusty, then nitro-alcoholic, animalic, oily.

Example 35 The procedure was carried out analogously to Example 5. 422 g (0.8 mol) of 10-carboxidecyltriphenylphosphonium bromide and 204 g (1.81 mol) of potassium t-butylate were reacted in 1.8 liters of THF. and treated with 200 g (1.12 mol) of 70% 3-methyl-5-oxo-pentanol acetate from Example 2, Working in a manner analogous to Example 5, 297 g of crude product were obtained. This product was sterilized analogously to that of Example 5 and, after work and distillation, 168.9 g (70.9%) of 16-hydroxy-14-methyl-hexadec-11-enoate (Z / E = 95/5) were obtained. . IR (liquid) 3419; 3005; 2926; 2854; 1741; 1458; 1436; 1375; 1265; 1197; 1172; 1058. XH-NMR (CDC13) 5.4 (2H) m; 3.7 (3H) s; 2.3 (2H) t; 1.9 (2H) d.

ES 298 (0.39); 185 (7); 109 (22); 95 (33); 81 (100); 74 (18); 68 (31); 55 (57); 41 (30); 29 (9).

Example 36 The procedure was carried out analogously to Example 6. 42 g (0.14 mmol) of methyl 16-hydroxy-14-methyl-hexadec-11-enoate were reacted with 9 g of potassium hydroxide in 100 ml of methanol, treated with 150 ml of glycerol and the methanol and 50 ml of glycerol were distilled. The mixture was then reacted with 30 g of 3-chloropropan-1,2-diol at 150 ° C for 1 hour and evaporated to 70 ml under 3 mm vacuum. After the addition of 3 ml of 30% potassium methylate solution in methanol, the mixture was refluxed for 58 hours at 170-190 ° C. (3-4 mbar) as in Example 6 using the special top piece. After working as described in the Example 6, 35.8 crude product was obtained. After distillation, 26.3 g (70%) of 15-methyl-oxacicloheptadec-12-en-2-one, Z / E = 95/5, were obtained. IR (film) 3006; 2927; 2855; 1736; 1460; 1347; 1250; 1174; 1150; 1118; 1052. XH-NMR (CDC13) 5.4 (2H) m; 4.18 (1H) m; 4.10 (1H) m; 2.3 (2H) t; 0.96 (3H) d. 13 C-NMR (CDCl 3) 173.7 (s); 131 (d); 127.7 (d); 62.4 (t); 35.1 (t); 34.6 (t); 34.2 (t); 30.6 (d); 28.4 (t); 28.1 (t); 27.9 (t); 27.4 (t); 27.21 (t); 27.15 (t); 26.0 (t); 24.4 (t); 19.2 (c). ES 266 (4); 251 (2); 238 (5); 224 (10); 123 (7); 109 (19); 95 (30); 81 (100); 68 (47); 55 (53); 41 (43); 29 (15). Smell: musky, woody, animal, sweet, earthy, fruity, homogeneous.

Example 37 The procedure was carried out analogously to Example 3. 68.1 g (149 mmol) of (4-carboxy-3-methyl-butyl) -triphenylphosphonium bromide were placed in 150 ml of THF and treated with 33.4 g ( 298 mmol) of potassium t-butylate in 50 ml of THF. 35 g (149 mmol) of 10-bromodecanal were added to this mixture. After working in a usual manner, 111.8 g of crude product were obtained and, after chromatography, 29 g of 3-methyl-5Z-15-bromopentadec-5-enoic acid were obtained. IR (film) 3005; 2926; 2853; 1707; 1309. X H-NMR (CDCl 3) 1 (3 H) d; 3.4 (2H) m; 5.4 (2H) m.

ES 272 (31); 252 (14); 230 (4); 192 (6); 151 (10); 123 (12); 110 (18); 95 (43); 81 (67); 68 (100); 55 (70); 41 (50); 29 (15).

Example 38 The procedure was carried out analogously to Example 8. 17.4 g of potassium carbonate were placed in 320 ml of N-methylpyrrolidone and treated dropwise with a solution of 28 g (84 mmol) of 3-methyl- 5Z-15-bromopentadec-5-enoic in 240 ml of N-methylpyrrolidone. After working in a usual manner, 21.2 g of crude product were obtained. After chromatography and distillation in a bulb tube, 15.4 g of Z-4-methyloxacyclohexadec-6-en-2-one were isolated. IR (film) 3006; 2927; 2855; 1735; 1458; 1379; 1305; 1252; 1172; 1147; 1079. XH-NMR (CDC13) 1 (3H) d; 4.01 (1H) m; 4.3 (1H) m; 5.4 (2H) m. ES 252 (4); 210 (4); 192 (5); 149 (4); 135 (8); 121 (12); 110 (25); 95 (43); 81 (78); 67 (78); 55 (78); 41 (100); 27 (33). Smell: musky, fruity, woody, earthy, mossy.

Example 39 0.5 g of 10 percent palladium on carbon was added to 5.1 g (20 mmol) of Z-4-methyloxacyclohexadec-6-en-2-one in 20 ml of ethanol and the mixture was subsequently hydrogenated under normal pressure during 2 hours. The mixture was then filtered by suction over Celite, and the solution was concentrated, subjected to chromatography, and distilled in a bulb tube. 4 g (78%) of 4-methyloxacyclohexadecane-2-one were obtained. IR (film) 2928; 2857; 1735; 1460; 1380; 1252; 1174; 1113. XH-NMR (CDC13) 0.95 (3H) d; 2.22 (2H) d; 4.03 (1H) m; 4.21 (1H). X3C-NMR (CDC13) 173.3 (s); 63.8 (t); 42 (t); 35 (t); 30 (d); 28.2 (t); 26.8 (t); 26.6 (t); 26.3 (t); 26.2 (t); 25.6 (t); 25.5 (t); 25.0 (t); 24.8 (t); 20.1 (c). ES 254 (0.7); 194 (10); 166 (4); 152 (4); 138 (6); 124 (9); 110 (15); 96 (32); 87 (35); 82 (44); 69 (66); 55 (100); 41 (86); 29 (30). Smell: musk, fresh, animal, dusty, woody after pine needles.

Example 40: Perfume compositions a) Chord: Fresh, floral, pink, violet, suitable, for example, for female Cologne water.

Parts by Weight Compound of Example 4 10 BENZYL EXTRA ACETATE 40 3-CIS-HEXENYL ACETATE 1 PHENYLETHYL ALCOHOL 80-HEXYLCINAMALDEHYDE 100 RECONSTRUCTION OF BERGAMATE 150 BERRY FLORA 30 EXTRACT CITRONELO 40 CYCLAL C 2 ß-DAMASCONNE IN 10% DPG 2 DIPROPILEN GLYCOL 90 EBANOL 5 ETHYLINALOOL 100 FLORHYDRAL 6 FORMAT OF CITRONELYL 7 GARDENOL 4 GIVESCONA 8 HEDIONA 50 HIDROXICITRONELAL '30 INDOLLEN IN DPG AT 10% 5 ISORALDEINE 95 80 CIS-JASMONA 2 CEFALIS 50 LILIAL 50 ROSE OXIDE 1 HEXYL SALICYLATE 5 OIL OF MANDARIN 2 TERPINEOL PURE 30 TROPIONAL 20 1000 • In this composition, the compound of Example 4 confers volume and musky odor, rounds the floral notes and gives the chord more cosmetic character. b) Chord: Floral, green, spice, suitable, for example, for shampoos, soaps and toiletries.

Weight Parts Compound of Example 4 15 BENCILO EXTRA ACETATE 60 DIME ACETATE ILBENCILCARBINOL 30 GERANILO ACETATE 40 ALCOHOL FENILETILICO 120 a-HEXILCINAMALDEHIDO 120 10-UNDECEN-1-AL 5 85% PHENYLACETALDEHYDE IN ALCOHOL FENILETILICO 2 BERGAMOTA GIVCO 104 140 OIL VIRGIN CEDAR WOOD 10 CYCLOHEXAL 40 PURE GERANIOL 50 ESSENCE OF NAIL SPROUT 5 HEDIONA 40 HELIOTROPIN • 10 ISOEUGENOL 2 ISORALDEIN 95 50 LILIAL 50 SYNTHETIC LINALOOL 60 COMMON MANDARIN OIL 20 PURE PURE 1 BENCILO SALICYLATE 80 3-CIS SALICYLATE HEXENILO 10 TROPIONAL 10 VERTOFIX COEUR 30 1000 The compound of Example 4 confers volume to the composition by its musk character and similar to that of the lactone, rounds the green notes and combines the notes of spices with the floral notes. In addition, the compound of Example 4, substantively improving the composition. c) Fresh, floral aroma, for example, for cosmetics and for soaps.

Parts by weight Compound of Example 8 20 EXCITING BENZYL ACETATE 30 PURE L-BORNYL ACETATE 6 SYNTHETIC LINALYL ACETATE 80 p-TER ACETATE BUTILCICLOHEXYL 100 VERDYL ACETATE 15 a-HEXYLCINAMALDEHYDE 130 ALYL AMYLLO GLYCOLATE 3 VIRGIN CEDAR WOOD OIL 10 DAMASCENONE IN 10% DPG 5 DIHYDROMIRCENOL 80 DIMETHYLLOGENONE 7 DIPROPILEN GLICOL 30 GIVESCONA 10 HEDIONA 40 INDOLLEN 4 ISORALDEINE 95 100 LEMAROME N 5 SYNTHETIC LINALOOL 200 NECTARILUS 10 OKOUMAL 10 MANDARIN OIL 1 VERTOFIX COEUR '100 1000 This fresh, floral scent for cosmetics and soaps is further enriched by the addition of the compound of Example 8, and has the desired musk and volume note, and imparts a cosmetic effect to the composition. d) Oriental, feminine floral accord, for example, for cosmetics, for example Colonies.

Parts by weight Compound of Example 28 20 EXCELLENT BENCIHL ACETATE 30 CITRONELYL ACETATE 6 SYNTHETIC LINALYL ACETATE 50 PHENYLETHYL ALCOHOL 50 a-AMYLCINAMALDEHYDE 150 10-UNDECEN-1-AL IN 10% DPG 3 ALYL AMYL4 GLYCOLATE 4 GIVCO BERGAMATE 104 80 CARBITOL 30 4 ESSENCE OF THE CARILAM OF CEILAN 2 CASIONA (FIRMENICH) IN DPG AT 10% 5 CUMARINE CRYSTALLINE PURE 5 CYCLAL C IN DPG AT 10% 5 DIPROPILEN GLICOL 100 EBANOL 10 ETHYL LINALOOL 80 GERANIOL EXTRA 20 GERANIOL PURE 8 HEDIONA 100 INDOL IN DPG AT 10% 3 ISO E SUPER 50 CIS-JASMONA IN DPG AT 10% 6 RECONSTUCTION OF MANDARINE OIL ESSENCE 50 IRON-FREE PACHULI OIL 20 BENCILO SALICYLATE 60 3-CIS-HEXENYL SALICYLATE 30 STEMON 3 VAINILLINA 20 ==== 1000 This oriental, feminine floral chord is further enriched by the addition of the compound of Example 28. With its character similar to that of musk, moderate, the composition gives the composition more volume and velvety character, which comes into play especially in cosmetics and Colonies. e) Floral accord, for example for cosmetics and shampoos.

Parts by weight Compound of Example 8 or 24 30 EXCELLENT BENCIHL ACETATE 100 DIMETHYLBENCILCARBINOL ACETATE 30 GERANILO ACETATE 30 3-CIS-HEXENYL 2 ACETATE LINALYL ACETATE 50 P-TER ACETATE BUTILCICLOHEXYL 80 VERDYL ACETATE 50 ALCOHOL FENILETILICO 100 UNDEC-10- EN-1-AL 3 2-METHYL-UNDECANAL 3 BERRY FLOWER 50 CITRONELOL EXTRA 60 CYCLAL C 3 CYCLHEXILALYL PROPIONATE 15? -DECALACTONE 2 DIHYDROMIRCENOL 40 DIPROPILEN GLYCOL 20 EUGENOL PURE 20 FLORHYDRAL (3- (3-ISOPROPYLPHENYL) BUTANOL) 10 FRUCTONA (ETHYL ESTER OF 2-METHYL-3-DIOXOLAN-2-ACETIC ACID) 5 GARDENOL 20 GERANONITRILE 5 HELIOTROPIN CRYSTALINE 20 ß-IONONE 0 JASMONYL 50 LILY 80 LINALOOL 50 ROSE OXIDE 2 TERPINEOL 40 1000 This floral scent can be enriched by the addition of the compounds of Example 24 or Example 8. The composition takes a mild musk effect and has more volume. f) Floral lime accord, for example, for detergents.

Parts by weight Compound of Example 24 or 28 10 CITRONELYL ACETATE 50 VERDYL ACETATE 100 PHENYLETHYL ALCOHOL 60 HEXYLCINAMALDEHYDE 150 4-METOXY BENZALDEHYDE 25 METHYL BENZOATE 5 CUMARIN 15 DIHYDROMIRCENOL 60 DIPROPILEN GLYCOL 30 3-CIS-HEXENOL 10 ISO E SUPER 90 ISORALDEINE 70 140 LILIAL 130 NECTARILLO 20 OKOUMAL 15 UNDECAVERTOL (4-METHYL-DEC-3-IN-5-OL) 40 VERDANTIOL (LILIAL ANTHRILYLATE METHYL) 50 ===== 1000 The compound of Example 28 or Example 24 gives chord of soft floral quick lime, volume similar to that of musk and more substantivity; in particular, the note similar to that of soft musk comes into play in wet or dry washing. g) Floral accord, fruity, for example, for cosmetics, for example, Colonies.

Parts by weight Compound of Example 6 10 EXCITING BENZYL ACETATE 80 VETIVENYL ACETATE 40 PHENYLETHYL ALCOHOL 150 a-HEXILCINAMALDEHYDE 120 DECANAL 2 10-UNDECEN-1-AL 1 EXTRA METHYL ANTHRANYLATE 1 GIVCO BERGAMINE 104 120 DIPROPILEN GLYCOL 30 ETHYL LINOLOOL 100 EUGENOL PURE 20 GARDENOL 5 INDOLLEN 3 ISOEUGENOL 3 ISORALDEIN 70 60 METHYL CEDRIL CETONE 80 NECTARILUS 5 NONADILO 30 SALICLATE OF BENCILO 100 SALICILATE OF 3-CIS-HEXENILO 20 SANDALORA 20 1000 In this floral, fruity, feminine chord with woody subtones, the compound of Example 6 with its character similar to that of musk accompanies the floral notes and gives more strength to the fruit elements. This chord is especially suitable for Colognes and cosmetics. h) Fresh, spicy, woody chords, for example, for cosmetics, for example, Colognes for men.

Parts by weight Compound of Example 6 10 EXCITING BENZYL ACETATE 30 PURE GERANILO ACETATE 50 ALYL AMYLLO GLYCOLATE 3 EXTRA METHYL ANTHRANYLATE 1 ESSENCE OF BASILO 10 BERGAMOTA RGV 2 200 CARBITOL 60 a-ISOMETILIONONE (a-CETONA) 50 ARGENTINE OIL OF LEMON 100 CUMARINA 20 DIHYDROMIRCENOL 100 TARRAGONA OIL 5 EVERNILO 3 NAIL NAIL DRINK 15 HEDÍONA 50 ISO E SUPER 50 ISOEUGENOL 3 ESSENCE OF NUT MOSCADA 20 PACHULI OIL 30 PARAGUAY PAPILA OIL 7 SANDALORA 20 VAINILLINA 2 1000 The compound of Example 6 confers to this fruity, spicy, woody chord more volume and impression similar to that of musk, velvety and rounded to the composition. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, property is claimed as contained in the following:

Claims (42)

1. CLAIMS 1 . A perfume or odorant composition characterized in that it contains a compound or a mixture of the formula wherein, the dotted line means an optional additional bond, X and Y mean methylene or C2-12 polymethylene / optionally substituted with an additional methyl group, and A means hydrogen or methyl in the case of the unsaturated compound and methyl in the case of the saturated compounds, with the proviso that the unsaturated compounds are present in more than 80% in the cis form when A means hydrogen and are present in more than 50% in the cis form when A means methyl, with the exception of Z-oxacyclopentadec-6-en-2-one (15-membered ring), Z-oxacycloheptadec-8-en-2-one (17-membered ring) and Z-oxacycloheptadec-11-en-2-one (ring of 17 members).
2. 2. The perfume composition according to claim 1, characterized in that it contains a compound corresponding to Examples 1 to 39.
3. 3. The perfume composition according to claim 1, characterized in that it contains oxaciclo-heptadec-12-en-2 ona
4. 4. The perfume composition according to claim 1, characterized in that it contains oxaciclo-heptadec-9-en-2-one.
5. 5. The perfume composition according to claim 1, characterized in that it contains oxacycloheptadec-7-en-2-one.
6. 6. The perfume composition according to claim 1, characterized in that it contains oxaciclo-heptadec-13-en-2-one.
7. The perfume composition according to claim 1, characterized in that it contains oxaciclo-heptadec-10-en-2-one.
8. 8. The perfume composition according to claim 1, characterized in that it contains oxaciclo-heptadec-1-en-2-one.
9. 9. The perfume composition according to claim 1, characterized in that it contains 15-methyl-oxacicloheptadec-12-en-2-one.
10. 10. The perfume composition according to claim 1, characterized in that it contains 13-methyl-oxaciclopentadec-10-en-2-one.
11. 11. The perfume composition according to claim 1, characterized in that it contains R-Z-13-methyl-oxaciclopentadec-10-en-2-one.
12. 12. The perfume composition according to claim 1, characterized in that it contains S-Z-13-methyl-oxaciclopentadec-10-en-2-one.
13. The perfume composition according to claim 1, characterized in that it contains oxacyclohexadec-5-en-2-one.
14. 14. The perfume composition according to claim 1, characterized in that it contains 10-methyl-oxaciclopentadec-9-en-2-one.
15. 15. The perfume composition according to claim 1, characterized in that it contains 10-methyl-oxaciclopentadecan-2-one.
16. 16. The perfume composition according to claim 1, characterized in that it contains 8-methyl-oxaciclopentadec-7-en-2-one.
17. 17. The perfume composition according to claim 1, characterized in that it contains 8-methyl-oxaciclopentadecan-2-one.
18. 18. The perfume composition according to claim 1, characterized in that it contains 9,13-dimethyl-oxaciclopent-8-en-2-one.
19. 19. The perfume composition according to claim 1, characterized in that it contains 7-methyl-oxacyclohexadec-6-en-2-one.
20. 20. The perfume composition according to claim 1, characterized in that it contains 4-methyl-oxacyclohexadecan-2-one.
21. 21. The perfume composition according to claim 1, characterized in that it contains 7-methyl-oxacyclohexadecan-2-one.
22. 22. The perfume composition according to claim 1, characterized in that it contains 8,15-dimethyl-oxaciclopent-7-en-2-one.
23. 23. The compounds of the formula wherein, the dotted line means an optional additional bond, X and Y mean methylene or C2-12 polymethylene, optionally substituted with an additional methyl group, and A means hydrogen or methyl in the case of the unsaturated compound and methyl in the case of saturated compounds, with the proviso that the unsaturated compounds are present in more than 80% in the cis form when A means hydrogen and are present in more than 50% in the cis form when A means methyl, with the exception of the Z-oxaciclopentadec- 3- (or 6-or 13-) en-2-one, Z-oxacyclohexadec-3- (or 6-, 11-, 12- or 13-) en-2-one and Z-oxacicloheptadec-8- (or 10-, 11-, 12-, 13- or 15-) en-2-one.
24. 24. The compounds according to claim 23, characterized in that they correspond to Examples 1 to 39.
25. 25. The 13-methyl-oxacyclopentadec-10-en-2-one according to claim 23.
26. 26. The RZ-13 -methyl-oxacyclopentadec-10-en-2-one according to claim 23.
27. 27. SZ-13-methyl-oxacyclopentadec-10-en-2-one according to claim 23.
28. 28. Oxacyclohexadec-5 -en-2-one according to claim 23.
29. 29. The 10-methyl-oxaciclopentadec-9-en-2-one according to claim 23.
30. 30. The 10-methyl-oxacicclopentadecan-2-one in accordance with claim 23.
31. 31. The 8-methyl-oxacyclopentadec-7-en-2-one according to claim 23.
32. 32. The 8-methyl-oxaciclopentadecan-2-one according to claim 23.
33. 33. The 15-methyl-oxacicloheptadec-12 -en-2-one according to claim 23.
34. 34. The 9, 13-dimethyl-oxaciclopent-8-en-2-one according to claim 23.
35. 35. The 7-methyl-oxaciclohexadec-6-en -2-one according to claim 23.
36. 36. The 7-methyl-oxacyclohexadecan-2-one according to claim 23.
37. 37. The 4-methyl-oxacyclohexadecan-2-one according to claim 23.
38. 38 8, 15-dimethyl-oxaciclopent-7-en-2-one according to claim 23.
39. 39. A process for the manufacture of the compounds of formula I, according to claim 1, characterized in that it comprises lactonized of the compound of the formula wherein A, X and Y have the meaning given in claim 1 and W represents OH, O-alkanoyl or a leaving group, such as mesylate, tosylate, I, Br, Cl etc., in a manner known per se, namely at elevated temperature and under basic conditions, and, if desired, by hydrogenating the unsaturated formula I compound thus obtained.
40. 40. The process according to claim 39, characterized in that it comprises a compound of formula II, which means a leaving group, such as mesylate, tosylate, I, Br, Cl etc., is lactonized using a base, such as for example, potassium carbonate or sodium carbonate, and with the addition of N-methylpyrrolidone as a solvent.
41. 41. The method according to claim 39, characterized in that the compound of formula II is prepared by subjecting a compound of the formula Br " to a Wittig reaction with a compound of the formula ? v-
42. 42. The use of a compound of formula I is defined in claim 1 or a mixture of compounds of formula I as a perfume or odorant.