Title of Invention	A METHOD OF PREPARING IMPROVED PERFUME COMPOSITION
Abstract	preparing improved perfume composition having enhanced and long lasting aroma properties comprising the step of adding upto 25% by weight of cyclic isolonglfolanone ketals of the general formula A wherein the wavy lines means α or β con¬figuration and R and R1 Independently mean radicals selected froa hydrogen, methyl group or ethyl group to conventional perfumes, PRICE : THIRTY RWCE8

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The present invention relates to a method of preparing, improved perfume composition having, enhanced and long lasting aroma properties. Nowadays, industrially manufactured perfume oils consist of syn¬thetic odorants largely. The traditional application of essential oils or extracts of vegetable or animal origin is now mainly re¬stricted to the area of alcoholic perfumery. Perfume for deter¬gents, soaps, household cleaners and similar products requires the use of odorants which meet the technical demands of stability and substantivity. To comply with these demands, perfumes which are used in technical consumer products are essentially composed of synthetic odorants. Because these perfume oils are needed in large quantities as a result all major perfume companies and manufac¬turers of aroma chemicals have dedicated their research work over the last decades to produce new aroma chemicals. It has become increasingly appearant during the last 10 years that synthetic odorants which were originally destinated for the te •:; • nical perfumery, and which due to their low prices and high stabi¬lity were accordingly positioned in the market are now more and more used in the alcoholic perfumery. Perfumers have used their perfumistic know-how gained from the use of synthetic aroma chemi¬cals in technical perfumes and applied it also to alcoholic perfu¬mery as aesthetic chances may allow. Nowadays, a successfull new aroma chemical has to meet the following demands: 1. it has to present a high olfactory and aesthetic value and must be applicable in as wide a range of fragrance products as possible; 2. it has to be stable in most technical applications; 3. it has to show a good value-/for money-ratio; 4. it should be manufactured from generally available raw mate¬rials from renewable resources, whenever possible. Such a raw material of natural origin available in large quanti¬ties is Longifolene (1) which is to be found as a main component in the Indian oil of turpentine and as a minor component in many other :turpentine oils and other essential oils. About 20 years ago, research laboratories of the aroma chemical industry produced a number of derivative products from Longi¬folene, which had odorant qualities. As reported in a summary by G. Ohloff in his book "Iliechstoffe und Geruchssinn" (Springer-Ver-lag, Berlin, 1990, ISBN-Nr. 3-540-52560-2, pages 87-88) at least 4 commercial odorants are derived from the Longifolene (1). The Isolongifolene (2) which is obtained by the isomerization of Lon¬gifolene (1) can be proved to have fathered 13 commercial pro¬ducts . It is all the more surprising therefore, odorants could be found in the area of the Longifolene derlvates such as the herewith claimed new cyclic acetales of the general formula A. The acetales of the general formula A present unique olfactory qualities clearly standing out from the known odorants derivated from Isolongifolene (2) and superior to them. The new compounds of the general formula A present strongly woody olfactory qualities with flowery-fresh effects and with a velvety moss/ambra accent (see example 1); they are especially long-lasting and act as fixatives. For the manufacture of compounds of the general formula A, Longi¬folene (1) has been treated as is well known with a mixture of acetic acid and sulphuric acid [U.R. Nayak, S. Dev, Tetrahedron 8., 42-48 (I960)] or with bortrifluorid-etherate [R.E. Beyler, G. Ourisson, J.Org.Chem. 10, 2838-2839 (1965)] to obtain Isolongi-folene (2) by isomerization. The epoxide (3) [L.K. Lala, J.B. Hall, J.Org.Chem. H, 1172,.(1970); J.R. Prahlad, R. Ranganathan, W. Ramdas Nayak, T.S. Santhanakrishnan, S. Dev, Tetrahedron Lett. S, 411 (1964)] obtained by epoxidation of Isolongifolene (2) has been transformed, as is well known, into the mixture of the epimer ketones 4a/4b [R. Ranganathan, U.R. Nayak, T.S. Santhanakrishnan, S. Dev, Tetrahedron H, 621 (1970)]. In known conditions of the kinetic reaction the ring-opening of the epoxide produced a mix¬ture of ketones 4a/4b concentrated in The mixture equilibrated by basic catalysis of ketones 4a/4b (9:91, in example 3) had to undergo ketalisation reactions as well. Depending on the solvent used, different mixtures of 5a/5b were obtained, but which differed from the ketal mixtures 5a/5b obtained from the ketone mixtures 4a/4b (86:14, of example 2) so far as their relative concentrations were concerned. This varying reaction may be understood as kinetically controlled reaction during during the ketalisation. Analogues to the ketals 5a/5b the ketals 6a/6b/6c/6d were obtained by reaction of 4a/4b with 1,2-propandiol, the ketals 7a/7b/7c/7d with 1,2-butandiol, the ketals 8a/8b/8c/8d with 2,3-butandiol -each of them as a mixture. The methyl- or ethyl groups of the ketal radical may appear in an a- or B-configuration. The compounds 5a, 6a, 6c, 7a, 7c, 8a, 8c are established as SB-configurated; the compounds 5b, 6b, 6d, 7b, 7d, 8b, 8d as 5a-con-figurated. Because starting from (+)-Longifolene the chiral ketals of the general formula A were obtained by means of the chiral ketones 4a/4b; '4a/4b exist as a mixture of epimers (5a/5b), respectively as diastereo isomeres. 6a/6b and 7a/7b are constitu¬tionally isomer to 6c/6d, respectively 7c/7d. Starting from (-)-Longif olene each of the enantiomer compounds 5a,b - 8a-d are accessable. Since both the composition of the ketal mixtures depends on the conditions of the reaction (example 5), and, the single diastereo isomers may be obtained in purity (example 6, 7), the proportions within the mixtures may be adjusted to any level. The attribution of the structure of the new compounds 5-8 has been based on the spectroscopical results (examples 5 - 10). The 1H-NMR-spectra of the compounds 5a, 5b (designs 1,2) have been interpreted in analogy to the attributions given by C W Greengrass and R Ramage, Tetrahedron 31, 689 (19758) for the ketones 4a, 4b. The new compounds of the formula A are well suited as odorants due to their olfactory qualities and their stability. They may be used successfully for perfume compositions of any fragrance type either as a main component or in traces to good avail. Accordingly the present invention provides a method of preparing improved perfume composition having enhanced and long lasting aroma properties comprising the step of adding upto 25% by weight of cyclic isolongifolanone ketaLs of the general formula A. wherein the wavy lines mean α or β configuration and R and R1 independently mean radicals selected from hydrogen, methyl group or ethyl group to conventional perfumes. The examples quoted may not be understood as limitations. EXAMPLE 1 Manufacture of Isolongifolene (2) Over a period of 30 minutes 240 g (0.79 mol) of Longifolene (1) (80 % ex Indian oil of turpentine [α]D = + 39.4°) were dropped into a heated solution (60 °C) of 90 g toluene and 10 g (0.07 mol) BF3-etherate. This was stirred at 100 °C for 3 hours, than cooled down to room temperature and neutralized. After drying above Na2SO4 the solvent was distilled at reduced pressure. A raw pro¬duct of 198 g (of 70.2 % according to GLC) remained. Gaschromatogramme (HP 5890, DBWAX-30 N, 30 m, 150 °C - 240 *C, 8 'C/min). EXAMPLE 2 Manufacture of an Isolongifolanene mixture 4a/4b (86:14) A threeneck-roundbottom-flask with jacketed coil condenser and dropping funnel was charged with 198 g (0.68 mol) Isolongifolene (2) (70.2 % according to GLC) from example 1 plus 80 g toluene and 68 g (1.48 mol) formic acid and heated at 60 - 70 °C. Into this was dropped over a period of 1 hour 136 g (1.4 mol) H2O2 at 35 % concentration. After stirring for 3 hours at 80 - 85 'C it was cooled to room temperature and worked up. The separated organic phase was neutralized with natrium carbonate solution and water, dried above Na2S04 and the solvent distilled at reduced pressure. 199 g raw product remained. GLC 4a (71 %), 4b (2.5 %) [96;4]. Distillation with a 15 cm Vigreux-column produced 165 g raw pro¬duct of 4a/4b; b.p.2mm 120 - 153 °C. GLC: 4a (74 %), 4b (3 %). A subsequent distillation with a column with metallic packing pro¬duced: 110 g 4a/4b (74.4 % theoretical yield) b.p.2mm 137 - 141 °C; GC 4a (77 %), 4b (12.8 %) [86:14]. EXAMPLE 3 C-3-Epimerization of Isolongifolanone (4a/4b) 880 g (4 mol) raw (undistilled) ketone mixture 4a/4b from example 2 (purity according to GLC: 4a (63.3 %), 4b (2.48 %) [96:4]; 7 50 g methanol, 40 g (0.5 mol) NaOH 50 % were charged into a three-neck-roundbottom-flask and stirred for 8 hours under reflux. After this period 30 g (0.5 mol) concentrated acetic acid were added to cool down to room temperature. After the distillation of the solvent at reduced pressure the residual was mixed with water. The organic phase was then separated. The waterphase was extracted with 100 ml benzene. The mixed organic phases were washed first with natrium carbonate solution, then with water and dried above Na2SO4. The solvent was distilled at reduced pressure. 860 g dark brown oil remained. GLC: 4a (6.3 %), 4b (59.3 %) [9 : 91] EXAMPLE 4 C-3-Epimerization of pure Isolongifolanone (4a/4b) 440 g (2 mol) purely distilled ketone mixture 4a/4b from example 2 [purity according to GLC: 4a (77 %), 4b (12.8 %) [86:14]; 400 ml methanol, 20 g (0.25 mol) NaOH 50 % were charged into a 2 1 three-neck-roundbottom-flask and stirred for 5 hours under reflux. After cooling to room temperature, 15.5 g (0.25 mol) concentrated acetic acid were added; the solvent was distilled at reduced pressure. The residual was then mixed with water. The organic phase was separated and the waterphase was extracted with 100 ml benzene. The mixed organic phases were neutralized with natrium carbonate solution and water; after concentration 430 g brown oil remained. EXAMPLE 5 Reaction of Isolongifolanone 4a/4b with ethylene glycol 220 g (0.6 mol) ketone mixture 4a/4b from example 2, 3 or 4, 186 g (3 mol) ethylene glycol, 1 g p-toluene sulfonic acid plus 300 ml solvent (toluene, cyclohexane, benzene (63 - 80 °C), n-pentane) were charged in a 1 1 three-neck-roundbottom-f lask with water separator and heated at boiling point for 48 - 78 hours and stir¬red with water separation. During the reaction about 20 ml water each were separated at each stage. After cooling to room tem¬perature, the mixture was neutralized with natrium carbonate solu¬tion and water, dried above Na2SO4, and the solvent distilled at reduced pressure. 245 - 265 g raw product of either yellow or brown oil respectively were obtained. Distillation with a 15 cm Vigreux-column produced 230 g raw 4a/4b (b.p.2,, 68 - 170 °c). The subsequent distillation with a 40 cm column with metallic packing produced about 140 g (53 % theor. yield) 5a/5b of light yellow oil. Tabular 1 shows the results in a summary. EXAMPLE 8 Manufacture of 5-{1'-Methylethylenedioxy)-isolongifolane 6a/6b/6c/6d 440 g (2 mol) of purified ketone mixture 4a/4b from- example 2; (purity according to GLC: 4a (77 %), 4b (12.8 %) [86:14], 760 g (10 mol) propylene glycol-1.2, 600 ml toluene, 2 g p-toluene sul¬fonic acid were charged into a 4 1 three-neck-roundbottom-flask with water separator. The mixture was stirred for 30 hours under reflux. After cooling to room temperature it was neutralized with natrium carbonate soltuion and water, dried above NazSO4 and the solvent was distilled at reduced pressure. 540 g of light brown raw product remained. EXAMPLE 9 Manufacture of 5-(l'-Ethyl-ethylenedioxy)-isolongifolane 7a/7b/7c/7d 220 g (1 mol) purified ketone mixture 4a/4b from example 2 (purity according to GLC: 4a (77 %), 4b (12.8 %) [86:15], 270 g (3 mol) L ,2-butandiol, 300 ml cyclohexane, and 1 g p-toluene sulfonic acid •/ere charged into all three-neck-roundbottom-flask with water separator. The mixture was stirred for 50 hours. After cooling to room temperature it was then neutralized with natrium carbonate solution and water and dried above NazSO4. After distillation of the solvent at reduced pressure 328 g of light brown oil remained. A subsequent distillation with a 15 cm Vigreux-column produced 195 g (66.8 % theor. yield) 7a/7b/7c/7d; b.p.zmm 152 - 157 'C as light yellow oil. EXAMPLE 10 Manufacture of 5-(1',2'-dimethyl-ethylene dioxy)-isolongifolane 8a/8b/8c/8d 220 g (1 mol) of purified ketone mixture 4a/4b from example 2 (purity according to GLC: 4a (77 %) , 4b (12.8 %) [86:14]; 270 g (3 mol) 2,3-butandiol, 300 ml cyclohexane, and 1 g p-toluene sul¬fonic acid were charged into all three-neck-roundbottom-flask and stirred for 50 hours under reflux. After cooling to room tem¬perature it has been neutralized with natrium carbonate solution and water and dried above NaaSO4. The solvent was distilled at reduced pressure. 275 g light brown raw product remained. EXAMPLE 11 Description of odours of ketals 5 to 8 The olfactory qualities of the materials at 10 % in Ethanol have been evaluated by a group of experts using smelling strips. Their findings were as follows: 5a/5b [86:14] from example 5b: strong, sweet-woody, with a velvety-ambra accent and flowery aspects. 5a from example 6: strongly woody with a mossy ambra-accent and a fresh effect. 5b from example 7.' woody, light flowery, with a softly earthy ambra note, a bit . weaker than compound 5a. 6a/6b/6c/6d (from example 8): strongly woody, powdery, with a fresh ambra accent. 7a/7b/7c/7d (from example 9): dry, woody 8a/8b/8c/8d (from example 10): strongly woody, with aspects of mossy, earthy and sweet-animal no¬tes . The odors of all compounds were found to be extremely longlasting and could be smelled after several weeks. The perfume base of the indicated formula presents a well balanced flowery-woody character which may be markedly amplified and harmo¬nized by addition of 32 parts of 5a/5h (80:20). The perfume base of the indicated formula shows a fresh herbal fougere odor. An addition of 7.5 parts 6a/6b/6c/6d smoothes the composition and puts an accent on the ambra-woody note. Alternati¬vely, an addition of 7.5 parts 8a/8b/8c/8d also smoothes the com¬position but puts the accent on an animal woody aspect. The perfume oil of ; the indicated formula shows a harmonic flowery green character. Alternative addition of either 7.5 parts 5a/5b or 7a/7b/7c/7d produces a very desirable balancing in a very natural effect. Indian Patent No. 180456 describes a process for preparing cyclic isolongifolanone ketals. WE CLAIM: 1. A method of preparing improved perfume composition having enhanced and Jong lasting aroma properties comprising the step of adding upto 25% by weight of cyclic isoJongifolanone ketals of the general formula A A wherein the wavy lines mean oc or β configuration and R and R1 independently mean radicals selected from hydrogen, methyl group or ethyl group to conventional perfumes. 2. A method of preparing improved perfume composition, substantially as herein described with reference to the accompanying drawings.

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