Reduced reaction product of protonic acid catalyzed reaction of methyl ethyl ketone and benzaldehyde and perfume uses thereof

Abstract: Described is a process for producing phenyl-and cyclohexyl-substituted oxybutane derivative-containing mixtures by means of first reacting methyl ethyl ketone with benzaldehyde in the presence of a sulfonic acid catalyst to produce a mixture of phenyl pentenone derivatives; and then hydrogenating the resulting mixture of phenyl pentenone derivatives in the presence of a hydrogenation catalyst, as well as the product produced thereby; and perfumery uses thereof for augmenting, enhancing or imparting aromas in or to perfume compositions, colognes and perfumed articles.

Description: Our invention concerns phenyl- and cyclohexyl-substituted oxybutane derivative-containing mixtures produced by means of first reacting methyl ethyl ketone with benzaldehyde in the presence of a sulfonic acid catalyst to produce a mixture of phenyl pentenone derivatives having the structures: and then hydrogenating the resulting mixture of phenyl pentenone derivatives in the presence of a hydrogenation catalyst thereby producing a mixture of compounds having the structures: Our invention also concerns perfumery uses thereof for augmenting, enhancing or imparting aromas in and to perfume compositions, colognes and perfumed articles. According to the present invention, there is provided a mixture of compounds containing from 80 up to 95% by weight of the compound having the structure: from 4 up to 12% by weight of the compound having the structure: up to 5 weight percent of the compound having the structure: and up to 5 weight percent of the compound having the structure: wherein all four compounds are present. Our invention is also drawn to a process for forming the afore-mentioned phenyl- and cyclohexyl-substituted oxybutane derivative-containing mixtures comprising the steps of: 1. first reacting methyl ethyl ketone with benzaldehyde in the presence of a sulfonic acid catalyst at a temperature of from 20°C up to 90°C for a period of time of from one hour up to six hours with the mole ratio of methyl ethyl ketone:benzaldehyde reactants being from 1:1 up to 3:1 and with the number of moles of sulfonic acid per mole of benzaldehyde being from 0.1 up to 0.4 according to the reaction: thereby forming a first mixture of phenyl pentenone derivatives having the structures: with the ratio of the compounds having the structures: the compounds having the structures: being from 88:12 to 95:5 and the ratios of the compounds having the structure: the compound having the structure: and the ratio of the compound having the structure: the compound having the structure: being 98:2; and then 2. reacting the first mixture of phenyl pentenone derivatives with hydrogen at a temperature of from 150°C up to 200°C, at a pressure of from 18.25 to 42.38 bar (250 psig-pounds per square inch gauge-up to 600 psig) for a time of from one hour up to ten hours in the presence of copper chromite according to the reaction: This differs from the prior art. Thus, Chmielarz, et al, Chemical Abstracts, Volume 83:147254h, abstract of Tluszcze, Srodki, Piorace, Kosmet., 1975, 19 (3), pages 109-18 discloses the perfume use of the compound having the structure in substantially pure form (98.5-99.5 pure crystalline) prepared according to the reaction: With respect to the first step of the above-mentioned process according to the invention, that is, the reaction of methyl ethyl ketone with benzaldehyde, the sulfonic acid useful in the practice of our invention may be: 69-90% sulfuric acid; para-toluene sulfonic acid; methane sulfonic acid; or xylene sulfonic acid. As stated, supra, the period of time of reaction may vary from one up to six hours. However, a preferable period of time of reaction is from two up to four hours. The reaction product resulting from the reaction of the methyl ethyl ketone and benzaldehyde yields the isomers having the structures: The mole ratios of the compounds having the structures: to the compounds having the structures: vary from 80:12 up to 95:5. The mole ratios of the "trans" to "cis" reaction products are 98:2. More specifically, the mole ratio of the compound having the structure: to the compound having the structure: is 98:2. By the same token, the mole ratio of the compound having the structure: to the compound having the structure: is also 98:2. The hydrogenation reaction, to wit: as stated, supra, may vary insofar as the time of the reaction from one hour up to ten hours with a preferable time of reaction being between six hours and nine hours. The reaction may take place in the presence of any alcohol solvent such as an isopropyl alcohol solvent; or the reaction may take place in the absence of solvent. The phenyl- and cyclohexyl-substituted oxybutane derivative-containing mixture of our invention has uses in augmenting, enhancing or imparting an aroma of or to perfume compositions, colognes and perfumed articles including but not limited to perfumed polymers, cosmetic powders, anionic, cationic, nonionic or zwitterionic detergents, fabric softener compositions, fabric softener articles including drier-added fabric softener articles (e.g., BOUNCE® marketed by the Procter & Gamble Company of Cincinnati, Ohio). The phenyl- and cyclohexyl-substituted oxybutane derivative-containing mixture of our invention is capable of imparting, augmenting or enhancing intense and long-lasting "wet floral", muguet, rose, green, lilac and ozoney aromas with natural green, floral, muguet and rose topnotes to perfume compositions, colognes and perfumed articles including soaps, anionic, cationic, nonionic or zwitterionic detergents, fabric softener articles and other perfumed articles. The phenyl- and cyclohexyl-substituted oxybutane derivative-containing mixture of our invention gives rise to unexpected, unobvious and advantageous perfumery properties when compared with single compounds known in the prior art to be useful in augmenting, enhancing or imparting aromas to perfume compositions, colognes and perfumed articles. Furthermore, when other processes are used to prepare such mixtures of phenyl- and cyclohexyl-substituted oxybutane derivative-containing mixture, completely different results ensue. Thus, for example, when carrying out a first reaction to form phenyl pentenone derivatives, thusly: followed by a hydrogenation reaction, thusly: whereby the compounds having the structures: and are produced, such compounds are produced in proportions completely different from those produced using the instant invention. Furthermore, using the process of our invention no compound having the structure: is produced. The only cyclohexyl pentanol produced has the structure: The resulting mixture of compounds having the structures: and has a sweet, cinnamon, blackberry and raspberry aroma with sweet, fruity and rose topnotes. On a scale of 1-10, the quality of such mixture has a value of "5"; the substantivity of such mixture has a value of "4" and the intensity has a value of "5". On the other hand, the phenyl- and cyclohexyl-substituted oxybutane derivative-containing mixture of our invention, on a scale of 1-10 has a quality of "9"; an intensity of "9" and a substantivity of "10". EXAMPLE A PREPARATION OF PHENYL PENTENONE DERIVATIVES Into a 2 liter reaction vessel equipped with stirrer, thermometer, reflux condenser and heating mantle are placed 12 grams (0.21 moles) of potassium hydroxide and 300 grams of methyl alcohol. While maintaining the reaction mass at 25°C, 6.0 moles (636 grams) of benzaldehyde is added with stirring. Over a period of two hours, 432 grams of methyl ethyl ketone is added to the reaction mass while maintaining the reaction mass at 25-30°C. The reaction mass is then maintained at 30°C with stirring for a period of one hour. The reaction mass is then washed with 500 ml water yielding two phases; an organic phase and an aqueous phase. The organic phase is separated from the aqueous phase and dried over anhydrous magnesium sulfate. The resulting product is then distilled on a fractional distillation column yielding the following fractions: Fraction Number Vapor Temperature (°C) Liquid Temperature (°C) (Vacuum mm/Hg.Pressure) Vacuum Pa.Pressure 1 23/40 23/120 15.0/1.00 2000Pa/133.3 2 85 140 4 533.3 3 123 144 2 266.6 4 123 142 2 266.6 5 121 153 1 133.3 6 107 178 0.21 28 7 119 218 0.23 30.7 8 145 230 0.25 33.3 Fractions 3-6 are bulked. NMR, IR and mass spectral analysis yield the information that the resulting product (bulked distillation Fractions 3-6) have the structures: EXAMPLE B PREPARATION OF PHENYL- AND CYCLOHEXYL-SUBSTITUTED OXYBUTANE DERIVATIVE-CONTAINING MIXTURE Into a 1 liter autoclave are placed the following materials: 240 grams of the mixture of compounds having the structures: prepared according to Example A; 225 grams of isopropyl alcohol; and 2.0 grams of Raney Nickel. The autoclave is closed and hydrogen is pumped into the autoclave while maintaining the reaction temperature at 125-130°C and maintaining the pressure at 28.59 bar (400 pounds per square inch gauge (psig)). The reaction is carried out for a period of five hours. At the end of the five hour period, the autoclave is cooled and opened and the reaction mass is filtered. The resulting filtrate is then fractionally distilled on a fractional distillation column yielding the following fractions: Fraction Number Vapor Temperature (°C) Liquid Temperature (°C) (Vacuum mm/Hg. Pressure) Vacuum Pa.Pressure 1 23/27 23/120 120/120 16x10 3 Pa/16x10 3 2 92 124 2 266.6 3 96 126 3 400 4 96 126 2 266.6 5 96 126 3 400 6 98 126 3 400 7 96 127 3 400 8 97 128 3 400 9 99 130 3 400 10 99 130 3 400 11 99 140 3 400 Distillation Fractions 3-8 are bulked. Bulked distillation fractions are a mixture of the compounds having the structures: and as confirmed by NMR, IR and mass spectral analysis. The resulting product has a sweet, cinnamon, blackberry and raspberry aroma profile with sweet, fruity and rose topnotes. The following examples are illustrative of the invention claimed and result in a mixture of products which falls within the ranges specified in the claims. EXAMPLE I PREPARATION OF PHENYL PENTENONES Into a 3 liter reaction vessel equipped with stirrer, thermometer, reflux condenser and heating mantle is placed a mixture of 864 grams methyl ethyl ketone (12.0 moles); 66 grams of 90% sulfuric acid (0.63 moles) and 22 grams of water. The resulting mixture is heated to 60°C and over a period of three hours while maintaining the reaction mass at 60°C, 1,060 grams of benzaldehyde (10.0 moles) is added to the reaction mass. The reaction mass is then maintained at a temperature of 60°C for a period of one hour. Over a period of 0.5 hours while maintaining the reaction mass at 60°C, an additional 60 grams of 90% sulfuric acid is added to the reaction mass. The reaction mass is then maintained at 60°C with stirring for a period of 1.5 hours. At the end of the 1.5 hour period, the reaction mass is admixed with 175 grams of water. The reaction mass is then washed with 175 grams of a 10% aqueous sodium bicarbonate solution. The organic phase is separated from the aqueous phase and the organic phase is dried over anhydrous magnesium sulfate and then fractionally distilled on a fractional distillation column yielding the following fractions: Fraction Number Vapor Temperature (°C) Liquid Temperature (°C) (Vacuum mm/Hg. Pressure) Vacuum Pa.Pressure 1 23/33 23/100 2.00/1.00 266.6/133/3 2 72 125 1 133.3 3 73 125 1 133.3 4 118 189 0.3 40 The resulting product is a mixture of compounds having the structures: The resulting product is then utilized in Example II. EXAMPLE II PREPARATION OF PHENYL- AND CYCLOHEXYL-SUBSTITUTED OXYBUTANE DERIVATIVE-CONTAINING MIXTURE An 1 liter autoclave is charged with 355 grams of the mixture of compounds having the structures: prepared according to Example I; 7.0 grams of a copper chromite catalyst and 65 grams of isopropyl alcohol. The autoclave is sealed and hydrogen is fed into the autoclave while maintaining the temperature within the autoclave at 180-185°C and while maintaining the pressure within the autoclave at 35.49 bar (500 psig.) The hydrogenation is carried out over a period of eight hours. At the end of the eight hour period, the autoclave is cooled and opened and the contents are filtered. The resulting filtrate is then fractionally distilled on a fractional distillation column yielding the following fractions: Fraction Number Vapor Temperature (°C) Liquid Temperature (°C) (Vacuum mm/Hg. Pressure) Vacuum Pa.Pressure 1 23/28 23/120 12.0/3.0 1600/400 2 95 113 1.0 133.3 3 97 113 1.0 133.3 4 98 114 1.0 133.3 5 98 115 1.0 133.3 6 98 115 1.0 133.3 7 97 115 1.0 133.3 8 98 116 1.0 133.3 9 98 115 1.0 133.3 10 97 115 1.0 133.3 11 97 115 1.0 133.3 12 97 115 1.0 133.3 13 98 115 1.0 133.3 14 98 115 1.0 133.3 15 98 115 1.0 133.3 16 99 175 1.0 133.3 17 29 210 0.5 66.7 Fractions 6-16 are bulked. The resulting bulked fractions contain the compounds having the structures: as confirmed by GLC, IR, NMR and mass spectral analysis. The resulting product has an intense and long-lasting "wet floral", muguet, rose, green, lilac and ozoney aroma with natural green, floral, muguet and rose topnotes. EXAMPLE III The following Chypre formulation is prepared: The mixture of compounds having the structures: prepared according to Example II, bulked distillation Fractions 6-16 imparts to this Chypre formulation "wet floral", muguet, rose, green, lilac and ozoney undertones with natural green, floral, muguet and rose topnotes. Accordingly, the fragrance formulation of Example III can be described as "a Chypre aroma with "wet floral", muguet, rose, green, lilac and ozoney undertones and with natural green, floral, muguet and rose topnotes". EXAMPLE IV PREPARATION OF COSMETIC POWDER COMPOSITIONS Cosmetic powder compositions are prepared by mixing in a ball mill 100 grams of talcum powder with 0.25 grams of each of the substances set forth in Table I below. Each of the cosmetic powder compositions has an excellent aroma as described in Table I below.

Claims: A mixture of compounds containing from 80 up to 95% by weight of the compound having the structure: from 4 up to 12% by weight of the compound having the structure: up to 5 weight percent of the compound having the structure: and up to 5 weight percent of the compound having the structure: wherein all four compounds are present. A process for forming the phenyl and cyclohexyl-substituted oxybutane derivative-containing mixture of claim 1, comprising the steps of: (1) first reacting methyl ethyl ketone with benzaldehyde in the presence of a sulfonic acid catalyst at a temperature of from 20°C up to 90°C for a period of time of from one hour up to six hours with the mole ratio of methyl ethyl ketone:benzaldehyde reactants being from 1:1 up to 3:1 and with the moles of sulfonic acid per mole of benzaldehyde being from 0.1 up to 0.4 according to the reaction: thereby forming a first mixture of phenyl pentenone derivatives having the structures: with the ratio of the compounds having the structures: the compounds having the structures: being from 88:12 to 95:5 and the ratios of the compound having the structure: to the compound having the structure: and the ratio of the compound having the structure: to the compound having the structure: being 98:2; and then (2) reacting said first mixture of phenyl pentenone derivatives with hydrogen at a temperature of from 150°C up to 200°C; at a pressure of from 18.25 bar up to 42.38 bar (250 psig up to 600 psig) for a period of time of from one hour up to ten hours in the presence of copper chromite according to the reaction: The process of Claim 2 wherein in the reaction: the sulfonic acid is 90% sulfuric acid and the reaction is run at 60C; and in the reaction: the hydrogenation catalyst is a copper chromite catalyst. A process for augmenting, enhancing or imparting an aroma to or in a perfume composition, a cologne or a perfumed article comprising the step of intimately admixing with a perfume composition, a cologne or a perfumed article, an aroma augmenting, enhancing or imparting quantity of the composition of matter defined according to Claim 1. A perfume composition comprising a perfume base and intimately admixed therewith an aroma augmenting, enhancing or imparting quantity of a composition of matter defined according to Claim 1. A perfumed article comprising a perfumed article base and intimately admixed therewith, an aroma augmenting, enhancing or imparting quantity of a composition of matter defined according to Claim 1. A cologne comprising ethyl alcohol, water and an aroma imparting quantity of a composition of matter defined according to Claim 1. A perfumed polymer comprising a microporous polymer and contained in the interstices thereof an aroma imparting quantity of a composition of matter defined according to Claim 1.

Inventors: HANNA MARIE R, SPRECKER MARK A, WEISS RICHARD A, HANNA, MARIE R., SPRECKER, MARK A., WEISS, RICHARD A.
Applicants: INT FLAVORS & FRAGRANCES INC, INTERNATIONAL FLAVORS & FRAGRANCES INC.
Application year: 1995
Main classification: C07C33
IPC codes: C07C29, C07C49, C07C33, C11B9, C07C31, C07C45