1.ApplicationNumber: US-39379864-A
1.PublishNumber: US-3383284-A
2.Date Publish: 19680514
3.Inventor: BELL EDWARD W.
COWAN JOHN C.

4.Inventor Harmonized: BELL EDWARD W()
COWAN JOHN C()

5.Country: US
6.Claims:

7.Description:
(en)United States Patent 3,383,284 0SMETI CUMPOSiTiONS CONTAlNiNG 'CYCLIC C AND C ALCGHGLS Edward W. Bell and John C. Cowan, Peoria, Ill., assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Griglnai appiication Mar. 10, 1964, Ser. No. 350,917. Divided and this application June 19, 1964, Ser. No. 393,7?8
3 Claims. ((Jl. 167-91) AESCT 0F TEE DISCLGSURE Rapidly absorbable cosmetic creams and lotions that are highly resistant to the development of rancidity and that do not require the masking of odoriferous constituents are provided by re lacing the conventional lanolin and cetyl alcohol components with disubstituted cyclohexane type saturated (I -C alcohol mixed isomers from the catalytic reduction of the corresponding vegetable oil-derived saturated cyclic acids.
This application is a divisional of applicants copending application S.N. 350,917, filed Mar. 10, 1964.
A nonexclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.
This invention relates to novel very low melting, odorless C and C saturated cyclic alcohols (disubstituted cyclohexanes) that exhibit unobvious properties in cosmetic preparation such as body lotions and hand creams.
More specifically, this invention relates to novel liquid alcohols, which are prepared by catalytically reducing the linolenate-derivcd saturated C cyclic acids of Scholfield et al., JOACS 36: 631 (1959) or the corresponding C ethylene adducts of Bea], US. Patent No. 3,005,840. We have also discovered that our odorless saturated cyclic alcohols may be advantageously substituted in whole or in part for the distinctly odoriferous palmityl (cetyl) alcohol that is a conventional constituent of cosmetic creams and lotions to provide cosmetics that require little if any masking and to give creams that have an appealingly softer texture and an exceptionally rapid, lanolin-like absorption by the skin. Our cyclic aicohols which are storage stable and not readily subject to oxidative deterioration may also be substituted for lanolin to provide rapidly absorbable cosmetics that are free of lanolins susceptibility to rancidity.
Also, as taught and specifically claimed in copcnding and commonly assigned application S.N. 350,925 of Theile et al., now US. Patent No. 3,287,223, when substituted for, e.g., spcrmaceti or other conventional fatty alcohol, fatty acid, or fatty ester in an aluminum oxychloride-containing antiperspirant formulation, our novel cyclic alcohols eliminate the objectionable tacky sensation caused by the aluminum salt astringent.
One object of our invention is the peparation of stable, high molecular weight, very low-melting alcohols having no unsaturation. Another object is the preparation of odorless liquid alcohols that are not only very rapidly absorbed by the skin but which also appear to improve the absorption of the other constituents of a cosmetic emulsion. The subjective and objective comments of a test panel clearly indicated an improved feel and texture and an excellent emollient action.
The above and other objects will be understood more clearly by reference to the following specification and claims.
3,383,284 Patented May 14, 1968 Our novel C and C saturated cyclic alcohols are isomeric mixtures having the following structures:
II. OH CH2) -X 0 H3 H2 (CH2)10yCH2OH where (x-l-y) 10 The starting materials for our unique alcohols are the known crude or purified isomeric mixtures of the vegetable oil-derived C saturated cyclic acids (vicinally disubstituted cycohexanes) having the formula where x+y= 10.
The crude saturated cyclic acid starting materials are mixtures comprising about 40 percent of purifiable cyciic acid monomers along with about 53 percent of byproduct stearic acid and about 7 percent of palmitic acid.
Moreover, since our novel cyclic alcohols are formed by catalytic reduction, it is not necessary to limit the starting materials to the C and C saturated cyclic acids or crudes thereof. Esters of the cyclic acids, and more economically the precursor unsaturated cyclohexadiene and cyclohexene type acids can be directly reduced to the saturated cyclic alcohols, and the same is true of their alkyl, e.g., methyl ester analogs. Furthermore, it is not necessary to isolate the'above starting materials from their crudes prior to the catalytic reduction since terminal isolation is practicable. It will be appreciated that when the copper chromite-catalyzed reduction is applied to a crude cyclic acid material, the associated aliphatic acids (stearic, oleic, palmitic, unreacted linoleic, linolenic after inciden reduction of mono, di, and triene unsafuration) are also reduced to the corresponding alcohols so that the final crude is a mixture of the C or the C cyclic alcohol isomers and saturated aliphatic alcohols. Since the byproduct aliphatic alcohol constituents in the crude cyclic alcohol mixtures are rather conventional components of cosmetic formulations, the lower cost of the crude cyclic alcohol products may result in their being preferred by industry over the pure cyclic acid isomeric mixtures.
Examples 14 show the preparation of the ester intermediates which are then catalytically reduced to the correspondin saturated alcohols as shown in Examples 58. Examples 9 and 10 show the direct reduction of the cyclic acids to the cyclic alcohols. Examples 11-20 are presented to show cosmetic formulations in which our novel cyclic alcohols have been substituted for the conventional cetyl alcohol and/or for lanolin. Table I provides chemical and physical data on our cyclic alcohol products.
EXAMPLE 1 Crude C cyclic acid monomer material (250 g.) prepared by alkali cyclization of linseed oil and comprising 40 percent unsaturated C cyclic acid isomers along with 52 percent C aliphatic acids (stearic, oleic, unreacted isometric linolenic and linoleic) and 8 percent palmitic acid were refluxed for 2 hours with 200 ml. absolute methanol, 100 ml. dimethoxypropane, and 1 ml. concentrated HCl. The mixed methyl esters (255.6 g.) were recovered and then flash distilled at 0.1 mm. Hg pressure to give 255.3 g. of the mixed ester product.
EXAMPLE 2 Purified hydrogenated, i.e., saturated C cyclic acid monomers (183.4 g.) that were freed of dimeric and polymeric materials by flash distillation after acidification of the crude acids and of aliphatic acids by low temperature crystallization from acetone, were refluxed with 500 ml. absolute methanol and 4 ml. concentrated H 50 190.2 g. of essentially pure methyl esters of the saturated C cyclic acid isomers were recovered by flash distillation of 0.1 mm. Hg.
EXAMPLE 3 A crude C unsaturated ethylene adduct mixture (501.7 g.) from the cyclization of soybean oil fatty acids in the presence of ethylene, see Friedrich et al., JOACS 39: 420 (1962) was refluxed with 1400 ml. absolute methanol and 10 ml. concentrated H 50 The crude product comprising 46.9 percent by weight of esterit'ied unsaturated C cyclic acid methyl esters was recovered and flash distilled at 0.1-0.2 mm. pressure (yield 464 g. of the methyl esters of the mixed C cyclic and the aliphatic acids).
EXAMPLE 4 The C ethylene adduct (632 g.) of unsaturated acid product from substantially (96%) pure linoleic acid, sec Friedrich ct al., JOACS 39, ibid, was refluxed with 1700 ml. absolute methanol and 12.5 ml. concentrated H 50 Flash distillation of the esters gave 582 g. of unsaturated C cyclic acid methyl ester product analyzing 83.6 percent methyl ester of the C unsaturated cyclic acids, 6.8 percent of isomeric methyl linoleate, 3.2 percent of methyl stearate, 4.2 percent of methyl oleate, and 2.2 percent of methyl palmitate.
Substantially identical yields were obtained when the sulfuric acid catalyst was replaced by boron trifluoride etherate or by a hydrogen chloride-dimethoxy propane catalyst system.
EXAMPLE 5 A 500 ml. stainless steel autoclave equipped with a magnetic stirrer, pressurized gas admission means, and heating mantle was charged with 200 g. of the crude C unsaturated cyclic methyl ester mixture of Example 1 and 20 g. by weight) of a commercial copper chromite catalyst comprising 40 percent CuO, 47 percent Cr O and 10 percent BaO. After flushing, the autoclave was pressurized with hydrogen to 2100 p.s.i. at room temperature and then rapidly heated with stirring to 280 C. At 145 C. and 2,525 p.s.i., a rapid uptake of hydrogen began. During the third (final) hour of reaction at 280 C. the hydrogen uptake was almost negligible. After cooling, the contents were diluted with 200 ml. acetone and the catalyst removed by filtration on a steam-heated funnel. The acetone was stripped off, and the alcohols were flash distilled using a nitrogen sweep at 0.07-0.14 mm. and a steam-heated condenser; 168.2 g. of a distilled fraction boiling at ll8l68 C. and representing a 98 percent conversion of the esters of both the C cyclic acids and the aliphatic acids to the saturated alcohols was obtained along with 15.7 g. of residue.
4- EXAMPLE 6 190 g. of the methyl esters of purified saturated C cyclic acid isomers of Example 2 were reduced in the apparatus of Example 5. Since the ring portion of the cyclic acid esters was already saturated, the reaction did not require additional hydrogen for that purpose. Upon stripping the acetone there remained 155 g. of saturated C cyclic alcohol isomers. Distillation gave 1.7 g. of a fraction boiling at 103129 C./0.l5 mm.; 142.9 g. of a fraction boiling at 129-152 C./0.15 mm; and 6.8 g. of residue. Because the main fraction showed only 69 percent conversion of ester to alcohol (by hydroxyl determination), the alcohols were redistiiled in a vacuumjacketed Vigreux column. The first fraction (18.5 g.) in a vacuum-jacketed Vigrcux column. The first fraction (18.5 g.) boiling at -129 C./0.07 mm. had a refractive index 11 of 1.4638 and by GLC analysis represented a 79 percent conversion of ester to alcohol along with the formation of 21 percent hydrocarbon. The second fraction (64.9 g.) boiling at 129134 C./0.07 mm. and representing a 98.8 percent conversion had a refractive index of 1.4685. The third fraction (44.8 g.) boiling at 134-138 C./0.07 mm. had a refractive index of 1.4694. Since GLC analysis showed the second and third fractions to be identical, they were combined, 11 1.4689.
EXAMPLE 7 450 g. of the mixed methyl esters of the C unsaturated cyclic acid mixture of Example 3 (46.9 percent C cyclic acid methyl esters, 6.6 percent unreacted conjugated methyl esters, 6.6 percent unreacted conjugated methyl linoleate, 2.60 percent methyl oleate, 5.4 percent methyl stearate, and 15.1 percent methyl palmitate) were placed in a 1000 ml. stainless steel autoclave along with 45 g. of copper chromite catalyst and then treated exactly as in Example 5. Distillation of the crude alcohol mixture (414.3 g.) yielded 8 g. of a fraction boiling at 90-131 C./0.04 mm.; 379 g. boiling at 131-180 C./0.04-0.05 mm.; and 32.3 g. residue. The conversion to the saturated alcohols was 96.5 percent.
EXAMPLE 8 500 g. of the mixed methyl ester product of Example 4 and containing 83.6 percent of the esterified unsaturated C cyclic acids, 6.8 percent unreacted conjugated methyl linoleate, 3.2 percent methyl stearate, 4.2 percent of methyl oleate, and 2.2 percent methyl palmitate were hydrogenated in the presence of 42 g. of copped chromite catalyst exactly as in Example 7. Distillation of the alcohols (441.8 g.) gave 1.8 g. boiling at 130 C./O.l mm.; 389 g. boiling at 180 C./0.10.2 mm.; and 40.2 g. residue. Conversion of ester to alcohol was 93 percent.
EXAMPLE 9 A 2 liter autoclave of the type used in Example 5 was charged with 400 g. of crude unsaturated C cyclic acid material obtained by an alkali cyclization of linseed oil. This crude material comprised 37.4 percent C unsaturated cyclic acid monomers and 9.5 percent polymeric residue. After introducing 40 g. of commercial copper chomite catalyst, the autoclave was flushed and pressurized with hydrogen to 2100 p.s.i. at room temperature, followed by a rapid heating to 280 C. A sample taken at 5 hours had an iodine value of 20 and acid value of 10.5; at 9 hours of reduction the respective values were 14 and 6; and at 11 hours they were 14 and less than 1. The crude cyclic alcohols (370 g.) were recovered as described in Example 5, using 400 ml. acetone. To determine whether there was residual unsaturation, 112 g. of the acetone-free crude alcohols were flash distilled, yielding 108.5 g. of a fraction having an iodine value of 6.5 and 2.4 g. of a residue with an iodine value of 49.5. After rccombing the distillate fractions and the remaining crude alcohols, 36 g. of fresh catalyst was added to the 360 g.
of crude cyclic alcohol mixture, and hydrogenation was resumed for 4 hours at 280 C. Following the recovery of the crude saturated C cyclic alcohols (322.8 g.) having an iodine value of 2.7 and acid value of 0.6, distillation of a 176 g. portion thereof gave 7.5 g. of a fraction boiling at 90-120 C./ 0.15 mm.; 155 g. of a fraction boiling at 120-160' C./0.15 mm.; and 12.2 g. of residue. GLC analysis of the first fraction showed it to consist of 36 percent saturated C cyclic alcohols, 40.6 percent stearyl alcohol, 14.3 percent palmityl alcohol, and 9.1 percent hydrocarbon. The main fraction (96 percent conversion of acids to alcohols) having an acid value of 0.65, iodine value of 0.48, and melting at 38-46 C. analyzed 37.8 percent saturated C cyclic alcohol isomers, 57.5 percent stearyl alcohol, and 4.7 percent palmityl alcohol.
EXAMPLE The glass liner of a 300 ml. high pressure rocker autoclave was charged with 63 g. of the pure C unsaturated cyclic aoid obtained by the 1,4-addition of ethylene to 9,1l-t,t-octadec-adienoic acid and 6.3 g. of copper chromite catalyst. After prcssurizing with hydrogen to 2100 p.s.i. at room temperature, the autoclave was heated to 280 C. and the contents reacted for 4 hours. After cooling and diluting the contents with 200 ml. acetone, the catalyst 6 EXAMPLE 12 Part A: Percent Crude C cyclic (47.6%) alcohol of Example 7 (in place of cetyl alcohol) 5 Paraflin 10 Light mineral oil 5 Part B:
Cetyl trimethyl ammonium chloride 0.5 H 0 69.5
EXAMPLE 13 Part A: Percent Crude C linseed cyclic (40%) alcohol of 15 Example 5 (in place of cetyl alchol) 16.0 Lanolin 16.0 Isopropyl myristate 16.0 Part B:
Isooctylphenyl-polyethoxy ethanol 4.0 20 B 0 48.0
EXAMPLE 14 Part A: Percent Crude C soybean cyclic (47.6%) alcohol of was filtered off. Distillation of the product (50 g.) :gave Experiment 7 (substituted for cetyl alcohol) 16.0 4 g. of a fraction boiling at 108-150 C./0.07-0.1 mm., Lanolin 16.0 11 1.4650; 34 g. of a fraction boiling at 150-165 C./ Isopropyl myristate 16.0 0.1-0.2 mm., n 1.4668; and 4 g. residue. GLC analysis Part B: of the main fraction showed only extremely faint traces of Isooctylphenyl-polyethoxy ethanol 4.0 stearyl alcohol and hydrocarbons. H O 48.0
TABLE I Saturated cyclic alcohols Irom Cyclic, OH, LV. Acid V. M.P., Viscosity Percent Percent C. (cps), 60 0. C15 linseed-derived monomers (crude) 6.14 0.7 0. 42-53 11. 65 C18 (purified) 0 6. 2 1.1 0. 45 1 -40 1s. 7 C20 soybean monomers (crude) 47.9 6. 8 1.3 0. 56 37-51 14. 8 020 (from ethylene adduct of methyl linoleate 30.2 5.4 1.0 0.47 23-25 18.7 020 from ethylene adduct of pure 9,11-t,t-
oetadecadienoie acid 100 5.5 0.3 0.99 22-25 28.0
1 Pour point.
In the following standard hand creams and body lotion EXAMPLE 15 formulations shown in Sagarin, Cosmetics, Science and Part A: "Percent Technology, published 1957 by Interscience Publ. Co., Crude C linseed cyclic (40%) alcohol of Ex- Inc., New York, our crude or highly pure C or C ample 4 (substituted for cetyl alcohol and cyclic alcohols have been substituted, as shown, for cetyl 5O lanolin) 32.0 alcohol or for lanolin or both. The emulsions were pre- Isopropyl myristate 16.0 pared by the conventional procedure of separately pre- Part B: paring the phases, slowly adding the oil phase (Part A) Isooctylphenyl-polyethoxy ethanol 4.0 at 70-75 C. to the aqueous (external) phase (Part B) at H O 48.0 the same temperature with stirring that was maintained until room temperature was reached. The visoosities of the formulations containing the C cyclic alcohol mate- EXAMPLE 16 nials were generally somewhat lower than in the corre- Part A: Percent sponding formulations employing the C cyclic alcohols Crude C18 11118364 cychc (40%) filcohol of 6 and this difference was greater in the non-ionic formula- 60 ample 5 (Substltuted for lanolm) 1 tions. However, the slight dilferences in viscosity did not Cetyl noticeably atfect the very rapid absorption nor the supe- Isopmpyl mynstate rior esthetic qualities. Examples 11 and 12 are c-ationic, Part B: examples 13-17 are non-ionic, and Examples 18-20 are Isooctylphenylpolyethoxy ethanol anionic non-soap formulations. All percentages refer to E20 parts by weight.
EXAMPLE 11 EXAMPLE 17 (LOTION) Part A: Percent Part A: Percent Crude C18 saturate? cychc (40%) alcohol of Crude soybean C cyclic (47.6%) alcohol of Example S (substituted for cetyl alcohol) 15 Example 7 (substituted for lanolin) 16D i 10 Cetyl alcohol 16.0 Llght numeral 011 n 5 Isopropyl myristate 16.0 Part B: Part B:
Cetyl trimethyl ammonium chloride 0.5 Isooctylphenyl-polyethoxy ethanol 4.0 H 0 69.5 H O 48.0
7 EXAMPLE 18 (LOTION) Part A: Percent Crude (40%) linseed cyclic (40%) alcohols of Example 5 10.0 Sodium cetyl sulfate 2.0 Stearic acid 8.0 Stearyl alcohol 3.0 Part B:
Glycerol 8.0 Sodium cetyl sulfate 1.0 H 68.0
EXAMPLE 19 Part A: Percent Crude soybean C cyclic (47.6%) alcohols of Example 7 10.0 Sodium cetyl sulfate 2.0 Stearic acid 8.0 Stearic alcohol 3.0 Part B:
Glycerol 8.0 Sodium cetyl sulfate 1.0 H 0 68.0
EXAMPLE 20 Part A: Percent Purified C saturated cyclic alcohols of Example 6 10.0 Sodium cetyl sulfate 2.0 Stearic acid 8.0 Stearyl alcohol 3.0 Part B:
Glycerol 8.0 Sodium cetyl sulfate 1.0 H 0 68.0
It is clear that those skilled in the cosmetic art can make many obvious adjustments and modifications based on the present disclosure without departing from the spirit of our invention.
We claim:
1. A hand cream having the following percentage composition 2. A hand cream having the following percentage composition Percent CH2(CH2)lu-XCII3 GHz(CH2)l0-yCHzOTI wherein (x+y)=1 Paraffin 10 Light mineral oil S Cetyl trimethyl ammonium chloride 0.5 H 0 69.5
3. A hand cream having the following percentage com- 20 position Percent CH2(CH2)s- CH -CH (CH)g 1CII2OII wherein (x-l-y)=8 Sodium cetyl sulfate -c 2.0 Stearic acid 8.0 Stearyl alcohol 3.0 Glycerol 8.0 Sodium cetyl sulfate 1.0 H 0 68.0 100.0
References Cited UNITED STATES PATENTS 5 2,815,388 12/1957 Inhoffen et al. 260-617 3,287,223 11/1966 Theile et al. 16790 ALBERT T. MEYERS, Primary Examiner.
D. R. MAHANAND, Assistant Examiner.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,383,284 May 14, 1968 Edward W. Bell et a1.
It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:
Column 4, line 32, "2 .60" should read 26.0
Signed and sealed this 30th day of September 1969,
(SEAL) Attest:
Edward M. Fletcher, Jr. Commissioner of Patents Attesting Officer