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Publication numberUS3835169 A
Publication typeGrant
Publication dateSep 10, 1974
Filing dateJun 23, 1971
Priority dateJun 23, 1971
Publication numberUS 3835169 A, US 3835169A, US-A-3835169, US3835169 A, US3835169A
InventorsKraft E, Schlossman M
Original AssigneeKraft E, Schlossman M
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Lanolin derivatives essentially comprising esters of lanolin alcohol with lactic acid
US 3835169 A
Lanolin derivatives essentially comprising esters of lanolin alcohol with lactic acid and higher fatty acids are provided. The derivatives are prepared by direct reaction of lanolin alcohol with the higher fatty acid.
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Description  (OCR text may contain errors)

United States Patent 1191 Kraft et al.

11] 3,835,169 Sept. 10, 1974 LANOLIN DERIVATIVES ESSENTIALLY COMPRISING ESTERS OF LANOLIN ALCOHOL WITH LACTIC ACID [76] Inventors: Elise Kraft, 2109 Broadway, New

York, N .Y. 10023; Mitchell L. Schlossman, 20 Lake Shore Dr., Rockway, NJ. 07866 22 Filed: June 23, 1971 21 App1.No.: 156,023

[52] US. Cl 260/397.2, 260/410, 260/410.6,

260/410.9, 260/484 R, 424/70, 424/365, 424/64 [51] Int. CL... Cllb 11/00, C07c 69/68, A61k 7/00 [58] Field of Search 260/410, 410.9 R, 397.2,

OTHER PUBLICATIONS Conrad et al., American Perfumer and Cosmetics, vol.

Pattison, Fatty Acids and Their Industrial Applications, Marcel Dekker, Inc, N.Y., (1968) pp. 221-224.

Van Dam et al., American Perfumer and Cosmetics 84 8/69, PP. 37-40.

Condensed Chemical Dictionary, 6th ed., Reinhold Publishing Corp., New York, 1961 p. 484.

Primary Examiner-Lewis Gotts Assistant Examiner-Diana G. Rivers [5 7] ABSTRACT Lanolin derivatives essentially comprising esters of lanolin alcohol with lactic acid and higher fatty acids are provided. The derivatives are prepared by direct reaction of lanolin alcohol with the higher fatty acid.

The lanolin derivatives disclosed are especially adapted for use as essential or advantageous ingredients of various cosmetic compositions.

2 Claims, No Drawings LANOLIN DERIVATIVES ESSENTIALLY COMPRISING ESTERS OF LANOLIN ALCOHOL WITH LACTIC ACID This invention relates to new compounds which are derivatives of lanolin. More particularly the invention relates to esters of lanolin alcohols with lactic acid and higher fatty acids.

As is well known, lanolin (frequently termed wool wax or wool fat) is extensively used in cosmetic compositions, as well as in various other products, including pharmaceutical preparations, textile lubricants, textile softening agents, etc.

Lanolin is generally considered to consist of a mixture of naturally formed esters, derived from higher alcohols and higher fatty acids. A highly valuable constituent of lanolin is cholesterol.

The alcohol and acid components of lanolin have become of increasing importance in recent years. Processes for obtaining these two components'by saponifying lanolin and then separating the lanolin alcohols from the lanolin acids are quite well known.

A recently described process for such separation is referred to in an article by Van Dam which appears at pages 37-40, Vol. 84 of American Perfumer and Cosmetics (August, 1969). As there described, the process entails first saponifying the wool wax (as by alcoholic alkali), and separating the alkaline soaps of the lanolin acids from the unsaponifiable portion containing the lanolin alcohols.

The lanolin alcohol portion of lanolin wax is believed to be of the following composition (determined by column chromatography):

Cholesterol 32.5% lsocholesterol 44.2% Aliphatic alcohols l4.7% Aliphatic diols 3.2% Hydrocarbons 0.9%

n-alkanoic acids 7 iso-alkanoic acids 23 ante-iso-alkanoic acids hydroxy-alkanoic acids 28 unidentified l2 Lanolin alcohols and lanolin acids separated from wool wax and isolated from each other by the procedure above described are of technical grade.

Previous efforts to produce fatty acid esters of wool wax alcohols by esterification of lanolin alcohol with such acids have resulted in producing commercially un satisfactory yields of the esters, and in producing esters which fail to exhibit desired properties.

The principal object of the invention is to provide new compounds constituting derivatives of lanolin.

More specifically, it is an object of the invention to provide derivatives of lanolin which are lactic acid esters and fatty acid esters of lanolin alcohols.

Another object of the invention is to provide a method for the preparation of such esters.

Still another object of the invention is to provide a method for producing, in satisfactory yields, compounds constituting improved lactic acid esters and fatty acid esters of lanolin alcohols.

A still further object of'the invention is to provide improved cosmetic and other industrial compositions utilizing lactic acid and fatty acid esters of lanolin alcohols as an active ingredient thereof, whereby to impart various desirable properties and advantages to such compositions.

The aforementioned objects of the invention may be achieved by the esters of lanolin alcohol herein described, produced by the esterification procedure hereinafter more fully set forth.

Briefly stated, the lanolin alcohol esters of the present invention may be produced by the direct reaction of refined lanolin alcohol with lactic acid or with one of the enumerated fatty acids. The lanolin alcohol utilized is the entire wool wax alcohol fraction containing all of the sterols (including cholesterol) isolated from the wool wax.

In accordance with the invention, not only does the lanolin alcohol used in forming the esters hereof consist of the entire alcohol fraction of wool wax, but it is further characterized by being refined from the technical lanolin alcohols normally isolated from wool wax.

By the term refinedas employed herein to refer to the lanolin alcohols utilized in producing the esters of the present invention, is meant lanolin alcohols resulting from a distillation and deodorization treatment of technical lanolin alcohols. A preferred form of such treatment is described in the US. Pat. Nos. to Richey et al, 3,272,850 and 3,272,851.

The aforesaid treatment, briefly stated, consists of subjecting the technical lanolin alcohols, in the form of a slowly moving, whirling or so-called wiped film of relatively minute thickness, to contact with a heated surface while held under vacuum, and simultaneously subjecting the thus heated film to the stripping action of a counter-current flow of steam.

The described action apparently results in so modifying and deodorizing the technical lanolin alcohols as to enable them to react in a more desirably effective manner in the esterification reaction with the hereinmentioned acids, and thus to yield the lanolin alcohol esters of the invention.

Preferably, the thus refined lanolin alcohol is also treated to bleach or decolorize the same, following the refining treatment.

The fatty acids employed in esterifying the refined lanolin alcohols to produce the esters of the present invention may be selected from among the fatty acids of 10 or more, preferably 12 to 18, carbon atoms.

In addition to the esters made with the aforementioned fatty acids, lanolin alcohol esters embodying the invention may be made with lactic acid.

The acids employed for esterifying the refined lanolin alcohols in accordance with the invention preferably include lauric, myristic, palmitic, isostearic and oleic, as well as lactic acid.

As above indicated, the esters are formed by direct reaction of the refined lanolin alcohol with the selected acid, without necessity of using a solvent during the reaction.

In the practice of the esterification method of the invention, it is preferred that the reaction be performed in the presence of a suitable catalyst. To that end, para-toluenesulfonic acid in the amount of about 0.5 gram per mol of lanolin alcohol has been found to be suitable.

The lanolin alcohol and the selected acid are mixed, the catalyst then added, and the mixture heated. Nitrogen sparge was utilized, as was also stirring of the mixture. Temperature ranges were generally from 85C to' 170 C. Water of reaction was removed through a suitable condenser, and the reactions were continued until an acid value of 15 or less was attained. Esterification was achieved within a heating time of from approximately four to eleven hours.

Upon completion of the esterification, the reaction products were washed to remove excess acid. For that purpose, the compounds were dissolved in benzene and a calculated amount of a 10% solution of potassium hydroxide was added. After the formed emulsion had separated, the benzene layer was washed with saturated salt water until neutral. Where necessary, or desirable, the color of the compound was lightened by solution in isopropanol and treatment with charcoal. The compounds are thereby rendered ready for testing and use.

The esters of lanolin alcohol produced with the above-named acids, together with the temperature range and heating time utilized in the preparation As hereinabove indicated, the esters embodying the invention are prepared by esterifying refined lanolin alcohols containing the cholesterol and other sterol components of wool wax, with the named acids. The resulting esters are in sharp contrast to the compounds referred to in the above-mentioned article by Van Dam, formed by esterification of so-called wool wax alcohols L0. The expression wool wax alcohol L, as indicated by Van Dam, refers to the residual wool wax alcohols remaining after the cholesterol has been removed.

Herebelow are set forth examples of a number of lanolin esters embodying the invention, together with the method for preparing the same.

EXAMPLE I LANOLIN LAURATE 200.3 grams (1m) of lauric acid, 362 grams (1m) of refined lanolin alcohol and 0.5 gram para-toluenesulfonic acid were charged into a suitable reaction vessel having four necks. Provision for stirring the mixture was made, a nitrogen sparge was attached, and a condenser for water take-off was also hooked up.

Heat was applied until the reactants were melted, whereupon agitation was initiated. Water began to appear and be driven off at about C. Heating was continued for ten hours, maintaining the reaction mixture at a temperature of from 1 15C to about C. A total of 14 cc. water was obtained. Aliquot portions of the reaction were taken until an acid value of 15 was reached. 100 grams of the reaction product were dissolved in 300 cc. of benzene. This solution was shaken with 40 cc. of a ten percent aqueous solution of potassium hydroxide, the benzene layer was separated from the aqueous layer and washed with three 100 cc. portions of water. Benzene was stripped from the washed solution in vacuo, thereby yielding the lanolin laurate. The product was then decolorized by means of isopropanol as solvent, and charcoal as the decolorizing agent.

EXAMPLE II LANOLIN PALMITATE 724 grams (2m) of refined lanolin alcohol, 512 grams (2m) of palmitic acid and 1 gram of para-toluenesulfonic acid were charged to a four-neck reaction vessel fitted with a nitrogen sparge, a water take-off condenser, and a stirrer. After melting of the components of the reaction mixture in the vessel through the application of heat, water was evolved at 140C. Heating of the mixture was continued for five and one-half hours, during which the temperature of the mixture maintained was in the range of from 135C to C. A total of approximately 17 cc. of water was obtained in the reaction, and the final acid value was 15.4. 100 grams of the reaction product were dissolved in benzene, as in Example I, and the solution shaken with alkali removal of excess acid, following which the benzene layer was separated from the aqueous layer and the benzene distilled in vacuo. After elimination of the benzene, the product could be crystallized readily from solution in isopropanol.

EXAMPLE III LANOLIN ISOSTEARATE 181 grams (%m) of lanolin alcohol, 142.2 grams of isostearic acid, 1 gram of para-toluenesulfonic acid, and 300 cc. of benzene were charged into a suitable reaction vessel, fitted with a Dean Stark trap, with a condenser and a stirrer. The reaction mixture in the vessel was refluxed and the amount of water accumulated in the Dean Stark trap was recorded. Heating of the mixture at reflux conditions was continued for approximately 21 hours, until 8.1 cc. of water was removed. 12 grams KOH in 600 cc. of water were added in a separatory funnel and the layers were separated. The benzene layer was washed with two 100 cc. portions of water, and the benzene was then stripped under vacuo.

The foregoing examples of procedure for preparing certain of the esters of lanolin alcohol embodying the invention, should make it evident that the same or similar procedure will be suitable for the preparation of others of the esters of lanolin alcohol embodying the present invention.

As will be evident to those skilled in the art, the precise physical constants of the esters embodying the invention will vary to some extent, depending primarily upon the properties of the starting materials.

properties at a relative-low concentration and without necessity for the presence of any auxiliary emulsifier. The composition is non-greasy and serves as an excellent base for cleasing creams and so-called night creams. 1t very effectively removes lipstick and eye make-up by use of tissue.

Vanishing Cream (O/W) of wool wax, with the same acids.

The preparation of the lanolin lactate differed from that utilized for preparation of the other esters listed in W that the reaction of the lanolin alcohol and the lactic Tegacid, Reg. 2.00 acid was carried out under vacuum (water pump 54 g zlg 238 mm) Also, with respect to this ester, the procedure lsopropyl palmitate 4 3:00 utilized for washing the same differed from that utilized Lanolm Myrislate 5-00 for the washing of the other esters listed, in that in this W1,tcr phase instance the washing was performed with water only. Deionized water 55.40

In Table B herebelow are set forth the physical con- "?8 stants for a number of the preferred acid esters of lano- Propylene glycol 10.00 1m alcohol embodying the invention. 0000 TABLE B Acid M.P Color- Sap. Water OH 1 Val. "C Gardner Val. Absorp. Val Val.

Lanolin Lactate 1.2 42.1 9 /240 125.5 340 118.9 29.5 Lanolln Laurate .24 47.3 4-5 98.1 184 7.0 28.3 Lanolin Myristate .61 41 992-10 102.7 96 12.0 30.7 Lanolin Palmitate .25 49.7 2-3 88.8 102 7.5 29.6 Lanolin lsostearate .40 Semi- 1213 82.9 198 9.9 27.0

liquid Lanolin Oleate .75 Liquid 11 12 83.9 120 7.6 55.3

Methods of analysis: This vanishing cream composition is characterized by g a ggs cgg gl 21, its ability to spread easily on the skin, and to leave a Hydroxyl Value Saponification Value Water Absorption USP (Modified for 3 hours) USP, Hanus Special Procedure of Malmstrom Chemical Corporation Reference has hereinabove been made to the fact that the lanolin esters of the invention possess properties which render them especially suitable and advantageous for use in the preparation of cosmetic compositions. In the Examples herebelow, formulations for a variety of cosmetic compositions are set forth, wherein these esters constitute essential ingredients of the formulations. These formulations are as follows:

EXAMPLE 1 W/O Emulsion Phase A W W% Beeswax, white 16 Mineral oil (70 visc.) 50 Lanolin oleate 2 Phase B Deionized water Borax I semi-matt film; also by ability to aid in retention of facial powder.

The following formulations are for enriched moisture creams, each made with a higher fatty acid ester of lanolin alcohol, embodying the invention:

Moisture Cream which possess long term thermal stability, and have excellent gloss, smoothness with a slightly oily-feel, and are non-tacky and cosmetically elegant.

The formulations shown in the following tabulation illustrate serveral lipstick compositions utilizing lanolin lactate or one of the higher fatty acid esters of lanolin alcohol embodying the invention:

The mixture of the above ingredients is heated until it is uniform (80C.). and is then cooled to room temperature. 1n the foregoing formulation. the lanolin lactate functions as a highly effective emulsifier when Lipsticks W/W% W/W% W/W% Candclilla wax 5.00 5.00 5.00 Carnauba wax 2.00 2.00 2.00 Ozokcrite 1.50 1.50 1.50 Spermaceti 1.50 1.50 1.50 Myristyl lactate 4.00 4.00 4.00 Mineral oil, 70 visc. 5.00 5.00 5.00 Tenox 2 butylated hydroxyanisole; 0.30 0.30 0.30

6% propyl gallate',

4% citric acid;

70% propylene glycol Yellow beeswax 8.00 8.00 8.00 Nodorlan" (lanolin purified) 10.00 10.00 10.00

according to process of U.S. Pat. No. 3,272,850) Lantrol (lanolin fraction prepared 5.00 5.00 5.00

according to the process of U.S. patent 2,758,125 and purified according to process of U.S. patent 3,272,850) Perfume 0.75 0.75 0.75 castor oil soln of TiO 31.95 31.95 31.95 C-l5004 (brilliant scarlet barium lake dye) 6.00 6.00 6.00 076001 (permanent orange, barium lake dye) 6.00 6.00 6.00 3621 (pale bromo dye) 3.00 3.00 3.00 Lanolin Myristate 10.00 Lanolin Lactate 10.00 Lanolin Oleate 10.00

The ester of lanolin alcohol and lactic acid has been found to possess properties which enable it to impart advantageous characteristics not only to lipstick compositions, but to other cosmetic compositions as well.

Illustrating such cosmetic compositions are those of the formulations shown below:

No. 1 O/W Ointment Base Qil Ehasc A WZW% Lanolin lactate 19.24 Petrolatum 16.00 Propyl Parabcn 0.10

Water Phase B Sodium lauryl sulphate 0.66 Propylene glycol 12.00 H20 $1.90 Methyl Paraben 0.10 100.00

Phase A is heated to 75C.. and phase B is heated to 75C. Phase A is added to phase B at 75C. The resultant composition is then cooled to C.

The resultant composition is an ointment of heavy lotion-like character. It exhibits a relatively high degree of gloss and sheen and a desirable cosmetic look". lts phase properties enable it to be packaged in and used from either a jar or other container.

No. 2 Absorption Base W/W% Mineral oil 31.9

Lanolin lactate 38.0

Wool wax alcohol 100 Petrolatum 16.0

Paraffin 4.0

Propyl Paraben 0.1

No. 3 Zinc Oxide Ointment W/W% Zinc oxide 40.0) C Talc 5.0) Petrolatum 33.0) A Mineral oil 10.0) Lanolin lactate 7.0) B Water 5.0)

the latter is added to the former. The zinc oxide and talc are then slowly added, and the composition is allowed to cool to room temperature. It exhibited a desirable white color and a very good appearance and a highgloss.

No. 4 Cake Mascara W/W% Carnauba wax Beeswax Glycerol Monostearate,

(non-self emulsifying) Stearic acid (3x) Sodium stearate (C-l) Propyl Paraben Lanolin lactate Triethanolamine Cab-O-Sil M-S (silicon dioxide, fine form sub-micron size) Carbon black No. Lip Ice W/W% Carnauba wax Castor oil 7 Ozokerite Candelilla wax Propyl Paraben Lanolin lactate 1 Camphor No. 6 Hair Pomade W/W% Petrolatum 50.0

Lanolin lactate 15.0

High Viscosity Mineral oil 30.0

PEG monostearate 5.0

"The ingredients are' fnixed. maritime is heated until uniform and is poured into jars at 65-70C. The tests of this composition show that the lanolin lactate present therein enables the composition to yield an improved and superior hair groom, as compared to the same composition utilizing fatty alcohol (e.g.. cetyl) lactates and not lanolin lactate. The hair grooming product above set forth is more homogenous and without substantial tackiness. lt imparts a very good sheen to the hair. and one in which the presence of petroleum in the composition is not discernible by showing through.

No. 7 Barrier Cream Oil phase Stearic acid (3x) 3.5 Span 60 2.0 Tween 60 1.5 Lanolin lactate 10.0 Propyl Paraben 0.10

Water phase Carbopol 934 0.25 Water q.s. Triethanolamine 0.25 Propylene glycol 10.0 Methyl Paraben 0.10

The ingredients of th oiTpliase are mixed, and this phase is heated to C. The Carbopol is added slowly to the water phase under good agitation. This phase is heated to 75C. and the other three ingredients of this phase are added thereto. The oil phase is then added to the water phase at 75C. Upon com pletion of formation of the emulsified product. it is cooled to 30C. The resulting cream exhibits a substantially improved capacity for serving as a barrier against water, as compared to bamer cream formulations heretofore proposed.

What is claimed is:

l. A derivative of lanolin consisting essentially of an ester of a lanolin alcohol consisting of the entire wool wax alcohol fraction containing all of the sterols, including cholesterol, isolated from the wool wax, the acid fraction of said ester being derived from lactic acid.

2. The compound of claim 1, wherein said alcohol is refined lanolin alcohol.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2385849 *Feb 4, 1943Oct 2, 1945Chemsearch CorpEsters
US2686191 *Jan 30, 1952Aug 10, 1954Henkel & Cie GmbhEsters from sperm oil
US3098795 *Nov 4, 1958Jul 23, 1963Dyk & Company Inc VanCosmetic compositions containing lactic acid esters of fatty alcohols
Non-Patent Citations
1 *Condensed Chemical Dictionary, 6th ed., Reinhold Publishing Corp., New York, 1961 p. 484.
2 *Conrad et al., American Perfumer and Cosmetics, vol. 77, 10/62, pp. 97 103.
3 *Pattison, Fatty Acids and Their Industrial Applications, Marcel Dekker, Inc, N.Y., (1968) pp. 221 224.
4 *Van Dam et al., American Perfumer and Cosmetics 84 8/69, pp. 37 40.
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3953591 *Apr 29, 1974Apr 27, 1976The Procter & Gamble CompanyFatty acid, polysiloxane and water-soluble polymer containing skin conditioning emulsion
US3957971 *Jul 29, 1974May 18, 1976Lever Brothers CompanyCosmetics, liposomes, humectants
US4005210 *Jul 3, 1975Jan 25, 1977Estee Lauder, Inc.Protein containing emollient composition for a skin moisturizer
US4035514 *Feb 17, 1976Jul 12, 1977Ici United States Inc.Cetyl alcohol, lanolin, sorbitol
US4066789 *Mar 12, 1976Jan 3, 1978Emery Industries, Inc.Blends of lanolin wax and esters of aliphatic polyols and fatty acids
US4146649 *Oct 14, 1976Mar 27, 1979Faberge, IncorporatedWater, a salt, and urea or an amino acid
US4382919 *Sep 15, 1980May 10, 1983Bristol-Myers CompanyWith polymeric acid
US4416868 *Aug 8, 1975Nov 22, 1983Societe Anonyme Dite: L'orealEther oils and waxes
US5399730 *Aug 1, 1991Mar 21, 1995Development Products, Inc.Heating wool fat to esterify alcohols and acids, dissolving product in nonaqueous polar solvent, cooling to precipitate sediment, dissolving sediment in nonpolar organic solvent, water flushing, dehydration, chromatography, desolventizing
US5783725 *Feb 13, 1997Jul 21, 1998Haarmann & Reimer GmbhAddition of alkali and/or alkaline earth metal carbonates and/or bicarbonates
US6544349Nov 16, 2000Apr 8, 2003The Fanning CorporationFatty ester to remove waste deposits
USRE29814 *May 6, 1977Oct 24, 1978The Procter & Gamble CompanySynergistic
EP0474946A1 *Sep 13, 1990Mar 18, 1992SarpapProcess for producing fatty acid esters, corresponding isolated products and compositions for human or veterinary use containing same
EP0837049A1 *Oct 2, 1997Apr 22, 1998Rohm And Haas CompanyA process for preparing monomers
U.S. Classification552/545, 424/64, 560/188, 554/170, 424/70.1
International ClassificationC11C3/00
Cooperative ClassificationC11C3/003
European ClassificationC11C3/00B
Legal Events
Jan 16, 1990ASAssignment
Effective date: 19891013