This following text has been automatically extracted from the original PDF supplied by the patent office. Please refer to the original PDF document to view the text in its original format.
Q~ 111W. 11111&8___ 3.6 MICROCOPY RESOLUTION TEST CHART NAPfONAL BUREAU OF STANDARD -1963 -A AUSTRALIA PATENT APPLICATION FORM (CONVENTION) Form 4 COMMONW EALTH OF AUSTRALIA Pa ten ts A ct 14 26/79 30CT 979 1CONVENTION APPLIC FOR A PATENT Insert full ()CARROLL PRODUCTS-INCORIPORATED sdre() /W ofaplcants Wood River Junction, hereby apply for the grant of a Patent for an invention entitled Insert title "ALLANTOIN UROCANIC ACID COMPLEXES" which is described in the accompanying complete specification. This application is a convention application and is based on the application or applications for a patent or patents or similar protection made in the following country or countries on the following date or dates: Insert i0 Ja o e No. country In ndon().. nur, 17228 basicapplication in on No. was made. Insert in on No. date(s) of appilcatIon(s), in on No. inseart ~,rnber of in on No. basic application. in on No. *YfOur address for service is care of ARTHUR S. CAVE CO., Patent and Trade Mark Attorneys, 1 Alfred Street, Sydney, New South Wales, Australia 2000. Wg ,Insert date Dated this nd day of o. t.0b. e. r. 19 FPorm signed. Signature(s) (I 5 ARROLL PRODUCTS INCORPORATED,,of applicant(s). ,if a cmpanyAtre sto be xctdBy Is P tn In a manner B t aetAtres corde ARTHJJ R S. CAVE CO. ,()SaIf an Th~ Commissioner of Patents, C~MON WEALTH OF AUSTRALI-A ARTHUR S. CAVE a CO. ATENT AND TRADE MARK ATTORNEYS JAMES G. SIELY. F.I.P.A.A. SYDNEY Ak C.-2 K AUSTRALIA PATENT DECLARATION FORM (CONVENTION) Form 8 COMMONWEALtH O01F AUSTRALIA Patents Act'19S2 t~,cI~ARATI9N IN SUPPORT 01 A CONVENTION APPLICATION UNDER ~PALT XVI FOR A PATENT OR PATENT OF ADDITION To be signed by the applicant(s) or in the case of a Company, to be 4 signed by a person authorised by the Company5 .42i/1 In support of the Convention application made for a patentofadtnfranivtoneild (a Iset ite Urocariic Acid. Comlexes of invention. Insert full IWN aes..Gordon..Si ely., .Pa t name(s) of IW I) JmsGro tn declarant(s). (c)Insrtof A Ithu r 5 ad(cs) o f Q addresrn(s)of 1 Alfred Street, Sydney Cove, 2000 a do solemnly and sincerely declare as follows: *ptn 1. 1 am/we are the applicant(s) for the ptnpatent of addition. o (OR, IN THE CASE OF AN APPLICATION BY A BODY CORPORATE.) 1. IamwearautorisdbyCarroll Products Incorporated the applicant for the patent t aeti elrto patent of addition t aeti elrto on its behalf. The basic, application(s) as definled by Section 141 of the Act was/were made in the following a I, country or cov..trses on the following date(s) namely:- Insert in(d) 5 A. on(e) pA14Ary.,.79NO. 2~~a which bSebastian9 B. 'Mecca walIs il in No. Insert date of bas~c by OR (f apIcanset (d on number of by 0*00 basic application. 00006 In sert full 3. I am/we are the actual inventor(s) of the invention referred to in the basic application. names of applicnt~s)(OR, WHERE A PERSON OTHER THAN THE INVENTOR IS THE APPLICANT) *(ii)lInsert full 3. (.Se ba sti an B. M ecc a names(s of S ~~~~Inventor(s) fi 61 heae od bntn enyvna Insert 21'.homl.r..R~dAiri~~n... address(es) of U. S.A acu l. a Inventor(s). is/are the actual inventor(s) of the invention and the facts upon which I mWe entitled to make the application are as follows: the Company is Mk Set out how (k arroll Products Incorporated is the as C ne of applicant(s) derive(s) .t.room. .t from actual Inventor(s) assignee of frthe atual The basic application(s) referred to in paragraph 2 of this Declaration was/were the first lnventor(s). application(s) made in a Convention country in respect of the invention the subject of the application. Attestation or legalization niot required. Decl&red at SYDNEY this 2nd day of October 19 79 To: The Commissioner of Patents,2 COMMON4WEALTH OF AUSTRALIA ARTUR CVE Co (Signature Declarant) PATENT AND TRADE MARK ATTORNEYSAES OR NSIEYFI.PA.A SYQM4EY AE ODNSEYFIPAA MISTRAL A ~z (11) AU-A 1-51,426/79 (12) PATENT SPECIFICATION ABSTrRACT (19) AU 51,426/79 2289 17.7.80 C07D 233/88 A61K 7/44 (22) 3.10.79 (32) 10.1.79 (24) 10.1.79 (33) US C07D 233/64 A61K 7/42 Allantoin urocanic acid complexes Carroll Productis Inc. Mecca, S.B. 1. An allantoin urocanic acid complex of the formula[CH':N 40 3 [cH No wherein a and b are each about 1. 120A ND 26-4 AUSTRALIA. PATENTS ACT 1952-1973 COMPLETE SPECIF ICAT ION (ORIGINAL) FOR OFFICE USE 51 426/79 50CT1979 Application Number: Lodged: Complete Specification Lodged: Accepted: Puliished: Priority: :Related Art: TO BE COMPLETED oY APPLICANT Name "of Applicant: CARROLL PRODUCTS INCORPORATED Addret;s of Appl1icant: P.O. Box 66, Route 91, Wood River Junction, RHODE ISLAND, UT.S.A. ~Acta~iInventor: Sebastian B. Mec6ca Address for Service: ARTHUR S. CAVE CO., Patent Attorneys, 1 Alfred Street, SYDNEY COVE, 2000 Complete Specification for the invention entbitled "ALLANTOIN UROCANIC ACID COMPLEXES" ,The following statement is a full description of this invention, including -the best method of performing it known to me:- ~I f b E t a~E 11 1,426 m BACKGROUND O5HE INVENTION Allantoin is recognized as possessing soothing, keratolytic, moisturizing and anti-irritant properties. Allantoin salts and allantoin complexes are the subject of U.S. Patents No. 3,107,252; 3,275,643; 3,290,323; 3,290,324; 3,305,557; 3,578,656; 3,632,596; 3,898,243; 3,927,021; 3,954,989; 3,970,748; and 3,970,756. Urocanic acid is a metabolite derived from histidine. -j It is found in human sweat and mammalian epidermis, and is reported to have a role in protecting skin from ultraviolet light. A description of urocanic acid, its properties and uses is found in an article entitled Urocanic Acid published by Ajinomoto Co., Inc. of Tokyo, Japan. This article points out that urocanic acid may be effective as a natural sun screen in cosmetics. It is known, however, that alkaline salts, especially sodium salts of urocanic acid exhibit a high solubility in water but that such solutions undergo relatively rapid changes in color when exposed to sunlight or heat. Urocanic acid in epidermis is said to absorb 50% of ultraviolet radiation to which it is exposed. It is an object of this invention to provide novel complexes of allantoin and urocanic acid which are not sensitive to sunlight or heat and which may be used in a variety of cosmetic formulations for beneficial effects. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel complexes of allantoin and urocanic acid, and, more particularly to an allantoin urocanic acid complex, an allantoin urocanic acid salt complex and to cosmetic compositions containing these complexes. The complexes of the invention may be depicted as having <,he formulas: [4H5N40a IC6 H6 N202 b (allantoin urocanic acid complex); 4 H N 0 3 ]a L6H6 N2 0Xlb (allantoin urocanate complex); n Z _w grein a and b are each about 1 and-" -fer to the number of q mois of each component and X is a member selected from the group con sisting of sodium, potassium and ammonium. L3D The complexes are prepared by thoroughly mixing allantoin with urocanic acid forming a semidry mass which is oven dried to provide the desired complex. Alternatively, allantoin and urocanic acid may be dissolved in an alkali metal hydroxide solution, acidified to precipitate the desired complex and oven dried. Allantoin and urocanic acid are available commercially, and are used in such form in preparing the complexes of this invention. As mentioned, allantoin is known to possess soothing, cleansing, tiealing, moisturizing, anti-irritant and skin softening properties, and urocanic acid is recognized as a natural ultraviolet absorber contained in human sweat. Urocanic acid (iimidazole-4-acrylic acid), exists in trans and cis isomeric forms. Natural urocanic acid consists of the trans isomer with slight contamination of the cis isomer. The trans isomer is slightly soluble in water, slightly more soluble in boiling water, but almost insoluble in organic solvents. The maximum absorption of ->traviolet light by urocanic acid varies with the pH of solutions of the acid, with maximum absorption of 28-290 mu occurring with solutions having a pH of 7 to Allantoin and urocanic acid or alkali metal salts or urocanic acid are preferably combined in a mol ratio of about 1:1. In preferred embodiments of the invention, all antoin and urocanic acid are combined in a mol ratio of a out 1:1 to form allantoin urocanic acid complex. LikeWise, allantoin and sodium, potassium or ammonium urocanate are combined in a mol ratio of about 1:1 to form r-4 an allantoin urocanic complex. Elevated temperatures are required for formation of the desired complexes. Thus, the reaction mixtures are heated to temperatures of from about 1600 to 180 F. for about 10 to 12 hours during formation of the complexes. The complexes of this invention have the combined attributes of the healing anti-irritant cleansing, emollient, moisturizing and skin softening properties of allantoin, and the ultraviolet absorption (sun screening) properties of urocanic acid. Remarkably, the complexes of this invention have been found to pose no problem of skin irritation. Quantities effective to absorb about 100% of the ultraviolet rays of the sun, and thus are signi- ficantly more effective than conventional ultraviolet absorbers. Also, the complexes surprisingly have been found to be soluble in organic solvent including alcohol, thus permitting the formation of topical compositions with a urocanic acid content capable of maximum absorption of ultraviolet light. The complexes are useful in solution form or in lotions or creams, where they demonstrate the ability to maintain tissue moisture balance when the skin is exposed' to ultraviolet rays of the sun. The complexes prevent severe burning of the skin through absorption of ultraviolet rays while allowing controlled tanning of the skin. At the same time, the complexes permit the skin to remain r- moisturized, supple and soft and reduce possible blemishes resulting from exposure to the sun's rays. Generally, the d" complexes are formulated in pharmaceutically acceptable T-4 Scarriers at levels from 4 to 10 per cent, by weight, based on the weight of the product, to form the desired sun screening lotions and creams. The following examples illustrate properties of the complexes of this invention and suggested uses for the complexes. The examples are illustrative only, and not intended to limit the scope of the invention. EXAMPLE 1 537 5. of allantoin is thoroughly mixed with 463 g. of urocanic acid with vigorous trituration. 2 to 10% water is added and thoroughly mixed forming a semidry mass which is dried for 10 to 12 hours at 160° to 180 F. The complex formed is soluble up to 0.4 to 0.6% in water, and soluble in hot water, and analyzes allantoin 53% 5% and urocanic acid 47% EXAMPLE 2 537 g. of allantoin and 463 g of urocanic acid is dissolved in 3000 cc. of a 10% solution of sodium hydroxide. The solution is acidified with 50% acetic acid to a pH of 4.5 to 5 with constant mixing. The solution is allowed to stand overnight in an ice bath, and allantoin urocanic acid is removed by filtration. The allantoin urocanic acid is washed with distilled water and dried at 1600to 180 F. for 10 to 12 hours forming a complex slightly soluble in water and soluble in hot water. The complex analyzes allantoin 20% 5% and urocanic acid 80% The example may be repeated using potassium hydroxide or ammonium hydroxide in place of sodium hydroxide. Infrared spectral analysis establishes that the allan- toin urocanic acid complexes of this invention are distinct chemical entities, and this fact is supported by the physical and chemical properties of the complexes. Additionally, aluminum derivatives of the allantoin urocanic acid derivatives may be prepared by reacting allantoin aluminum derivatives with urocanic acid. The following formulations were made to demonstrate the usefulness of allantoin urocanic acid complexes. SUN SCREENING CREAM INGREDIENTS Ceraphyl 424 Isopropyl Myristate Witconal APM Promulgen D Cetyl Alcohol Lexemul 561 Myrj 52S Span 65 Tegosept P Escalol 507 Deionized Water Germall WEIGHT PER CENT INGREDI.FNTS Tegosept M Sodium Benzoate Sorb is tat Sequestrene AA Spectra Sorb UV-284 Urocanic Acid Allantoin Pararn-inobenzoic Acid Allantoin Urocanate Triethanolamine FD&C Yellow =1[5 FD&C Yellow =11--6 Perf\,rnie RSC jf8 WEIGHNT VER CENT SUN SCREEN GEL Snow White Petrolatum Allantoin Paramino Benzoic Acid Urocanic Acid Allantoin Urocanate Ozokerite Spermwax Snow White Petrolatum Carnation Oil Butyl Stearate Dipiopylene Glycol Salicylate Giv Tan F Tegosept B Tegosept P Red 4A.17 (K7007) 0.06% in Corn Oil Violet ff-2 (0701.4) 0.06% in Corn Oil Perfume RSC 48~ SUNSCREEN CREAM INGREDIENTS Cer-aphyl 424 Isopropyl Myristate Witconal APM Promulgen D Cetyl iAlcoho1 Lexemul 561 Myrj 52S Span 65 Tegosept P Escalol 507 Deionized Water Allantoin Paraminobenzoic Acid Germal 1 Tegosept M Sodium Benzoate Sorbistdt Sequestrene AA Spectrasorb UV-284 Allantoin Urocanate Urocanic Acid (Ajimonto) Trimethanolamine Perfume RSC :118 W~EIGHT PER CENT The claims defining the invention are as follows: 1. An allantoin urocanic acid complex of the formula I 4 HN 403 a [C6H6N20]b wherein a and b are each about 1. 2. An allantoin urocanate complex of the formula S~C4 H5 N4 3 a LCH6N 2lb wherein a and b are each Sabout 1 and refer to the number of mols of each component and X is a member selected from the group consisting of -4 sodium, potassium an, ammonium. 3. An allantoin urocanic acid complex according to claim 1 substantially as herein described with reference to example 1. 4. An allantoin urocanate complex according to claim 2 substantially as herein described with reference to example 2. A pharmaceutical preparation comprising a complex according to any one of the preceding claims, in admixture with solid or liquid pharmaceutically acceptable carriers. 6. A process for producing complexes according to any one of claims 1 to 4 substantially as herein described. 7. A method of preventing severe burning of skin exposed to ultra-vioet light while allowing controlled tanning of the skin which comprises applying to said skin a pharmaceutical preparation as defined in claim wherein the ultra-violet light is absorbed by the urocanic acid content of the preparation. DATED this 2nd day of October, 1979. CARROLL PRODUCTS INCORPORATED By Its Patent Attorneys, ARTHUR S. CAVE CO.