US3625976A - Coumarin ether sun-screening compounds - Google Patents

Coumarin ether sun-screening compounds Download PDF

Info

Publication number
US3625976A
US3625976A US88323969A US3625976A US 3625976 A US3625976 A US 3625976A US 88323969 A US88323969 A US 88323969A US 3625976 A US3625976 A US 3625976A
Authority
US
Grant status
Grant
Patent type
Prior art keywords
compounds
coumarin
carbon
atoms
sun
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
Inventor
Ernst Theodore Theimer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
International Flavors and Fragrances Inc
Original Assignee
International Flavors and Fragrances Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Grant date

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D311/00Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/16Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/30Cosmetics or similar toilet preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4973Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
    • A61K8/498Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom having 6-membered rings or their condensed derivatives, e.g. coumarin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations

Abstract

WHEREIN R1 is alkenyl, cycloalkenyl, alkadienyl, cycloalkadienyl, alkatrienyl, alkoxyalkadienyl, acyloxyalkadienyl, alkoxyalkenyl, cyclialkoxyalkenyl, aryl, alkaryl, or aralkyl and R2 is hydrogen or lower alkyl and such compounds having ultraviolet absorption maxima within the range of 2,900 A. up to about 3,400 A. The compounds wherein R2 is lower alkyl and R1 is alkadienyl or where R1 is cycloalkadienyl or cycloalkenyl are novel compounds.

The use as sun-screening agents of essentially colorless, stable, odorless, nonirritating, nonsensitizing, and oilcompatible coumarin ether compounds, such compounds having the formula:

Description

Unite States Patent [72] Inventor Ernst Theodore Thelmer Rumson, NJ.

[21 Appl. No. 883,239

[22] Filed Dec. 9, 1969 [45] Patented Dec. 7, 1971 [73] Assignee International Flavors & Fragrances, Inc.

New York, N.Y.

[54] COUMARIN ETHER SUN-SCREENING COMPOUNDS 3 Claims, No Drawings [52] U.S. Cl 260/343.2R,

424/59, 252/300 [51] Int. Cl C07d 7/26 [50] Field of Search 260/343.2R

[56] References Cited UNITED STATES PATENTS 3,282,938 l H1966 Ritter et al 260/3432 X 3,35l,482 ll/l967 Raue 260/343.2X

Primary ExaminerJohn M. Ford Attorneys-Arthur L. Liberman and Ward, McElhannon,

Brooks & Fitzpatrick ABSTRACT: The use as sun-screening agents of essentially colorless, stable, odorless, nonirritating, nonsensitizing, and oil-compatible coumarin ether compounds, such compounds wherein R is alkenyl, cycloalkenyl, alkadienyl, cycloalkadienyl, alkatrienyl, alkoxyalkadienyl, acyloxyalkadienyl, alkoxyalkenyl, cyclialkoxyalkenyl, aryl, alkaryl, or aralkyl and R is hydrogen or lower alkyl and such compounds having ultraviolet absorption maxima within the range of 2,900 A. up to about 3,400 A. The compounds wherein R is lower alkyl and R is alkadienyl or where R is cycloalkadienyl or cycloalkenyl are novel compounds.

COUMARIN ETHER SUN-SCREENING COMPOUNDS THE INVENTION The invention relates to composition containing specific sun-screen compounds; to methods for protecting the human skin against the burning, tanning and degradation effects of sunlight, to certain new and useful sun-screen compounds, and in particular to cosmetic compositions incorporating the compounds including the novel compounds of this invention which are outstandingly useful for protecting the skin against sunlight.

No one material possessing all of the desirable characteristics of sun-screening compounds including (l) stability; (2) lack of odor; (3) no causation of irritation to the skin; (4) no causation of sensitization of the human skin on exposure to sunlight; (5) oil compatibility; (6) protection against both the burning rays and the tanning rays of the sun; have heretofore been described.

Sun-screening compounds in general have been developed which afford satisfactory protection against the burning rays of the sun but which would permit the tanning rays to be transmitted. In the approximate range of from about 2,900 to 3,100 Angstrom Units are found the most detrimental burning wavelengths in the sun's rays. The effect of these wavelengths on the human skin is to produce a severe burning, reddening, blistering and edema which is characteristic of many burns. Obviously, this is not only not desirable from an esthetic point of view, but is a severe detriment to human health. In order, therefore, to overcome this effect of the burning rays of the sun, chemical compounds have been heretofore employed to screen out these burning rays. On the assumption and general acceptance by the public that tanning is a desirable phenomenon and is somewhat related to good health," the ublic has been educated to accepted the numerous products currently available to screen out the burning rays of the sun but to permit tanning to occur. Within the recent years it has become generally accepted that while tanning may have some beneficial effects especially in that it protects the skin from further burning where there is continued exposure to the sun, nevertheless, tanning in and of itself is associated with a general deterioration of the skin due to the effect of the actinic radiation thereon. While the great majority of people are not severely affected by tanning, there are a great number who are so sensitive to even the tanning rays of the sun that exposure to these wavelengths creates serious health hazards. Others have not quite accepted the notion that tanning is beautifying and would prefer to remain untanned. Consequently for those who must have protection against both burning and tanning rays of the sun, and for those who do not desire to be tanned, there has been a need for broad spectrum sun-screening compositions, which would give adequate protection to the skin, would be sufficiently stable under conditions of use to remain effective for several hours, which could be readily applied to the skin, which would be compatible with the various oily cosmetic compositions currently on the market, which would be aesthetically pleasing (for example, odorless) which would be nonirritating and nonsensitizing to the skin and which would not be readily removed such as by simple water-wash. The need for the latter characteristic is evident since it would leave one with a false sense of security if the material were readily removed as, for example, in bathing.

The term "nonsensitizing" is used herein to mean that the compounds of this invention will not induce or enhance or augment photosensitivity of the skin on exposure to ultraviolet light for a wavelength in the range of from about 2900 A. to about 3400 a.

In order, therefore, to achieve the ends of the present invention, it is necessary to provide a composition (1 which has an outstanding filtering action on those rays of the sun from about 2900 A. to about 3400 A.; which range encompasses the burning and tanning wavelengths present in sunlight, and (2) which is odorless, nonirritating and nonsensitizing to the skin.

it is further necessary to provide a composition having the foregoing properties which is either substantially oil-miscible or capable of forming a nongranular smooth suspension in oils [such as those used in standard cosmetic sun-screen compositions for application to the skin] so as to be compatible with the various cosmetic compositions currently available to the public.

It is further necessary to provide a composition having the foregoing properties, the ultraviolet radiation absorption properties of which will not be transformed as a result of a change in the pH of the environment of the compound.

One of the objects, therefore, of the present invention is to provide outstanding and useful compounds and compositions containing same which have excellent filtering action on the ultraviolet rays of solar light and particularly those wavelengths of from about 2,900 A. to about 3,400 A., as well as the ability to absorb the said rays even if the pH of the environment of the compound varies moderately.

it is still another object of the present invention to provide oily compositions, and particularly cosmetic compositions,

which may be applied to the human skin to protect it against T1 the burning and tanning rays of the sun and which are odorless, nonirritating and nonsensitizing to the skin;

It is a still further object of the present invention to provide processes for preparing certain of the compounds with which the present invention is concerned and further, to provide processes for protecting the human skin against the burning and tanning rays of the sun.

Other objects will appear hereinafter as the description proceeds.

in accordance with the objects of the present invention, it has now been discovered that (l) a class of compounds hereinafter to be described has outstanding screening characteristics for the burning and tanning rays of the sun, and particularly those wavelengths in the ultraviolet region of from about 2,900 A. to about 3,400 A.; (2) that such compounds have unexpected superior light fastness and stability upon exposure to ultraviolet radiation; (3) that such compounds maintain their screening characteristics notwithstanding a change in the pH of the environment of said compounds; 4) that such compounds are compatible (that is, form stable suspensions or are miscible) with oily compositions suitable for application to the human skin; and (5) that such compounds are odorless, nonirritating and nonsensitizing to human skin.

Known compositions containing 4-methyl-7-hydroxycoumarin [See British Pat. 464,732 and Gregoire et al. Ann. Pharm. Franc, 9, 493-513 (ll] have not been found to have all of the foregoing advantages. Such compounds do not have such stability that their screening characteristics are maintained in the event of a change in the pH of the environment of the compound; nor are they considered to be compatible with oily compositions suitable for application to the human skin, as are the compounds of this invention. By the same token, known compositions containing 4-methyl-7- methoxy coumarin or other 4-methyl-7-lower alkoxy coumarin or esculin (6,7dihydroxy coumarin-o-glucoside) have not been found to have all of the advantageous properties of the compounds of this invention; particularly with regard to compatibility with oily compositions, and consistency of sunscreening characteristics (in the event of a change in the pH of the environment of the compound).

The compounds found to be useful in the present invention and those which are employed in the compositions and processes of this invention have the following general formulas:

wherein R is alkenyl, cycloalkenyl, alkadienyl, cycloalkadienyl, alkatrienyl, alkoxyalkadienyl, acyloxyalkadienyl, alkoxyalkenyl, cyclialkoxyalkenyl, aryl, alkaryl or aralkyl and R is hydrogen or lower alkyl.

Suitable R groups are:

. alkenyl of three to 15 carbon atoms;

. cycloalkenyl of five to eight carbon atoms;

. alkadienyl of five to 20 carbon atoms;

. cycloalkadienyl of six to carbon atoms;

. aralkyl of seven to 30 carbon atoms;

. alkaryl of seven to 30 carbon atoms;

aryl ofsix to 14 carbon atoms;

. alkatrienyl of eight to carbon atoms;

alkoxyalkadienyl of eight to 30 carbon atoms; 10. acyloxyalkadienyl of eight to 30 carbon atoms; l l. alkoxyalkenyl of eight to 30 carbon atoms; 12. cyclialkoxyalkenyl of eight to 30 carbon atoms. Suitable R groups are:

. hydrogen;

methyl;

ethyl;

. n-propyl;

. i-propyl;

n-butyl;

Compounds of R classes (2) and (4) and compounds of class (3) wherein R is lower alkyl are novel compounds. The novel methyl-substituted compounds of class (3) are surprisingly oil soluble.

The general procedure for preparing the compounds found to be useful in this invention involves the reaction of a suitable halide with either 7-hydroxy coumarin (umbelliferone) or 7- hydroxy-4-lower alkyl coumarin. Suitable halide reactants are: alkenyl chlorides or bromides having three to 15 carbon atoms;

2. cycloalkenyl chlorides or bromides having three to 15 carbon atoms;

3. alkadienyl chlorides or bromides having from five to carbon atoms;

4. cycloalkadienyl chlorides or bromides having from six to 10 carbon atoms;

5. aralkyl chlorides or bromides having from seven to carbon atoms;

6. alkaryl chlorides and bromides having from seven to 30 carbon atoms;

7. aryl chlorides, bromides and iodides having from six to 14 carbon atoms;

8. alkatrienyl chlorides of eight to 15 carbon atoms;

9. alkoxyalkadienyl chlorides of eight to 30 carbon atoms;

10. acyloxyalkadienyl chlorides of eight to 30 carbon atoms;

1 l. alkoxyalkenyl chlorides of eight to 30 carbon atoms;

l2. cyclialkoxyalkenyl cuclialkoxyalkenyl chlorides of eight of 30 carbon atoms;

The condensation is carried out in the presence of a base, such as an alkali metal carbonate or bicarbonate, for example, potassium carbonate or sodium carbonate and in an organic solvent compatible with the reactants preferably an alkyl or alicylic ketone such as acetone or cyclohexanone. Most preferably in view of convenience and economy the reaction is carried out at atmospheric pressure and at reflux conditions. Higher temperatures of reaction, and consequently higher pressures, will reduce the time of reaction. It is desirable, to add a catalyst such as potassium or sodium iodide in order to speed the reaction. At higher temperatures, the period of reaction varies from about 10 hours up to about 30 hours depending upon the particular halide used as the reactant and the yield of product desired. At the end of the period of reaction, the reaction product is isolated in the usual manner by means of crystallization or distillation where feasible.

Compounds of R classes 8,9,l0,10,l l, and 12 may also be produced using the procedures set forth in Caglioti et al., Helvetica Chim. Acta, Volume XLIl, Fasciculus Vll, 1959, No. 273-4, pages 2557-2564.

Among suitable ethers useful in this invention are:

7-allyloxy-4-methyl coumarin; 7( 3-methyl-2-butenl -oxy)-4-methyl coumarin; 7-neryloxy-4-t-butyl coumarin; 7-geranyloxy-4-n-propyl coumarin; 7-geranyloxy-4( l-n-butyl) coumarin; 7-benzoxy-4-methyl coumarin; 7-benzoxy-4-ethyl coumarin; 7-allyloxy coumarin; 7-(3-methyl cyclo hex-2-en) oxy-4-methyl coumarin; 7-geranyloxy 4-methyl coumarin; 7-neryloxy-4-methyl coumarin; 7( 3-methyl-2butenl -oxy) coumarin; 7( 3-methyl-2-butenl -oxy )-4-n-propyl coumarin; 7-benzoxy coumarin; 7(6-ethyl-cycloocta-2,4dien) oxy-4-methyl coumarin; A mixture of 7-geranyloxy and 7-neryloxy coumarin; A mixture of 7-geranyloxy and 7-neryloxy-4-methyl coumarins. The compound of the structure:

r, I i

Umbelliprenine having the structure:

The range of usage of these compounds which are novel which have been herein shown to be useful in oil sun-screening compositions is from about 1 percent up to about 10 percent (based on the weight of the final formula which is ready for use) with the preferred range being from about 1 up to about 6 by weight Any oily carrier suitable for application to the human skin may be used, for example, lanolin, cetyl alcohol, wheat germ oil, sesame oil, polyethylene glycol stearate (wherein the polyethylene glycol moiety has a molecular weight of less than 400), other fatty acid esters of polyethylene glycol (wherein the polyethylene glycol moiety has a molecular weight of less than 400) and the like. After producing the formulation, application to the human skin may be made in any convenient and comfortable manner. An expedient application quantity is in the range of from 5 up to about 200 milligrams (of active ultraviolet absorption compound (coumarin ether)) per square meter of skin, depending upon the environment of exposure and the nature of the skin being exposed. Thus, for example, exposure to high intensity ultraviolet radiation of highly sensitive skin would necessitate application concentrations at the upper part of the foregoing range.

The following examples serve only to illustrate the present invention. Percentages by weight are set forth therein unless otherwise indicated.

EXAMPLE I PREPARATION OF A MIXTURE OF 7-GERANYLOXY-4- METHYL COUMARIN AND 7-NERYLOXY-4-METHYL COUMARIN To a flask fitted with a stirrer, a condenser and a thermometer was added 200 g. 1.14 moles) 4-methyl umbelliferone 280 g. 1.2 moles 77 percent) cold myrcene hydrochloride. consisting predominantly of geranyl and neryl chlorides produced by the process of U.S. Pat. No. 2,882,323,680 g. of potassium carbonate, 10 g. of potassium iodide and 3.5 liters of acetone. The mixture was stirred and refluxed for hours. The solution was filtered, and the supernatant liquid was retained for subsequent workup. Solid residue from this filtration was dissolved in a 2N NaOH solution and this solution was then extracted with 3 500 ml. volumes of CHgClz- The organic phases (the aforesaid supernatant liquid and the CH,CI extracts) were combined and washed with 2 equal volumes of 2N sodium hydroxide solution, followed by two equal volumes of 20 water. 310 g. of crude reaction material was thereby produced. This crude product was steam distilled, to give 55 g. of steam volatiles. The residue after steam distillation was taken up in methylene chloride, and separated from the water layer. The organic layer was subjected to crystallization from petroleum ether to give 225 g. of a mixture of cis and trans isomers, 7-geranyloxy-4-methyl coumarin and 7-neryloxyl-4- methyl coumarin. The following structures were confirmed by NMR data:

(7-neryloxy coumarin) (7geranyloxy coumarin) s at 3220 A.=18100 (Extinction Coeflicient) NMR data: p.p.m. 1.58, 1.63 (singlet, 3H each) 1.74 (doublet 3H,

set-@l) (singlet, 3H,

6.08 (singlet, 1H,

6.85 (2H, two aromatic protons), 7.54 (doublet, 1H, a om ti J EXAMPLE ll The product of example I was incorporated into a neutral sun-screen cream as follows:

The unexpected high miscibility of the product of example I made it possible to fon'nulate the above homogeneous cream. This cream was then used separately by five people in a bathing procedure, and thereafter the live persons were exposed to the summer afternoon sun for 2 hours. A similar group of five persons used a similar cream but devoid of the product of example I, and these individuals were exposed similarly to the first group. All of the persons in the second group, after exposure, showed considerable reddening of the skin whereas none of the persons in the first group had any visible evidence of sunburn. This demonstrates the sun- 'screening properties of the compound of example I.

Examples Ill-V in the following examples, example I was carried out except that in place of myrcene hydrochloride, there were used the Examples Vl-Vlll The compounds of example [ll-V were each added to a separate sample of the cream set forth in example ll. Substantially identical results were obtained using the compounds of examples lll-V, in place ofthe compound ofexample l, except that the compounds of examples Ill-V apparently formed suspensions rather than miscible systems with the oily sunscreen materials. Nevertheless, the products of examples lll-V were found to be compatible with the oily carrier.

What is claimed is:

l. A compound ofthe formula:

wherein R is selected from the group consisting of alkenyl of three to carbon atoms, cycloalkenyl of five to eight carbon atoms, alkadienyl of five to carbon atoms, cycloalkadienyl of six to 10 carbon atoms, carbocyclic aryl of six to 14 carbon atoms, alkatrienyl of eight to [5 carbon atoms, alkoxyalkadienyl of eight to 30 carbon atoms, lower alkanoyloxyalkadienyl of eight to 30 carbon atoms, alkoxyalkenyl of eight to 30 carbon atoms and cyclialkoxyalkenyl of eight to 30 carbon'atoms and R, is selected from the group consisting of hydrogen and lower alkyl, comprising the steps of intimately admixing in the presence of potassium or sodium iodide, the 'compouncLR x and a compound having the structure:

wherein R is hydrogen or lower alkyl, R, is as defined as above, and X is selected from the group consisting of chlorine, bromine and iodine.

' I v i Page 2 UNITED STATES PATENT 3 0F vCQRYECTION Patent No. 3,625,97 Dated- December 7, Q1971 lnv ntefle) ERNST THEODORE TEEIMER' It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col-.1, line 28 underline "not" second occurrence Col. 1, line 35 change "accepted" to --accept -5 Col. 3, line 53 Col. 3, lineBM change "of" to --to-; Col. 3, lines 58/59- change "alicylic" to --alicyclic---;"

Col. 3, line 71 eshould read: --Compounds of R classes 8, 9, 10, 11 and 12, may also be-;

Col. L, line 13 insert -a hyphen-e after "2;

Col. L,line 5O insert or---- before "which" at the beginning of the line;

L, line 50 change "011 to -oily-3 Col. LL, line 53 insert -percent after "1"; 7

L, line 5 L insert -percentafter "6";

Col. L, line 5M insert a -period after "weight";

Col. 5, line 17 change '3 500 ml." to three 500 mi.--; Col. 5, line #5 underline "CH both occurrences;

v Pae Of 2 UNITED STATES PATENT OFFICE x CERTIFICATE OF CORRECTION Patent No. 3,625,976 Dated December 7, 1971 Inventor(s) ERNST THEODORE THEIMER It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 5, line #6 insert a comma-- after "3";

5, line 5 I underline "H Col; 5, line 51 underline H; both occurrences;

Col. 5, line 55 underline "H second occurrence;

Col. 5, line 75 should read:

I CH3 ,--5. L1 (broad, C=CHCH -s I 1/ 2 6, line 1 underline "H second occurrence;

(fol. 6, line 5 underline "H" first occurrence;

CO1, .6, lines 24/25 put in parentheses "A mixture of methyl and n-propyl parahydroxy benzoate-s in a weight ratio ofv 1:5";

Col. 6, Examples III-V, last Column in the Table should read: Ultraviolet Data at 3220A)".

Signed and sealed this J tll day of July 1972.

(SEAL) Attest:

EDWARD MELETGdHR; JE- ROBERT GOTTSGlIAL-ll Attestirig Officer Commissioner of Patents

Claims (2)

  1. 2. A mixture of 7-geranoxy-4-methyl coumarin and 7-neryloxy-4-methyl coumarin.
  2. 3. A process for preparing a compound having the formula:
US3625976A 1969-12-09 1969-12-09 Coumarin ether sun-screening compounds Expired - Lifetime US3625976A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US3625976A US3625976A (en) 1969-12-09 1969-12-09 Coumarin ether sun-screening compounds

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US3625976A US3625976A (en) 1969-12-09 1969-12-09 Coumarin ether sun-screening compounds
US3712947A US3712947A (en) 1969-12-09 1971-07-22 Compositions containing coumarin ether sun-screening compounds

Publications (1)

Publication Number Publication Date
US3625976A true US3625976A (en) 1971-12-07

Family

ID=25382248

Family Applications (1)

Application Number Title Priority Date Filing Date
US3625976A Expired - Lifetime US3625976A (en) 1969-12-09 1969-12-09 Coumarin ether sun-screening compounds

Country Status (1)

Country Link
US (1) US3625976A (en)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2395025A1 (en) * 1977-06-23 1979-01-19 Henkel Kgaa cosmetics intended to be protected against light, in particular light in the region to the ultraviolet spectrum
US5034213A (en) * 1986-09-22 1991-07-23 L'oreal Photostable cosmetic composition containing an ethylrutin derivative as protective agent against sunlight and its use in the protection of the skin and the hair
US5100914A (en) * 1988-10-13 1992-03-31 Basf Aktiengesellschaft Arylalkoxycoumarins
US6051602A (en) * 1998-03-16 2000-04-18 The Procter & Gamble Company Methods for regulating skin appearance
US6555143B2 (en) 2001-02-28 2003-04-29 Johnson & Johnson Consumer Products, Inc. Legume products
US6750229B2 (en) 1998-07-06 2004-06-15 Johnson & Johnson Consumer Companies, Inc. Methods for treating skin pigmentation
US7192615B2 (en) 2001-02-28 2007-03-20 J&J Consumer Companies, Inc. Compositions containing legume products
US7309688B2 (en) 2000-10-27 2007-12-18 Johnson & Johnson Consumer Companies Topical anti-cancer compositions and methods of use thereof
US20100227039A1 (en) * 2009-03-03 2010-09-09 Givaudan S.A. Off-Taste Masking
US7985404B1 (en) 1999-07-27 2011-07-26 Johnson & Johnson Consumer Companies, Inc. Reducing hair growth, hair follicle and hair shaft size and hair pigmentation
US8039026B1 (en) 1997-07-28 2011-10-18 Johnson & Johnson Consumer Companies, Inc Methods for treating skin pigmentation
US8093293B2 (en) 1998-07-06 2012-01-10 Johnson & Johnson Consumer Companies, Inc. Methods for treating skin conditions
US8106094B2 (en) 1998-07-06 2012-01-31 Johnson & Johnson Consumer Companies, Inc. Compositions and methods for treating skin conditions
US8431550B2 (en) 2000-10-27 2013-04-30 Johnson & Johnson Consumer Companies, Inc. Topical anti-cancer compositions and methods of use thereof
JPWO2011108499A1 (en) * 2010-03-03 2013-06-27 株式会社エリナ Osteoblast differentiation promoting agent for aurapten analogous compounds as an active ingredient, a bone formation promoting pharmaceutical composition and health functional food

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3282938A (en) * 1961-08-12 1966-11-01 Cassella Farbwerke Mainkur Ag 3-tertiary aminoloweralkyl-4-lower alkyl or phenyl-7-lower carbalkoxy lower alkyl or carboxy lower alkyl coumarins
US3351482A (en) * 1961-02-21 1967-11-07 Bayer Ag Synthetic textiles brightened with 3-phenyl-7-hydroxy-coumarin

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3351482A (en) * 1961-02-21 1967-11-07 Bayer Ag Synthetic textiles brightened with 3-phenyl-7-hydroxy-coumarin
US3282938A (en) * 1961-08-12 1966-11-01 Cassella Farbwerke Mainkur Ag 3-tertiary aminoloweralkyl-4-lower alkyl or phenyl-7-lower carbalkoxy lower alkyl or carboxy lower alkyl coumarins

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2395025A1 (en) * 1977-06-23 1979-01-19 Henkel Kgaa cosmetics intended to be protected against light, in particular light in the region to the ultraviolet spectrum
US5034213A (en) * 1986-09-22 1991-07-23 L'oreal Photostable cosmetic composition containing an ethylrutin derivative as protective agent against sunlight and its use in the protection of the skin and the hair
US5100914A (en) * 1988-10-13 1992-03-31 Basf Aktiengesellschaft Arylalkoxycoumarins
US8039026B1 (en) 1997-07-28 2011-10-18 Johnson & Johnson Consumer Companies, Inc Methods for treating skin pigmentation
US6093411A (en) * 1998-03-16 2000-07-25 The Procter & Gamble Company Compositions for regulating skin appearance
US6235773B1 (en) 1998-03-16 2001-05-22 The Procter & Gamble Company Compositions for regulating skin appearance
US6051602A (en) * 1998-03-16 2000-04-18 The Procter & Gamble Company Methods for regulating skin appearance
US8106094B2 (en) 1998-07-06 2012-01-31 Johnson & Johnson Consumer Companies, Inc. Compositions and methods for treating skin conditions
US6750229B2 (en) 1998-07-06 2004-06-15 Johnson & Johnson Consumer Companies, Inc. Methods for treating skin pigmentation
US8093293B2 (en) 1998-07-06 2012-01-10 Johnson & Johnson Consumer Companies, Inc. Methods for treating skin conditions
US7985404B1 (en) 1999-07-27 2011-07-26 Johnson & Johnson Consumer Companies, Inc. Reducing hair growth, hair follicle and hair shaft size and hair pigmentation
US7879823B2 (en) 1999-11-05 2011-02-01 Johnson & Johnson Consumer Companies Topical anti-cancer compositions and methods of use thereof
US8431550B2 (en) 2000-10-27 2013-04-30 Johnson & Johnson Consumer Companies, Inc. Topical anti-cancer compositions and methods of use thereof
US7309688B2 (en) 2000-10-27 2007-12-18 Johnson & Johnson Consumer Companies Topical anti-cancer compositions and methods of use thereof
US7897144B2 (en) 2001-02-28 2011-03-01 Johnson & Johnson Comsumer Companies, Inc. Compositions containing legume products
US7192615B2 (en) 2001-02-28 2007-03-20 J&J Consumer Companies, Inc. Compositions containing legume products
US6555143B2 (en) 2001-02-28 2003-04-29 Johnson & Johnson Consumer Products, Inc. Legume products
CN102413713A (en) * 2009-03-03 2012-04-11 奇华顿股份有限公司 Off-taste masking
US8329239B2 (en) * 2009-03-03 2012-12-11 Givandan S.A. Off-taste masking
US20100227039A1 (en) * 2009-03-03 2010-09-09 Givaudan S.A. Off-Taste Masking
JPWO2011108499A1 (en) * 2010-03-03 2013-06-27 株式会社エリナ Osteoblast differentiation promoting agent for aurapten analogous compounds as an active ingredient, a bone formation promoting pharmaceutical composition and health functional food
JP2017105798A (en) * 2010-03-03 2017-06-15 株式会社エリナ Osteoblast differentiation promoter comprising aurapten analog as active ingredient, pharmaceutical composition for promoting bone formation and health-promoting food

Similar Documents

Publication Publication Date Title
US5089250A (en) Cosmetic containing benzotriazole diorganopolysiloxanes
US4457911A (en) Dialkyl malonates as organic sunscreen adjuvants
US5730960A (en) Benzylidenenorcamphor derivatives
US5399785A (en) Tyrosinase activity inhibitor
US2933506A (en) 1, 1-dimethyldecaline lactones and their 6-and 7-pyridyl, thienyl and furyl substituted derivatives
US4154816A (en) Solid antiperspirant composition and process for its preparation
US4387089A (en) 4-(1,1-Dimethylethyl)-4'-methoxydibenzoylmethane
US3822287A (en) Process for preparation of substituted 3,4-(diphenyl)chromans
US4061730A (en) Anti-solar agent and compositions containing the same
US3681263A (en) Process for the preparation of perfume compositions or perfumed articles respectively
US3952016A (en) 2-Keto-6-substituted dioxane-(1,4) compounds
US5116604A (en) Sunscreen compositions containing novel neopentanoate esters
DE10055940A1 (en) new indanylidene
US4617390A (en) S-triazine derivatives
EP0507691A1 (en) S-triazine derivatives substituted with benzalmalonates, process for their preparation, filtering cosmetic compositions containing them and their use as UV-protectors for skin and hair
EP0694521B1 (en) Ketotricyclo(5.2.1.0)decane derivatives
Ward et al. Synthesis of some poly‐unsaturated aldehydes
US5670140A (en) Photostable cosmetic filter composition containing a UV-A filter and a substituted dialkylbenzalmalonate, the use of substituted dialkylbenzalmalonates in cosmetics as broad-band solar filters and novel substituted dialkylmalonates
EP0100651A1 (en) Dialkyl malonates as organic suncreen adjuvants
US3517031A (en) 1,5-benzoxepin- and -benzodioxepin-3-ones as flavor and odorant agents
EP0165458A2 (en) (+)-Ambrox, process for production thereof and use thereof
US5266592A (en) Compositions which have a physiological cooling effect, and active compounds suitable for these compositions
US5160494A (en) Alkylmethylsiloxane containing perfume compositions
Long et al. Synthesis of Ketone Derivatives of Biphenyl by the Friedel-Crafts Reaction1
Mehr et al. Tetraarylcyclopentadienes1