US3462479A - Hydrazone sun-screening compounds - Google Patents

Hydrazone sun-screening compounds Download PDF

Info

Publication number
US3462479A
US3462479A US517443A US3462479DA US3462479A US 3462479 A US3462479 A US 3462479A US 517443 A US517443 A US 517443A US 3462479D A US3462479D A US 3462479DA US 3462479 A US3462479 A US 3462479A
Authority
US
United States
Prior art keywords
hydrazine
methyl
sulfobenzaldehyde
sulfophenyl
phenyl
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
US517443A
Other languages
English (en)
Inventor
Albert F Strobel
Sigmund C Catino
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.)
GAF Corp
Original Assignee
GAF Corp
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
Application filed by GAF Corp filed Critical GAF Corp
Application granted granted Critical
Publication of US3462479A publication Critical patent/US3462479A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier 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
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/466—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/72—Hydrazones

Definitions

  • R H I wherein in the free acid form (Ar) and (Ar) represent benzene rings; Y and Z are salt-forming groups selected from SO H and COOH; R is an aliphatic radical, e.g., alkyl, hydroxyalkyl, cyclohexyl; and n and m are integers from 1 to 3.
  • Such compound has an absorption maxima within the range 2900 A. to about 3500 A.
  • This invention relates to new and useful sun-screen compounds, to compositions containing such compounds, and to methods for protecting the human skin against the burning, tanning and degradation effects of sunlight, and in particular to cosmetic compositions incorporating the novel compounds of this invention which are outstandingly useful for protecting the skin against sunlight.
  • Sun-screening compounds in general have been developed which afford quite 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 2900 to 3100 A. we find the most detrimental burning wavelengths in the suns 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, quite satisfactory compounds have been heretofore employed to screen out these burning rays.
  • compositions which has an outstanding filtering action on those rays of the sun from about 2900 A. to about 3500 A.; the range of from about 3200 A. to 3500 A. encompassing the tanning wavelengths present in sunlight.
  • One of the objects, therefore, of the present invention is to provide outstanding and useful compounds which have excellent filtering action on the ultraviolet rays of solar light and particularly those wavelengths of from about 2900 A. to about 3500 A.
  • compositions and particularly cosmetic compositions, which may be applied to the human skin to protect it against the burning and tanning rays of the sun.
  • 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 2900 A. to about 3500 A., and that such compounds have outstanding K values as well as unexpected superior light fastness and stability upon exposure to ultraviolet radiation.
  • the K value is a measure of the efficiency of the compound to filter out specified wavelengths of light.
  • a compound with a K value of 1 is one which, at a concentration of 0.1% in a thickness of 1 cm. reduces the light transmitted to 10% of the incident radiation.
  • Y and Z are salt or salt-forming groups, particularly sulfonic or carboxylic;
  • R is an aliphatic radical and preferably lower alkyl of 1 to 6 carbon atoms.
  • R Ar J N-I I Ar m 2 03M)n wherein (Ar) and (Ar) are benzene rings; Z is SO M or --COOM; n and m have values from 1 to 3; R is lower alkyl of from 1 to 6 carbon atoms; and M is hydrogen or a salt-forming cation which preferably is an alkali metal anion, e.g., sodium, potassium, lithium, etc., or ammonium or amine.
  • alkyl of 1 to 50 carbon atoms alkenyl of 3 to 50 carbon atoms cycloalkyl of 3 to 50 carbon atoms cycloalkenyl of to 50 carbon atoms haloalkyl of 1 to 50 carbon atoms (e.g., chloroethyl,
  • the benzene nuclei may contain, in addition to the salt or salt-forming group, other substituents which are non-chromophoric (i.e., avoid chromophores such as nitro, azo, azoxy and the like).
  • substituents which are non-chromophoric (i.e., avoid chromophores such as nitro, azo, azoxy and the like).
  • an oxy group i.e., hydroxy, alkoxy or alkenoxy
  • an auxochrome i.e., hydroxy, alkoxy or alkenoxy
  • no more than one of such groups should be present since the absorption maxima of compounds with two or more oxy groups would in most instances be too close, if not in a visible region of the spectrum, tending thereby to lessen the effectiveness of these compounds for the use as sunscreen agents as herein contemplated.
  • the compounds of, and used in, this invention do not contain amine groups, particularly bonded directly to the benzene nuclei since such compounds, in general, have inferior light fastness albeit they may have satisfactory absorption characteristics for the purposes of the present invention.
  • the general procedure for preparing the compounds of this invention involves a condensation of a sulfoor carboxybenzene aldehyde with a sulfoor carboxy phenyl- (R-substituted) hydrazine.
  • the condensation may be carried out in an aqueous medium especially since the reactants are, in general, soluble in water or in any selected solvent medium and isolated in the usual way by distillation, extraction, crystallization or precipitation.
  • refluxing of the reactants with the aldehyde in the form of the sodium salt results in high yields after about 1 to 2 hours of refluxing.
  • aldehydes which may be employed as reactants in preparing the compounds of this invention are: 2-sulfobenzaldehyde (o-formyl benzene sulfonic acid) 4-chloro-2-sulfobenzaldehyde S-chloro-2-sulfobenza1dehyde 6-chloro-2-sulfobenzaldehyde 4-hydroxy-2-sulfobenzaldehyde 3-sulfobenzaldehyde 4-bromo-3-sulfobenzaldehyde 4-chloro-3-su1fobenzaldehyde 4-fiuoro-3-sulfobenzaldehyde 4-iodo-3-sulfobenzaldehyde 4-hydroxy-3-sulfobenzaldehyde 2,6-dichloro-3-sulfobenzaldehyde 4-sulfobenzaldehyde 2-chloro-4-sulfobenzaldehyde S
  • the N-alkyl anilines may be sulfonated first and then nitrosated and reduced.
  • the N-alkyl aniline contains a para substituent such as alkyl, halogen, cyano, sulfonyl, carbalkoxy and the like, the sulfonation will take place in the ortho position. Where these substituents are ortho or meta, sulfonation will be para.
  • a para substituent such as alkyl, halogen, cyano, sulfonyl, carbalkoxy and the like
  • Example 1 Into a 3-liter flask equipped with a stirrer, thermometer, reflex condenser and heating mantle, there are charged the following ingredients:
  • Example 2 Example 1 is repeated employing in place of the sodium salt of 2-sulfobenzaldehyde, the same Weight of 3-sulfobenzaldehyde (i.e., 46.3 g. on a basis).
  • the product is l-methyl-l-(p-sulfophenyl)-2 sulfophenyl hydrazone sodium salt.
  • Example 3 Example 1 is once again repeated using an equivalent weight on a 100% basis of 2,4-disulfo benzaldehyde sodium salt in place of the sulfobenzaldehyde of Example 1.
  • the product obtained is l-methyl 1 (2,4 disulfophenyl)-Z-sulfophenyl hydrazone sodium salt.
  • Example 4 Example 2 is repeated except that in place of the p-sulfonated hydrazine used in that example, there is used an equal weight of the o-sulfonated product.
  • the product obtained is 1-methyl-1-(o-sulfophenyl)-2-sulfophenyl hydrazone sodium salt.
  • Example 5 Example 4 is repeated except that in place of the osulfonated hydrazine, there is used an equivalent weight of the o-carboxylated hydrazine.
  • the product obtained is 1-methyl-l-(o-carboxyphenyl)-2 sulfophenyl hydrazone sodium salt.
  • Example A The product of Example 1 is incorporated into a neutral detergent composition in the form of a bar, and which contains as the main detersive ingredient a cocoanut oil acid ester of sodium isethionate.
  • the amount of the product of Example 1 which is used is 0.2% by weight based on the total weight of the detergent bar.
  • the bar is then used separately by five individuals in a bathing procedure, and thereafter the five persons are exposed to the afternoons summer sun for two hours.
  • a similar group of five persons uses a similar detergent bar but devoid of the product of Example 1, and these individuals are similarly exposed as the first group.
  • Each of the persons in the second group, after exposure, shows considerable reddening of the skin whereas none of the persons in the first group has any visible evidence of sunburn. This performance demonstrates not only the excellent sunscreen characteristics of the compound of Example 1, but also its outstanding substantivity for human skin from the detergent bar which is used for bathing.
  • Example B The procedure of Example A is repeated except that in place of a detergent bar, there is used a conventional bar of soap (pH about containing 0.3% of the product of Example 1. Comparable results are obtained as in Example A.
  • Example C The product of Example 1 is prepared as a 10% by weight solution in water, and to this solution there is immersed a sample of cellulose textile material which has been previously dyed with a dark red cotton dye. After removal and drying of the sample, it is placed in a vadeometer along with a similarly dyed sample which has not been treated with the product of Example 1. After four hours exposure, the untreated sample shows severe fading whereas the treated goods shows no fading of the dyeing.
  • Example 6-25 In the following examples, Example 1 is repeated except that in place of 2-sulfobenzaldehyde, there are used the following benzaldehydes in equivalent amounts:
  • Y and Z are salt-forming groups selected from sulfonic acid and carboxyl;
  • R is a radical selected from alkyl, hydroxyalkyl,
  • n and m are integers from 1 to 3; the compound having an absorption maxima within the range of 2900 A. to about 3500 A.
  • R is alkyl of 1 to 6 carbon atoms.
  • R is alkyl of 1 to 6 carbon atoms and n and m are 1.
  • R is alkyl of 1 to 6 carbon atoms and n and m are 1.
  • a water-soluble salt of a compound as defined in claim 1 wherein the cation is selected from the class consisting of alkali metal, ammonium, and amine cations.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Organic Chemistry (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Chemical & Material Sciences (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Dermatology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)
US517443A 1965-12-29 1965-12-29 Hydrazone sun-screening compounds Expired - Lifetime US3462479A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US51744365A 1965-12-29 1965-12-29

Publications (1)

Publication Number Publication Date
US3462479A true US3462479A (en) 1969-08-19

Family

ID=24059822

Family Applications (1)

Application Number Title Priority Date Filing Date
US517443A Expired - Lifetime US3462479A (en) 1965-12-29 1965-12-29 Hydrazone sun-screening compounds

Country Status (7)

Country Link
US (1) US3462479A (instruction)
BE (1) BE691462A (instruction)
CH (1) CH495959A (instruction)
DE (1) DE1568725A1 (instruction)
FR (1) FR1506841A (instruction)
GB (1) GB1172509A (instruction)
NL (1) NL6617904A (instruction)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6998113B1 (en) 2005-01-31 2006-02-14 Aquea Scientific Corporation Bodywashes containing additives
US7001592B1 (en) 2005-01-31 2006-02-21 Aquea Scientific Corporation Sunscreen compositions and methods of use
US7025952B1 (en) 2005-01-31 2006-04-11 Aquea Scientific Corporation Methods of preparation and use of bodywashes containing additives
US7037513B1 (en) 2005-01-31 2006-05-02 Aquea Scientific Corporation Bodywash additives
US20060173709A1 (en) * 2005-01-31 2006-08-03 Traynor Daniel H Bodywash additive business methods
US20080112904A1 (en) * 2005-03-08 2008-05-15 Daniel Henry Traynor Sunscreen Compositions And Methods Of Use
US20080317795A1 (en) * 2007-05-21 2008-12-25 Daniel Henry Traynor Highly charged microcapsules
US9456966B2 (en) 2012-11-06 2016-10-04 CoLabs International Corporation Composition containing a cellulose derived capsule with a sunscreen
US10322301B2 (en) 2012-11-06 2019-06-18 CoLabs International Corporation Compositions containing a cellulose derived capsule with a sunscreen active agent
US11491088B2 (en) 2012-11-06 2022-11-08 CoLabs International Corporation Compositions containing a capsule with a moisturizing agent
US11690793B2 (en) 2012-11-06 2023-07-04 Colabs Int'l Corp. Composition containing a cellulose derived capsule with a sunscreen
US11707421B2 (en) 2012-11-06 2023-07-25 Colabs Int'l Corp. Compositions containing a flexible derived capsule with an active agent
US11724134B2 (en) 2012-11-06 2023-08-15 CoLabs International Corporation Compositions containing a cellulose derived capsule with a sunscreen active agent
US11839674B2 (en) 2018-06-27 2023-12-12 CoLabs International Corporation Compositions comprising silicon dioxide-based particles including one or more agents

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3176608D1 (en) * 1980-05-21 1988-02-18 Ciba Geigy Ag Process for the preparation of a uv-absorbing mask

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1935712A (en) * 1928-03-02 1933-11-21 Gen Aniline Works Inc Ketone hydrazones, and process of making the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1935712A (en) * 1928-03-02 1933-11-21 Gen Aniline Works Inc Ketone hydrazones, and process of making the same

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6998113B1 (en) 2005-01-31 2006-02-14 Aquea Scientific Corporation Bodywashes containing additives
US7001592B1 (en) 2005-01-31 2006-02-21 Aquea Scientific Corporation Sunscreen compositions and methods of use
US7025952B1 (en) 2005-01-31 2006-04-11 Aquea Scientific Corporation Methods of preparation and use of bodywashes containing additives
US7037513B1 (en) 2005-01-31 2006-05-02 Aquea Scientific Corporation Bodywash additives
US20060173709A1 (en) * 2005-01-31 2006-08-03 Traynor Daniel H Bodywash additive business methods
US20060188458A1 (en) * 2005-01-31 2006-08-24 Traynor Daniel H Sunscreen compositions and methods of use
US20060188457A1 (en) * 2005-01-31 2006-08-24 Traynor Daniel H Bodywashes containing additives
US7226582B2 (en) 2005-01-31 2007-06-05 Aquea Scientific Corporation Sunscreen compositions and methods of use
US7226581B2 (en) 2005-01-31 2007-06-05 Aquea Scientific Corporation Bodywashes containing additives
US20080112904A1 (en) * 2005-03-08 2008-05-15 Daniel Henry Traynor Sunscreen Compositions And Methods Of Use
US20080317795A1 (en) * 2007-05-21 2008-12-25 Daniel Henry Traynor Highly charged microcapsules
US9456966B2 (en) 2012-11-06 2016-10-04 CoLabs International Corporation Composition containing a cellulose derived capsule with a sunscreen
US9456967B2 (en) 2012-11-06 2016-10-04 CoLabs International Corporation Composition containing a cellulose derived capsule with a sunscreen
US9456968B2 (en) 2012-11-06 2016-10-04 CoLabs International Corporation Composition containing a cellulose derived capsule with a sunscreen
US9468591B2 (en) 2012-11-06 2016-10-18 CoLabs International Corporation Composition containing a cellulose derived capsule with a sunscreen
US9592184B2 (en) 2012-11-06 2017-03-14 CoLabs International Corporation Composition containing a cellulose derived capsule with a sunscreen
US10098823B2 (en) 2012-11-06 2018-10-16 CoLabs International Corporation Composition containing a cellulose derived capsule with a sunscreen
US10321678B2 (en) 2012-11-06 2019-06-18 CoLabs International Corporation Composition containing a cellulose derived capsule with a sunscreen
US10322301B2 (en) 2012-11-06 2019-06-18 CoLabs International Corporation Compositions containing a cellulose derived capsule with a sunscreen active agent
US10357669B2 (en) 2012-11-06 2019-07-23 CoLabs International Corporation Composition containing a cellulose derived capsule with a sunscreen
US10375952B2 (en) 2012-11-06 2019-08-13 CoLabs International Corporation Composition containing a cellulose derived capsule with a sunscreen
US10376718B2 (en) 2012-11-06 2019-08-13 CoLabs International Corporation Composition containing a cellulose derived capsule with a sunscreen
US11491088B2 (en) 2012-11-06 2022-11-08 CoLabs International Corporation Compositions containing a capsule with a moisturizing agent
US11690793B2 (en) 2012-11-06 2023-07-04 Colabs Int'l Corp. Composition containing a cellulose derived capsule with a sunscreen
US11707421B2 (en) 2012-11-06 2023-07-25 Colabs Int'l Corp. Compositions containing a flexible derived capsule with an active agent
US11724134B2 (en) 2012-11-06 2023-08-15 CoLabs International Corporation Compositions containing a cellulose derived capsule with a sunscreen active agent
US11839674B2 (en) 2018-06-27 2023-12-12 CoLabs International Corporation Compositions comprising silicon dioxide-based particles including one or more agents

Also Published As

Publication number Publication date
FR1506841A (fr) 1967-12-22
BE691462A (instruction) 1967-05-29
GB1172509A (en) 1969-12-03
NL6617904A (instruction) 1967-06-30
CH495959A (de) 1970-09-15
DE1568725A1 (de) 1970-04-16

Similar Documents

Publication Publication Date Title
US3462479A (en) Hydrazone sun-screening compounds
US4522808A (en) Anti-sunburn compositions containing 2-phenyl-indole derivatives
US3275520A (en) Methods for protecting the skin against actinic radiations
JP3637055B2 (ja) 光保護フィルターとしてのベンズイミダゾール誘導体の使用
JPH02231463A (ja) ベンジリデン―カンファースルホン化誘導体および紫外線防止剤
US4726942A (en) Cosmetic composition for protection against ultraviolet radiation and its use for this purpose
JPH05230040A (ja) ｓ−トリアジン誘導体、その製造方法、および濾光性化粧品組成物
JP2781415B2 (ja) 紫外線吸収剤
FR2555572A1 (fr) Composes de la famille des 2,4-dinitrobenzene-disubstitues
US4171203A (en) Hair dye compositions containing 3,5-diamino-2-substituted-alkylbenzenes
JPS6396120A (ja) 日焼け止め化粧品
DE1645989A1 (de) Verfahren zur Herstellung von substituierten Oxazolverbindungen
US3705234A (en) Skin-protective sun-screening composition and method
US3414650A (en) Sunscreening methods
Inscoe et al. The Relation between the Absorption Spectra and the Chemical Constitution of Dyes. XXX. Photoisomerization of Azo Dyes in Aqueous Solution1, 2
US4333920A (en) Benzalphthalides and broad spectrum sun screens
US3375271A (en) Sun-screening compounds
DE1569603C3 (de) Verfahren zur Herstellung von Oxazinfarbstoffen
US3419659A (en) Sun screening methods
US5600007A (en) Use of α-hydroxyketoalkyl derivatives as light protection filters
US2865916A (en) Triazole brighteners
US3992450A (en) 2,3-Disubstituted-1-indanones
US3050393A (en) Filter layer for photographic elements
Tedder et al. 315. Heterocyclic diazo-compounds. Part II. 2-Diazopyrroles
JPH06207114A (ja) 新規な３−ピリジンアゾ染料並びに３−ピリジンアゾ染料を含有する毛髪染色用薬剤