WO1986002350A1 - Ultra violet agents - Google Patents

Ultra violet agents Download PDF

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Publication number
WO1986002350A1
WO1986002350A1 PCT/AU1985/000242 AU8500242W WO8602350A1 WO 1986002350 A1 WO1986002350 A1 WO 1986002350A1 AU 8500242 W AU8500242 W AU 8500242W WO 8602350 A1 WO8602350 A1 WO 8602350A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
alkyl
methyl
compounds
amino
Prior art date
Application number
PCT/AU1985/000242
Other languages
English (en)
French (fr)
Inventor
Walter Clark Dunlap
Bruce Edward Chalker
Original Assignee
Australian Institute Of Marine Science
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 Australian Institute Of Marine Science filed Critical Australian Institute Of Marine Science
Publication of WO1986002350A1 publication Critical patent/WO1986002350A1/en

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Classifications

    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
    • C07D295/112—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
    • C07D295/116—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings with the doubly bound oxygen or sulfur atoms directly attached to a carbocyclic ring

Definitions

  • THIS INVENTION relates to a new and useful class of ultra violet light absorbing compounds and to their use in sunscreen compositions and the protection of paint films and plastics materials from solar degradation.
  • UV agents Chemical compounds which absorb light in the ⁇ V portion of the spectrum
  • sunscreen agents have a number of important commercial applications. The best known of these are probably their use as sunscreen agents to protect the skin from the erythermal effect of sunlight and to shield paint films and plastics materials from solar degradation. They have also been used elsewhere as, for example, as energy transfer means in UV light crosslinking of certain polymers.
  • Common commercially available UV agents include for example, para amino benzoic acid derivatives, benzotriazoles, benzophenones, methoxycinnamates and salicylates. It has also been proposed, for example in United Kingdom Patent Application 2 , 120, 549 A, that certain vinylogous amide compounds may also be used as sunscreen agents.
  • UV agents exhibit strong radiation absorption in the UV region, the actual value of the absorption maximum being important in relating the compounds to their intended end use.
  • human skin is particularly sensitive to damage at wavelengths between about 290-320 nm (nanometer), the so-called UV-B region, with some likely carryover of harmful effects into the wavelength in excess of 320 nm, the UV-A region.
  • UV agents used to protect plastics and paint films commonly have absorption maxima in the region of 340-355 nm and higher.
  • UV agents for commercial purposes will have absorption maxima in excess of about 290 nm. They should also have acceptable permanence, stability and compatibility with media to which they are to be applied or incorporated. In particular, when the UV agents are to be used on living tissue, they must be non-toxic and not otherwise harmful to the host surface. These various criteria are often in conflict and limit the choice of UV agents available for specific end uses. Furthermore, the final selection, when it is made, is often a compromise in which for example, efficacy must be sacrificed for stability or freedom from toxic side-effects.
  • the chromophore has the structure:
  • the oxygen subsitutent at the 2 position is fundamental to the UV absorption characteristics UV compounds of the invention.
  • certain compounds containing the above chromophore have an absorption maximum at 305-340 nm.
  • analogous carbonylsare prepared in which there is no oxygen function at the 2 position e.g. ethyl 3-octylamino-2-butencate
  • the absorption maximum drops to about 285 nm, which is significantly below the abovementioned useful absorption range achieved by UV compounds of this invention.
  • Preferred novel UV absorbing compounds of the invention, which are particularly useful in sunscreens are of formula (2) or (3) below:
  • R 1 is selected from hydrogen, alkyl or alkenyl
  • NR 2 is an amino group or a secondary or tertiary amine moiety in which the N atom bears either one or two unsubstituted or substituted alkyl, aryl or alkenyl groups which may be the same or different when two are present;
  • R is a moiety selected from alkyl, substituted alkyl, hydroxyl, carboxylic acid, ester or ether at positions 4, 5 or 6 on the ring;
  • n 0-4.
  • the oxygen atom at the 2- position on the ring structure is a characteristic feature of all of our novel compositions.
  • R 1 When the substituent R 1 is alkyl or alkenyl, it may be a straight or branched chain, which in turn may bear further substituent groups or be interrupted by a hetero-atom.
  • R 1 may be methyl, ethyl, propyl, methoxy methyl or methoxy ethyl. It may also be cyclic, for example it may be cyclohexly.
  • Our most preferred compositions are those in which R 1 is an alkyl chain containing 1 - 4 carbon atoms.
  • -NR 2 is a amino group.
  • One or both of the hydrogen atoms of that group may be replaced as described hereinabove by the same or different substituents selected from alkyl, aryl or alkenyl groups, which may themselves be branched, linear or contain a cyclical structure.
  • the selected substituent may itself contain a further substituent.
  • the substituent groups may together form a carbocyclic or heterocyclic ring system.
  • suitable components -NR 2 are, for example, cyclohexylamino, anilino, undecylamino, hexylamino, octylamino, decylamino, heptylamino, benzylamino, octadecylamino, pentylamino, nonylamino, N-methyl-N-benzylamino, di-butylamino, N-morpholino dodecylamino, phenethylamino, 1,1,3,3 tetramethyl butylamino, N-pyrolidinyl, N-piperidenyl, di-butylamino, N-methyl-N-cyclohexylamino, components of the structures -NHCH 2 COOCE 3 , -NHCH (CH 3 )COOCH 3 , -NHCH(CH 2 OH)COOCH 3 and -NHCH(HO-4-C 6 H 4 )COOC
  • -NR 2 is alkylamino, arylamino, amino acid and amino acid ester.
  • -NR 2 be a disubstituted amino.
  • composition of the component R when present is not usually critical and it is chosen with regard to such factors as, for example, the required solubility of hydrophilic/lipophilic balance of the molecule as a whole.
  • suitable components R are, for example, alkyl, substituted alkyl, hydroxyl, alkoxy, carboxylic acid ester or ester moieties. That is R may be, for example, 5-hydroxyl, 5 carboxylic acid or ester thereof, 5-hydroxymethyl, 5,5-dimethyl, 5-t-butyl and 4,4,6,6-tetramethyl.
  • compositions are those in which the component R when present, is methyl or ethyl.
  • the compounds (4c) below may be prepared by an appropriate standard method of organic synthesis.
  • Compounds (4a) are acidic and can be alkylated at the 2-hydroxyl group with suitable alkylating agents such as dialkyl sulphates, alkyl tosylates or diazoalkanes (when there is no 3-hydroxyl) to give the alkyl derivatives (4b).
  • suitable alkylating agents such as dialkyl sulphates, alkyl tosylates or diazoalkanes (when there is no 3-hydroxyl) to give the alkyl derivatives (4b).
  • Compounds (4b) can be reacted with amino compounds to effect a substitution at the 3-position to give compounds (4c).
  • Compounds of structure (4a) may be prepared by a number of routes from various starting materials depending on the desired size and substitution of the carbocycle.
  • UV agents have an absorption maximum in the region of 305-340 nm.
  • the UV compound according to our invention will comprise a six-membered ring as structure (2) since derivatives of the five-membered enaminoketones tend to absorb UV-light in the region of 287-297 nm.
  • sun-screen agents we prefer to use compounds according to structure (2).
  • UV compounds of the invention are readily compounded by the standard methods of the art into, for example, creams or lotions, making use of conventional emollients, emulsifiers, preservatives, anti-oxidants, perfumes and colouring agents.
  • suitable emollients are, mineral oil, squalene, octyl palmitate, cocoa butter, sesame oil, and pristane, either singly or in combination.
  • Typical emulsifiers including for example, polyoxyethylene (3) olyl ether, polyglyceryl-4-oleate and polysorbate 80. The invention is illustrated by the following examples, in which all parts are given by weight.
  • Cyclopentanone (16 g, 0.15 mol) and cupric chloride (240 g, 1.5 mol) were refluxed for 1.5 h in 800 ml of a 50% solution of dioxane in water. This was allowed to cool, then water (400 ml) was added, filtered and extracted 3-5 times with diethyl ether (total 2.0 1). The organic phase was backwashed with water (200 ml), dried over sodium sulphate and evaporated to collect crude product, mp 130°. The crude material was dissolved in a large quantity of dichloromethane, treated with charcoal and filtered. This solution was evaporated to a suspension then filtered to collect the product as pale yellow crystals, mp 140-141°C.
  • 2,3-Dihydroxy-cyclohex-2-enone (15 g) was dissolved in 4N NaOH (45 ml) and cooled to 5°C.
  • Dimethyl sulfate (18 ml; freshly distilled and stored over KOH pellets) was added dropwise with vigorous stirring while maintaining the internal temperature below 10°C.
  • the reaction was maintained above pH 7 throughout the addition while under an atmosphere of nitrogen.
  • a further quantity of 4N NaOH (45 ml) was added after the addition of dimethyl sulfate was completed and the reaction was allowed to stir overnight (16 h) at room temperature.
  • the mixture was cooled to 5°C and acidified to congo red with 4N H 2 SO 4 while still under nitrogen.
  • the resulting yellow solution was evaporated to ca.
  • Example 25 The compounds described in Table 5 and Table 6 below were prepared following essentially the proceedures described in Example 19.
  • Example 25 The compounds described in Table 5 and Table 6 below were prepared following essentially the proceedures described in Example 19.
  • Example 25 The compounds described in Table 5 and Table 6 below were prepared following essentially the proceedures described in Example 19.
  • 2,3-Dihydroxy-cyclohex-2-enone (15 g) was dissolved in ethanol (50 ml) and cooled to 5°C in an ice bath. Aqueous 4NNaOH (45 ml) was added to the ethanolic solution under nitrogen. Diethyl sulfate (22 ml) was added dropwise with vigorous stirring while maintaining the internal temperature below 10°C. The reaction was maintained above pH 7 throughout the addition under an atmosphere of nitrogen. A further quantity of 4N NaOH (45 ml) was added after the addition of diethyl sulfate was completed and the reaction allowed to stir at room temperature for 24 h. The organic solvent was removed under reduced pressure.

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  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Dermatology (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/AU1985/000242 1984-10-10 1985-10-03 Ultra violet agents WO1986002350A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
AUPG7572 1984-10-10
AUPG757284 1984-10-10
AUPG7681 1984-10-17
AUPG768184 1984-10-17

Publications (1)

Publication Number Publication Date
WO1986002350A1 true WO1986002350A1 (en) 1986-04-24

Family

ID=25642856

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU1985/000242 WO1986002350A1 (en) 1984-10-10 1985-10-03 Ultra violet agents

Country Status (6)

Country Link
EP (1) EP0196328A4 (enrdf_load_stackoverflow)
AU (1) AU587211B2 (enrdf_load_stackoverflow)
ES (1) ES8801184A1 (enrdf_load_stackoverflow)
GR (1) GR852436B (enrdf_load_stackoverflow)
WO (1) WO1986002350A1 (enrdf_load_stackoverflow)
ZA (1) ZA857767B (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2803201A1 (fr) * 1999-12-30 2001-07-06 Gelyma Extrait d'algue a activite filtrante vis a vis des radiations ultraviolettes
WO2015195546A1 (en) * 2014-06-17 2015-12-23 TopGeniX, Inc. Topical formulations for uv protection
US9234204B2 (en) 2012-08-07 2016-01-12 TopGeniX, Inc. Topical composition comprising transformed bacteria expressing a compound of interest

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4371603A (en) * 1980-12-30 1983-02-01 Polaroid Corporation Amino hydroxy cyclohexenone developing agents
US4515982A (en) * 1981-12-28 1985-05-07 Basf Aktiengesellschaft Aminoreductones

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3690872A (en) * 1970-12-02 1972-09-12 Eastman Kodak Co Photographic developing process with amino hydroxy cycloalkenone
US4514383A (en) * 1982-05-05 1985-04-30 Johnson & Johnson Baby Products Company Sunscreen compositions containing vinylogous amides
DE3312425A1 (de) * 1983-04-07 1984-10-11 Basf Ag, 6700 Ludwigshafen Stoffmischungen mit wachstumsfoerdernder und leistungssteigernder wirkung sowie futtermittel und traenkfluessigkeiten, die geringe mengen dieser stoffmischungen enthalten

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4371603A (en) * 1980-12-30 1983-02-01 Polaroid Corporation Amino hydroxy cyclohexenone developing agents
US4515982A (en) * 1981-12-28 1985-05-07 Basf Aktiengesellschaft Aminoreductones

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0196328A4 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2803201A1 (fr) * 1999-12-30 2001-07-06 Gelyma Extrait d'algue a activite filtrante vis a vis des radiations ultraviolettes
US9234204B2 (en) 2012-08-07 2016-01-12 TopGeniX, Inc. Topical composition comprising transformed bacteria expressing a compound of interest
US9453232B2 (en) 2012-08-07 2016-09-27 TopGeniX, Inc. Topical composition comprising transformed bacteria expressing a compound of interest
US9868957B2 (en) 2012-08-07 2018-01-16 TopGeniX, Inc. Topical composition comprising transformed bacteria expressing a compound of interest
WO2015195546A1 (en) * 2014-06-17 2015-12-23 TopGeniX, Inc. Topical formulations for uv protection
JP2017519823A (ja) * 2014-06-17 2017-07-20 トップジェニックス, インク.Topgenix, Inc. Ｕｖ保護用局所製剤
EP3164196A4 (en) * 2014-06-17 2017-12-06 Topgenix, Inc. Topical formulations for uv protection
US10064797B2 (en) 2014-06-17 2018-09-04 TopGeniX, Inc. Topical formulations for UV protection

Also Published As

Publication number Publication date
EP0196328A1 (en) 1986-10-08
ZA857767B (en) 1986-05-28
ES547726A0 (es) 1986-11-16
EP0196328A4 (en) 1987-03-12
ES8801184A1 (es) 1986-11-16
GR852436B (enrdf_load_stackoverflow) 1986-02-10
AU4968985A (en) 1986-05-02
AU587211B2 (en) 1989-08-10

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