DE1144441B - Protective agent for human skin against ultraviolet radiation - Google Patents
Protective agent for human skin against ultraviolet radiationInfo
- Publication number
- DE1144441B DE1144441B DEC19048A DEC0019048A DE1144441B DE 1144441 B DE1144441 B DE 1144441B DE C19048 A DEC19048 A DE C19048A DE C0019048 A DEC0019048 A DE C0019048A DE 1144441 B DE1144441 B DE 1144441B
- Authority
- DE
- Germany
- Prior art keywords
- parts
- human skin
- ultraviolet radiation
- compounds
- oxazole
- 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.)
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- 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
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
-
- 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
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
- C08K5/3447—Five-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/35—Heterocyclic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
- Engineering & Computer Science (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Dermatology (AREA)
- Textile Engineering (AREA)
- Plural Heterocyclic Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Coloring (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
C 19048 IVa/30iC 19048 IVa / 30i
BEKANNTMACHUNG
DER ANMELDUNG
UNDAUSGABE DER
AUSLEGESCHRIFT: 28. F E B RU AR 1963NOTICE
THE REGISTRATION
AND ISSUE OF
EDITORIAL: FEB 28, RU AR 1963
Es wurde gefunden, daß Oxazolverbindungen, in welchen die zwei benachbarten Kohlenstoffatome des Oxazolringes gleichzeitig Glieder eines Benzolringes sind und das zwischen den zwei Heteroatomen des Oxazolringes befindliche Kohlenstoffatom an ein Kohlenstoffatom eines Pyridinringes gebunden ist, deren mineralsaure Salze oder quaternäre Ammoniumsalze wertvolle Schutzmittel für die menschliche Haut gegen ultraviolette Strahlung darstellen.It has been found that oxazole compounds in which the two adjacent carbon atoms of the Oxazole ring are also members of a benzene ring and that between the two heteroatoms of the Oxazole ring is bonded to a carbon atom of a pyridine ring, their mineral acid salts or quaternary ammonium salts are valuable protective agents for human skin against ultraviolet radiation.
Die als Schutzmittel für die menschliche Haut gegen ultraviolette Strahlung zu verwendenden Oxazolverbindungen lassen sich nach üblichen, an sich bekannten Methoden herstellen. Sie können beispielsweise erhalten werden, indem man primäre Aminogruppen enthaltende o-Aminooxyverbindungen der Benzolreihe zusammen mit Pyridincarbonsäuren oder deren funktionellen Derivaten, z. B. Alkylestern, vorzugsweise in Gegenwart von wasserabspaltenden Mitteln, erhitzt. Man kann hierbei in Abwesenheit von Lösungsmitteln oder in Anwesenheit von organischen Lösungsmitteln mit hohem Siedepunkt arbeiten. Als wasserabspaltendes Mittel kann z. B. Borsäure verwendet werden, welche die Wasserabspaltung katalytisch beeinflußt. Als besonders vorteilhaft erweist sich die Umsetzung in einem Überschuß von Polyphosphorsäure. Diese Verbindung wirkt einerseits als Lösungsmittel für Ausgangsstoffe und Endstoffe, anderseits aber auch als wasserabspaltendes Mittel.Those to be used as a means of protecting human skin against ultraviolet radiation Oxazole compounds can be prepared by customary methods known per se. You can can be obtained, for example, by using o-aminooxy compounds containing primary amino groups the benzene series together with pyridinecarboxylic acids or their functional derivatives, e.g. B. Alkyl esters, preferably in the presence of dehydrating agents, heated. You can use Absence of solvents or in the presence of organic solvents with high Working boiling point. As a dehydrating agent, for. B. boric acid can be used, which the The elimination of water is catalytically influenced. The implementation in one has proven to be particularly advantageous Excess of polyphosphoric acid. This compound acts on the one hand as a solvent for Starting materials and end materials, but also as a water-releasing agent.
Weiterhin kann man diese Oxazolverbindungen auch herstellen, indem man durch Erhitzen und/oder Behandlung mit wasserabspaltenden Mitteln aus Acylverbindungen, welche sich von Pyridincarbonsäuren und o-Aminooxyarylverbindungen der Benzolreihe mit primärer Aminogruppe ableiten, Wasser abspaltet. Die hierbei als Ausgangsstoffe dienenden Acylverbindungen können durch Umsetzung der o-Aminooxyarylverbindungen mit Pyridincarbonsäurehalogeniden, vorzugsweise den Säurechloriden, erhalten werden. Die Wasserabspaltung aus den Acylverbindungen kann in der für die Umsetzung von o-Aminooxyarylverbindungen mit Pyridincarbonsäuren weiter oben angegebenen Weise erfolgen. Als weiteres hier in Betracht kommendes Mittel zur Wasserabspaltung sei die Zinkchloridschmelze erwähnt. Die o-Aminooxyarylverbindungen der Benzolreihe können als Kernsubstituenten beispielsweise niedrigmolekulare Alkyl- oder Alkoxygruppen, insbesondere Methyl- oder Methoxygruppen, Phenylreste oder Chloratome enthalten.Furthermore, these oxazole compounds can also be prepared by heating and / or Treatment with dehydrating agents made from acyl compounds, which differ from pyridinecarboxylic acids and derive o-aminooxyaryl compounds of the benzene series with a primary amino group, water splits off. The acyl compounds used as starting materials here can be obtained by reacting the o-Aminooxyaryl compounds with pyridine carboxylic acid halides, preferably the acid chlorides, can be obtained. The elimination of water from the acyl compounds can take place in the for the reaction of o-aminooxyaryl compounds with pyridinecarboxylic acids are carried out in the manner indicated above. Zinc chloride melt may be mentioned as another means for dehydration which may be considered here. The o-aminooxyaryl compounds of the benzene series can be used as core substituents, for example low molecular weight alkyl or alkoxy groups, in particular methyl or methoxy groups, phenyl radicals or contain chlorine atoms.
Als Beispiele geeigneter Ausgangsstoffe seien folgende Verbindungen genannt:The following compounds may be mentioned as examples of suitable starting materials:
Schutzmittel für die menschliche Haut
gegen ultraviolette StrahlungProtective preparations for human skin
against ultraviolet radiation
Anmelder:Applicant:
CIBA Aktiengesellschaft, Basel (Schweiz)CIBA Aktiengesellschaft, Basel (Switzerland)
Vertreter: Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Puls ίο und DipL-Chem. Dr. rer. nat. E. Frhr. v. Pechmann, Patentanwälte, München 9, Schweigerstr. 2Representative: Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Pulse ίο and DipL-Chem. Dr. rer. nat. E. Frhr. v. Bad luck man, Patent Attorneys, Munich 9, Schweigerstr. 2
Beanspruchte Priorität:
Schweiz vom 23. Mai 1958 (Nr. 59 827)Claimed priority:
Switzerland of May 23, 1958 (No. 59 827)
Dr. Max Dünnenberger, Birsfelden,
Dr. Erwin Maeder, Münchenstein,
und Dr. Adolf-Emil Siegrist, Basel (Schweiz),
sind als Erfinder genannt wordenDr. Max Dünnenberger, Birsfelden,
Dr. Erwin Maeder, Münchenstein,
and Dr. Adolf-Emil Siegrist, Basel (Switzerland),
have been named as inventors
1 -Amino-2-oxybenzol,
l-Amino^-oxy^- oder -5-methylbenzol,
l-Amino-2-oxy-3,5-dimethylbenzol,
l-Amino-2-oxy-5-tertiärbutylbenzol,
1 -Amino^-oxy-S-chlorbenzol,
l-Amino^-oxy-SjS-dichlorbenzol,
Pyridincarbonsäure-(2) [Picolinsäure],
Pyridincarbonsäure-(3) [Nicotinsäure],
Pyridincarbonsäure-(4) [Isonicotinsäure].1-amino-2-oxybenzene,
l-amino ^ -oxy ^ - or -5-methylbenzene,
l-amino-2-oxy-3,5-dimethylbenzene,
l-amino-2-oxy-5-tert-butylbenzene,
1-amino ^ -oxy-S-chlorobenzene,
l-amino ^ -oxy-SjS-dichlorobenzene,
Pyridinecarboxylic acid (2) [picolinic acid],
Pyridinecarboxylic acid (3) [nicotinic acid],
Pyridinecarboxylic acid- (4) [isonicotinic acid].
Als besonders wertvolle Mittel zum Schütze für die menschliche Haut gegen ultraviolette Strahlung erweisen sich beispielsweise die Verbindung der FormelAs a particularly valuable means of protecting the human skin against ultraviolet radiation turn out to be, for example, the compound of the formula
worin Xi ein Wasserstoffatom, ein Chloratom, eine niedrigmolekulare Alkylgruppe oder einen Phenylrest
und X2 und X3 Wasserstoffatome oder Chloratome bedeuten.
Die als Schutzmittel für die menschliche Haut gegen ultraviolette Strahlung zu verwendenden
Oxazolverbindungen der angegebenen Zusammensetzung können in einfacher Weise kosmetischenwherein Xi represents a hydrogen atom, a chlorine atom, a low molecular weight alkyl group or a phenyl radical, and X2 and X3 represent hydrogen atoms or chlorine atoms.
The oxazole compounds of the specified composition to be used as protective agents for the human skin against ultraviolet radiation can be cosmetic in a simple manner
309 537/382309 537/382
Präparaten, wie Haut- und Gesichtscremes, Puder, Repellents und insbesondere Sonnenschutzöle und -cremes, einverleibt werden.Preparations such as skin and face creams, powders, repellents and, in particular, sun protection oils and -creams, to be incorporated.
Die Mengen des den betreifenden Materialien einzuverleibenden Lichtschutzmittels können innerhalb ziemlich weiter Grenzen schwanken, beispielsweise etwa 0,01 bis 10%, vorzugsweise 0,1 bis 2% betragen.The amounts of the light stabilizer to be incorporated into the materials concerned can be within vary fairly wide limits, for example about 0.01 to 10%, preferably 0.1 to 2% be.
Die in der Patentanmeldung B 25244 IVa / 30i beschriebenen und beanspruchten Desinfektionsmittel enthalten 2-Pyridylbenzimidazole. Bei gewissen, in dieser Anmeldung beschriebenen Verwendungsarten der Imidazolverbindungen als Fungicide muß zweifellos auch Lichtschutzwirkung eingetreten sein. Diese wurde aber nicht erkannt und konnte somit auch für die Oxazolverbindungen, deren Verwendung als Fungicide nicht vorbekannt ist, nicht vorausgesehen werden. In der deutschen Patentschrift 676 108 dagegen werden Strahlungsschutzmittel beansprucht und beschrieben, die als wirksamen Bestandteil in 2-Stellung durch einen aromatischen Kern substituierte Benzoxazole enthalten können. Gegenüber diesen 2-Phenyl-benzoxazolen weisen die 2-Pyridyl-benzoxazole den Vorteil auf, daß sie befähigt sind, wasserlösliche mineralsaure oder quaternäre Ammoniumsalze zu bilden, und daß durch den Pyridinrest die Absorptionskurve der ultravioletten Strahlen derart günstig nach längeren Wellen verschoben wird, daß die schädlichen Erythem bildenden Strahlen gerade noch absorbiert, die pigmentierenden Strahlen dagegen nicht wesentlich beeinflußt werden.The disinfectants described and claimed in patent application B 25244 IVa / 30i contain 2-pyridylbenzimidazoles. For certain types of use described in this application the imidazole compounds as fungicides must undoubtedly also have a photoprotective effect. These but was not recognized and could therefore also be used for the oxazole compounds as Fungicide is not known beforehand, cannot be foreseen. In the German patent specification 676 108 against it Radiation protection agents are claimed and described that are used as an active ingredient in 2-position substituted by an aromatic nucleus may contain benzoxazoles. Compared to these 2-Phenyl-benzoxazoles have the 2-pyridyl-benzoxazoles the advantage that they are capable of water-soluble mineral acid or quaternary ammonium salts to form, and that by the pyridine residue the absorption curve of the ultraviolet rays such favorably after longer waves is shifted that the harmful erythema-forming rays straight is still absorbed, but the pigmenting rays are not significantly influenced.
In den nachfolgenden Herstellungsvorschriften A und B, in welchen die Herstellung einiger als Schutzmittel für die menschliche Haut gegen ultraviolette Strahlung zu verwendenden Oxazolverbindungen beschrieben ist, und in den Beispielen bedeuten die Teile, sofern nichts-anderes bemerkt wird, Gewichtsteile, die Prozente Gewichtsprozente, und die Temperaturen sind in Celsiusgraden angegeben. Die Schmelzpunkte sind unkorrigiert. Die UV-Spektren sind in Äthanol aufgenommen.In the following manufacturing instructions A and B, in which the manufacture of some as protective agents oxazole compounds to be used for human skin against ultraviolet rays is described, and in the examples, unless otherwise noted, the parts mean parts by weight, the percentages are percentages by weight, and the Temperatures are given in degrees Celsius. The melting points are uncorrected. The UV spectra are taken up in ethanol.
Herstellungsvorschrift AManufacturing specification A
12,3 Teile l-Amino-2-oxy-5-methylbenzol, 12,3 Teile Isonicotinsäure und 200 Teile Polyphosphorsäure werden unter Luftausschluß 3x/2 Stunden bei 240 bis 245° verrührt. Hierauf wird das Gemisch auf 100° abgekühlt, auf 300 Teile Eis ausgetragen und mit 30%iger Natriumhydroxydlösung alkalisch gestellt. Die ausgefallene Substanz wird genutscht, mit Wasser neutral gewaschen und getrocknet. Man erhält auf diese Weise etwa 18 Teile der Verbindung der Formel12.3 parts of 1-amino-2-oxy-5-methylbenzene, 12.3 parts of isonicotinic acid and 200 parts of polyphosphoric acid are stirred 3 × / 2 hours at 240 ° to 245 ° with the exclusion of air. The mixture is then cooled to 100 °, poured onto 300 parts of ice and made alkaline with 30% sodium hydroxide solution. The precipitated substance is suction filtered, washed neutral with water and dried. In this way, about 18 parts of the compound of the formula are obtained
l-Amino-2-oxy-5-methylbenzol, so erhält man die Verbindung der Formell-Amino-2-oxy-5-methylbenzene, the compound of the formula is obtained
Nach zweimaligem Umkristallisieren aus Alkohol—Wasser schmelzen die farblosen Kristalle bei 102 bis 102,5°.After recrystallizing twice from alcohol-water, the colorless crystals melt at 102 to 102.5 °.
Analyse: C13H10ON2.
Berechnet ... C 74,27, H 4,79, N 13,33; gefunden ... C 74,37, H 4,70, N 13,38.Analysis: C13H10ON2.
Calculated ... C 74.27, H 4.79, N 13.33; Found ... C 74.37, H 4.70, N 13.38.
= 230 Πΐμ (ε = 9200). ! = 308 ΐημ (ε = 20 000).= 230 Πΐμ (ε = 9200). ! = 308 ΐημ (ε = 20,000).
In ähnlicher Weise lassen sich aus entsprechenden Ausgangsstoffen die nachfolgenden Verbindungen der Formeln (4), (5) und (7) herstellen:The following compounds can be prepared in a similar manner from corresponding starting materials using formulas (4), (5) and (7):
Nach dreimaligem Umkristallisieren aus Alkohol— Wasser schmilzt das Analysenprodukt bei 153 bis 154,4°.After three recrystallization from alcohol Water melts the analysis product at 153 to 154.4 °.
Analyse: Ci2H7ON2Cl.
Berechnet ... C 62,49, H 3,05, N 12,15; gefunden ... C 62,42, H 3,12, N 12,19. lmax = 305 πΐμ (ε = 20 800).Analysis: Ci 2 H 7 ON 2 Cl.
Calculated ... C 62.49, H 3.05, N 12.15; Found ... C 62.42, H 3.12, N 12.19. l max = 305 πΐμ (ε = 20 800).
(5)(5)
ClCl
Nach dreimaligem Umkristallisieren aus Dimethylformamid schmilzt das Produkt bei 171,5 bis 172°.After three recrystallization from dimethylformamide, the product melts at 171.5 ° to 172 °.
Analyse: Ci2H5ON2Cl3.
Berechnet ... C 48,11, H 1,68, N 9,35; gefunden ... C 48,19, H 1,70, N 9,36.Analysis: Ci 2 H 5 ON 2 Cl 3 .
Calculated ... C 48.11, H 1.68, N 9.35; Found ... C 48.19, H 1.70, N 9.36.
lmaxx = 296 Πΐμ (ε = 21 000). λ»β*ϊ= 306 πΐμ (ε = 20 800). lmax x = 296 Πΐμ (ε = 21,000). λ »β * ϊ = 306 πΐμ (ε = 20 800).
(6)(6)
v\0/v \ 0 /
H3C-H 3 C-
(2)(2)
Nach dreimaligem Umkristallisieren aus Alkohol— Wasser erhält man farblose Prismen vom Schmelzpunkt 134 bis 134,5°.After three recrystallization from alcohol Water gives colorless prisms with a melting point of 134 to 134.5 °.
Analyse: Ci3HioON2.Analysis: Ci 3 HioON 2 .
Berechnet C 74,27, H 4,79, N 13,33;Calculated C 74.27, H 4.79, N 13.33;
gefunden C 74,17, H 4,93, N 13,21.Found C 74.17, H 4.93, N 13.21.
ληναχ = 309 Πΐμ (ε = 19000). ληναχ = 309 Πΐμ (ε = 19000).
Verwendet man an Stelle der Isonicotinsäure die gleiche Menge Nicotinsäure zur Umsetzung mit demIf the same amount of nicotinic acid is used instead of isonicotinic acid to react with the
5555
6o Das zweimal aus Alkohol—Wasser umkristallisierte Analysenprodukt schmilzt bei 138 bis 139°. 6o The product of analysis, recrystallized twice from alcohol-water, melts at 138 ° to 139 °.
Analyse: CiSHi2ON2.Analysis: CiSHi 2 ON 2 .
.. C 79,39, H 4,44, N 10,29; .. C79,37, H4,30, N 10,16. 250 πΐμ (ε = 26600). 313 πΐμ (ε = 19 300)... C 79.39, H 4.44, N 10.29; .. C79.37, H4.30, N 10.16. 250 πΐμ (ε = 26600). 313 πΐμ (ε = 19 300).
Berechnet
gefundenCalculated
found
ληαχι = λ ηαχι =
(7)(7)
Nach fünfmaligem Umkristallisieren des Rohproduktes aus Alkohol—Wasser erhält man dieAfter the crude product has been recrystallized five times from alcohol-water, the
in Form farbloser schmelzen.melt in the form of colorless ones.
Verbindung der Formel (7)
Kristalle, die bei 109 bis 110'Compound of formula (7)
Crystals at 109 to 110 '
Analyse: Ci2H8ON2.
Berechnet ... C 73,46, H 4,11, N 14,28;
gefunden ... C 73,54, H 4,14, N 14,47.Analysis: Ci 2 H 8 ON 2 .
Calculated ... C 73.46, H 4.11, N 14.28;
Found ... C 73.54, H 4.14, N 14.47.
lmaXi = 294 πΐμ (ε = 21 300). l maxi = 294 πΐμ (ε = 21 300).
XmaXl = 302 ηΐμ (ε = 22 000). X maxl = 302 ηΐμ (ε = 22,000).
Herstellungsvorschrift BManufacturing specification B
10 Teile der Verbindung der Formel (3), 11 Teile p-Chlorbenzylchlorid und 60 Teile Dimethylformamid werden 4 Stunden unter Luftausschluß bei 240° verrührt. Dann wird unter Vakuum die Hälfte des Dimethylformamids abdestilliert, das Reaktionsgemisch auf 0° abgekühlt, wobei die Verbindung der Formel10 parts of the compound of formula (3), 11 parts of p-chlorobenzyl chloride and 60 parts of dimethylformamide are stirred for 4 hours with exclusion of air at 240 °. Then half under vacuum of the dimethylformamide is distilled off, the reaction mixture is cooled to 0 °, whereby the compound the formula
(8)(8th)
als farblose Prismen ausfällt.fails as colorless prisms.
Nach dreimaligem Umkristallisieren aus Dimethylformamid—Aceton schmelzen sie bei 195 bis 196,3°.After three recrystallization from dimethylformamide-acetone they melt at 195 to 196.3 °.
Analyse: C20Hi6ON2Cl2.Analysis: C 20 Hi 6 ON 2 Cl 2 .
Berechnet ... C 64,70, H 4,34, N 7,54;
gefunden ... C 64,71, H 4,58, N 7,66.Calculated ... C 64.70, H 4.34, N 7.54;
Found ... C 64.71, H 4.58, N 7.66.
XmaXi = 244 πΐμ (ε = 12 000). X maxi = 244 πΐμ (ε = 12,000).
lmaXl = 323 ΐημ (ε = 16 000). JS l max = 323 ΐημ (ε = 16,000). JS
5 Teile der Verbindung der Formel (3), 10 Teile Adipinsäureisopropyltetrahydrofurfurylester und 1 Teil Glycerinmonostearat werden in 84 Teilen Äthylalkohol gelöst. Man erhält eine gegen Sonnenbestrahlung schützende und Insekten abwehrende Lösung, die sich zum Einreiben unbedeckter Körperstellen ausgezeichnet eignet.5 parts of the compound of the formula (3), 10 parts of isopropyl tetrahydrofurfuryl adipate and 1 part of glycerol monostearate are dissolved in 84 parts of ethyl alcohol. One receives one against solar radiation Protective and insect repellent solution that is used to rub in uncovered parts of the body excellent.
2 Teile der Verbindung der Formel (3), 10 Teile Glycerinmonostearat, 4 Teile Cetylalkohol, 1 Teil Natriumcetylsulfat, 1 Teil Stearinsäure und 5 Teile Glycerin werden zusammen innig vermengt und in Teilen Wasser emulgiert. Man erhält eine Emulsion, die sich als nicht fettende Hautcreme sehr gut eignet und die behandelten Stellen gegen Sonnenbestrahlung schützt.2 parts of the compound of formula (3), 10 parts of glycerol monostearate, 4 parts of cetyl alcohol, 1 part Sodium cetyl sulfate, 1 part stearic acid and 5 parts glycerol are intimately mixed together and in Share water emulsified. The result is an emulsion that can be used as a non-greasy skin cream well suited and protects the treated areas against solar radiation.
5 Teile Adipinsäureisopropyltetrahydrofurfurylester, 5 Teile Toluylsäurediäthylamid, 3 Teile der Verbindung der Formel (3), 6 Teile Cetylalkohol, Teile Vaselinöl, 10 Teile weißes Bienenwachs, Teile Lanolin, 3 Teile Kakaobutter, 39,7 Teile Wasser und 0,3 Teile Natriumbenzoat werden durch inniges Vermischen zu einer ausgezeichnet wirkenden,5 parts of adipic acid isopropyltetrahydrofurfuryl ester, 5 parts of toluic acid diethylamide, 3 parts of the Compound of formula (3), 6 parts of cetyl alcohol, parts of vaseline oil, 10 parts of white beeswax, Parts of lanolin, 3 parts of cocoa butter, 39.7 parts of water and 0.3 part of sodium benzoate are through intimate mixing to an excellent looking,
ίο Insekten abwehrenden Sonnenschutzcreme verarbeitet. ίο Insect repellent sun protection cream processed.
In den Beispielen 1 bis 4 können an Stelle der Verbindung der Formel (3) z. B. auch die Verbindungen der Formeln (2), (4), (7) oder (8) verwendet werden.In Examples 1 to 4, instead of the compound of the formula (3), for. B. also the connections of the formulas (2), (4), (7) or (8) can be used.
Claims (2)
Deutsche Patentschriften Nr. 676 103, 831755; deutsche Auslegeschriften Nr. 1 023 859, 1 012 610; B 25244 IVa/30i (bekanntgemacht am 22. 3. 1956); USA.-Patentschrift Nr. 2 727 879.Considered publications:
German Patent Nos. 676 103, 831755; German Auslegeschriften No. 1 023 859, 1 012 610; B 25244 IVa / 30i (published March 22, 1956); U.S. Patent No. 2,727,879.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH5982758A CH370874A (en) | 1958-05-23 | 1958-05-23 | Use of oxazole derivatives for protection against ultraviolet radiation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1144441B true DE1144441B (en) | 1963-02-28 |
Family
ID=4522587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEC19048A Pending DE1144441B (en) | 1958-05-23 | 1959-05-22 | Protective agent for human skin against ultraviolet radiation |
Country Status (4)
| Country | Link |
|---|---|
| CH (1) | CH370874A (en) |
| DE (1) | DE1144441B (en) |
| FR (1) | FR1228524A (en) |
| GB (1) | GB901648A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2733439A1 (en) * | 1976-08-04 | 1978-02-09 | Sandoz Ag | N-SUBSTITUTED BENZIMIDAZOLES |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4281005A (en) | 1979-03-05 | 1981-07-28 | Merck & Co., Inc. | Novel 2-pyridylimidazole compounds |
| EP0251760B1 (en) * | 1986-07-01 | 1994-01-26 | Bridgestone Corporation | Rubber composition |
| EP0496433B1 (en) * | 1987-10-22 | 1999-03-24 | The Procter & Gamble Company | Photoprotection compositions comprising chelating agents |
| US5654436A (en) * | 1995-06-07 | 1997-08-05 | American Home Products Corporation | 2-substituted benzimidazole derivatives |
| JP3520177B2 (en) | 1996-05-09 | 2004-04-19 | 明治製菓株式会社 | Serotonin 5-HT3 receptor partial activator |
| JP5369854B2 (en) | 2008-04-21 | 2013-12-18 | 住友化学株式会社 | Harmful arthropod control composition and condensed heterocyclic compound |
| TWI652014B (en) * | 2013-09-13 | 2019-03-01 | 美商艾佛艾姆希公司 | Heterocyclic substituted bicycloazole insecticide |
| WO2016071499A1 (en) * | 2014-11-06 | 2016-05-12 | Basf Se | 3-pyridyl heterobicyclic compound for controlling invertebrate pests |
| ES2751159B2 (en) * | 2018-09-27 | 2023-02-22 | Birding Natura Innovacions S L | TRANSPARENT LAMINATED GLASS WITH A REFLECTIVE COMPOUND OF ULTRAVIOLET LIGHT AND PROCEDURE FOR MANUFACTURING SAID LAMINATED GLASS |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE676103C (en) * | 1933-03-31 | 1939-05-25 | I G Farbenindustrie Akt Ges | Radiation protection agents |
| DE831755C (en) * | 1950-04-15 | 1952-02-18 | Basf Ag | Light stabilizers |
| US2727879A (en) * | 1951-12-11 | 1955-12-20 | Du Pont | Stabilized ethylene polymer compositions |
| DE1012610B (en) * | 1951-03-09 | 1957-07-25 | Gen Aniline & Film Corp | Process for the preparation of dioxy-dialkoxybenzophenones |
| DE1023859B (en) * | 1955-08-22 | 1958-02-06 | Gen Aniline & Film Corp | Ultraviolet absorber |
-
0
- FR FR1228524D patent/FR1228524A/fr not_active Expired
-
1958
- 1958-05-23 CH CH5982758A patent/CH370874A/en unknown
-
1959
- 1959-05-22 DE DEC19048A patent/DE1144441B/en active Pending
- 1959-05-25 GB GB17743/59A patent/GB901648A/en not_active Expired
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE676103C (en) * | 1933-03-31 | 1939-05-25 | I G Farbenindustrie Akt Ges | Radiation protection agents |
| DE831755C (en) * | 1950-04-15 | 1952-02-18 | Basf Ag | Light stabilizers |
| DE1012610B (en) * | 1951-03-09 | 1957-07-25 | Gen Aniline & Film Corp | Process for the preparation of dioxy-dialkoxybenzophenones |
| US2727879A (en) * | 1951-12-11 | 1955-12-20 | Du Pont | Stabilized ethylene polymer compositions |
| DE1023859B (en) * | 1955-08-22 | 1958-02-06 | Gen Aniline & Film Corp | Ultraviolet absorber |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2733439A1 (en) * | 1976-08-04 | 1978-02-09 | Sandoz Ag | N-SUBSTITUTED BENZIMIDAZOLES |
Also Published As
| Publication number | Publication date |
|---|---|
| CH370874A (en) | 1963-07-31 |
| GB901648A (en) | 1962-07-25 |
| FR1228524A (en) | 1960-08-31 |
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