70356-09-1 Usage
Description
Avobenzone, also known as butyl methoxydibenzoylmethane, is a full-spectrum ultraviolet A (UVA) blocker that inhibits UVA-induced increases in melanin levels and tyrosinase activity in B16/F10 melanoma cells. It also reduces the production of reactive oxygen species (ROS) and 8-hydroxy-2''-deoxyguanosine (8-OH-dG), as well as prevents the depletion of glutathione (GSH) in these cells. Avobenzone is used in sunscreen products to provide sun protection and is approved for use up to 3 percent in the United States and 5 percent in the European Union.
Uses
Used in Sunscreen Industry:
Avobenzone is used as a component of sunscreen that absorbs the full spectrum of UVA rays, offering broad-range protection against UVA radiation. It is particularly effective in providing strong absorption through a large portion of the UVA spectrum, including the majority of the UVA I range with peak absorption at 360 nm.
Used in Cosmetics Industry:
Avobenzone is used as a sedative and neurosedative in cosmetics, helping to reduce the harmful effects of UVA radiation on the skin and providing a protective barrier against sun damage.
Used in Pharmaceutical Industry:
Avobenzone is used in pharmaceutical formulations to increase the nuclear translocation of nuclear factor erythroid 2-related factor 2 (Nrf2) and upregulate the antioxidant response element (ARE) in UVA-irradiated B16/F10 cells, thus providing additional skin protection.
However, Avobenzone is associated with some photoinstability, which can be overcome in the overall sunscreen formulation. The use of octocrylene and some newer sunscreens, including BEMT stabilized avobenzone, can help improve photostability. Non-UV filters such as diethylhexyl 2,6 naphthalate may also be used as triplet–triplet quenchers to enhance the overall formulation with avobenzone.
Properties
Avobenzone belongs to a dibenzoyl methane derivative. It is oil soluble ingredient. Since it is very sensitive to light, photostablizers are added in the sunscreen product to increase its stability and duration of action. Avobenzone has an absorption maximum of 357 nm. Sunscreens containing avobenzone is indicated for providing protection from the sun. In addition to limiting the skin's exposure to the sun, using sunscreen agents may help reduce long-term sun damage such as premature aging of the skin and skin cancer. It is capable of blocking UVA I, UVA II and UVB wavelengths, thereby limiting the impact of UV rays on skin. Diminish the penetration of ultraviolet (UV) light through the epidermis by absorbing UV radiation within a specific wavelength range. The amount and wavelength of UV radiation absorbed are affected by the molecular structure of the sunscreen agent[15, 16].
Toxicity
Although avobenzone itself has very low toxicity, when exposed to light in a chlorinated water solution, avobenzone can be broken down into a combination of aromatic acids, aldehydes, phenols and acetyl benzenes, several of which are highly toxic[14].
References
http://www.ewg.org/skindeep/ingredient/700596/AVOBENZONE/
Karlsson I, Hillerstr?m L, Stenfeldt AL, M?rtensson J, B?rje A. "Photodegradation of dibenzoylmethanes: potential cause of photocontact allergy to sunscreens." Chemical Research in Toxicology. November 2009. doi: 10.1021/tx900284e.
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N.A.Shaath,Photochem.Photobiol.Sci.9(2010)464
D. Veierov, T. Bercovici, E. Fischer, Y. Mazur, A. Yogev, J. Am. Chem. Soc. 99 (1977) 2723
H. Gonzenbach, T. J. Hill, T. G. Truscott, J. Photochem. Photobiol., B 16 (1992) 377
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M.Yamaji,M.Kida,J.Phys.Chem.,A117(2013)1946
P.K.Verma,F.Koch,A.Steinbacher,P.Nuernberger,T.Brixner,J.Am.Chem.Soc.136 (2014) 14981
A. D. Dunkelberger, R. D. Kieda, B. M. Marsh, F. F. Crim, J. Phys. Chem., A 119 (2015) 6155
P. K. Verma, A. Steinbacher, F. Koch, P. Nuernberger, T. Brixner, Phys. Chem. Chem. Phys. 17 (2015) 8459
https://www.upi.com/Science_News/2017/06/27/Sunscreen-chemical-breaks-down-into-toxic-compounds-when-exposed-to-sun-and-water/1241498577662/
Zawadiak J, Mrzyczek M (October 2012). "Influence Of Substituent On UV Absorption And Keto–Enol Tautomerism Equilibrium Of Dibenzoylmethane Derivatives". Spectrochim Acta a Mol Biomol Spectrosc. 96: 815–819. Bibcode:2012 AcSpA..96..815Z. doi:10.1016/j.saa.2012.07.109. PMID 22925908.
Vielhaber G, Grether-Beck S, Koch O, Johncock W, Krutmann J (March 2006). "Sunscreens with an absorption maximum of > or =360 nm provide optimal protection against UVA1-induced expression of matrix metalloproteinase-1, interleukin-1, and interleukin-6 in human dermal fibroblasts". Photochem Photobiol Sci. 5 (3): 275&ndash, 282. doi:10.1039/b516702g. PMID 16520862.
Originator
Avobenzone,AroKor Holdings
Inc.
Manufacturing Process
356.0 g (2 mol) of p-t-butylbenzoic acid, 243.0 g (7.6 mol) of methyl alcohol
and 35.0 g of sulfuric acid (96%) are added to a four-necked round flask
which is provided with a stirrer and a condenser. The mixture is held for 8 h at
reflux temperature with slight stirring. The condenser is then replaced by a
distillation column and the excess methyl alcohol is distilled off, towards the
end under a slight vacuum but without the temperature exceeding 100°C. The
mixture is cooled and poured on to ice. The phases are left to separate, the
organic phase is washed with ice-water, with a saturated sodium carbonate
solution in the presence of ice and finally with ice until neutral. The organic
phase is dried over sodium sulfate and there is thus obtained a precipitate. By
distillation on a Widmer column (120 mm) there are obtained 345.0 g (90%
yield) of the p-t-butylbenzoic acid methyl ester, boiling point 76°C/0.02
mmHg.
2 methods of producing of 4-(1,1-dimethylethyl)-4'-methoxydibenzoylmethane from p-t-butylbenzoic acid methyl ester:
1). To a round flask which has been well dried and flushed with nitrogen are
added 85.0 g (1.1 mol) of sodium amide (50% suspension in toluene) and
180.0 g of isopropyl ether and there are now added dropwise thereto at a
temperature of 50°-60°C 150.2 g (1 mol) of acetylanisole in 180.0 g of
isopropyl ether. Reaction sets in immediately and a white paste-like mass
forms. After completion of the addition, the mixture is stirred for a further 0.5
h and then 192.3 g of p-t-butylbenzoic acid methyl ester are added rapidly at
25°-30°C. The mixture is stirred for 0.5 h at room temperature, then for 3 h
at 60°-70°C and left to stand for 12 h. 200.0 g of ice are then added and the
mixture is acidified with 128.0 g (1.1 mol) of technical hydrochloric acid and
200 ml of ice-water. The mixture is stirred until the sodium salt of the product
has dissolved. The phases are separated and the organic phase is washed with
ice-water until neutral. The organic phase is concentrated on a rotary
evaporator and there are thus recovered 290.0 g of isopropyl ether. The yield
of 4-(1,1-dimethylethyl)-4'-methoxydibenzoylmethane, melting point 83.5°C is
199.8 g (64.5%) (recrystallisation from methanol).
2). 36.0 g (1.2 mol) of 80% sodium amide and 300.0 g of dry toluene are
added to a round flask which was flushed with nitrogen. The mixture is heated
to 50°C and 150.2 g (1 mol) of acetylanisole in 309.0 g of toluene are added
within 1.5 h. After completion of the addition, the mixture is held at 50°C for
15 min and there are then added thereto at this temperature within 1 h 50
min 192.3 g (1 mol) of p-t-butylbenzoic acid methyl ester. The mixture is
stirred for a further 1 h at 50°C and then heated at 100°C for 1 h, after which
time the product has separated out in the form of a solid precipitate. The
mixture is left to stand for 12 h and there are then added thereto 300 ml of
ice-water followed by a mixture of 100 ml of pure hydrochloric acid and 250
ml of ice-water. The phases are separated and the organic phase is washed
twice with water. The organic phase is dried over sodium sulfate and treated
simultaneously with 20.0 g of active carbon. After filtration, the filtrate is
concentrated until crystallisation begins. 50 ml of hexane are added, the
mixture is cooled and then filtered over a Buchner funnel. There is obtained a
total yield of 220.91 g (71.2%) of the desired 4-(1,1-dimethylethyl)-4'-
methoxydibenzoylmethane, of melting point 83.5°C (recrystallisation from 600
ml of methanol).
Flammability and Explosibility
Nonflammable
Check Digit Verification of cas no
The CAS Registry Mumber 70356-09-1 includes 8 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 5 digits, 7,0,3,5 and 6 respectively; the second part has 2 digits, 0 and 9 respectively.
Calculate Digit Verification of CAS Registry Number 70356-09:
(7*7)+(6*0)+(5*3)+(4*5)+(3*6)+(2*0)+(1*9)=111
111 % 10 = 1
So 70356-09-1 is a valid CAS Registry Number.
InChI:InChI=1/C20H22O3/c1-2-3-10-15-23-20(18(21)16-11-6-4-7-12-16)19(22)17-13-8-5-9-14-17/h4-9,11-14,20H,2-3,10,15H2,1H3
70356-09-1Relevant articles and documents
Photodegradation of avobenzone: Stabilization effect of antioxidants
Afonso,Horita,Sousa E Silva,Almeida,Amaral,Lob?o,Costa,Miranda, Margarida S.,Esteves Da Silva, Joaquim C.G.,Sousa Lobo
, p. 36 - 40 (2014)
Avobenzone is one of the most common UVA-filters in sunscreens, and is known to be photounstable. Some of the strategies used to stabilize this filter present some drawbacks like photosensitization reactions. Antioxidants are widely used as cosmetic ingredients that prevent photoageing and complement the photoprotection offered by the UV-filters preventing or reducing photogenerated reactive species. The purpose of this work was to study the effect of antioxidants in the photostabilization of avobenzone. The filter dissolved in dimethyl sulfoxide or incorporated in a sunscreen formulation was irradiated with simulated solar radiation (750 W/m2). The tested antioxidants were vitamin C, vitamin E, and ubiquinone. The area under the curve of the absorption spectrum for UVA range and the sun protection factor (SPF) were calculated. Vitamin E (1:2), vitamin C (1:0.5) and ubiquinone (1:0.5) were the more effective concentrations increasing the photostability of avobenzone. In sunscreen formulations, the most effective photostabilizer was ubiquinone which also promoted an increase in SPF. This knowledge is important to improve effectiveness of sunscreen formulation. Antioxidants can be valuable ingredients for sunscreens with a triple activity of filter stabilization, SPF boosting and photoageing prevention.
Novel Bifunctionalization of Activated Methylene: Base-Promoted Trifluoromethylthiolation of β-Diketones with Trifluoromethanesulfinyl Chloride
Sun, Dong-Wei,Jiang, Min,Liu, Jin-Tao
supporting information, p. 10797 - 10802 (2019/07/03)
A novel bifunctionalization of activated methylene was achieved successfully through the base-promoted trifluoromethylthiolation of β-diketones or β-ketoesters with trifluoromethanesulfinyl chloride. A series of α-trifluoromethylthiolated α-chloro-β-diketones and α-chloro-β-ketoesters were obtained in moderate to good yields under mild conditions. When β-diketones containing a phenyl group with a hydroxyl or amino substituent at the ortho position were used as substrates, intramolecular trifluoromethylthiolation/cyclization reaction took place to give the corresponding cyclic products. Furthermore, the protocol could be extended to perfluoroalkylthiolation with the sodium perfluoroalkanesulfinate/POCl3 system. On the basis of experimental results, plausible mechanisms are proposed.
ONE-STEP, FAST, 18F-19F ISOTOPIC EXCHANGE RADIOLABELING OF DIFLUORO-DIOXABORININS AND USE OF SUCH COMPOUNDS IN TREATMENT
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Paragraph 0019; 0206-0207, (2019/12/15)
A compound according to Formula (I) or a pharmaceutically acceptable salt and/or solvate thereof, wherein X1 and X2 are each independently 18F or 19F; R1 and R2 are each independently alkyl, amine, perfluoroalkyl, alkenyl, alkynyl, aryl, or aralkenyl; and R3 is H, halo, alkyl, alkyl ester, alkenyl, alkynyl, aryl, or aralkenyl; or wherein: R1 and R3 or R2 and R3 join to form a 6-membered cycloalkyl or heterocyclyl; or R1 and R3, R2 and R3, or R1, R2, and R3 join to form a substituted or unsubstituted polycyclic ring, wherein the polycyclic ring comprises fused cycloalkyl, heterocycloalkyl, aryl, or heteroaryl rings.
