Photoenolization as a means to release alcohols

We have designed molecules which release alcohols upon exposure to UV light independent of the reaction media, making it possible to liberate alcohols in a controlled manner in applications. Photolysis of 2-(2-isopropylbenzoyl)benzoate ester derivatives 4 in various solvents and in thin films results in the liberation of the alcohol moiety from the ester. The reaction mechanism for the release of the alcohol has been elucidated by time-resolved laser flash photolysis. Upon irradiation the triplet excited state of ketone, 4 is formed, and its lifetime can be estimated to be between 0.08 and 0.8 ns. The triplet excited state decays by efficient intramolecular H-atom abstraction to form a 1,4-biradical, 8, that has a lifetime of less than 17 ns and is trapped by molecular oxygen. In the absence of oxygen, biradical 8 intersystem crosses to form photoenols (Z)-9 and (E)-10 in a ratio of 5:2, respectively. Photoenol (Z)-9 has a lifetime of approximately 3000 ns in protic solvents and returns to the starting material through 1,5 intramolecular hydrogen transfer. The other isomer, (E)-10, is much longer lived (>1 ms) and releases the alcohol moiety through an intramolecular lactonization.     

Photoenolization of 2-(2-methyl benzoyl) benzoic acid, methyl ester: effect of E photoenol lifetime on the photochemistry

[reaction: see text] Photolysis of 3 in argon-saturated 2-propanol led to formation of 5 via intermolecular H-atom abstraction followed by lactonization. Irradiation of 4 in 2-propanol gave compounds 6 and 7 that also come from intermolecular H-atom abstraction. In contrast, photolysis of an oxygen-saturated solution of 3 in 2-propanol yields products 8, 9, and 10, which were all formed from intramolecular H-atom abstraction and trapping of the corresponding biradical with oxygen. Laser flash photolysis of 3 in methanol showed formation of biradical 3BR (lambda(max) 330 nm, and tau = 50 ns) via intramolecular H-atom abstraction as the main photoreactivity of 3. Biradical 3BR decayed into photoenols 3Z and 3E (lambda(max) 390 nm, tau = 6.5 micros and tau = 162 micros, respectively). In comparison, laser flash photolysis of 4 yielded photoenols 4Z and 4E (lambda(max) 390 nm, tau = 15 micros and tau = 3.6 ms, respectively). Thus photoenol 3E is unusually short-lived, and therefore it does not undergo the intramolecular lactonization as we have observed for the analogous photoenol 1E. Photoenol 3Z decays back to 3 via an intramolecular 1,5-H shift, whereas photoenol 3E reforms 3 efficiently via the solvent with the aid of the ortho ester group. The intramolecular lactonization of photoenols 1E and 3E must be a slow process, presumably because the photoenols are rigid and the hydroxyl group is inhibited, by intramolecular hydrogen bonding, from acquiring the correct geometry for lactonization. Thus only photoenols that are resistant to reformation of their ketone via the solvent are long-lived enough to undergo lactonization and release the alcohol moiety.     

Fluoromethylene Transfer from Diarylfluoromethylsulfonium Salts: Synthesis of Fluorinated Epoxides

Diarylfluoromethyl sulfonium salts are efficient fluoromethylene transfer reagents equivalent to fluorocarbene, which is difficult to access. This was demonstrated by the development of a monofluorinated Johnson–Corey–Chaykovsky reaction with ketones and aldehydes, delivering uncommon 2-unsubstituted fluoroepoxides. This is the first evidence for the feasibility of sulfur fluoromethylylide and its action as a reaction intermediate.     

Recent investigations and applications of azidoazomethine-tetrazole tautomeric equilibrium (microreview)

Chemistry of Heterocyclic Compounds - Recent investigations of azidoazomethine-tetrazole (azide-tetrazole) tautomeric equilibrium reported from 2014 to 2019 are summarized. Pyridine, pyrimidine,...