82027-52-9

Upstream product

• 75-89-8 2,2,2-trifluoroethanol 
• 19255-01-7 2-oxo-1,2-diphenylethylmethanesulfonate 
• 103-30-0 (E)-1,2-diphenyl-ethene 
• 3491-28-9 2-diethylphosphoryloxy-1,2-diphenylethanone 

Relevant academic research and scientific papers

Electrophilic fluorinating reagent mediated synthesis of fluorinated α-keto ethers, benzil, and 6,6′-dialkoxy-2,2′-bipyridines

Interactions of various fluorinated and nonfluorinated alcohols with trans-stilbene in the presence of electrophilic reagents were studied. Under neat conditions, reactions of trans-stilbene (1) with fluorinated alcohols, RfOH (Rf = CF3CH2-, CFH2CH2-, CF3CF2CH2-, CF2H(CF2)3CH2-, (CF3)2CH-, (CF3)3C-(2a-f) in the presence of an electrophilic reagent, 1-(chloromethyl)-4-fluoro-1,4-diazoniabicyclo-[2.2.2]octane bis(tetrafluoroborate) (Selectfluor) or N,N-difluoro-2,2′-bipyridinium bis(tetrafluoroborate) (MEC-31), gave α-keto ethers (3a-f) and benzil (4) in good to moderate yields. α-Keto ether and benzil formation was very much dependent on the reaction time, the degree of fluorination of the alcohols, and whether a solvent such as CH3CN, DMF or DMA was utilized. In solution, α-keto ethers and benzil did not form. Interestingly, under neat conditions, nonfluorinated alcohols, ROH (R = CH3-, CH3CH2-, CH3CH2CH2-, CH3CH2CH2CH2-, CH3CH2CH 2CH2CH2CH2-) (5g-k) did not react with trans-stilbene in the presence of MEC-31 but gave 6,6′-dialkoxy-2,2′-bipyridines (6g-k), regioselectively, in excellent isolated yields. On the other hand, fluorinated alcohols did not react with MEC-31. Reaction of MEC-31 with an excess of diethylene glycol (7) gave the bipyridine derivative (8) in 88% isolated yield. Reaction of 8 either with diethylaminosulfur trifluoride (DAST) or bis(2-methoxyethyl)aminosulfur trifluoride (Deoxofluor) readily produced the corresponding difluoro derivative (9) in 85% isolated yield. All new compounds have been characterized by spectroscopic and elemental analysis.

Kinetics and mechanism of phosphate photorelease from benzoin diethyl phosphate: Evidence for adiabatic fission to an α-keto cation in the triplet state

The photodissociation of benzoin diethyl phosphate (1, 'caged' phosphate) was studied by nanosecond and picosecond laser flash photolysis. The lowest triplet state of 1, 31, was identified as the reactive excited state with an absorption maximum around 340 nm and a lifetime of 10-25 ns, depending on the solvent. Two different reaction paths were identified, both of which involve the release of diethyl phosphoric acid from 31 within 25 ns. In addition to a fast cyclization-elimination process leading to 2- phenylbenzofuran (2) and diethyl phosphoric acid, heterolytic adiabatic dissociation of 31 yields a triplet cation and diethyl phosphate anion in water, trifluoroethanol, and hexafluoro-2-propanol solutions. The triplet cation (570 nm, τ ? 430 ns in water) undergoes intersystem crossing to the singlet ground state before it reacts with the solvent molecules.

Competing, kc, Borderline, ks, and Carbonyl Addition Processes in Solvolyses of α-Keto Mesylates and Triflates. α-Keto Cations. 5

Solvolysis studies on tertiary α-keto mesylates show quite varying responses in rate to solvent ionizing power.The m values are 1.01 for 2-benzoyl-2-adamantyl mesylate (12), 0.66 for the mesylate derivative of 2-hydroxy-2,4,4-trimethyl-3-pentanone (4), and 0.63 for the mesylate derivative of 2-hydroxy-2-methylpropiophenone (3).The mesylate derivative of methyl α-hydroxyisobutyrate (5) does not correlate well with YOTs values, but instead it gives behavior that parallels that of isopropyl tosylate.Mesylates 3-5 solvolyze giving varying ratios of elimination and substitution products at rates comparable to that of isopropyl mesylate. β-d6 isotope effects for 3 and 4 range from 1.69 to 2.08 and are consistent with the intermediacy of α-keto cations. β-Deuterium isotope effects for 5 are quite variable (1.40-2.52) and parallel the amount of elimination product formed (22-94percent).This is consistent with the intermediacy of a reversibly formed ion-pair intermediate which can suffer proton loss.However, the SN2 (intermediate) mechanism remains a possibility in solvolyses of 5.Mesylate 3 solvolyzed in trifluoroethanol with added triethylamine to give an alkoxyoxirane.With small amounts of added 2,6-lutidine the 1,2-elimination product was major , while with added methanesulfonic acid the rearranged trifluoroethyl ester of dimethylphenyl acetic acid was major.These variable products were interpreted in terms of competing carbonyl addition processes and processes involving the α-keto cation.Secondary triflates derived from α-hydroxypropiophenone, 2,2-dimethyl-4-hydroxy-3-pentanone, and ethyl lactate solvolyzed giving the simple substitution product.Rates parallel solvent nucleophilicity and suggest a ks process involving negligible cationic character at the carbon α to the carbonyl group. kΔ processes are also not involved in solvolyses of these secondary triflates.