Acta Chemica Scandinavica (1947-1973) published new progress about 971-66-4. 971-66-4 belongs to pyridine-derivatives, auxiliary class Pyridine,Benzene, name is Triphenyl(pyridin-1-ium-1-yl)borate, and the molecular formula is C10H10CoF6P, Quality Control of 971-66-4.
Torssell, Kurt published the artcilePositive halogen compounds. VI. Preparation of alkoxydimethylsulfonium salts and their role in the Kornblum oxidation. Revision of the structure for the olefin-bromotrinitromethane adduct, Quality Control of 971-66-4, the publication is Acta Chemica Scandinavica (1947-1973) (1967), 21(1), 1-14, database is CAplus.
cf. CA 63: 6839b; 65: 19963b. Structure I for the reaction product of BrC(NO2)3 and cyclohexene was revised to II (R = 2-trans-bromocyclohexyl) (III). Treatment of 0.2 g. III in 1 ml. EtOAc with 0.2 g. NaBPh4 gave ROS+Me2B-Ph4 (IV, R = 2-bromocyclohexyl) (V), m. 138-40° (decomposition). III (0.2 g.) was heated with 1 ml. iso-BuOH at 55-6° 45 min. and treated with 0.2 g. NaBPh4 in 1 ml. EtOAc to give 0.19 g. IV (R = iso-Bu) (VI) m. 141-3° (decomposition). ClCO2Bu-iso prepared from 0.16 g. iso-BuOH and a slight excess of COCl2 (10% in ether) was treated, after evaporation of ether, with 1 ml. Me2SO and, after 0.5 hr., 0.7 g. NaBPh4 in 6 ml. 1:1 MeOH-water mixture to give 0.4 g. IV (R = Et), m. 150-60°, remelts ∼260°. III (1 g.) in 4 ml. MeOH kept at 40-50° 20 min., evaporated to half volume in vacuo, and treated with 10 ml. CCl4 to give 0.55 g. II (R = Me). II (R = Me) (0.25 g.) in 1 ml. MeOH was treated with 0.4 g. NaBPh4 in 1 ml. MeOH to give 0.38 g. IV (R = Me) (VII). Me2SO (0.3 g.) was mixed with 0.5 g. Me2SO4, kept at room temperature 24 hrs., treated with 0.75 g. KC(NO2)3 in 5 ml. dimethoxyethane, filtered from KMeSO4, concentrated to 0.5 volume in vacuo, and treated with 10 ml. CCl4 to give 0.3 g. VII, m. 51-2° (decomposition). Treatment of a mixture of 0.5 g. Me2SO4 and 0.3 g. Me2SO with 1.4 g. NaBPh4 in 10 ml. MeOH gave 0.9 g. VII. A bromonium ion (VIII) is suggested. VII (0.2 g.) was heated to 190° in a small bulb tube until gas evolution ceased (∼10 min.) to give 40 mg. condensate composed of benzene and MeOCH2SMe (ir and N.M.R.); the remainder was partially crystalline and gave Ph3BOSMe2 (IX), m. 160-3°. IX can also be obtained by addition of 0.1 ml. concentrated HCl to 0.2 g. NaBPh4 in 2 ml. water. Treatment of 50 mg. IX in 3 ml. EtOAc with 50 mg. pyridine gave Ph3BQ (Q = 1-pyridyl), m. 210° (decomposition), which was also obtained by Pfitzner-Moffat oxidation Pyrolysis of V at 130-40° 5 min. gave mostly benzene and a small amount IX, and pyrolysis of V in Me2SO gave a somewhat higher yield of carbonyl compounds and trans-2-bromocyclohexanol. Thus, the Kornblum oxidation and Barton’s modification (CA 61: 2958e) proceeds via an intermediary sulfonium ion, which collapses to a carbonyl compound and Me2S either by the reaction (1) or a cyclic mechanism (2), giving Me2S and CD3SCD2H when Me2CHCH2OS+(CD3)2B-Ph4 was pyrolyzed. The oxidation follows the mechanism (1) only if the α-proton is activated as in p-BrC6H4COCH2OS+Me2. A mechanism (3) for Pfitzner and Moffat oxidation (CA 64: 6709g) was suggested to proceed via a complex (X). Magnetic nonequivalence for S-methyl resonance peak of V (a doublet, separation 1.7 Hz.) was found. N.M.R. spectrum of VII or II (R = Me) underwent a drastic change when the compounds were heated in (CD3)2SO at 65°. After 1 hr., the absorption of SMe at δ = 3.29 disappeared and a new peak appeared at δ = 2.57 ppm. The peak at δ = 3.97 ppm. had the same intensity as before and only traces of Me2S were detected. The result suggested a carbonium ion exchange (4) comparable with proton exchange in water. The reaction is completely reversible because when XI was dissolved in Me2SO, VII was regenerated. Addition of NaI to VII gave a rapid change of spectrum showing a reaction, Me2SO+Me + NaI → Me2SO + MeI + Na+. Pyrolysis of VII to MeOCH2SMe resembles the Pummerer rearrangement.
Acta Chemica Scandinavica (1947-1973) published new progress about 971-66-4. 971-66-4 belongs to pyridine-derivatives, auxiliary class Pyridine,Benzene, name is Triphenyl(pyridin-1-ium-1-yl)borate, and the molecular formula is C10H10CoF6P, Quality Control of 971-66-4.
Referemce:
https://en.wikipedia.org/wiki/Pyridine,
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