Meerwein, Hans; Hederich, Volker; Morschel, Hans; Wunderlich, Klaus published the artcile< Intermolecular anion transfer during organic reactions>, Formula: C6H11NO2, the main research area is .
A class of reaction mechanisms, RA + R’+ → R’A + R+, is considered, where R+ is the more stable carbonium ion, A = hydride, cyanide, or alkoxide; isolation of the R+ salts is attempted. Ph3C+ is chosen as R’+ and prepared by stirring 44.5 g. BF3-EtOAc, b13 49-51°, into 61 g. Ph3COEt in 170 cc. EtOAc with exclusion of H2O and alc., separation of Ph3CBF3 (I) by filtering after 24 hrs., and washing with low-boiling petroleum; total yield after recovery of 2nd crop 90%, m. 197-8°. Addition of 7.4 g. 1,3-dioxolane to 16.5 g. I in 60 cc. liquid SO2 under reflux (dry ice condenser) results in hydride transfer and, after evaporation and treatment with CH2Cl2 and Et2O, isolation of 88.5% 1,3-dioxolenium fluoborate, m. 83°; β-iodoethyl formate b15 65-70°, prepared with NaI in MeCN. From the CH2Cl2 washings, 58% Ph3CH, m. 90.5-1.5°, is isolated. Similarly, 2-methyl-1,3-dioxolane, the 2-Ph compound (II), and the 2,4,4,5,5-Me5 compound yield, resp., 84, 83, and 77% Ph3CH, and 69, 100, and 76% (m. 150-2°) dioxolenium fluoborates. In order to substitute for I the nonexistent Et +, 9.5 g. (Et3O) (BF4) and 9 g. II is heated to 40°, 81% Et2O distilled, and 50% II-BF4 salt and C2H6 isolated. Another H- donor is (PhCH2)3N, reacting with I in MeCN at 40-50° to yield 84% Ph3CH and 94% benzylidenedibenzylimonium fluoborate, m. 132-4°, hydrolyzed in hot 30% NaOH to (PhCH2)2NH. Cyanide transfer occurs by cooling 5 g. 2-cyano-2-methyl-1,3-dioxolane (III) in 25 cc. MeCN with 14.5 g. I, filtering off after 1 hr. 6.5 g. Ph3CCN, m. 128.6-29° (total yield 82%), and adding Et2O to isolate 59% 2-methyldioxolenium fluoborate (IV), m. 162-4°, and recover more Ph3CCN from the filtrate. III reacts with (EtO)2CHBF4, m. 20°, in CH2Cl2 to yield 88% IV and 81% (EtO)2CHCN, b760 163-4°, b15 58-9.5°, n20D 1.3978. Alkoxide transfer is reversible and usually more rapid than hydride transfer. Camphor diethyl acetal, b10 99.5-101°, (18 g.) added to 16.5 g. I in 25 cc. MeCN precipitates 95% O-ethylcamphoroxonium fluoborate, decomposed at 104-5%, isolated by washing with Et2O; 90% Ph3COEt (V), m. 82°, is obtained by evaporation of the filtrate. Similar high-yield reactions of ROEt with I or HC(OEt)2BF4 (VI) give the R salt and V or HC(OEt)3 for R = O.CH2.CH2.O.CMe (both I and VI), C(OEt)3 (both I and VI), O.CMe2.CMe2.O.CH (I only), O.CHMe.CHMe.O.CH (I only), HC(OEt)2 (Ph3CSbCl6), Me2NCHOEt [Ph3CSbCl6, VI, and HC(OEt)2SbCl6]. V is cleaved by R’BF4 (R’ = 2-methyl-, 4,5-dimethyl-, or 2,4,4,5,5-pentamethyldioxolenium) with isolation of Ph3CH and AcH. With ROEt (R = O.CH2.CH2.CH), I in CH2Cl2 yields 88% RBF4 and 95% Ph3CH, but in MeCN the same reaction produces 91% Ph3COCH2CH2COCPh3 (VII), m. 188-9° (MeCOEt), and by attack on O and ring cleavage, some RBF4, and VI. When not isolated, VII decompose to Ph3CH. RBF4 in turn reacts with V in MeCN to yield 33% VII, and VII with VI in CH2Cl2 to yield 75% RBF4. From 13.2 g. I in 20-25 cc. dry CH2Cl2, treated with 8.5 g. RNMe2 (R = O.CH2.CH2.O.CMe), b. 142°, with cooling and stirring 30 min. after slow addition, Et2O precipitates [RN(CPh3)Me2]BF4, stable, m. 170°; the iodide, obtained by treatment with NaI in MeCN, decompose at 110° to 88.5% AcNMe2, b30 76-7°, recovered by distillation, and 78.6% ICH2CH2OCPh3, m. 136-7°, obtained by crystallization of the residue from alc. or MeCN. The ether is obtained independently for comparison from Ph3CH and HO(CH2)2Br in C5H5N via the Br compound, m. 126-7%, and refluxing the latter with NaI in MeCN. The mechanisms are discussed. The new (OCMe2CMe2OCH)BF4 m. 110-12° and (Me2NCHOEt)SbCl6 m. 156-8°.
Annalen der Chemie, Justus Liebigs published new progress about Anions. 6136-93-2 belongs to class nitriles-buliding-blocks, and the molecular formula is C6H11NO2, Formula: C6H11NO2.
Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts