Butyl alcohol Spectroscopy

The more acidic fluorene in tert-butyl alcohol solution, or in DMSO solution, reacts by a process that involves the carbanion in equilibrium with hydrocarbon. Thus, fluorene and 9,9-dideuteriofluorene oxidize at identical rates. We have established that the oxidation of the anion of fluorene can be catalyzed by a variety of electron acceptors (v), including various nitroaromatics (18). The catalyzed oxidation rates were found to follow the rates of electron transfer measured by ESR spectroscopy in the absence of oxygen. These results established the catalyzed reaction as a free radical chain process without shedding light upon the mechanism of the uncatalyzed reaction. 

Treatment of diphenylmethane in basic solution with a trace of oxygen in DMSO solutions fails to produce significant amounts of a paramagnetic product detectable by ESR spectroscopy. On the other hand, treatment of benzhydrol with traces of oxygen in basic solution can produce significant amounts of the ketyl. Pyridylthiazolylcarbinols are readily converted to the ketyls by base in alcoholic solution. (24). In pure DMSO significant amounts of the ketyl are formed whereas in tert-butyl alcohol or DMSO (80% )-tert-butyl alcohol (20% ) only traces of the ketyl can be detected. These results are consistent with the formation of the ketyl under oxidative conditions by Reaction 31. Only under the most basic conditions (pure DMSO) is the dianion formed by... 

Trapped by a suitable compound, a transient intermediate can be converted into a more stable species for unequivocal identification. Stepanov and Luzgin (82) investigated the reaction of acetonitrile with 1-octene or tert-butyl alcohol on acidic zeolite HZSM-5 ( 2si/ Ai = 49) at 296 K by in situ MAS NMR spectroscopy under batch reaction conditions. Upon coadsorption of acetonitrile and 1-octene, a C MAS NMR signal at 108 ppm was observed, indicative of TV-alkylnitrilium ions 2 in Scheme 3. As depicted in Scheme 3a, the formation of these cations was explained by trapping the chemically unstable alkylcarbenium ions (formed from the adsorbed... 

By in situ MAS NMR spectroscopy, the Koch reaction was also observed upon co-adsorption of butyl alcohols (tert-butyl, isobutyl, and -butyl) and carbon monoxide or of olefins (Ao-butylene and 1-octene), carbon monoxide, and water on HZSM-5 (Ksi/ Ai — 49) under mild conditions (87,88). Under the same conditions, but in the absence of water (89), it was shown that ethylene, isobutylene, and 1-octene undergo the Friedel-Crafts acylation (90) to form unsaturated ketones and stable cyclic five-membered ring carboxonium ions instead of carboxylic acids. Carbonylation of benzene by the direct reaction of benzene and carbon monoxide on solid catalysts was reported by Clingenpeel et al. (91,92). By C MAS NMR spectroscopy, the formation of benzoic acid (178 ppm) and benzaldehyde (206 ppm) was observed on zeolite HY (91), AlC -doped HY (91), and sulfated zirconia (SZA) (92). 

We have characterized (8e-i) this intermediate using solid-state 13C CP/MAS NMR, 2H NMR, and two dimensional (2D). /-resolved 3C NMR spectroscopy in the course of dehydration of isobutyl alcohol and /er/-butyl alcohol in HZSM-... 

For /er/-butyl alcohol, we have observed (8f) with l3C CP/MAS and 2H NMR spectroscopy, the formation of tert-butyl silyl ether (TBSE) at temperatures as low as 296 K. In these experiments,, 3C and 2H-labeled tert-butyl alcohols were used ... 

The photocyanation and the photohydrolysis of 4-chloroanisole and 4-fluoroanisole have been studied with time-resolved spectroscopy and by measurement of the photoconductivity in anhydrous and aqueous acetonitrile and tert-butyl alcohol solutions632. The mechanism is depicted in equation 167. The transient species which have been... 

Photolysis of 3-thietanone involves both singlet and triplet excited states the initial products are sulfene and ketene, as determined by IR spectroscopy at liquid nitrogen temperatures in a pentane matrix.When the photolysis is done in methanol, isopropyl alcohol, or r-butyl alcohol, these intermediates are trapped as the acetate and methanesulfonate esters. In diphenylmethanol solvent, the bis-diphenylmethyl ether is formed by displacement of the alcohol on the sulfonate ester. Photolysis of tetramethyl-3-thietanone 1,1-dioxide gives dimethylketene. ... 

Known quantities of reactants are allowed to react for known lengths of time from time to time, samples of the reaction mixture are analyzed quantitatively. You can follow either the disappearance of the reactants or the appearance of the products. Analysis of the reaction might include gas chromatography, infrared or nmr spectroscopy (methyl iodide decrease or ether increase), or reaction with aqueous silver nitrate to precipitate insoluble silver iodide. We shall use still another method—titration of the unreacted base, potassium f-butoxide, with an acid. When using this method aliquots (known fractions) of the reaction mixture are removed and immediately diluted with ice water to stop the reaction. Unreacted f-butoxide ion will react with the water to form hydroxide ion and f-butyl alcohol the base is titrated to a phenolphthalein end point with standard perchloric acid. 

Attenuated total reflectance infrared spectroscopy was employed to determine the possible chemical modification of the PVC specimen exposed to t-butyl alcohol and methyl t-butyl ether. Infrared spectroscopy has been used to study solvent absorption (17), oxidation (18) and other degradation reactions of polymers (19). In the studies of the hostile effects of methyl t-butyl ether and acetone, the solvent was concentrated and examined using conventional infrared techniques. 

Reduced and unreduced copper Y zeolites are prepared from sodium Y zeolites (NaY) and their catalytic activity towards dehydration of tertiary butyl alcohol (t-BuOH) is evaluated in relation to pure NaY and HY zeolites. They are characterised by chemical analysis, XRD, TG/DTA and IR spectroscopy. The catalytic activity followed the order NaY < CuY < HY < Cu(R). The activities of the catalyst could be correlated to the corresponding acid strength determined by temperature progranuned desorption of ammonia. 

Y = F) with sodiiun methoxide, but undergoes ring-opening with potassium hydroxide in t-butyl alcohol to give the acid o-C F4H-CF CF-C02H, whidi is converted into the dichloro-compound o-CsFaH-CFCl-CFCl-COaH by treatmmt with phosphorus pentachloride followed by hydrolysis. Both 3-chloroh tafluoro-and octafluoro-indene are converted into the oxo-sulphonic add (32) by 20% oleum, and the dibromide (33a) or the nitro-indane (33b) is formed when octa-fluoioindene reacts with bromine or HNOa-HF, respectively. The fomiation of the antiaromatic cabocation (34) when octafluoroindene dissolves in SbFs-SOa at -40°C has been briefly studied by n.m.r. spectroscopy. ... 

Figure 3 Isometric plots of fluorescence showing the EEMs of (A) a pyrene-fluanthrene mixture in 1 % f-butyl alcohol (B) a pyrene-fluanthrene mixture in 1 % f-butyl alcohol and 100 mmol I iodide (C) a pyrene-fluanthrene mixture in 1% f-butyl alcohol, 100 mmol M iodide, and I.Smmoir -CD (D) a pyrene-fluanthrene mixture in 1% f-butyl alcohol, lOOmmoll" iodide and 3.8mmoir y-CD. (Reprinted with permission from Nelson G, Neal SL, and Warner IM (1986) Resolution of mixtures by cyclodextrin complexation and multidimensional data analysis. Spectroscopy 3 24—28.)...

The molecular mobility of solid deuterated tert-butyl alcohol (TBA) has been studied by Nishchenko et al. over a broad temperature range (103-283 K) by means of solid-state NMR spectroscopy, including both line shape and anisotropy of spin lattice relaxation analyses. It has been found that, while the hydroxyl group of the TBA molecule is immobile on the H NMR time scale (xc> 10 s), its butyl group is highly mobile. The mobility... 

Scheme 5.3 illustrates the use of superacid media in the study of carbonium ion generation, structure, and reactions by NMR spectroscopy. The behavior of primary, secondary, and tertiary aliphatic alcohols on being dissolved in FS03H-SbF5-S02 at —60 C provides direct support for the dictum that tertiary carbonium ions are more stable than secondary, which are more stable than primary. Primary and secondary alcohols are protonated under these conditions, and the protonated alcohols are the species observed (entry 1), while tert-butyl alcohol yields tert-butyl cation at rates too... 

The photolysis of aromatic species with tetranitromethane in perfluoro alcohol solvent has been studied, in which the radical cations were observed by EPR spectroscopy.284 Photo-stimulated reaction of 1- and 2-haloadamantanes and 1,2- and 1,3-dihaloadamantanes with various carbanionic nucleophiles afforded products rationalized through an SrnI mechanism.285 286 Photolysis of the cycloadduct formed between a functionalized derivative of C6o and diazomethane has been shown to afford a pah of ling-opened structures (125) and (126) via a proposed biradical intermediate (127) (Scheme 19). The UV-photolytic fragments of /-butyl iodide (T and /-Bu ) have been ionized by resonance-enhanced multiphoton ionization for TOF mass spectro-metric analysis.287 A two-dimensional position-sensitive detector provided angular distribution and translational energy data. 

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