Z-butyl chloride

The API bumetanide reacts under acidic conditions to the convert the secondary amine into the corresponding primary amine (Fig. 41) (62). The mechanism is analogous to the Hofmann-Martius reaction resulting in the debutylated amine and z-butyl chloride (the chloride presumably comes from HC1) (63). 

Equation (50) correlates rate constants for a number of solvolysis reactions and Figure 13 illustrates the Grunwald-Winstein plot for the solvolysis of z-butyl chloride against a K value from 1-adamantyl chloride where w = 0.78. 

The solvent structure can be altered by solutes and, for example, heats of solution of Z-butyl chloride in ethanol-water mixtures are markedly non-linear in solvent composition. Enthalpies and entropies of... 

To a solution of 0.30 mol of ethyllithium (note 1) in about 270 ml of diethyl ether (see Chapter II, Exp. 1) v/as added 0.30 mol of methoxyallene at -20°C (see Chapter IV, Exp. 4) at a rate such that the temperature could be kept between -15 and -2Q°C. Fifteen minutes later a mixture of 0.27 mol of >z-butyl bromide and 100 ml of pure, dry HMPT ivas added in 5 min with efficient cooling, so that the temperature of the reaction mixture remained below 0°C. The cooling bath was then removed and the temperature was allowed to rise. After 4 h the brown reaction mixture was poured into 200 ml of ice-water. The aqueous layer was extracted twice with diethyl ether. The combined solutions were washed with concentrated ammonium chloride solution (which had been made slightly alkaline by addition of a few millilitres of aqueous ammonia, note 2) and dried over potassium carbonate. After addition of a small amount (2-5 ml) of... 

In DMF/Tetrabutylammoniuinjodid bei —2.2 V liefert die Elektrolyse von Chinolin an Quecksilbcr in Ge-genwart von tert.-Butyl-chlorid ein komplexes Reaktionsgemisch mit z. T. partiell hydrierten Verbindungcn6. 

In 1948, Grunwald and Winstein2 4 attempted to define the ionizing power of a solvent by the Y parameter, based on the comparison of the rate for the solvolysis of t-butyl chloride. In 1956, Kosower5 made an attempt to define the polarity of a medium (solvent) by introducing the Z parameter based on the spectroscopic properties (in various solvents)... 

Z. Fodor and R. Faust, Polyisobutylene-based thermoplastic elastomers. IV. Synthesis of poly (styrene-block-isobutylene-block-styr-ene) triblock copolymers using n-butyl chloride as solvent, J. Macromol. Sci.-Chem., 33(3) 305-324, March 1996. 

C2HBr302, is used as a polymerization catalyst. Tfibromo-Z -butyl alcohol [76-08-1], C4H7Br30, is a modifier in the polymerization of vinyl chloride. 

Determinative and confirmatory methods of analysis for PIR residue in bovine milk and liver have been developed, based on HPLC-TS-MS (209). Milk sample preparation consisted of precipitating the milk proteins with acidified MeCN followed by partitioning with a mixture of -butylchloride and hexane, LLE of PIR from aqueous phase into methylene chloride, and SPE cleanup. The dry residue after methylene chloride extraction was dissolved in ammonium hydroxide, and this basic solution was transferred to the top of Cl8 SPE column. The PIR elution was accomplished with TEA in MeOH. For liver, the samples were extracted with trifluoroacetic acid (TFA) in MeCN. The aqueous component was released from the organic solvent with n-butyl chloride. The aqueous solution was reduced in volume by evaporation, basified with ammonium hydroxide, and then extracted with methylene chloride. The organic solvent was evaporated to dryness, and the residue was dissolved in ammonium acetate. The overall recovery of PIR in milk was 94.5%, RSD of 8.7%, for liver 97.6%, RSD of 5.1 %. A chromatographically resolved stereoisomer of PIR with TS-MS response characteristics identical to PIR was used as an internal standard for the quantitative analysis of the ratio of peak areas of PIR and internal standard in the pro-tonated molecular-ion chromatogram at m/z 411.2. The mass spectrometer was set for an 8 min SIM-MS acquisition. Six samples can be processed and analyzed in approximately 3 hours. 

The decomposition rates of butyl chlorides decreased in the following order tert > sec > //-butyl chloride. It is highly plausible that the formation of butene is caused by both the decomposition of butyl chloride over the copper surface and by the decomposition of zwitterion intermediate formed by the reaction of silylene on the surface of the silicon-copper contact mass with butyl chloride.80,81 From the reaction with //-butyl chloride, sec-butyldichlorosilane is also obtained as a minor product along with /z-butylchlorosilanes.80... 

Evaluation of solvent-sensitive properties requires well-defined referena i ran eis. A macroscopic parameter, dielectric constant, does not always give interpretable correlations of data. The first microscopic measure of solvent polarity, the Y-value, based on the solvolysis rate of t-butyl chloride, is particularly valuable for correlating solvolysis rates. Y-values are tedious to measure, somewhat complicated in physical basis, and characterizable for a limited number of solvents. The Z-value, based on the charge-transfer electronic transition of l-ethyl-4-carbomethoxy-pyridinium iodide , is easy to measure and had a readily understandable physical origin. However, non-polar solvent Z-values are difficult to obtain b use of low salt solubility. The Et(30)-value , is based on an intramolecular charge-transfer transition in a pyridinium phenol b ne which dissolves in almost all solvents. We have used the Er(30)-value in the studies of ANS derivatives as the measure of solvent polarity. Solvent polarity is what is measured by a particular technique and may refer to different summations of molecular properties in different cases. For this reason, only simple reference processes should be used to derive solvent parameters. 

It can recombine with a free electron pair of an ion or molecule other than Z present in the reaction mixture. Thus in the diazotiza-tion of n-butylamine, the butyl carbonium ion can react with water, chloride ion, or nitrite ion, and the corresponding products, butanol, butyl chloride, and butyl nitrite, have been isolated.10... 

Coelho and co-workers have recently reported another use of water in living polymerisation in the synthesis of a block copolymer [poly(vinyl chloride)-b-poly(/z-butyl acrylate)-b-poly(vinyl chloride)].3 The new material was synthesised by single electron transfer/degenerative chain transfer-mediated living radical polymerisation (SET-DTLRP) in two steps. 

Croucher and Hair (1978) have presented a plot of temperature dependence of the interaction parameter y(7) as a function of temperature for poly(a-methyl styrene) in -butyl chloride. This is shown in Fig. 12.7. The curve was computed from equation (12.88) using the following numerical values for the parameters 0i )=O-12 (Cowie and McEwen, 1975), 0ya LCFT=254 K and 9l UCFT=403 K (Croucher and Hair, 1978). These results allowed the value of I to be calculated from equation (12.88) since [i—z(T)] =0 at T= ( =-0-483). 

The following commercially available dialkyl peroxides are produced according to equations 24—27 di-Z fZ-butyl peroxide from hydrogen peroxide and sulfated tert-huty alcohol or isobutylene dicumyl peroxide from a-cumyl hydroperoxide and cumyl alcohol, cumyl chloride, and/or a-methylstyrene m- and -di(2-/ f2 -butylperoxyisopropyl)ben2ene [2781-00-2] from tert-huty hydroperoxide [75-91-2] and m- and -di(2-hydroxyisopropyl)ben2ene ... 

The reactions of tri-ATZ-butylplumbyllithium with various phosphorus chlorides have been investigated. For example, reaction of the lithium compound with diphenylchlorophosphane afforded hexa-tert-butyldiplumbane and tetraphenyldiphosphane as the isolated products. Analogous reactions with -butyl-substituted phosphorus chlorides yielded (tri-A, 7-butylplumbyl)di- -butylphosphane or tri- z -butylplumbyl(amino)-, t -butylphosphane. These and other molecules were characterized by multinuclear magnetic resonance spectroscopic studies.24... 

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