Z-butyl alcohol

A solution of 14.8 g. (0.20 mole) of Z-butyl alcohol in 125 ml. of benzene (Note 1) is placed in a 500-ml. three-necked flask equipped with a stirrer, a thermometer, and an addition funnel, and 26.0 g. (0.40 mole) of sodium cyanate (Note 2) is added. The suspension is stirred as slowly as possible (ca. 120 r.p.m. Note 3) while 48.0 g. (31.2 ml., 0.42 mole) of trifluoroacetic acid is added dropwise at a rapid rate. The temperature slowly rises to about 37° after three-quarters of the trifluoroacetic acid has been added (ca. 7 minutes). At this point (Note 4) the mixture is cooled to 33-35° by brief immersion in an ice-water bath, then the addition is continued. When the addition of the acid is completed (10-12 minutes total time), the temperature slowly... 

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

A. t-Butyl S-methylthiolcarbonate. In a 5-1. round-bottomed flask, fitted with mechanical stirrer, reflux condenser, and dropping funnel are placed 430 ml. (422 g., 5.33 moles) of pyridine, 508 ml. (395 g., 5.33 moles) of Z-butyl alcohol, and 1.61. of chloro-... 

In order to have several dilferent positions available a study of some derivatives of heptane was begun. In the normal heptane it is possible to have a single substituent in four different positions in the molecule. The dipole moments of the four alcohols, heptanol-i ( -heptyl alcohol), heptanol-2 (methyl-/z-amy 1-alcohol), heptanol-3 (ethyl-/z-butyl-alcohol) and heptanol-4 (dipropyl-carbinol) have been measured. 

The final results are summarized in Table 8.1. It is to be noted that component 2, Z-butyl alcohol, is being transported towards the interface when its own driving force suggests transfer away from the interface. However, it can clearly be seen in Figure 8.7 that the driving force for t-butyl alcohol is rather small and the effects of coupling between species transfers, quantified by the terms k[2 2 21 significant here (see Table 8.1)... 

In a test run with the ternary mixture ethanol-Z-butyl alcohol-water, the following results were obtained for a particular tray. 

The configuration of the adduct with dimethyl acetylenedicarboxylate depends on the nature of the solvent used protic solvents, such as methanol or ethanol (but not tert-butyl alcohol), favor formation of (Z)-25a, whereas in nonprotic solvents, such as benzene, chloroform or acetonitrile, ( )-25a is the major product. 

Scheme 6.76 Generation of l-oxa-2,3-cyclohexadiene (351) from 5-bromo-3,4-dihydro-2H-pyran (376) and trapping products of351 obtained from furan, 2,3-dimethyl-1,3-butadiene, 1,1-diphenyl-ethylene, ( )-l-phenylpropene, ( )-2-butene, (Z)-2-butene and tert-butyl alcohol , according to Schlosserand co-workers.

Studies of dimensiosolvatic effects have continued with an attempt to quantify them for solvolyses of 2-bromoadamantane in water-alcohol mixtures. Product selectivities S = fc(ether)/fc(alcohol) were measured at various concentrations of water in an alcohol and at various temperatures. The reciprocals of the averages of S values for 1.0 0.8 alcohol-water mixtures at all the experimental temperatures (120-150 °C) were proposed as measures D of dimensiosolvatic effects when a solvent molecule intervenes into contact ion pair to form solvent-separated ion pair. The scale runs from Z) = 1.0 (by definition) to D = 10.0 for r-butyl alcohol and is essentially a measure of the bulkiness of solvent molecules. 

A third route developed by this group started with the commercially available alcohol 32," a compound which has also been the subject of considerable process development due to its use as a common intermediate in the synthesis of several HMGR inhibitors.Conversion of 32 to the 4-halo or 4-nitrobenzenesulfonate 33 followed by displacement with sodium cyanide provided 34 in 90% yield, which is the z-butyl-ester analog of 29. It was noted that this procedure was most scaleable employing the 4-chlorobenzenesulfonate 33a due to the instability of the 4-bromo and 4-nitro-analogs to aqueous hydrolysis. Ra-Ni reduction as before provided the fully elaborated side-chain 35 as the f-butyl ester (Scheme 8). 

Yamasaki, I. 1939. Flavins that are formed during the acetone-butyl alcohol fermentation. Part I. Flavins from rice. Biochem. Z. 300, 160-166. (German)... 

The method of Kim et al.[89-93] starts from the synthesis of the three-carbon phosphonium salt according to the modified method of Corey et alJ94,95] The Wittig reaction of the phosphonium salt with a Z-protected a-amino aldehyde using potassium hexamethyldisilazanide provides the ds-alkene without racemization. Efficient hydrolysis of the orthoester without double bond migration is achieved by acidolytic hydrolysis with aqueous hydrochloric acid in tert-butyl alcohol under reflux conditions. Then, an a-amino acid methyl ester is coupled. The desired epoxide product is obtained by treatment with 3-chloroperoxybenzoic acid. The epoxidation reaction is stereoselective and predominantly provides one isomer (R,S S,R = 4-10 1). The trans-epoxide can also be prepared using a trans-alkene-containing peptide. A representative synthetic procedure to obtain the ds-epoxide isostere is detailed below. 

Similar high diastereoselectivities are observed for the addition reaction of t-butyl alcohol to (E)- and (Z)-1628. High diastereoselectivities are also observed for the reaction with ethanol at low concentration, but the selectivity decreases rather sharply by increasing the ethanol concentration. The diastereoselectivities for the reaction of ethanol, i.e. the [syn /[anti product ratios, are linearly and inversely correlated with the concentration of the alcohol ... 

Because of the experimental difficulties discussed above, there is limited opportunity for direct comparison between the different scales. There is a satisfactory qualitative trend in all the scales (including dielectric constant) for water, methanol, ethanol, propan-2-01, and f-butyl alcohol. However, it has been noted that a graph of Z versus Ej for pure alcohols and water is markedly curved (Fig. 16) and that 2,2,3,3-tetrafluoropropan-l-ol does not fit the curve (Dimroth et al., 1963). The results for both Y and Z scales suggest that the ET parameter for water is surprisingly low. Consequently,... 

Many anhydrous metal halides will form alcoholates if the presence of water is avoided during the preparations. The reactions of alcohols with vanadium trichloride were originally thought,1 to produce hexaalcoholates, but subsequent work cast some doubt on this.23 In a recent publication4 it was established that the species formed in solution by treating vanadium trichloride with methanol, ethanol, n- and z-propyl alcohol (1- and 2-propanol), n-, i-, and s-butyl alcohol (1-butanol, 2-mothyl-l-propanol, and 2-butanol), and cyclohexanol are of the type [V(R0H)4C12]C1 in each ease. In some cases the species precipitated from the above solutions have the same structural type,... 

The product from Step 2 (1.16 mol), ethyl succinate (1.85 mol), potassium t-butoxide (1.74 mol) and 2.5 L t-butyl alcohol were mixed and a temperature rise to 45 °C observed. Thereafter, the mixture was stirred for 7 hours at ambient temperature and then poured into ice water acidified with HCl to pH 3. The product was extracted with diethyl ether and dried. Overnight the Z isomer precipated from solution, was filtered from the mixture, re-crystallized in isopropanol, and had a mp = 184-186 °C. The corresponding (E) isomer was obtained upon evaporation of the solvent. 

Dehydrochlonnation. The dehydrochlorination of the sterically hindered meso-3,4-dichloro-2,2,5,5-tetramethylhexane (1) by potassium /-butoxide in DMSO proceeds normally by anti-coplanar elimination to give the less stable (E)-olefin 2 as the major product. However, syn-elimination to the (Z)-isomer 3 becomes the main reaction in THF or r-butyl alcohol. The difference may be related to the differing aggregates of the base in the various solvents. ... 

It is interesting to note that the cyclic salt 12 did not react with benzenesul-finic acid however, when treated with sodium benzenesulfinate in an alcohol, it gave dibenzoselenophene 21 and Z-alkoxyvinylsulfones 17a-c in moderate yields (51-77%). When the reaction was carried out in t-butyl alcohol, bis(phenylsulfonylvinyl)ether (22) was formed in 30% yield (Eq. 4). 

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