T-Potassium butanolate

To a stirred solution of 5.52 parts of t-potassium butanolate in 60 parts of dimethylsulfox-ide are added 1.7 parts of ethyl-1 -(3[Pg.485]

Divide the saturated solution of n-butyl alcohol in water into three approximately equal parts. Treat these respectively with about 2-5 g. of sodium chloride, potassium carbonate and sodium hydroxide, and shake each until the soli have dissolved. Observe the effect of these compounds upon the solubility of n-butanol in water. These results illustrate the phenomenon of salting out of organic compounds, t.e., the decrease of solubility of organic compounds in water when the solution is saturated with an inorganic compound. The alcohol layer which separates is actually a saturated solution of water in n-butyl alcohol. 

Table 8 summarizes domestic consumption by use for amyl alcohols. About 55% of the total 1-pentanol and 2-methyl-1-butanol production is used for zinc diamyldithiophosphate lubrication oil additives (150) as important corrosion inhibitors and antiwear additives. Amyl xanthate salts are useful as frothers in the flotation of metal ores because of their low water solubiUty and miscibility with phenoHcs and natural oils. Potassium amyl xanthate, a collector in flotation of copper, lead, and zinc ores, is no longer produced in the United States, but imports from Germany and Yugoslavia were 910 —1100 t in 1989 (150). 

The reactions of the cis and irons isomers of 4-/-butylcyclohexyltrimethylammonium chloride with potassium t-butoxide in r-butanol have been compared. The cis isomer gives 90% 4-r-butylcyclohexane and 10% AyV-dimethyl-4-r-butylcyclohexylamine, while the irons isomer gives only the latter product in quantitative yield. Explain the different behavior of the two isomers. 

The stereochemistry of hydrogen-deuterium exchange at the chiral carbon in 2-phenylbutane shows a similar trend. When potassium t-butoxide is used as the base, the exchange occurs with retention of configuration in r-butanol, but racemization occurs in DMSO. The retention of configuration is visualized as occurring through an ion pair in which a solvent molecule coordinated to the metal ion acts as the proton donor... 

Ethynylation of the totally synthetic racemic 18-methyl-17-ketone (63) with acetylene and potassium t-butoxide in t-butanol-toluene or with alkali metal acetylide in liquid ammonia gives a low yield of rac-18-methyl-17a-ethynyl-3-methoxyestra-l,3,5(10)-trien-17/ -ol (64). 

The direct base-catalyzed alkylation of 3-keto steroids is generally not a very satisfactory method for the preparation of monoalkylated products. However, under optimum conditions (short reaction time with methyl iodide, a Modest excess of potassium t-butoxide in boiling t-butanol) modest yields of... 

Potassium /-butoxide is prepared by dissolving potassium metal in t-butanol followed by removal of the excess of -butanol by distillation under reduced pressure. The resultant cake is powdered and used directly in the dibromocarbene additions. 

Base catalyzed pinacol rearrangement of vicinal m-glycol monotosylates is a simple and useful general method for preparing perhydroazulenes. Thus, treatment of cholestane-5a,6a-diol 6-tosylate (115a) with either one mole-equivalent of potassium t-butoxide in f-butanol at 25° or with calcium carbonate in dimethylformamide at 100° gives a quantitative yield of 10(5 6/5H)... 

A solution of ketone (85) in t-butanol and excess potassium -butoxide and potassium hydroxide is heated at refluxjinder an atmosphere of oxygen for 8 hr to give the C-norpregnane acid (87), in about 46% yield. Yields tend... 

It is evident from the foregoing sections that simple alkylvinyl halides do not react via an Sn 1 mechanism, if at all, even under extreme solvolytic conditions (146,149). More reactive leaving groups, such as arylsulfonates, were clearly needed to investigate the possible solvolytic behavior of simple alkylvinyl systems, but the preparation of vinyl sulfonates until recently was unknown. Peterson and Indelicato (154) were the first to report the preparation of vinyl arylsulfonates via reaction of the appropriate disulfonate with potassium t-butoxide in refluxing f-butanol. They prepared and investigated the solvolysis of 1-cyclohexenyl tosylate 169 and c/s-2-buten-2-yl tosylate 170 and the corresponding p-bromobenzenesulfonates (brosylates). Reaction... 

Al-Sahhaf, T. and Kapetanovic, E. Salt effects of lithium chloride, sodium bromide, or potassium iodide on liquid-liquid equilibrium in the system water + 1-butanol, J. Chem. Eng. Data, 42(l) 74-77, 1997. 

A Aqueous NaOH, B t-Butanol-water-potassium hydroxide. In parentheses references reporting different yields... 

As can be seen from current-voltage curves the lower amines are about 10 times faster oxidized than the corresponsing alcohols In a competitive preparative electrolysis (0.3 M potassium hydroxide in 50% t-butanol 50 % water, 40 °Q 1-decylamine is 5.3 times faster oxidized than 1-decanol The electrochemical kinetics have been investigated . ss.es.es) following mechanism proposed... 

Molybdenum-based catalysts are highly active initiators, however, monomers with functionalities with acid hydrogen, such as alcohols, acids, or thiols jeopardize the activity. In contrast, ruthenium-based systems exhibit a higher stability towards these functionalities (19). An example for a molybdenum-based catalyst is (20) MoOCl2(t-BuO)2, where t-BuO is the tert-butyl oxide radical. The complex can be prepared by reacting M0OCI4 with potassium tert-butoxide, i.e., the potassium salt of terf-butanol. 

Hydroxyandrost-5-en-17-one252 A solution of 10 g of pregnenolone in a mixture of 50 ml of tetrahydrofuran and 140 ml of t-butanol containing potassium t-butoxide (from 6.4 g of potassium metal) is oxygenated at 5-7°C until 1.1 molar equivalents of oxygen have been consumed. Nitrogen... 

The synthesis of 2C-T-17 R required starting with the S isomer of secondary butanol. The S 2-butanol in petroleum ether gave the lithium salt with butyllithium which was treated with tosyl chloride (freshly crystallized from naphtha, hexane washed, used in toluene solution) and the solvent was removed. The addition of 2,5-dimethoxythiophenol, anhydrous potassium carbonate, and DMF produced S 2,5-dimethoxyphenyl s-butyl sulfide. The conversion to R 2,5-dimethoxy-4-(s-butyl-thio)benzaldehyde (which melted at 78-79 °C compared to 86-87 °C for the racemic counterpart) and its conversion in turn to the nitro-styrene, S -2,5-dimethoxy-4-(s)-butylthio-B-nitrostyrene which melted at 70-71 °C compared to 68-69 °C for the racemic counterpart, followed the specific recipes above. The preparation of the intermediates to 2C-T-17 S follows the above precisely, but starting with R 2-butanol instead. And it is at these nitrostyrene stages that this project stands at the moment. 

Attempts to add OH- and the more nucleophilic151 HOO to 86 in aqueous solution were unsuccessful. However, with the more stable t-butylhydroperoxide in (-butanol containing potassium t-butoxide, the only detectable products were phenols and diphenyl ether. Presumably the phenolate ion formed in situ from 86 was able to compete successfully with the alkoxide. 

When the bicyclic dienone 142 was treated with dimethyl malonate and potassium t-butoxide in t-butanol at 25°C for 10 days, the axial isomer 143 was obtained in 51% yield. None of the equatorial isomer 144 was isolated. When the reaction was carried out at reflux, a mixture of 143 and 144 was isolated in which the more stable equatorial isomer predominated (50). 

During studies directed towards a total synthesis of gibberellic acid, the lactone 1 was heated under reflux with potassium t-butoxide in t-butanol. Acidification of the reaction mixture and separation of the products gave compound 2 as the major product (30%). 

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