Butylated butyllithium

To a solution of 0.40 mol of butyllithium in about 280 ml of hexane were added 300 ml of dry THF at -20 to -40 0. Subsequently 0.40 mol of freshly distilled tert.-butyl propargyl ether was added, keeping the temperature below -30°C. Freshly distilled acetaldehyde (0.40 mol) was then added at the same temperature during about 15 min. The cooling bath was removed and, after an additional 15 min, 200 ml of an aqueous solution of 30 g of ammonium chloride were introduced. After separation of the layers the aqueous layer was extracted twice with diethyl ether and the combined solutions were dried over magnesium sulfate and concentrated in... 

In a related procedure A -melhyl-o-loluidine can be A-lithiated, carboxylated and C-lithiated by sequential addition of n-butyllithium, CO2, and n-butyl-lithium[5]. The resulting dilithiated intermediate reacts with esters to give 1.2-disubstituted indoles. 

The reaction of 2.4-dimethylthiazole with butyllithium shows that, in contrast to 2-methylthiazole, the benzyl position (the 2-position) is the most reactive. The effect of the substituent in the 4-position may well be steric 4-r-butyl-2-methylthiazole in the same reaction gives no 5-substituted product (223). 

The formation of bromine-free 4,5 -bipyrimidines from 5-bromopyrimidines and butyl-lithium by the Strekowski reaction is discussed above (Section 2.13.2.2.9). It should be distinguished from a single example wherein 5-bromopyrimidine and butyllithium give 5-bromo-3,4-dihydro-4,5 -bipyrimidine (484) and on oxidation, 5-bromo-4,5 -bipyrimidine (485) <65ACS(19)1741>. 

Thiophene, bromotetrahydromethyl-pyrolysis, 3, 902 Thiophene, 5-t-butyl-2-methyl-dealkylation, 4, 800 Thiophene, chloro-polymerization, 4, 758 reaction with n-butyllithium, 4, 831 synthesis, 4, 835, 882, 933 Thiophene, 2-chloromercurio-reactions... 

If an excess of butyllithium (2 5 1 molar ratio) is used during metalation, a mixture of butylated naphthyllithium compounds is formed Reactions of this mixture with electrophiles give a mixture ot 6 and 7-butyl-substituted hexa-fluoronaphthalene derivatives in respective ratios of 4 1 [38] (equation 16)... 

Halogen-metal interconversion between bromothiophenes and n-butyllithium, leading to thienyllithium derivatives and n-butyl bromide, occurs almost instantaneously and in very high yield even at... 

However, reaction of 218 (E = P, R = R = H, R = r" = Me) with rerr-butyl-lithium most probably yields 221. The phospholyl loses its electrophilicity and the iron atom bears a considerable negative charge. Addition of rerr-butyllithium (one equivalent) followed by methyl iodide (one equivalent) does not give any isolable product but leads to recovery of the starting 218 only. In excess tert-butyllithium and methyliodide, 222 (R = r-Bu, R = Me) was isolated (81IC3252). 

The yield of 17 is 50 62% in the reactions involving butyl- or. vw-butyllithium due to competitive transfer of the butyl or sec-butyl group. Yields of 17 are improved by using pyridine as the additive, but diastereoselectivity is not as high as when the alkyllithiums are employed. Without any additive, a complex mixture of syn- and anti-diastereomers plus products resulting from addition of the a-carbon of the substrate borane to the aldehyde are obtained. 

The reaction of butyllithium with 1-naphthaldehyde cyclohexylimine in the presence of (/C )-l,2-diphenylethane-1,2-diol dimethyl ether in toluene at —78 °C, followed by treatment with acetate buffer, gave 2-butyl-1,2-dihydronaphthalene-l-carbaldehyde, which was then reduced with sodium borohydride in methanol to afford (1 R,2.S)-2-butyl-1 -hydroxymcthyl-1,2-dihydronaphthalene in 80% overall yield with 91 % ee83. Similarly, the enantioselective conjugate addition of organolithium reagents to several a,/J-unsaturated aldimines took place in the presence of C2-symmetric chiral diethers, such as (/, / )-1,2-butanediol dimethyl ether and (/, / )- ,2-diphenylethane-1,2-diol dimethyl ether. 

Via the Z-enolate an oven dried Schlenk tube equipped with a rubber septum is flushed with argon and charged with 0.66 mL (1.0 mmol) of butyllithium (1.5 N in hexane). The Schlenk tube is cooled to 0°C (icc/salt) and 0.12 g (1.1 mmol) of diisopropylaminc are added slowly by a syringe. This mixture is stirred for 15 min and the rubber septum is replaced by a glass stopper. The hexane and the excess diisopropyl-amine are removed under reduced pressure. After the flask is filled with argon the stopper is replaced with a septum and 0.47 g (4.3 mmol) of HMPA and 2.5 mL of THF are added. This solution is immediately cooled to — 78 °C and 0.14 g (1.1 mmol) of tert-butyl propanoate arc added quickly by syringe. After stirring for... 

The reaction of butyllithium and /erf-butyl-1-naphthyl sulfone in diethyl ether at reflux for 5 hours followed by quenching the reaction mixture with water gives trans-X,2-dihydro-1-/m-butylsulfonyl-2-butylnaphthalene 2 3. 

Reaction of alkyl phenylmethanesulphinates 100 with n-butyllithium in tetrahydro-furan at — 80 °C afforded the corresponding benzyl n-butyl sulphoxide160 (equation 53). Preparation of optically active sulphoxides by this reaction will be discussed later in this chapter. 

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