Tert-Butyl chloride reaction with lithium

There has been growing interest in the detailed structure and reaction chemistry of monomeric forms of two-coordinate derivatives of Ge , Sn and Pb" since the first examples were unequivocally established in 1980. Thus, treatment of the corresponding chlorides MCI2 with lithium di-tert-butyl phenoxide derivatives in thf affords a series of yellow (Ge , Sn ) and red (Pb ) compounds M(OAr)2 in high yield.The O-M-O bond angle in M(OC6H2Me-4-Bu2-2,6)2 was 92° for Ge and 89° for Sn. Similar reactions... 

The reaction of 2,3-bis( art-butylsulfanyl)cyclopropenethione (47) with lithium indenide in tet-rahydrofuran, followed by addition of tert-butyl chloride, proceeded to give the 5,6-disulfanyl-benzo[7)]calicene derivative 48, which was converted to the doubly cross-conjugated (1-cyclo-propenylideneinden-3-yl)cyclopropenylium derivative 49 by further reaction with l,2-bis(tc/ t-butylsulfanyl)-3,3-dichlorocyclopropene in the presence of iron(III) chloride and treatment with 70% perchloric acid. ... 

Friedel-Crafts Reactions. Aluminum trifluoromethanesulfonate has been used for the Friedel-Crafts alkylation reaction of toluene with isopropyl and tert-butyl chlorides (eq 1), and for the acylation of benzene and toluene with acetyl and benzoyl chlorides in low to moderate yields. Intramolecular Friedel-Crafts acylation of an aromatic compound with Meldrum s acid has also been reported using catalytic amounts of Al(OTf)3. Acylation of 2-methoxynaphthalene with acetic anhydride has been reported using Al(OTf)3 and lithium perchlorate as an additive to afford the corresponding 6-acetylated adduct in 83% yield. Effective acylation of arenes with carboxylic acids has also been disclosed using polystyrene-supported Al(OTf)3. ... 

Larger chalcogen-phosphorus heterocycles, although less common in the literature, are accessible via a variety of synthetic routes.2,83,84 For example, the cyclic trimer (SPR)3 (R = 2,4,6-tri-tert-butylphenyl) contains a puckered six-membered P3S3 ring and is produced in the reaction of a phosphinic chloride with lithium sulfide (Equation 73).98 Additionally (R P)3Se5 (R = 2,4-di-tert-butyl-6-wopropoxyphenyl), synthesised from the oxidation of a primary phosphine with three equivalents of elemental selenium (Equation 74), has... 

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... 

The boronic acid ester B was synthesized by transesterification of the corresponding pinacolester A with (lR,2R)-l,2-dicyclohexyl-l,2-dihydroxyethane. Stereoselective chlorination of B was carried out with (dichloromethyl) lithium and zinc chloride. Reaction of the obtained chloroboronic ester C with lithio 1-decyne followed by oxidation of the intermediate D with alkaline hydrogen peroxide afforded the propargylic alcohol E. Treatment with acid to saponify the tert-butyl ester moiety and to achieve ring closure, produced lactone F. Finally, Lindlar-hydrogenation provided japonilure 70 in an excellent yield and high enantiomeric purity. 

Anhydrous samarium(III) chloride [Rare Earth Products, Johnson Matthey] (2.40 g, 9.40 mmol) is placed in a 200-mL Schlenk tube containing a magnetic stirring bar. Tetrahydrofuran (THF) (100 mL) is introduced via a cannula at 20 °C. The mixture is stirred at 20 °C for 2 h. Solid (2,6-di-tert-butylphenoxo)-lithium-diethyl etherate (8.13g, 28.4 mmol) is added to this slurry at 20 °C. A reflux condenser is then fitted to the Schlenk tube, and the reaction mixture is heated under reflux for 8 h. After h, the solid dissolves to yield a clear yellow-green solution. The solvent is removed at 25 °C and 10 torr, leaving a yellow-green solid, which is scraped from the sides of the Schlenk tube with a spatula and transferred to a sublimation tube. Sublimation at 255-260°C and 10 torr affords yellow crystals of tris(2,6-di-tert-butyl-phenoxo)samarium. Yield 4.46 g (62%). ... 

PHENYLETHYLENE (100-42-5) Forms explosive mixture with air (flash point 88°F/31°C). Unless inhibited (often with tert-butylcatechol) in adequate concentrations, polymerization may occur and container may explode. Polymerization can be caused by elevated temperatures above 151°F/66°C, oxidizers, butyl lithium, peroxides, UV light, or sunlight. Violent reaction with chlorosulfonic acid, strong oxidizers, sulfuric acid, xenon tetrafluoride. Incompatible with acids, rust, catalysts for vinyl polymerization, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, peroxides, metal salts (e.g., aluminum chloride, copper chlorate, manganese nitrate, etc.). Corrodes copper and its alloys. Attacks some plastics, rubber, or coatings. Flow or agitation of substance may generate electrostatic... 

Isomerization is observed with higher alkyl halides, as in Friedel-Crafts reactions isopropylphosphonic dichloride is stated to be the sole product from n-propyl chloride,190,191 and terf-pentyl chloride undergoes C-C fission, yielding the tert-butyl acid.193 On reduction by lithium tetrahydroaluminate the phosphonic chloride formed from w-butyl chloride gives a primary phosphine that is shown by 31P-nuclear magnetic resonance to consist of n- and sec-butylphosphine in the proportions 5 95 and the product from n-octyl chloride was similarly shown to contain all four position isomers.194... 

The same metallacycle l,l-diphenyl-3,3-dicyclopentadienyl-l-phospha-3-luteto-in-dane is also isolated as a product of the reaction of tert-butyl lithium with triphenylmethylenephosphorane and dicyclopentadienyl lutetium chloride in tetra-hydrofuran at -78°C and as the product of the NaH reduction of (C5H5)2Lu(Cl)CH2P(CgH5)3 in toluene at — 15°C (Schumann and Reier, 1984a, b) ... 

The presence of a heterosubstituent facilitates deprotonation. For example, the metalation of cyclic vinyl ethers with n-butyl-lithium/potassium tert-butoxide bas been successfully employed in the synthesis of C-glycosides. This reaction proceeds via metalation of the glucal, followed by reaction with tributyltin chloride, to afford the corresponding tin derivative that can be submitted to transition metal-catalyzed cross-coupling reactions (eq 9). 

The aldehyde intermediate can be isolated if a less powerful reducing agent such as lithium tri-tert-butoxyaluminum hydride is used in place of LiAlH4. This reagent, which is obtained by reaction of LiAlH4 with 3 equivalents of lert-butyl alcohol, is particularly effective for carrying out the partial reduction of acid chlorides to aldehydes (Section 19.2). 

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