Lithium aluminum hydride pyridines

An aiyl methane- or toluenesulfonate ester is stable to reduction with lithium aluminum hydride, to the acidic conditions used for nitration of an aromatic ring (HNO3/HOAC), and to the high temperatures (200-250°) of an Ullman reaction. Aiyl sulfonate esters, formed by reaction of a phenol with a sulfonyl chloride in pyridine or aqueous sodium hydroxide, are cleaved by warming in aqueous sodium hydroxide. ... 

Cyclodecanediol has been prepared by the hydrogenation of sebacoin in the presence of Raney nickel or platinum, by the reduction of sebacoin with aluminum isopropoxide or lithium aluminum hydride, and by the oxidation of cyclodecene with osmium tetroxide and pyridine. ... 

The azidohydrins obtained by azide ion opening of epoxides, except for those possessing a tertiary hydroxy group, can be readily converted to azido mesylates on treatment with pyridine/methanesulfonyl chloride. Reduction and subsequent aziridine formation results upon reaction with hydrazine/ Raney nickel, lithium aluminum hydride, or sodium borohydride/cobalt(II)... 

Cyclic enamines can also be obtained by the reduction of pyridine and isoquinoline with lithium aluminum hydride (163-165), and the latter reduction has also been accomplished with sodium in liquid ammonia (166). 

Reduce 3,5-dimethoxybenzoic acid with lithium aluminum hydride to 3,5-dimethoxybenzyl alcohol (I), to 10.5 g (I) in 100 ml methylene chloride at 0° C add 15 g PBr3 warm to room temperature and stir for one hour. Add a little ice water and then more methylene chloride. Separate and then dry, evaporate in vacuum the methylene chloride. Add petroleum ether to precipitate about 11.5 g of the benzyl bromide (II). To 9.25 g (II), 15 g Cul, 800 ml ether at 0° C, add butyl (or other alkyl)-Li (16% in hexane), and stir for four hours at 0° C. Add saturated NH4C1 and extract with ether. Dry and evaporate in vacuum the ether (can distill 100/0.001) to get about 4.5 g olivetol dimethyl ether (HI) or analog. Distill water from a mixture of 90 ml pyridine, 100 ml concentrated HC1 until temperature is 210° C. Cool to 140 0 C and add 4.4 g (III) reflux two hours under N2. Cool and pour into water. Extract with ether and wash with NaHC03. Make pH 7 and dry, evaporate in vacuum to get 3.8 g olivetol which can be chromatographed on 200 g silica gel (elute with CHC13) or distill (130/0.001) to purify. 

Add 78.5 g of the above benzoate in 300 ml of ether to a stirred suspension of 19 g lithium aluminum hydride in 200 ml of ether at such a rate as to give gentle reflux. After the addition, reflux for 2V2 hours, then cool. Add 50 ml of wet ether and 100 ml dilute sulfuric acid. Evaporate the ether extract in vacuo to get about 60 g of 3,5-dimethoxybenzyl alcohol and recrystallize with ether-pentane. To a cooled, stirred slurry of CrOs and 250 ml pyridine, add 8.4 g of the above alcohol in 25 ml pyridine and after the addition let stand at room temp for 1 hour. Add 60 ml of methanol, let stand 2 hours, and dilute with 500 ml of 5% NaOH and 500 ml ether. Extract the aqueous layer with ether and wash the combined ether layers with water (500 ml), then three 500 ml of 5% sulfuric acid, again with 500 ml water, and then 200 ml saturated NaCl. Dry and evaporate in vacuo to get 7 g 3,5-dimethoxybenzaldehyde. (This benzaldehyde is not much more suspicious to the DEA than the LAH used to make it. It may be cheaper for you to buy than to make.)... 

Lithium aluminum hydride dissolves in pyridine and forms lithium tetrakis-(A -dihydropyridyl)aluminate which itself is a reducing agent for purely aromatic ketones [440, 441]. 

Replacement of an allylic hydroxyl without saturation or a shift of the double bond was achieved by treatment of some allylic-type alcohols with triphenyliodophosphorane (PhjPHI), triphenyldiiodophosphorane (PhsPIj) or their mixture with triphenyl phosphine (yields 24-60%) [612]. Still another way is the treatment of an allylic alcohol with a pyridine-sulfur trioxide complex followed by reduction of the intermediate with lithium aluminum hydride in tetrahydrofuran (yields 6-98%) [67 J]. In this method saturation of the double bond has taken place in some instances [675]. 

Heteroaromatics are subdivided, according to the electron influence of the heteroatom, into w-electron-deficient compounds and compounds with an excess of it electrons on the ring carbon atoms. The typical ff-electron-delicient compound pyridine has so far been made to react only in one case the reaction of lithium tetrakis(A-dihydropyridyl)-aluminate (LDPA) [112-114), obtainable from pyridine and lithium aluminum hydride, with trifluoromethanesulfenyl chloride in an excess of pyridine affords 3-trifluoromethylmercaptopyridine in low yield (13%) (60). This reaction probably occurs through sulfenylation of the l,2-dihydrop5T idyl moiety of the LDPA with the formation of a 2,5-... 

Benzofuranyl)butanoic acid readily forms the acid chloride, and this undergoes intramolecular Friedel-Crafts acylation on treatment with tin(IV) chloride in carbon disulfide at room temperature, providing 1,2,3,4-tetra-hydro-l-dibenzofuranone (54%). " This intermediate has been converted to dibenzofuran by lithium aluminum hydride reduction and subsequent dehydrogenation, to 1-methyldibenzofuran by Grignard reaction and dehydrogenation, and to 1-dibenzofuranol by reaction with iV-bromosuccinimide and subsequent dehydrobromination with pyridine. 

Lithium aluminum hydride reacts readily with pyridine to yield lithium tetrakis-(A/-dihydropyridyI)aluminate, LiAI(NR2)4 (structures 108 and 109).152 The NR2 groups represent 1,4-dihydro- and/or, 1,2-dihydropyridyl residues. The two diverse N-ligands may be part of the same molecule in association with the A1 metal. The structure of the adduct has been investigated by IR and NMR spectroscopy and by deuterium-labeling experiments. The latter approach has been used to determine the 1,2 to 1,4 ratio, which is found to be close to 1 2 when the reaction is carried out at room temperature. The N—A1 bond is assumed to be covalent, though of a markedly more ionic character as compared to the N—H bond in dihydropyridines.152... 

Reduction of quinoline with lithium aluminum hydride gives 1,2-dihydroquinoline. Neutral pyridines bearing electron-withdrawing substituents are also reduced by sodium borohydride (Scheme 32). 

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