Sodium methanol

See Sodium Methanol and Sodium methoxide, both below Fluorine... 

A particularly interesting Michael acceptor is dimethyl 2-hexen-4-ynedioate since it can react at either position of the double or triple bond to form 1,4- or 1,6-addition products. Winterfeldt and Preuss183 treated this substrate with several secondary amines and observed exclusive attack at C-5 with formation of the 1,6-addition products (equation 78). In contrast to this, sodium methanolate added at CM to give the 1,4-adduct as a mixture of E/Z isomers (equation 79) with increasing reaction time, the product distribution was shifted towards the thermodynamically more stable , -product184. Acheson and... 

Imidazolidinium salts can also be transformed into the corresponding diamino ortho-esters by alkaline alkoxylate, and upon alcohol elimination at elevated temperature the imidazolidin-2-ylidenes can be trapped. The reaction of tria-zolium salts with sodium methanolate in methanol yields 5-methoxy-4,5-dihydro-IH-triazole which also eliminates methanol upon heating in vacuo. The resulting triazolin-5-ylidenes can either be isolated or trapped by an appropriate metal precursor [Eq. (19)]. Benzimidazolin-2-ylidenes are similarly accessible by this route. 

As mentioned earlier, triazolium salts can be converted into 5-methoxy-4,5-dihydro-lH-triazoles by reacting them with sodium methanolate in methanol. The heterocycles eliminate methanol upon heating in vacuo [Eq. (21)] and the formed triazolin-5-ylidenes can then be isolated. " The same method works with imidazolium and benzimidazolium salts." ... 

Upon hydrogenation of 24 a 1,2-rearrangement of the epoxide occurred generating aldehyde 25 as a mixture of diastereoisomers. After reaction with methyl lithium, the diastereomeric alcohols 26 and 27 were separated and isolated in yields of 23% and 71%. While alcohol 26 as the minor diastereo-isomer could be oxidized with pyridinium dichromate (PDC) and methyle-nated to give the enantiomer of kelsoene (cnM), its diastereoisomer 27 with the inverse configuration at C-7 required a supplementary epimerization step with sodium methanolate. The enantiomerically pure ent- allowed for the determination of the absolute configuration of natural kelsoene (1) [9, 10]. The previously reported assignment based on NMR-correlation experiments [5] was corrected. 

Treatment of Cg Clg with sodium methanolate or sodium ethanolate under reflux respectively at room temperature for some days leads to C5q(OR)5C1 in moderate yields [83]. A by-product of the reaction with EtO is l,4-(EtO)2CgQ, showing that... 

Similarly, complex 2//-pyran derivatives 273 were formed in 73 to 92% yields by elimination of methanol from 2,2,3,3-tetramethoxy intermediates 272 with sodium methanolate.294... 

The first metal chelates of dmit were reported by Steimecke and coworkers in 1975681. The general method applied to synthesize dmit chelates is the solvolysis of the dibenzoyl compound, (PhCO)2 dmit (160), by methanolic potassium or sodium methanolate followed by an in situ reaction of the generated dithiolate with the corresponding metal salt681 (reaction 167). 

Abbreviations Amberlite IRA 400 borohydride resin, commercially available resin for selective reduction of a,/3-unsaturated aldehydes and ketones DBU, 1,8-diazabicyclo [5.4.0]undec-7-en DCM, dichloromethane DMF, dimethylformamide EtOAc, ethyl acetate Et2NH, diethylamine Et3N, triethylamine HBr, hydrobromic acid HC1, hydrochloric acid MS, mass spectrometry MeOH, methyl alcohol NH4OH, ammonium hydroxide NaBHj, sodium borohydride NaOH, sodium hydroxide NaOMe, sodium methanolate PAMAM, polyaminoamide resin (commercially available) RT, room temperature THF, tetrahydrofuran. 

Solid-phase three-component domino-Knoevenagel-hetero-Diels-Alder reaction can also be performed using a resin-linked 1,3-dicarbonyl compound such as 100 with aldehydes and an enol ether to give dihydropyrans 102 via the intermediately formed 1-oxa-l,3-butadiene 101 (Scheme 5.18) [30], The resin can be deaved off after the reaction by solvolysis, for instance using sodium methanolate to give the corresponding methyl ester 103 as a mixture of diastereomers. The overall yield varies from 12 to 37% and the selectivity from 1 1 to 1 5 in favor of the tis-product depending on the applied aldehyde. The crude dihydropyrans thus obtained are reasonably pure (> 90% HPLC). 

Hydrogen bromide Sodium methanolate Silver trifluoroacetate... 

To the suspension of 2.66 g of l-(4-pyridyl)-3-(2-chloroethyl)urea in 4 ml of boiling methanol, 2.68 g of 30.8% methanolic sodium methanolate are added while stirring and the mixture is refluxed for 1 h. It is filtered hot, washed with hot methanol, the filtrate evaporated, to yield the l-(4-pyridyl)-2-imidazolidinone, melting point 204°-207°C, (recrystallized from 90% aqeuous ethanol). 

A mixture of l-(4-hydroxyphenyl)-4-(l-methylethyl)piperazine, cis-[2-(2,4-dichloro-phenyl)-2-(lH-l,2,4-triazol-l-ylmethyl)-l,3-dioxolan-4-ylmethyljmethanesulfonate, potassium carbonate and N,N-dimethylformamide is stirred and heated overnight at 120°C. The reaction mixture is cooled and poured onto water. The product is extracted twice with dichloromethane. The combined extracts are washed twice with a potassium carbonate solution, dried, filtered and evaporated. The residue is taken up in methanol and a sodium methanolate solution 30% are added. The whole is stirred and refluxed for 1 h. The mixture is poured onto water and the layers are separated. The organic phase is dried, filtered and evaporated. The cis-l-(4-((2-(2,4-dichlorophenyl)-2-(lH-l,2,4-triazol-l-ylmethyl)-l,3-dioxolan-4-yl)methoxy)phenyl)-4-(l-methylethyl)piperazine was obtained, melting point 116.3°C. 

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