Sodium t-amylate

Sodium borohydride-Palladium chloride. Sodium borohydride-Rhodium(lII) chloride. Sodium borohydride-Tin(II) chloride. Sodium cyanoborohydride. Sodium 9-cyano-9-hydrido-9-borabicyclo[3.3.1]nonane. Sodium dithionite. Sodium hydride-Sodium t-amyl oxide-Zinc chloride. Sodium trimethoxyborohydride. Tetra-/i-butylammonium borohydride. Tetra-n-butylammonium cyanoborohydride. Tetra-n-butylammonium octahydrotriborate. Tri-n-butyltin hydride. Triethoxy silane. Triisobutylaluminum-Bis(N-methyl-salicyclaldimine)nickel. Zinc borohydride. REDUCTIVE CYCLIZATION Cobaloximc(I). 

Sodium hydride-Sodium t-amyl oxide-Nickel acetate (NiCRA, 10, 365 14, 288). 

Sodium-t-amylate Methanol Acetic acid Acetic anhydride ... 

The effect of the basic reagent has been studied in the methylation of phenylacetone. Monomethylation proceeds better with sodium isopropoxide than with sodium ethoxide. Introduction of a second alkyl group is accomplished best with potassium t-butoxide. Sodium t-amylate allows many alkylations that fail or give poor results when carried out with sodium amide. " 1,1-Disubstituted 2-tetralones are conveniently prepared by alkylation in the presence of sodium hydride, no monosubstituted products being formed with this reagent, ... 

Amination. The conversion of aryl chlorides to amines is catalyzed by Ni(OAc)2-2,2-bipyridine and sodium t-amylate/NaOH in THF. 

S-Benzyloxy-4,5-seco-estra-9,11-diene-3,5-dione Sodium-t-amylate Acetic acid i Methanol... 

Further studies of complex reducing agents based on sodium hydride have shown that a mixture of sodium hydride, sodium t-amylate, and zinc chloride (ZnCRA) gives regioselective 1,2-reduction of a, 8-enones to allylic alcohols, in contrast to the 1,4-reduction preference shown by the earlier developed NiCRA (3,135). The activity is enhanced by the addition of MgBr2. 

Optimum conditions for the reduction of saturated ketones by the complex reducing agent formed from sodium hydride, sodium t-amylate, and Ni" acetate (NiCRA) have been delineated.Reoxidation of the secondary alcohol products is dramatically postponed by the addition of alkali- or alkaline-earth-metal salts, and catalytic ketone reductions are achieved with NiCRA-MgBr2 mixtures. Full details of the reducing properties of various complex metal hydrides (12) of copper, formed by reaction of UAIH4 with appropriate lithium methylcuprates [equation (1)], have been published for example enones are reduced pre-... 

In addition to their work on naphthocoumarins, Sen and Kakaji showed that 4-t-butyl-2-hydroxyphenones 50 gave exclusively coumarins 51 when treated with various anhydrides in the presence of their corresponding sodium carboxylates. They saw similar results with 4-t-amyl-2-hydroxyphenones. 

The reduction is carried out much as described in Procedure 2. Ammonia (950 ml) is distilled into a 5-liter reaction flask and 950 ml of t-amyl alcohol and a solution of the ketal in 950 ml of methylcyclohexane are added with good stirring. Sodium (57 g, 2.5 g-atoms) is added in portions. The reaction mixture becomes blue within 30-45 min after the sodium is added and the metal is consumed within about 3 hr after the blue color appears. After the mixture becomes colorless, 200 ml of ethanol is added and the ammonia is allowed to boil off through a mercury trap. Then 500 ml of water and 500 ml of 10% potassium bicarbonate solution are added and the organic layer is separated. The organic layer is washed once with 10 % potassium bicarbonate... 

Reduction of ketones. Reduction of ketones with metals in an alcohol is one of the earliest methods for effecting reduction of ketones, and is still useful since it can proceed with stereoselectivity opposite to that obtained with metal hydrides.1 An example is the reduction of the 3a-hydroxy-7-ketocholanic acid 1 to the diols 2 and 3. The former, ursodesoxycholic acid, a rare bile acid found in bear bile, is used in medicine for dissolution of gallstones. The stereochemistry is strongly dependent on the nature of the reducing agent (equation I).2 Sodium dithionite and sodium borohydride reductions result mainly in the 7a-alcohol, whereas reductions with sodium or potassium in an alcohol favor reduction to the 7p-alcohol. More recently3 reduction of 1 to 2 and 3 in the ratio 96 4 has been achieved with K, Rb, and Cs in f-amyl alcohol. Almost the same stereoselectivity can be obtained by addition of potassium, rubidium, or cesium salts to reductions of sodium in t-amyl alcohol. This cation effect has not been observed previously. 

Butyl lithium t-Amyl alcohol Citric acid Triethylamine Salicylaldehyde Morpholine Sodium azide... 

Ruthenium tetroxide, generated in situ from a suspension of the dioxide in CCI4, by adding aqueous sodium metaperiodate, appears to be an excellent reagent for the oxidation of secondary alcohols in neutral or basic media. t-Amyl or cumyl hydroperoxide, with molybdenum pentachloride, readily oxidizes steroidal alcohols cholesterol affords the 5a-hydroxy-3,6-dione in good yield. ... 

Materials. VEC was prepared by the catalyzed addition of CO2 to 3,4-epoxy-l-butene using conditions typical of that used industrially [77], then purified by vacuum distillation. Other raw materials were used as received without any additional purification. Mixed xylenes, vinyl acetate (VA), butyl acrylate (BA), butyl methacrylate (BMA), methyl methacrylate (MMA), styrene (St), and t-butyl hydroperoxide were obtained from Aldrich Chemical Company. Lupersol 575 (t-amyl peroxy (2-ethylhexanoate)) was supplied by Elf Atochem. Vazo 67 (2,2 -azobis(2-methylbutyronitrile)) was obtained from DuPont Chemical Company. Vinyl pivalate (NE05), vinyl 2-ethylhexanoate (V2EH), Tergitol NP-40 (non-ionic surfactant) and QP-300 (hydroxy ethyl cellulose) were obtained from Union Carbide Coq)oration. Aerosol OT-75 (surfactant) was obtained from Cytec. Sodium formaldehyde sulfoxylate was obtained from Henkel Corporation. Ethyl 3-ethoxy propionate (EEP), propylene glycol monomethyl ether (PM) and PM acetate (PM Ac) are Eastman Chemical Company products. 

Alkylation of the enolate of (138) with methallyliodide gave the product (149) whose stereochemistry was assigned on the basis of equilibration experiment. It was converted to the dione (150) by oxidation with osmium tetrooxide and sodiumperiodate. The aldol cyclization of (150) effected with sodium hydride and trace of t-amyl alcohol in refluxing benzene afforded the enone (151) in 88% yield. Normal protic conditions (sodium hydroxide, ethanol) were not effective in this transformation. All attempts for its conversion to aphidicolin (148) by intermolecular additions proved fruitless and therefore were turned to intramolecular methods. Molecular models show clearly that the top face of the carbonyl group is less hindered to nucleophilic attack than is the bottom face. Thus the reduction of (151) with lithium aluminium hydride afforded the alcohol (152) whose vinyl ether (153) was subjected to pyrolysis for 2 hr at 360 C in toluene solution containing a small amount of sodium t-pentoxide to obtain the aldehyde (154) in 69% yield. Reduction and then tosylation afforded the alcohol (155) and tosylate (156) respectively. Treatment of this tosylate with Collman s reagent [67] (a reaction that failed in the model system) afforded the already reported ketoacetonide (145) whose conversion to aphidicolin (148) has been described in "Fig (12)". 

Azobis (2-methyl-N-phenylpropionamidine) dihydrochloride 2,2 -Azobis (2-methylpropane) 2,2 -Azobis (2-methylpropionamide) dihydrate 2,2 -Azobis [N-(2-propenyl)-2-methylpropionamide] 2,2 -Azobis [2-(3,4,5,6-tetrahydropyrimidin-2-yI) propane] dihydrochloride 2,2 -Azobis (2,4,4-trimethylpentane) n-Butyl-4,4-bis (t-butylperoxy) valerate t-Butyl hydroperoxide t-Butyl peroxycrotonate t-Butyl peroxyneoheptanoate Cerium Cumene hydroperoxide Cumyl peroxyneodecanoate o-Cumylperoxyneoheptanoate 1 -[(1 -Cyano-1 -methylethyl) azo] formamide Decanoyl chloride Decanoyl peroxide Di-t-amyl peroxide 2,2-Di (t-butylperoxy) butane Dicetyl peroxydicarbonate Dicyclohexyl peroxydicarbonate Dimethyl 2,2 -azobis (2-methylpropionate) 2,5-Dimethyl-2,5-di (benzoylperoxy) hexane 2,5-Dimethylhexane-2,5-dihydro peroxide Dimyristyl peroxydicarbonate Di-n-propyl peroxydicarbonate Ethyidibutylperoxybutyrate 3,3,6,6,9,9-Hexamethyl 1,2,4,5-tetraoxa cyclononane Lauroyl chloride Pelargonyl peroxide, 2-Phenylazo-4-methoxy-2,4-dimethylvaleronitrile Phosphine Potassium persulfate Sodium persulfate Succinic acid peroxide... 

A stock solution of t-amyl chloroformate (1 mol, calculated on the basis of t-amyl alcohol) was slowly added to a solution of r-proline (69 g, 0.6 mol) in a mixture of methanol (150 mL) and 2 N aqueous sodium hydroxide (600 mL) at —5 to 0 °C. The mixture was agitated vigorously with a mechanical stirrer during the addition (over about 1 h). Stirring was continued for a further 2 h at 0 °C, and then for an additional 1 h at room temperature. (During the reaction, the solution should be kept at above pH 8 by the addition of 4 n aqueous sodium hydroxide. After the addition, the progress of the reaction should be monitored by TLC if an appreciable amount of proline remains, more reagent should be added). The reaction mixture was subsequently adjusted to pH 2-3 with 1 n hydrochloric add, and the product was extracted with ethyl acetate (1 x 300 mL 3 x 100 mL). The combined extracts were dried over sodium sulfate. On concentration of the dried solution, crystals were obtained, which were subsequently recrystallized from ethyl acetate/ petroleum ether yield 137 g (88%). 

Treatment of cyanide poisoning includes rapid administration of activated charcoal (although charcoal binds cyanide poorly, it can reduce absorption) and general supportive care. The conventional antidote kit available in the USA includes two forms of nitrite (amyl nitrite and sodium nitrite) and sodium thiosulfate. The nitrites induce methemoglobinemia, which binds to free CI T creating the less toxic cyanomethemoglobin thiosulfate is a cofactor in the enzymatic conversion of CN to the much less toxic thiocyanate (SCINT). Recently, the FDA approved a concentrated form of hydroxocobalamin, which is now available as the Cyanokit (EMD Pharmaceuticals, Durham, North Carolina). Hydroxocobalamin (one form of vitamin B12) combines rapidly with CN to form cyanocobalamin (another form of vitamin B12). 

---