Barium alcoholate

BaO reacts slowly with alcohols forming barium alcoholates. 

Another catalyst which may also involve a homogeneous catalysis mechanism is barium hydroxide. Barium hydroxide has been reported to catalyze the methanolysis of rapeseed oil at 65°C with over 80% of oil conversion in less than an hour. " However, Ba(OH)2 shows non-negligible solubility in water, methanol and polyols. " For instance, in alcohols Ba(OH)2 can form barium alcoholates (RO Ba OH and RO Ba-OR). A barium alcoholate of formula... 

It is very interesting that by using alkaline-earth catalysts in the ethoxylation reaction (Ca, Sr or Ba alcoholates or carboxylates), a narrower distribution of EO sequences per hydroxyl group resulted, compared to use of alkaline catalysts. For example, with barium alcoholate as catalyst around 80-85% primary hydroxyl, at 15% EO as terminal block, are obtained with polyether triols (MW of 5000 daltons), compared to 65-75% primary hydroxyl obtained in the presence of KOH. The explanation of this behaviour... 

White to yellowish-white powder or lumps. Very alkaline absorbs moisture and COj on exposure to air- Poisonous On contact with water it forms Ba(OH), with evolution of much heat. At 450 combines with oxygen to form BaO,. which is reduced to BaO above 60CT. d 5.7. mp about 192tr. Sol in water, dil adds. Slowly, but considerably sol in methanol, ethanol forming barium alcoholate. Keep lightly closed. 

Reactions on natural rubber or cis-l,4-polyisoprene, in the presence of various OA catalysts such as c -camphorsulfonic acid, percamphoric acid or sodium or barium active-isoamyl-alcoholate were reported by Minoura [189]. Optically active polymers, after hydrolysis of the optically active group, were only obtained with barium alcoholate. The rotatory powers are very small, even for the best reported value of the addition (20%). With other catalysts, there was no asymmetric induction. The mechanism producing the active adduct polymer was thought by the author to be as follows (Scheme LXXI) ... 

Barium is a metallic element, soft, and when pure is silvery white like lead it belongs to the alkaline earth group, resembling calcium chemically. The metal oxidizes very easily and should be kept under petroleum or other suitable oxygen-free liquids to exclude air. It is decomposed by water or alcohol. 

The most stable protected alcohol derivatives are the methyl ethers. These are often employed in carbohydrate chemistry and can be made with dimethyl sulfate in the presence of aqueous sodium or barium hydroxides in DMF or DMSO. Simple ethers may be cleaved by treatment with BCI3 or BBr, but generally methyl ethers are too stable to be used for routine protection of alcohols. They are more useful as volatile derivatives in gas-chromatographic and mass-spectrometric analyses. So the most labile (trimethylsilyl ether) and the most stable (methyl ether) alcohol derivatives are useful in analysis, but in synthesis they can be used only in exceptional cases. In synthesis, easily accessible intermediates of medium stability are most helpful. 

The a-thiocyanatoketones are easily obtainable from a-halocarbonyl compounds and metal thiocyanates (sodium, potassium, barium, or lead thiocyanate) (416, 484, 519, 659) in an alcoholic solution. Yields ranged from 80 to 95%. They are very sensitive substances that isomerize when reacted upon by acids, bases, or labile hydrogen and sulfur compounds. 

ALCOHOLS,HIGHERALIPHATIC - SURVEYAND NATURAL ALCOHOLSMANUFACTURE] (Vol 4) -in barium carbonate mgf [BARIUM COMPOUNDS] ( 7ol 3)... 

Tetrahydrofurfuryl alcohol reacts with ammonia to give a variety of nitrogen containing compounds depending on the conditions employed. Over a barium hydroxide-promoted skeletal nickel—aluminum catalyst, 2-tetrahydrofurfur5iarnine [4795-29-3] is produced (113—115). With paHadium on alumina catalyst in the vapor phase (250—300°C), pyridine [110-86-1] is the principal product (116—117) pyridine also is formed using Zn and Cr based catalysts (118,119). At low pressure and 200°C over a reduced nickel catalyst, piperidine is obtained in good yield (120,121). 

In the three-step process acetone first undergoes a Uquid-phase alkah-cataly2ed condensation to form diacetone alcohol. Many alkaU metal oxides, metal hydroxides (eg, sodium, barium, potassium, magnesium, and lanthanium), and anion-exchange resins are described in the Uterature as suitable catalysts. The selectivity to diacetone alcohol is typicaUy 90—95 wt % (64). In the second step diacetone alcohol is dehydrated to mesityl oxide over an acid catalyst such as phosphoric or sulfuric acid. The reaction takes place at 95—130°C and selectivity to mesityl oxide is 80—85 wt % (64). A one-step conversion of acetone to mesityl oxide is also possible. 

Analytical Methods. The official NIOSH recommended method for determining sulfur dioxide in air consists of drawing a known prefiltered volume of air through a bubbler containing hydrogen peroxide, thus oxidising the sulfur dioxide to sulfuric acid. Isopropyl alcohol is then added to the contents in the bubbler and the pH of the sample is adjusted with dilute perchloric acid. The resultant solution is then titrated for sulfate with 0.005 M. barium perchlorate, and Thorin is used as the indicator. 

Barium hydro sulfide [25417-81-6], Ba(HS)2, is formed by absorption of hydrogen sulfide into barium sulfide solution. On addition of alcohol, barium hydrosulfide tetrahydrate [12230-74-9], Ba(HS)2 4H2O, crystallizes as yellow rhombic crystals that decompose at 50 °C. Sohd barium hydro sulfide is very unstable. Its solubility in water is... 

For more selective hydrogenations, supported 5—10 wt % palladium on activated carbon is preferred for reductions in which ring hydrogenation is not wanted. Mild conditions, a neutral solvent, and a stoichiometric amount of hydrogen are used to avoid ring hydrogenation. There are also appHcations for 35—40 wt % cobalt on kieselguhr, copper chromite (nonpromoted or promoted with barium), 5—10 wt % platinum on activated carbon, platinum (IV) oxide (Adams catalyst), and rhenium heptasulfide. Alcohol yields can sometimes be increased by the use of nonpolar (nonacidic) solvents and small amounts of bases, such as tertiary amines, which act as catalyst inhibitors. 

Ethyl chloride can be dehydrochlorinated to ethylene using alcohoHc potash. Condensation of alcohol with ethyl chloride in this reaction also produces some diethyl ether. Heating to 625°C and subsequent contact with calcium oxide and water at 400—450°C gives ethyl alcohol as the chief product of decomposition. Ethyl chloride yields butane, ethylene, water, and a soHd of unknown composition when heated with metallic magnesium for about six hours in a sealed tube. Ethyl chloride forms regular crystals of a hydrate with water at 0°C (5). Dry ethyl chloride can be used in contact with most common metals in the absence of air up to 200°C. Its oxidation and hydrolysis are slow at ordinary temperatures. Ethyl chloride yields ethyl alcohol, acetaldehyde, and some ethylene in the presence of steam with various catalysts, eg, titanium dioxide and barium chloride. 

Ammonium cyanide may be prepared in solution by passing hydrogen cyanide into aqueous ammonia at low temperatures. It may also be prepared from barium cyanide and ammonium sulfate, or calcium cyanide with ammonium carbonate. It may be prepared in the dry state by gentiy heating a mixture of potassium cyanide or ferrocyanide and ammonium chloride, and condensing the vapor in a cooled receiver. Ammonium cyanide is soluble in water or alcohol. The vapor above soHd NH CN contains free NH and HCN, a very toxic mixture. 

Di-(/)-chlorophenyl)-acetic acid has been made by the action of alcoholic potassium hydroxide on l,l-di-(/>-chlorophenyl)-2,2-dichloroethane by the action of barium hydroxide on DDT in ethylene glycol and by the condensation of chlorobenzene with glyoxylic acid. ... 

The alcoholic filtrate is evaporated to 50 cc., and 50 g. of barium hydroxide and 150 cc. of distilled water are added (Note 4). The mixture is refluxed for two hours and the excess barium hydroxide is precipitated with carbon dioxide. The barium carbonate is removed by filtration and washed with hot distilled water. A slight excess of sulfuric acid is added to the filtrate to liberate the amino acid from its barium salt, and an excess of barium carbonate is added to remove sulfate ion. The mixture is digested on the steam bath until effervescence ceases, and it is then filtered and the precipitate is washed with hot distilled water. The filtrate and washings are concentrated on the steam bath to a volume of 100 cc., decolorized with i g. of active carbon, filtered, and concentrated to the point of crystallization (about 25 cc.). The amino acid is precipitated by the addition of 150 cc. of absolute alcohol and the product is collected and washed with absolute alcohol. 

The alcoholic filtrate contains appreciable amounts of pyrrolidone. The treatment with excess barium hydroxide converts this into the barium salt of the amino acid. ... 

Cellobiose was prepared first by Skraup and Konig by the saponification of the octaacetate with alcoholic potassium hydroxide, and the method was improved by Pringsheim and Merkatz.3 Aqueous barium hydroxide also has been employed for the purpose, and methyl alcoholic ammonia has been used extensively for the hydrolysis of carbohydrate acetates. The method of catalytic hydrolysis with a small quantity of sodium methylate was introduced by Zemplen,i who considered the action to be due to the addition of the reagent to the ester-carbonyl groups of the sugar acetate and the decomposition of the addition compound by reaction with alcohol. The present procedure, reported by Zemplen, Gerecs, and Hadacsy, is a considerable improvement over the original method (see Note 2). 

Somewhat better results have been obtained with octoates and benzoates but these still lead to some plate-out. The use of liquid cadmium-barium phenates has today largely resolved the problem of plate-out whilst the addition of a trace of a zinc salt helps to improve the colour. Greater clarity may often be obtained by the addition of a trace of stearic acid or stearyl alcohol. Thus a modem so-called cadmium-barium stabilising system may contain a large number of components. A typical packaged stabiliser could have the following composition ... 

Resoles are usually those phenolics made under alkaline conditions with an excess of aldehyde. The name denotes a phenol alcohol, which is the dominant species in most resoles. The most common catalyst is sodium hydroxide, though lithium, potassium, magnesium, calcium, strontium, and barium hydroxides or oxides are also frequently used. Amine catalysis is also common. Occasionally, a Lewis acid salt, such as zinc acetate or tin chloride will be used to achieve some special property. Due to inclusion of excess aldehyde, resoles are capable of curing without addition of methylene donors. Although cure accelerators are available, it is common to cure resoles by application of heat alone. 

Seheuing and Winterhalder treated 2 6-distr3rrylpyridine tetra-bromide with potassium hydroxide in alcohol, so producing 2 6-di-)3-phenylacetylenylpyridine (XI) which by the action of 50 per cent, sulphuric acid was converted into 2 6-diphenacylpyridine (XII), and this, on hydrogenation in presence of platinic oxide, barium sulphate and methyl alcohol, was reduced to 2 6-di-(6-hydroxy-(6-phenylethylpyridine, and the hydrochloride of this, on similar catalytic hydrogenation, yielded worlobelanidine (XIII). This can be methylated to lobelanidine, from which in turn dMobeline and lobelanine can be obtained. 

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