Hydroxy compounds alcohols

One of the most useful ways of introducing fluorine into organic compounds is the placement of the hydroxyl group in alcohols hydroxy compounds, and carboxylic acids Methyl alcohol reacts with anhydrous hydrogen fluoride at 100 500 °C in the presence of aluminum fluoride [60, 61], zinc fluoride [62] chromium fluonde [63], or a mixture of aluminum and chromium fluondes [64] to give a 20-78% yield of fluoromethane Attempted fluorinations of higher alcohols by this method failed [60]... 

Carbonyl azides react with alcoholic hydroxy compounds to form the corresponding urethanes. In the same manner, ferrocenoyl azide, and 3-fe-rrocenylpropionyl azide can derivatized, hydroxy-steroids and the resultant derivatives are determined electrochemically by LC with the detection limits at subpicomole levels. 2-[2-(Azidocarbonyl)ethyl]-3-methyl-1,4-naphthoquinone (AMQ) reacts with primary and secondary alcohols to produce carbamic acid derivatives and is used in LC with BCD and FL detections. 7-Methoxycoumarin-4-carbonyl azide (7-MC-4-CON3) and 3,4-dihydro-6,7-dimethoxy-4-methyl-3-oxoquinoxaline-2-carbonyl azide (DMEQ-CON3) are also applied to LC with FL detection as precolumn reagents. 

Water, alcohols and hydroxy compounds generally, and also primary and secondary amines, give the hydrocarbon corresponding to the Grignard reagent,... 

Supplement (combined with Volumes XVIII and XIX) XVII, 2nd 1934 2359-3031 Hydroxy compounds Furfuryl alcohol, 112. Carbonyl compounds Butyrolactone, 234. Furfural, 272. 2-Aoetyl-thio-phene, 287. Xanfhone, 366. Succinic anhydride, 404. Phthalio anhydride, 469. 

Reactions with Alcohols, Phenols, and Other Hydroxy Compounds... 

The reaction with sodium sulfite or bisulfite (5,11) to yield sodium-P-sulfopropionamide [19298-89-6] (C3H7N04S-Na) is very useful since it can be used as a scavenger for acrylamide monomer. The reaction proceeds very rapidly even at room temperature, and the product has low toxicity. Reactions with phosphines and phosphine oxides have been studied (12), and the products are potentially useful because of thek fire retardant properties. Reactions with sulfide and dithiocarbamates proceed readily but have no appHcations (5). However, the reaction with mercaptide ions has been used for analytical purposes (13)). Water reacts with the amide group (5) to form hydrolysis products, and other hydroxy compounds, such as alcohols and phenols, react readily to form ether compounds. Primary aUphatic alcohols are the most reactive and the reactions are compHcated by partial hydrolysis of the amide groups by any water present. 

The reaction of alcohols and acid chlorides in the presence of magnesium has been described (68). With primary and secondary alcohols the reaction is very smooth, and affords high and sometimes quantitative yields. Difficulty esteritiable hydroxy compounds such as tertiary alcohols and phenols can be esteritied by this method. The reaction carried out in ether or benzene is usually very vigorous with evolution of hydrogen. 

The most common impurities are the corresponding acid and hydroxy compound (i.e. alcohol or phenol), and water. A liquid ester from a carboxylic acid is washed with 2N sodium carbonate or sodium hydroxide to remove acid material, then shaken with calcium chloride to remove ethyl or methyl alcohols (if it is a methyl or ethyl ester). It is dried with potassium carbonate or magnesium sulfate, and distilled. Fractional distillation then removes residual traces of hydroxy compounds. This method does not apply to esters of inorganic acids (e.g. dimethyl sulfate) which are more readily hydrolysed in aqueous solution when heat is generated in the neutralisation of the excess acid. In such cases, several fractional distillations, preferably under vacuum, are usually sufficient. 

The purification of diethyl ether (see Chapter 4) is typical of liquid ethers. The most common contaminants are the alcohols or hydroxy compounds from which the ethers are prepared, their oxidation products (e.g. aldehydes), peroxides and water. Peroxides, aldehydes and alcohols can be removed by shaking with alkaline potassium permanganate solution for several hours, followed by washing with water, concentrated sulfuric acid [CARE], then water. After drying with calcium chloride, the ether is distilled. It is then dried with sodium or with lithium aluminium hydride, redistilled and given a final fractional distillation. The drying process should be repeated if necessary. 

The reduction of 1 l-keto-9 -H steroids gives an lla-ol, due to the fact that ring B or C must be in the boat form. The presence of bromine at the 2a-, 5a- and 12a-positions does not afifect greatly the isomer composition resulting from reduction of 3-, 6- and 11-ketones respectively. When in a 7-keto steroid the bromine is in the 6a-position a mixture of la- and 7 -ols results when the bromine is in the 6 -position only the 7jS-hydroxy compound is obtained. " The presence of bromine in the 16a- or 16 -positions seems to reduce the amount of 17 -alcohol formed. ... 

Hydrogenation of 11,12a- epoxides over Raney nickel produces the 1 la-alcohol in 15-20% yield.The corresponding ll,12jS-epoxide gives the 12)5-carbinol, while cleavage of the 5,6a-epoxide gives the 5a-hydroxy compound and the 5,6)8- and 4,5)8-epoxides give mixtures of products. 

In some cases products of rearrangement are obtained either partially or exclusively on treatment of Grignard reagents with epoxides. Thus, reaction of the 2/ ,3/ -epoxide (14) with methyl Grignard reagent affords a mixture of two epimeric secondary A-nor alcohols (15) in 80% yield and the tertiary hydroxy compound, 2a-methyl-5a-cholestan-2/f-ol (16) in 15 % yield. ... 

The stereochemistry of the product resulting from the reaction of a 17-keto steroid with ethylidenetriphenylphosphorane is different from that of the 17-ethylidene steroids obtained by dehydration of 17a-ethyl-17/ -hydroxy compounds, Wolff-Kishner reduction of A -20-keto steroids or by sodium-alcohol or sodium-ammonia " reductions of 17-ethynyl carbinols. These latter products have generally been assumed to possess the trans configuration (C-21 methyl away from the bulk of the ring system) because of anticipated greater stability. The cis configuration for... 

The use of benzyl alcohol as solvent produces the dibenzyl acetal at C-21, and this can be reductively removed to produce the 21-hydroxy compound... 

In contrast to phosphorus esters, sulfur esters are usually cleaved at the carbon-oxygen bond with carbon-fluorine bond formation Cleavage of esteri nf methanesulfonic acid, p-toluenesidfonic acid, and especially trifluoromethane-sulfonic acid (tnflic acid) by fluoride ion is the most widely used method for the conversion of hydroxy compounds to fluoro derivatives Potassium fluoride, triethylamine trihydrofluoride, and tetrabutylammonium fluoride are common sources of the fluoride ion For the cleavage of a variety of alkyl mesylates and tosylates with potassium fluoride, polyethylene glycol 400 is a solvent of choice, the yields are limited by solvolysis of the leaving group by the solvent, but this phenomenon is controlled by bulky substituents, either in the sulfonic acid part or in the alcohol part of the ester [42] (equation 29)... 

X0 to hydroxy compounds. Lower temperatures favor ketone formation and sterically hindered carbonyls, such as 2-thienyl t-butyl ketone, are not reduced. The sensitivity of desulfurization to steric factors is evident by the failure to desulfurize 2,5-di-i-butyl-3-acetylthiophene. The carbonyl groups of both aldehydes and ketones can be protected by acetal formation, as particularly cyclic acetals are stable during desulfurization in methanol at room temperature. " The free aldehydes give primary alcohols on desulfurization. Another method to obtain only keto compounds is to oxidize the mixtures of ketone and secondary alcohol with CrOs after the desulfurization. - Through the desulfurization of 5,5 -diacetyl-2,2, 5, 2"-terthienyl (228), 2,15-hexadecandione (229) has been obtained, which... 

These alkylamidodichlorophosphates react easily with water, alcohols, amines, etc. [60]. Higher molecular weight hydroxy compounds containing N in their molecule react with POCl3 in the presence of water [62]. 

The reagent reacts with primary and secondary amines and phenols but not aliphatic alcohols and is, thus, particularly useful for determining phenols in the presence of aliphatic hydroxy compounds. 

Monosaccharides in which an alcoholic hydroxy group has been replaced by an amino group are called amino sugars (see 2-Carb-14). When the hemiacetal hydroxy group is replaced, the compounds are called glycosylamines. 

Substituents replacing the hydrogen atom of an alcoholic hydroxy group of a saccharide or saccharide derivative are denoted as O-substituents. The 0- locant is not repeated for multiple replacements by the same atom or group. Number locants are used as necessary to specify the positions of substituents they are not required for compounds fully substituted by identical groups. Alternative periphrase names for esters, ethers, etc. may be useful for indexing purposes. For cyclic acetals see 2-Carb-28. 

Reaction with alcohols is general for diazo compounds, but it is most often performed with diazomethane to produce methyl ethers or with diazo ketones to produce ot-keto ethers, since these kinds of diazo compounds are most readily available. With diazomethane the method is expensive and requires great caution. It is used chiefly to methylate alcohols and phenols that are expensive or available in small amounts, since the conditions are mild and high yields are obtained. Hydroxy compounds react better as their acidity increases ordinary alcohols do not react at... 

The second compound above raises an important issue how do you name the functional group when you have two functional groups in a compound One will go in the suffix of the name and the other will be a prefix in the substituent part of the name. But how do we choose which one goes as the suffix of the name There is a hierarchy that needs to be followed. The six groups shown above are listed according to their hierarchy, so a carboxylic acid takes precedence over an alcohol. A compound with both of these groups is named as a ketone and we put the term hydroxy in the substituent part of the name. 

Some substituted hydroxy compounds give with poly (vinyl alcohol) firm, white gels which form clear coatings when dried in layer form. A few typical compounds are ... 

XVII XVII, 1st Supplement 1933 2359-2503 One Cyclic Oxygen (S, Se or Te). Stem nuclei Furan, 27. Thiophene, 29. Hydroxy compounds Furfuryl alcohol. 

Nitrosyl perchlorate Organic materials Perchloric acid Alcohols Permanganic acid Organic materials Peroxodisulfuric acid Organic liquids Potassium dioxide Ethanol Potassium perchlorate Ethanol Potassium permanganate Ethanol, etc. Ruthenium(VIII) oxide Organic materials Silver perchlorate Aromatic compounds Sodium peroxide Hydroxy compounds Uranium hexafluoride Aromatic hydrocarbons, etc. Uranyl perchlorate Ethanol See v-halomides Alcohols... 

A variety of alcohols, protected as t-butyldimethylsilyl (TBDMS) ether derivatives, can be rapidly regenerated to the corresponding hydroxy compounds on alumina surface using MW irradiation (Scheme 6.8) [42], This approach prevents the use of corrosive fluoride ions that are normally employed for cleaving the silyl protecting groups. 

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