Alcohols, aromatic primary

Aromatic primary amines differ markedly from aliphatic amines in their reaction with nitrous acid. Thus a cold aqueous solution of mono thylamine hydrochloride reacts with nitrous acid to give mainly the corresponding primary alcohol ... 

Aromatic primary alcohols diflfer from aliphatic primary alcohols in that they react with concentrated hydrochloric acid in the cold to yield the corresponding chlorides, for example ... 

The aromatic primary and secondary stibines are readily oxidized by air, but they are considerably more stable than their aHphatic counterparts. Diphenylstibine is a powerful reducing agent, reacting with many acids to Hberate hydrogen (79). It has also been used for the selective reduction of aldehydes and ketones to the corresponding alcohols (80). At low temperatures, diphenylstibine undergoes an addition reaction with ketene (81) ... 

Essential oils are obtained from fmits and flowers (61,62). Volatile esters of short- and medium-chain carboxyHc acids or aromatic carboxyHc acids with short- and medium-chain alcohols are primary constituents of essential oils, eg, ethyl acetate in wines, brandy, and in fmits such as pineapple ben2yl acetate in jasmine and gardenia methyl saHcylate in oils of wintergreen and sweet birch. Most of these naturally occurring esters in essential oils have pleasant odors, and either they or their synthetic counterparts are used in the confectionery, beverage, perfume, cosmetic, and soap industries (see Oils, essential). 

For aromatic alcohols and compounds with an----OH on a side chain, the alcohol contribution (primary, etc.) must be included. For example, o-chlorophenol ... 

Related (diisopropoxyphosphoryl)- and (diisobutoxyphosphoryl)formonitrile oxides (114), generated in basic media from the corresponding oximes react in situ with alcohols, phenols, alkanethiols, thiophenols, aliphatic and aromatic primary amines, hydrazines and hydrazides as well as 4-aminoantipyryne to give hydroxymates, thiohydroxymates, and amidoximes, respectively. It is important to note that the addition is stereoselective and gives E-adducts with the exception of (i-Pr0)2P(0)C( N0H)0Me, which is formed as a 1 1 mixture of E and Z isomers. 

The propargyl alcohol 316 reacts with carbon dioxide and aliphatic or aromatic primary amines RNH2 under tributylphosphine catalysis to yield 5,5-dimethyl-4-methylene-oxazolidin-2-ones 317374. 

Fig. 9.8 presents another, more complex type of phosphate prodrugs, namely (phosphoryloxy)methyl carbonates and carbamates (9-26, X = O or NH, resp.) [84], Here, the [(phosphoryloxy)methyl]carbonyl carrier appears quite versatile and of potential interest to prepare prodrugs of alcohols, phenols, and amines. The cascade of reactions leading from prodrug to drug as shown in Fig. 9.8 involves three steps, namely ester hydrolysis, release of formaldehyde, and a final step of carbonate hydrolysis (X = O) or A-decar-boxylation (X = NH). Three model compounds, a secondary alcohol, a primary aliphatic amine, and a primary aromatic amine, were derivatized with the carrier moiety and examined for their rates of breakdown [84], The alcohol, indan-2-ol, yielded a carrier-linked derivative that proved relatively... 

When electronegative substituents are present, oxadiazoles undergo nucleophilic reactions on the carbon atoms, both in position 3 or 5- The substitution of halogen, alkoxy and trichloromethyl derivatives has. been studied. 5-Halogeno-oxadiazoles react with ahphatic and aromatic primary and secondary amines, to give the corresponding amino-derivatives. With sodium hydroxide and -alcoholate, hydroxy and alkoxy oxadiazoles are obtained 25 a, 55 b). 

Reaction CXXXV. Action of Chloroform and Alcoholic Potash on Aliphatic and Aromatic Primary Amines. 

The number of published selective oxidations of allylic or benzylic alcohols with active M11O2 in the presence of primary amines is very limited 48 The published cases involve aromatic primary amines possessing an... 

The oxidation of alchols can be readily carried out using peroxygen reagents. The extensive range of methods available makes it possible to achieve the oxidation of a wide variety of both aliphatic and aromatic primary and secondary alcohols, often in a highly selective manner. 

Gasoline and petroleum ethers are complex mixtures of chemicals. Gasoline may contain over 500 different hydrocarbons as a mixture of both aliphatic and aromatic hydrocarbons. Gasoline also contains additives, including toluene, benzene, ether, and alcohols. The primary components responsible for the euphoric effects of sniffing gas are the aliphatic hydrocarbons. 

Character and Types.— Aromatic acids bear exactly the same relationship to aromatic primary alcohols and aldehydes that the aliphatic acids do to the aliphatic primary alcohols and aldehydes, i.e. the acids are the final oxidation products of the other two groups. In the aliphatic series we showed how the alcohols may be considered as the first oxidation products of the hydrocarbons. The entire series of oxidation relationships being illustrated as follows ... 

Urethanes were also obtained from a mixture of aromatic primary amine and alcohol by oxidative catalytic carbonylation with carbon monoxide in the presence of a catalyst mixture containing DBU (81GEP2908250 83EUP83096). 

Other oxidants of hexavalent chromium are chromyl chloride and di-/er/-butyl chromate. Chromyl chloride adsorbed on alumina-silica gel from its solution in dichloromethane oxidizes aliphatic and aromatic alcohols at room temperature within hours in 77-100% yields [675]. Di-tert-butyl chromate, prepared in situ from chromyl chloride in tert-butyl alcohol at -70 °C, gives comparable results under similar conditions [674. Di-tert-butyl chromate, prepared from chromium trioxide and tert-butyl alcohol, oxidizes primary aliphatic and aromatic alcohols to the corresponding aldehydes even at low temperatures (1-2 °C) [677, 678]. 

Place 1 drop of a solution of sulfacetamide on a filter paper, add 1 drop of coniferyl alcohol (0.1g/10 ml ethanol), and expose the paper to hydrochloric acid fumes. An orange color indicates the presence of an aromatic primary amine in which the amino group is attached directly to a bezene ring. 

Reactions with nucleophiles other than alcohols can produce other carbonic acid derivatives. For example, reaction with anhydrous ammonia yields urea, 0 = C(NH2)2. Aromatic primary amines can, depending on reaction conditions, react with phosgene to form carbamoyl chlorides (Csuros et al., 1969). 

The ease of acetal formation depends largely on the structures of the reacting carbonyl compounds and alcohol.905 Primary alcohols react better than secondary or tertiary ones the ease of reaction of carbonyl compounds decreases in the order formaldehyde, aliphatic aldehydes,, / -unsaturated aldehydes, aromatic aldehydes, ketones acetone gives cyclic ketals very readily with 1,2- and 1,3-diols. 

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