Hydrocarbons, hydroxyl derivatives

Steroids hydrocarbon, halogen, nitrogen and hydroxyl derivatives. (1955.)... 

The most widespread environmental carcinogens are the polycyclic aromatic hydrocarbons (PAHs), which are found, among other places, in automobile exhaust, cigarette smoke, and broiled meats. PAHs undergo two main pathways of bioactivation one-electron oxidation and oxygenation. The former yields cation radicals the latter produces hydroxyl derivatives. 

Any radical that may be converted to an amino group is capable of replacement by hydrogen. In certain instances such an indirect procedure may be of value. Since polynuclear phenols are transformed into amines by the Bucherer reaction,138 it has recently been suggested that the preparation of condensed ring hydrocarbons from the hydroxyl derivatives might best be achieved through the amines, rather than by the customary zinc dust fusion.189... 

Alcohols can be regarded as hydroxyl derivatives of hydrocarbons. They can be characterized by the number of hydroxyl groups (monohydric, dihydric, etc.), according to their structure (primary, secondary or tertiary), and by the structure of the hydrocarbon function to which the hydroxyl is attached (aliphatic, cyclic, saturated or unsaturated). 

SULT 2A and 2B sulfotransferase subfamily members sulfate the 3P-hydroxyl group of a variety of steroid hormones. Dehydroepiandrosterone (DHEA) is the prototypical substrate for the SULT 2 enzymes. However, other hydroxysteroids such as testosterone and its phase I hydroxylated derivatives are substrates for these enzymes. The SULT 2 sulfotransferases also are responsible for the sulfate conjugation of a variety of alcohols and xenobiotics that have undergone phase I hydro-xylation, including the polycyclic aromatic hydrocarbons (PAHs). The SULT 2 enzymes exhibit different patterns of tissue expression. SULT 2A1 is expressed primarily in the adrenal cortex, brain, liver, and intestine, while SULT 2B1 is expressed in the prostate, placenta, and trachea. 

Typical reactions in this category occur with 1-chloro-2,4-dinitrobenzene, 1,2-chloro-4-nitrobenzene, ethacrynic acid, trans-4-phenyl-3-buten-2-one and a range of hydroxylated derivatives of polycyclic hydrocarbons. 

Sulphuric Acid Derivatives.—In the aliphatic series we considered the hydroxyl derivatives immediately following the halogen derivatives because in that series the hydroxyl compounds are directly and eeisily prepared from the halogen substitution products by the action of silver hydroxide, AgOH, or sodium hydroxide, NaOH. In the benzene series the halogen derivatives are followed by the sulphuric acid derivatives because, in the first place, the halogen derivatives are not converted into hydroxyl compounds by treatment with silver hydroxide, and in the second place, because the sulphuric acid derivatives of the benzene hydrocarbons are easily formed directly from the hydrocarbons by action of sulphuric acid, which was not the case in the aliphatic series and because they are exceedingly important as they are readily transformed into other classes of compounds, e.g, hydroxyl compounds, phenols. 

We come now to the hydroxyl substitution products of the benzene hydrocarbons. These derivatives are of two classes A, phenols in which the hydroxyl group is substituted in the ring part of the compound. alcohols in which the hydroxyl group is substituted in the side chain of benzene homologues. Benzene having no side chain yields only the first class of derivatives. Toluene, however, and all the other homologues of benzene yield both classes as follows ... 

Benzyl Alcohol.—The simplest aromatic alcohol is the hydroxyl derivative of toluene and is known as benzyl alcohol, CeHs—CH2—OH. The radical, (CeHs—CH2—), is termed benzyl as in the alcohol and chloride above. The alcohol occurs as an ester in Peru balsam, in storax, a resin obtained from a plant sty rax, and in Tolu balsam from which the mother hydrocarbon toluene derives its name. On hydrolysis of the balsam benzyl alcohol is obtained. It is a liquid, b.p. 206.5°, slightly soluble in water and soluble in alcohol or ether. It may be prepared by those syntheses just given which yield primary alcohols. It may also be prepared by the reduction of the corresponding aldehyde, known as benzoic aldehyde or benzaldehyde (p. 655). On oxidation it yields the aldehyde and then an acid, benzoic acid. 

Constitution.—The composition of naphthalene is represented by the formula CioHg. What is its constitution In the first place it is a hydrocarbon similar in its chemical properties to benzene and not to methane. It readily forms nitro and sulphonic acid derivatives and its hydroxyl derivatives are analogom to phenols, not to alcohols. It also yields hydrogen and halogen addition products like benzene. The true constitution of the compound has been established by reactions both of decomposition and of synthesis. 

Nitro derivatives of the hydrocarbons, such as nitrotoluene am nitroxylene, also yield the corresponding aldehydes. The behavior of tin hydroxyl derivatives toward oxidizing agents under the above condition varies. Thus the methyl ether of para-crcsol gives an aldehyde withou difficulty, while the ortho-creso compounds give no aldehyde under tin same conditions. 

Zahlsen et al. (1993) found that C8-C10 hydrocarbons were extremely well absorbed and their tissue distribution in brain and fat were largely dependent on the number of carbon atoms. -Nonane is one component of JP-8 and it is metabolized at relatively high rates to hydroxyl derivatives, which are converted to the corresponding ketone. Other important hydrocarbons (from a... 

The majority of PCB photodegradation studies have been carried out in solution with organic or combined solvents preferred due to their low water solubility. Reductive dechlorination is the predominant photodegradation pathway in hydrocarbon solvents as well as alcohols. In aqueous media and alcohols photonucleophi 1 ic displacement reactions yielding phenols or alkoxy derivatives, respectively, also are detected. In the gas phase PCB are photochemically converted to hydroxylated derivatives (26). Photochemical reduction also is the major reaction pathway in thin films (7), solid phase (8) and on silica gel surfaces (9). 

Butyl Alcohols, C4H9OH.—Four butyl alcohols are known and four are possible according to the structure theory, if we consider alcohols as hydroxyl derivatives of the hydrocarbons. The formulas of the isomeric hydroxyl substitution-products of the two butanes are as follows ... 

The reaction is analogous to that by which alcohols are reduced to hydrocarbons. In the case of lactic acid, it shows that the compound is a hydroxyl derivative of propionic acid. The fact... 

The hydroxyl derivatives of the aromatic hydrocarbons are reduced when heated with zinc-dust —... 

This reaction, which furnishes a convenient way of converting a hydrocarbon into its hydroxyl derivative, is used in the industrial preparation of phenol and analogous compounds. 

Iodosylbenzene has been used as an effective oxidant in hydrocarbon hydroxylation catalyzed by metal-loporphyrins [687-696]. In particular, various iron(III) and manganese(in) porphyrins can be used as catalysts in hydroxylations of cyclohexane, cyclohexene, adamantane and aromatic hydrocarbons [687,688, 692]. Breslow and coworkers have reported regioselective hydroxylations of several steroidal derivatives catalyzed by metalloporphyrins [689-691]. In a specific example androstanediol derivative 644 was... 

Unlike monocarbonyl compounds, j3-diketones and their hydroxylated derivatives often do not correspond to the hydrocarbons in their chain length distribution (Tulloch, 1976). This difference apparently reflects the different pathways involved in the biosynthesis of these two classes of compounds. Genetic evidence obtained with barley mutants indicates that hydrocarbons and /3-diketones are generated by two genetically distinct enzyme systems... 

Gierycz, P. Rogalsid, M. Malanowski, S. Vapour-liquid equilibria in binary systems formed by N-methylpyrrolidone with hydrocarbons and hydroxyl derivatives Fluid Phase Equilib. 1985,22, 107-122... 

---