Aliphatic alcohol

Alcohols, like phenols, suffer O-sulfonation, but phenols also undergo C-sulfonation on the aromatic nucleus (see Chapter 4, p 61). Chlorosulfonic acid is 

Chlorosulfonic acid is generally the favoured reagent for the sulfation of alcohols the reaction is rapid, complete, goes at low temperatures and yields a good quality product. With liquid alcohols, no solvent is necessary, but when using solid alcohols, the sulfation may be performed in suitable solvents, for instance, chloroform, carbon tetrachloride or tetrachloroethane, at temperatures usually in the range of —10 to 30 °C. The use of the appropriate solvent may reduce the formation of byproducts. 

The chlorosulfonic acid-ether complex is a milder reagent than free chlorosulfonic acid for the sulfation of alcohols and is outstanding in respect of yield and purity of the alkyl hydrogen sulfates 45 produced. The use of chlorosulfonic acid in diethyl ether at low temperature (-50 °C) is a standard method for sulfation of higher (Cg-C28) primary and secondary alcohols. The latter have also been successfully sulfated using a mixture of chlorosulfonic acid in acetic acid the active entity here is probably acetyl sulfate. This method has been adapted for the synthesis of very pure sodium alkyl sulfates for use as detergents thus chlorosulfonic acid and 1-dodecanol were successively added to acetic acid at low temperature (—10 to -15 °C), the solid product was neutralized with sodium carbonate and unreacted alcohols extracted with solvents to give 98.6% pure dodecanyl sodium sulfate.  

The sulfation of higher alcohols, ethoxyalcohols and acid amides by chlorosulfonic acid and sulfur trioxide has been examined under various reaction conditions in an effort to optimize the manufacture of foam detergents.  

The batchwise sulfation of alcohols by chlorosulfonic acid may be effected by gradual addition of the reagent to the alcohol at ca. 30 °C, often in the presence of chloroform (25-35% by weight) as solvent. The process is performed in special steel or glass-lined reactors to avoid corrosion by the evolved hydrogen chloride gas. The continuous sulfation of higher alcohols, e.g. dobanol 23, has also been effected by reaction with chlorosulfonic acid in the presence of nitrogen 

Aliphatic alcohols with appropriate hydrocarbon chain can be used as good frother. For example, 4-methyl amyl alcohol (MIBC) is widely applied in the flotation industry [3]. Aerofroth type frothers produced hy American Cyanamid Corporation belong to aliphatic alcohols. For instance, aerofroth 70 is a methyl isobutyl methyl alcohol, aerofroth 71A is an alcohol with a linear chain and an endless chain of C5-Ce, and aerofroth 77A is an alcohol with a linear chain of C4-C8. The physical properties of various aerofroth type frothers are as follows  

There are over 70 alcohols in the atmosphere as a result of biogenic and anthropogenic emissions [67]. For example methanol and ethanol [68-70] have been used as fuels additives to reduce automobile emissions of carbon monoxide and hydrocarbons [71], in particular ethanol has been used in Brazil as a fuel for over 20 years [72]. 1-Propanol is widely used as a solvent in the manufacturing of different electronic components. The high volatility of these compounds causes their relative abundance in the troposphere and makes it relevant to determine their degradation pathways. During daytime the major loss process for alcohols is their reaction with OH radicals [68]. Accordingly, several experimental [69,70,73-84] and theoretical [85-88] kinetic studies of alcohols -F OH reactions have been performed. 

Intramolecular interactions in the transitions states (TS) are also relevant to properly predict or reproduce experimental rate constants, since they directly affect the TSs energies and small variations in reaction barriers have relative large impact on k since they enter exponentially in the rate constant equation. A detailed discussion on such interactions, in the TSs of different H abstraction paths, for 2-propanol -I- OH reacfion has been provided by Luo et al. [85]. These authors have also discussed the influence of fhe inferactions on the reaction barriers and rate coefficients. 

FIGURE 12.2 Intramolecular hydrogen bond like interactions in the transition state structures of channels a, p and y of the 1-butanol -I- OH reaction. 

TABLE 12.1 Calculated rate coefficients (cmV(inolecules)) for alcohols -I- OH radical gas phase reactions at 298 K, compared to the recommended ones 

The higher reactivity of 1-butanol gamma site [87] is in line with the results of Wallington and Kurylo [90] who have proven that in ketones there is a significant enhancement of the group reactivity toward OH for both CH3 and CH2 when moved from the alpha to beta positions. This has been taking into account in the Structure-Activity Relationship (SAR) method [91,92] by factors of F[-CH2C(0)] = f [ CHC(0)] = f [ CC(0)] = 3.9 [22]. In this improved version of 

Before discussing the mechanism of dehydration of primary alcohols, it might be worthwhile to consider some of the published results on the dehydration of ethyl alcohol. Chiefly, two products result ethyl ether and ethylene. Most of the discussions over the years have centered around the problem whether ether is formed simultaneously, in- 

The kinetic studies carried out in recent years on the dehydration of ethyl alcohol did not lead to identical conclusions. Much of the divergence is probably due to the fact that the various investigators paid no attention to the intrinsic acidities of the aluminas used in their studies. 

Ballaceanu and Jungers (22) suggested ethyl ether as a precursor of ethylene  

Topchieva and co-workers (5) proposed still another scheme for dehydration  

The latter mechanism is similar to that of Brey and Krieger (18) with the exception that a different bond to the catalyst is proposed. 

Reduction of esters of monobasic acids with sodium and absolute ethyl alcohol (method of Bouveault and Blanc), for example  

For reduction with lithium aluminium hydride, see Section VI,10. 

Reduction of aldehydes with iron and glacial acetic acid, for example  

Action of the Grignard reagent upon formaldehyde, for example  

It will be observed that the length of the carbon chain is increased by one carbon atom. 

CH3CH2CH2CH2COOC2H5 — CH3CH2CH2CH2CH2OH + C2H5OH Ethyl n-valerate n-Aniyl alcohol 

The synthetic methanol now available is suitable for most purposes without purification indeed some manufacturers claim a purity of 99.85 per cent with not more than 0.1 per cent by weight of water and not more than 0.02 per cent by weight of acetone. 

If the small proportion of acetone present in synthetic methanol is objectionable it may be removed when present in quantities up to 1 per cent by the following procedure (Morton and Mark, 1934). A mixture of 500 ml of methanol, 25 ml of furfural and 60 ml of 10 per cent sodium hydroxide solution is refluxed in a 2-litre round-bottomed flask, fitted with a double surface condenser, for 6-12 hours. A resin is formed which carries down all the acetone present. The alcohol is then fractionated through an efficient column, the first 5 ml which may contain a trace of formaldehyde being rejected. The recovery of methanol is about 95 per cent. 

Ethanol of a high degree of purity is frequently required in preparative organic chemistry. For some purposes ethanol of c. 99.5 per cent purity is satisfactory this grade may be purchased (the absolute alcohol of commerce), or it may be 

The method of Lund and Bjerrum depends upon the reactions  

Reaction (1) usually proceeds readily provided the magnesium is activated with iodine and the water content does not exceed 1 per cent. Subsequent interaction between the magnesium ethanolate and water gives the highly insoluble magnesium hydroxide only a slight excess of magnesium is therefore necessary. 

Few cases of allergy to glyceryl monoleate and glyceryl monostearate have been reported (Hjorth and Trolle Lassen 1963). Isopropyl myristate (a synthetic fatty alcohol) was an allergen in six cases reported by Calnan (1968). 

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On acetylation it gives acetanilide. Nitrated with some decomposition to a mixture of 2-and 4-nitroanilines. It is basic and gives water-soluble salts with mineral acids. Heating aniline sulphate at 190 C gives sulphanilic add. When heated with alkyl chlorides or aliphatic alcohols mono- and di-alkyl derivatives are obtained, e.g. dimethylaniline. Treatment with trichloroethylene gives phenylglycine. With glycerol and sulphuric acid (Skraup s reaction) quinoline is obtained, while quinaldine can be prepared by the reaction between aniline, paraldehyde and hydrochloric acid. 

The chlorides of secondary aliphatic alcohols are prepared by method 1, for example —... 

The chlorides of tertiary aliphatic alcohols are readily prepared by the action of concentrated hydrochloric acid upon the alcohol at the laboratory temperature, for example ... 

For properties of these reagents and their preparation from the corresponding acids, see under Aliphatic Alcohols, Section 111,27,1 and 2. 

Most aromatic alcohols exhibit the majority of the reactions given under Aliphatic Alcohols, Section 111,27, and may be converted into crystalline derivatives as there described. 

Primary aliphatic alcohols 3640-3630 (s) Only in very dilute solutions in nonpolar solvents... 

Secondary aliphatic alcohols 3625-3620 (s) 1350-1260 (s) 1125-1085 (s) See comments under primary aliphatic alcohols Also for a-unsaturated and cyclic tertiary aliphatic alcohols... 

Catalyst recovery is a major operational problem because rhodium is a cosdy noble metal and every trace must be recovered for an economic process. Several methods have been patented (44—46). The catalyst is often reactivated by heating in the presence of an alcohol. In another technique, water is added to the homogeneous catalyst solution so that the rhodium compounds precipitate. Another way to separate rhodium involves a two-phase Hquid such as the immiscible mixture of octane or cyclohexane and aliphatic alcohols having 4—8 carbon atoms. In a typical instance, the carbonylation reactor is operated so the desired products and other low boiling materials are flash-distilled. The reacting mixture itself may be boiled, or a sidestream can be distilled, returning the heavy ends to the reactor. In either case, the heavier materials tend to accumulate. A part of these materials is separated, then concentrated to leave only the heaviest residues, and treated with the immiscible Hquid pair. The rhodium precipitates and is taken up in anhydride for recycling. 

Higher aliphatic alcohols (C —C g) are produced ia a number of important industrial processes using petroleum-based raw materials. These processes are summarized in Table 1, as are the principal synthetic products and most important feedstocks (qv). Worldwide capacity for all higher alcohols was approximately 5.3 million metric tons per annum in early 1990, 90% of which was petroleum-derived. Table 2 Hsts the major higher aliphatic alcohol producers in the world in early 1990. 

Table 1. Synthetic Industrial Processes for Higher Aliphatic Alcohols...

Table 2. Major Cg and Higher Aliphatic Alcohol Producers ...

Amyl alcohol describes any saturated aliphatic alcohol containing five carbon atoms. This class consists of three pentanols, four substituted butanols, and a disubstituted propanol, ie, eight stmctural isomers four primary, three secondary, and one tertiary alcohol. In addition, 2-pentanol,... 

Aliphatic Alcohols and Thiols. Ahphatic alcohols on reaction with chloroformates give carbonates and hydrogen chloride. Frequendy, the reaction proceeds at room temperature without a catalyst or hydrogen chloride acceptor. However, faster reactions and better yields are obtained in the presence of alkaU metals or their hydroxides, or tertiary amines. Reactions of chloroformates with thiols yield monothiolocarbonates (14). 

Cobalt in Catalysis. Over 40% of the cobalt in nonmetaUic appHcations is used in catalysis. About 80% of those catalysts are employed in three areas (/) hydrotreating/desulfurization in combination with molybdenum for the oil and gas industry (see Sulfurremoval and recovery) (2) homogeneous catalysts used in the production of terphthaUc acid or dimethylterphthalate (see Phthalic acid and otherbenzene polycarboxylic acids) and (i) the high pressure oxo process for the production of aldehydes (qv) and alcohols (see Alcohols, higher aliphatic Alcohols, polyhydric). There are also several smaller scale uses of cobalt as oxidation and polymerization catalysts (44—46). 

Aliphatic Alcohols and Alkylene Glycols. Simple aliphatic alcohols, such as methanol [67-56-1], can be used to alkylate alkyleneamines. For example, piperazine reacts with methanol over a reductive amination catalyst to yield a mixture of 1-methyl- [109-01 -3J and 1,4-dimethylpiperazine [106-58-1] (12). 

Use of Azeotropes to Remove Water. With the aliphatic alcohols and esters of medium volatility, a variety of azeotropes is encountered on distillation (see Distillation, azeotropic and extractive). Removal of these azeotropes from the esterification reaction mixture drives the equihbrium in favor of the ester product (39). 

As may be expected of an amorphous polymer in the middle range of the solubility parameter table, poly(methyl methacrylate) is soluble in a number of solvents with similar solubility parameters. Some examples were given in the previous section. The polymer is attacked by mineral acids but is resistant to alkalis, water and most aqueous inorganic salt solutions. A number of organic materials although not solvents may cause crazing and cracking, e.g. aliphatic alcohols. 

Such materials are soluble in the lower aliphatic alcohols, e.g.ethanol, and in phenols. They also absorb up to 21 % of moisture when immersed in water. If this material is heated with 2% citric acid at elevated temperatures, typically for 20 minutes at 120°C, cross-linking will take place Figure 18.20). 

Figure 2. Graph of the Reciprocal of the Corrected Retention Volume against the Moderator Concentration for a Series of Aliphatic Alcohols...

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