Secondary/tertiary butyl alcohols

The reason for this is that reaction (i) is usually much slower than (ii) and (iii) so that the main reaction appears to be (Iv) (compare the preparation of tertiary butyl chloride from tertiary butyl alcohol and concentrated hydrochloric acid, Section 111,33). If the reaction is carried out in the presence of P3rridine, the latter combines with the hydrogen chloride as it is formed, thus preventing reactions (ii) and (iii), and a good yield of the ester is generally obtained. The differentiation between primary, secondary and tertiary alcohols with the aid of the Lucas reagent is described in Section III,27,(vii). 

The above-mentioned alcohols are by far the most common. Butyl alcohol is not as commonly used as the first four in the series, but it is used. Secondary butyl alcohol and tertiary butyl alcohol, so named because of the type of carbon atom in the... 

In this range of acidity the intermediate carbonium ions do not fragment to smaller species. Isobutylene (C4) produces Cg and C12 olefins but no C5, C(), C7, C9 Cio or Cu products. This lack of fragmentation has been demonstrated for the co-polymerization of secondary and tertiary butyl alcohols and for mixed butyl and amyl alcohols (Whitmore and Mixon, 1941 Whitmore et al., 1941). 

Unfortunately, secondary and tertiary butyl alcohols (SBA and TBA) cannot be made by the Oxo process. Instead they are produced either by indirect or direct hydration of the corresponding olefin. Normal butylene gives SBA and isobutylene gives TBA. The processes are similar to the corresponding routes to IPA. 

The above-mentioned alcohols are by far the most common. Butyl alcohol is not as commonly used as die first four in die series, but it is used. Secondary butyl alcohol and tertiary butyl alcohol, so named because of the type of carbon atom in the molecule to which the hydroxyl radical is attached, must be mentioned because they are flammable liquids, while isobutyl alcohol has a flash point of 100°F. All of the alcohols of the first four carbon atoms in the alkanes, therefore, are extremely hazardous because of their combustion characteristics. 

The area normali/aiion method was applied to the determination of norma -, secondary-, iso-, and tertiary-butyl alcohol. To determine the relative response factor for the alcohols, a standard solution of the alcohols was prepared and its gas chromatogram observed. The results were as follows ... 

The lower alcohols are liquids with low boiling points. Methanol, ethanol and propanol are all miscible with water but n-butanol is only soluble 1 part in 10 in water and amyl alcohol is immiscible with water. If the surface area of the hydrocarbon chain of the alcohol is decreased, then water solubility will increase. Thus the order of water solubility for the primary, secondary and tertiary butyl alcohols is t-butanol > butanol-2-ol > n-butanol (Fig. 5.3) t-butanol is freely soluble in water. The properties of some alcohols are shown in Table 5.1. 

Modifying the reaction medium to involve liquid ammonia with metallic lithium, f-butyl alcohol, and white phosphorus, to which is added the haloalkane, is reported to provide the primary alkylphos-phine derived from the haloalkane.19 Similar results are reported for the reaction of red phosphorus with sodium acetylides20 and by treatment of red phosphorus with sodium metal in an organic medium followed by the addition of two equivalents of f-butyl alcohol and the haloalkane.21 The latter approach is noteworthy in that moderate yields (45%) are obtained for primary phosphines derived from secondary haloalkanes (Figure 2.6). Mixtures of tertiary phosphines bearing one or two acetylenic linkages are produced in low yield ( 15%) by the reaction of lithium acetylides with white phosphorus in liquid ammonia followed by addition of a haloalkane.22... 

Tertiary alcohols dehydrate most readily, primary alcohols least readily, and, unsurprisingly, secondary alcohols are intermediate. This relates to the relative stability of the intermediate carbocation. The temperature and concentration of the acid depends upon the type of alcohol. A primary alcohol, such as ethanol, requires concentrated acid and a very high temperature (180 degrees Celsius), while a tertiary alcohol, such as t-butyl alcohol, requires 20 percent sulfuric acid at 85 to 90 degrees Celsius. The process follows an El mechanism and produces the thermodyncimically more stable product. 

Terminally unsaturated fluonnated alkenoic acids can be obtained from poly-fluorocycloalkenes by reaction with potassium hydroxide in terf-butyl alcohol [24] (equation 26) The use of a tertiary alcohol is critical because primary and secondary alcohols lead to ethers of the cycloalkenes The use of a polar aprotic solvent such as diglyme generates enols of diketones [26] (equation 27) The compound where... 

Many secondary and tertiary halides undergo El elimination in competition with the SN1 reaction in neutral or acidic solutions. For example, when tert-butyl chloride solvolyzes in 80% aqueous ethanol at 25°, it gives 83% tert-butyl alcohol by substitution and 17% 2-methylpropene by elimination ... 

The order of acidity of various liquid alcohols generally is water > primary > secondary > tertiary ROH. By this we mean that the equilibrium position for the proton-transfer reaction (Equation 15-1) lies more on the side of ROH and OHe as R is changed from primary to secondary to tertiary therefore, tert-butyl alcohol is considered less acidic than ethanol ... 

Tertiary alcohols react with sulfuric acid at much lower temperatures than do most primary or secondary alcohols. The reactions typically are SN1 and El by way of a tertiary carbocation, as shown here for ferf-butyl alcohol and sulfuric acid ... 

---