Alcohols from acid derivatives

Another example of the effect of resonance is in the relative acidity of carboxylic acids as compared to alcohols. Carboxylic acids derived from saturated hydrocarbons have ipK values near 5, whereas saturated alcohols have pA values in the range 16-18. This implies that the carboxylate anion can accept negative charge more readily than an oxygen on a saturated carbon chain. This can be explained in terms of stabilization of the negative charge by resonance, ... 

SECTION 32 ALCOHOLS AND THIOLS FROM ACID DERIVATIVES... 

Further examples of the reaction ROH -> RC02R are included in Section 107 (Esters from Acid Derivatives) and in Section 45 A (Protection of Alcohols and Phenols). 

Flexible aliphatic compounds are also selectively fluorinated. Such substrates may be alkanes, alcohols, carboxylic acid derivatives or ketones as long as the electron-withdrawing group is far enough from the reacting center (Table 2).44 There are differences in yields and reaction rates which are qualitatively easily understood and are directly related to the electron density of the reactive C —H bond. 

Acids can also be made by the oxidation of alcohols and acid derivatives are available from the acids via the acid chloride. Since acids can also be reduced to alcohols, there is a great deal of interdependence in all these methods. The synthesis of carbonyl compounds by one-group C-C disconnections is discussed more fully in chapter 13. 

As stated on page 115, the action of hydriodic acid on polyacid alcohols does not yield, as might be expected, the poly-iodine derivatives, but mono-iodine derivatives. Thus from glycerol, isopropyl iodide is obtained from erythrite, normal secondary butyl iodide from man-nite, the normal secondary hexyl iodide. These iodides, as pointed out, may be converted into the corresponding alcohols. The method is of practical value in the preparation of tertiary alcohols from acid-chlorides and zinc alkyls. — Butlerow s synthesis. Compare page 126. 

Esters from Acid Derivatives) and in Section 45A (Protection of Alcohols and Thiols). 

Hydrogen peroxide sulfuric acid Alcohols from ethylene derivatives... 

Hydration of carbon-carbon double bonds s. a. Alcohols from ethylene derivatives —, preferential 16, 194 19, 183 —, stercospecific 16, 194 Hydrazides s. Carboxylic acid... 

Stereospecific reactions alcohols from ethylene derivatives 19, 188 amines, axial, from sulfonic acid esters 19, 418 ethylene derivatives from glycols 19, 962... 

The residue in the flask is either a solution or a suspension of the potassium salt of the acid derived from the ester in diethylene glycol. Add 10 ml. of water and 10 ml. of ethyl alcohol to the residue and shake until thoroughly mixed. Then add a drop or two of phenolphthalein and dilute sulphuric acid, dropwise, until just acid. Allow the mixture to stand for about 5 minutes and then Alter the potassium sulphate. Use the clear filtrate for the preparation of a sohd derivative or two of the acid (see Section 111,85,4). 

The derivative selected in any particular instance should be one which clearly singles out one compound from among all the possibilities and thus enables an unequivocal choice to be made. The melting points of the derivatives to be compared should differ by at least 5-10°. Whenever possible, a derivative should be selected which has a neutralisation equivalent as well as a melting point (e.g., an aryloxyacetic acid derivative of a phenol. Section IV,114,4, or a hydrogen S nitrophthalate of an alcohol. Section 111,25,5). 

Aldehydes fiad the most widespread use as chemical iatermediates. The production of acetaldehyde, propionaldehyde, and butyraldehyde as precursors of the corresponding alcohols and acids are examples. The aldehydes of low molecular weight are also condensed in an aldol reaction to form derivatives which are important intermediates for the plasticizer industry (see Plasticizers). As mentioned earlier, 2-ethylhexanol, produced from butyraldehyde, is used in the manufacture of di(2-ethylhexyl) phthalate [117-87-7]. Aldehydes are also used as intermediates for the manufacture of solvents (alcohols and ethers), resins, and dyes. Isobutyraldehyde is used as an intermediate for production of primary solvents and mbber antioxidants (see Antioxidaisits). Fatty aldehydes Cg—used in nearly all perfume types and aromas (see Perfumes). Polymers and copolymers of aldehydes exist and are of commercial significance. 

Additives. Because of their versatility, imparted via chemical modification, the appHcations of ethyleneimine encompass the entire additive sector. The addition of PEI to PVC plastisols increases the adhesion of the coatings by selective adsorption at the substrate surface (410). PEI derivatives are also used as adhesion promoters in paper coating (411). The adducts formed from fatty alcohol epoxides and PEI are used as dispersants and emulsifiers (412). They are able to control the viscosity of dispersions, and thus faciHtate transport in pipe systems (413). Eatty acid derivatives of PEI are even able to control the viscosity of pigment dispersions (414). The high nitrogen content of PEIs has a flame-retardant effect. This property is used, in combination with phosphoms compounds, for providing wood panels (415), ceUulose (416), or polymer blends (417,418) with a flame-retardant finish. 

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