Alcohols and Amines

Primary alcohols are carbonylated to esters with ruthenium catalysts (Eq. 11.6) [2b, 22a]. 

Methanol reacts with CO in the presence of a Ru3(CO)i2 catalyst to give methyl formate. Although methyl formate is produced in industry from methanol and CO using bases as catalysts, more efScient catalysts are needed [22b]. Eormic or acetic esters of diols are carbonylated to give lactones or hydroxylic ester with [Ru(CO)3l3]7r catalysts (Eq. 11.7) [23]. 

Primary and secondary amines react with CO in the presence of Ru3(CO)j2 [24], RUCI3 3H2O [25] or Ru(II)(EDTA)(CO) [26] catalyst to give the corresponding N-sub-stituted formamides (Eq. 11.8). 

In-situ high-pressure IR spectroscopy revealed that in the carbonylation of piperidine by Ru3(CO)i2 catalyst under 0.1 to 1.0 MPa of CO, a mononuclear complex is the active reaction intermediate. A catalytic cycle involving RuH(NC5Hio)(CO)4 and RuH(CONC5Hio)(CO)3 has been proposed [27]. 

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A pletliora of different SA systems have been reported in tire literature. Examples include organosilanes on hydroxylated surfaces, alkanetliiols on gold, silver, copper and platinum, dialkyl disulphides on gold, alcohols and amines on platinum and carboxyl acids on aluminium oxide and silver. Some examples and references can be found in [123]. More recently also phosphonic and phosphoric esters on aluminium oxides have been reported [124, 125]. Only a small selection out of tliis number of SA systems can be presented here and properties such as kinetics, tliennal, chemical and mechanical stability are briefly presented for alkanetliiols on gold as an example. 

Although the acetylation of alcohols and amines by acetic anhydride is almost invariably carried out under anhydrous conditions owing to the ready hydrolysis of the anhydride, it has been shown by Chattaway (1931) that phenols, when dissolved in aqueous sodium hydroxide solution and shaken with acetic anhydride, undergo rapid and almost quantitative acetylation if ice is present to keep the temperature low throughout the reaction. The success of this method is due primarily to the acidic nature of the phenols, which enables them to form soluble sodium derivatives, capable of reacting with the acetic... 

The rather unreactive chlorine of vinyl chloride can be displaced with nucleophiles by the catalytic action of PdCb. The conversion of vinyl chloride to vinyl acetate (797) has been studied extensively from an industrial standpoint[665 671]. DMF is a good solvent. 1,2-Diacetoxyethylene (798) is obtained from dichloroethylene[672]. The exchange reaction suffers steric hindrance. The alkenyl chloride 799 is displaced with an acetoxy group whereas 800 and 801 cannot be displaccd[673,674]. Similarly, exchange reactions of vinyl chloride with alcohols and amines have been carried out[668]. 

In addition to the preparation of l-alkenes, the hydrogenolysis of allylic compounds with formate is used for the protection and deprotection of carboxylic acids, alcohols, and amines as allyl derivatives (see Section 2.9). 

At the other end of the reaction, deviations from idealized rate laws are attributed to secondary reactions such as degradations of acids, alcohols, and amines through decarboxylation, dehydration, and deamination, respectively. The step-growth polymers which have been most widely studied are simple... 

The salt is extremely hydroscopic and is used in dehumidification appHcations. It is very soluble in water (Table 4). The hydrates LiCl 2H20 [16712-19-9] and LiCl H2O [16712-20-2] precipitate at temperatures below 100°C. The anhydrous salt precipitates at 100°C. The salt has appreciable solubiHty in alcohols and amines. 

Nitro alcohols react with amines to form nitro amines. Such a reaction can be carried out with a wide variety of primary and secondary amines, both ahphatic and aromatic a basic catalyst is requited if aromatic amines are involved. The products of reactions between dihydric nitro alcohols and amines are nitrodiamines, many of which are good fungicides (qv). Dihydric nitro alcohols, primary amines, and formaldehyde react to yield nitrohexahydropyrimidines (4). Nitrohexahydropyrimidines can be reduced to the corresponding amines, some of which are good fungicides or bactericides, eg, hexetidine [141-94-6] (5-amino-l,3—bis(2-ethylhexyl)-5-methylhexahydropyrimidine). 

Oxalyl Chloride. This diacid chloride [79-37-8], ClCOCOCl, mol wt 126.9, is produced by the reaction of anhydrous oxaUc acid and phosphoms pentachloride. The compound vigorously reacts with water, alcohols, and amines, and is employed for the synthesis of agrochemicals, pharmaceuticals, and fine chemicals. 

Potassium Bases. Potassium metal is used to prepare potassium bases from reactions of the metal with alcohols and amines. 

Water is a by-product of the amination reactions in both methods. The mixture of ammonia, water, unconverted alcohol, and amines are... 

Halosdanes are very reactive toward protic chemicals. They generally react violendy with water, forming siUcon dioxide and the respective hydrohalogens. Other examples include reaction with alcohols and amines as follows ... 

Dicyanoacetylene, 2-hiitynedinitri1e, is obtained from dimethyl acetylenedicarboxylate by ammonolysis to the diamide, which is dehydrated with phosphoms pentoxide (44). It bums in oxygen to give a flame with a temperature of 5260 K, the hottest flame temperature known (45). Alcohols and amines add readily to its acetylenic bond (46). It is a powerhil dienophile in the Diels-Alder reaction it adds to many dienes at room temperature, and at 180°C actually adds 1,4- to benzene to give the bicyclo adduct (7) [18341 -68-9] C QHgN2 (47). 

PdCl2(Ph3P)2, dimedone, THF, 95% yield. This method is also effective for removing the allyloxycarbonyl group from alcohols and amines. 

The procedure described is essentially that of Shioiri and Yamada. Diphenyl phosphorazidate is a useful and versatile reagent in organic synthesis. It has been used for racemlzatlon-free peptide syntheses, thiol ester synthesis, a modified Curtius reaction, an esterification of a-substituted carboxylic acld, formation of diketoplperazines, alkyl azide synthesis, phosphorylation of alcohols and amines,and polymerization of amino acids and peptides. - Furthermore, diphenyl phosphorazidate acts as a nitrene source and as a 1,3-dipole.An example in the ring contraction of cyclic ketones to form cycloalkanecarboxylic acids is presented in the next procedure, this volume. 

Calcium oxide. (Preheated to 700-900° before use.) Suitable for alcohols and amines (but does not dry them completely). Need not be removed before distillation, but in that case the head of the distillation column should be packed with glass wool to trap any calcium oxide powder that might be carried over. Unsuitable for acidic compounds and esters. Suitable for drying gaseous amines and ammonia. 

Chirazymes. These are commercially available enzymes e.g. lipases, esterases, that can be used for the preparation of a variety of optically active carboxylic acids, alcohols and amines. They can cause regio and stereospecific hydrolysis and do not require cofactors. Some can be used also for esterification or transesterification in neat organic solvents. The proteases, amidases and oxidases are obtained from bacteria or fungi, whereas esterases are from pig liver and thermophilic bacteria. For preparative work the enzymes are covalently bound to a carrier and do not therefore contaminate the reaction products. Chirazymes are available form Roche Molecular Biochemicals and are used without further purification. 

Acylation of various oxygen functions by use of common and commercially available fluonnated carboxylic acid denvatives such as trifluoroacetic anhydride or the corresponding acyl halides have already been discussed sufficiently in the first edition [10] Therefore only exceptional observations will be described in this section In the past 15 years, many denvatizations of various nonfluonnated oxygen compounds by fluoroacylation were made for analytical purposes. Thus Mosher s acid chlorides for example became ready-to-use reagents for the determination of the enantiomeric purity of alcohols and amines by NMR or gas-liquid chromatographic (GLC) techniques [//] (equation 1)... 

Aryl esters, prepared from the phenol and an acid chloride or anhydride in the presence of base, are readily cleaved by saponification. In general, they are more readily cleaved than the related esters of alcohols, thus allowing selective removal of phenolic esters. 9-Fluorenecarboxylates and 9-xanthenecarboxylates are also cleaved by photolysis. To permit selective removal, a number of carbonate esters have been investigated aryl benzyl carbonates can be cleaved by hydrogenolysis aryl 2,2,2-trichloroethyl carbonates by Zn/THF-H20. Esters of electron-deficient phenols are good acylating agents for alcohols and amines. 

In the presence of DCC, 140 is allowed to react with both l-hydroxy-5-nitroindole (36) and 1-hydroxy-1,2,3-benzotriazole (141). Interestingly, their corresponding active esters, 142 and 143, are obtained in excellent yields as stable crystalline compounds. Both compounds are found to react with variety of nucleophiles, such as alcohols and amines, to produce 144 and 145 in good to excellent yields, as can be seen from the typical examples shown in Scheme 22 (2001H2361). As aresult, it becomes possible to produce various kinds of derivatives of wasabi phytoalexin utilizing 142 and 143. 

The Frumkin isotherm can be regarded as a general isotherm from which both the Temkin and Langmuir isotherms can be obtained as special cases. Szklarska-Smialowski and Wieczorek found that the adsorption of various aliphatic compounds (acids, alcohols and amines) on steel in H2SO4 conformed with the Frumkin isotherm. 

Table 18-L regularities in names of alkanes, alcohols, and amines...

Hlasta and Deng have developed a two-step solid-phase method for the decoration of azoles at C-2 [188]. First, imidazole was loaded onto a polystyrene-bound carbamyl chloride via a benzaldehyde bridge (Fig. 40). The 2-substi-tuted imidazole was efficiently cleaved in good yields in the presence of various nucleophiles (i.e., water, alcohols, and amines), trifluoroacetic acid, and boron trifluoride under microwave irradiation in a closed vessel at 120 °C for 5 min. 

Fig. 39. Molecules 141-145 and can function as host molecules for the selective complexation of salts, alcohols, and amines (146 and 147)...

Another philosophy would be the one-pot resolution of two different nucleophiles, alcohol and amine [39]. An acylated racemic alcohol reacts with a racemic amine in... 

Gotor-Fernandez, V., ReboDedo, F. and Gotor, V. (2007) Preparation of chiral pharmaceuticals through enzymatic acylation of alcohols and amines, in Biocatalysis in the Pharmaceutical and Biotechnology Industry, (ed. R.M. Patel), Dekker, Taylor and Francis, New York, Chapter 7, pp. 203-248. 

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