The Reactions of Hydroxy Compounds

To 2 ml of ethanol in a test tube, with the mouth directed away from you, add 5 drops of acetyl chloride. Note the gas evolved. Add 2 ml of water and note the odor of the product. Can this reaction be of any use for detection of the hydroxyl group Repeat the test, adding 5 drops of phosphorous trichloride. 

9 tubes in a rack. Place in each 10 ml of 0.05 per cent potassium permanganate solution (neutral) then add to eight of the tubes 

10 drops respectively of one of the following methanol, ethanol, 1-butanol, 2-butanol, trimethyl carbinol, cyclohexanol, phenol, and benzyl alcohol. Retain the ninth tube as a control. Shake for ten seconds, observe the color immediately afterwards, and allow 

The introduction of the hydroxyl group into the benzene nucleus increases the ease with which its hydrogen atoms can be replaced by substitutions. Add 1 ml of one per cent solution of bromine in carbon tetrachloride to 2 ml of 10 per cent solution of phenol. Recall the formation of bromobenzene. 

Note For semimicro work the student may choose between the preparation of ethyl and n-butyl ethers. The macro preparation of ethyl ether is not recommended for beginners, particularly vdien the group of students is large. 

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Both aromatic and aliphatic fluoroformates 7 can be readily prepared from phenols or alcohols and carbonyl difluoride and treated with sulfur tetrafluoride without isolation. Hydrogen fluoride evolved in the reaction of hydroxy compounds with carbonyl di fluoride serves as a catalyst for the consecutive reaction with sulfur tetrafluoride.15<)-162 This provides a general, convenient, direct synthesis of aryl and alkyl trifluoromethyl ethers 5 from phenols and alcohols. When the intermediate fluoroformate 7 is isolated prior to treatment with sulfur tetrafluoride, at least one mole equivalent of hydrogen fluoride is necessary to promote the fluorination reaction. 159 163 Representative examples of the conversion of hydroxy compounds 6 into trifluoromethyl ethers 5 via intermediate fluoroformates 7 are given (for other examples 7 -> 5, see Houben-Weyl, Vol. E4, pp 628. 629). 

In mixed trifluoroacetic anhydrides, the strong electron-withdrawing tri-fluoroacetyl group polarizes the bonds to the anhydride oxygen in such a way that it tends to split to acylium cation and trifluoroacetate anion [/0/. Generally, the products of the reaction of hydroxy compounds with acyl trifluoroacetates are esters of carboxylic acids and trifluoroacetic acid, because the acyl carbonyl is better fit for a nucleophilic attack than the carbonyl next to the trifluoromethyl group [707]. 

When Af-hydroxy-3,4,5-triphenylisoxazolidine is treated with cone. H2S04, a mixture of 3,4,5-triphenylisoxazolidine, 3,4,5-triphenyl-2-isoxazoline, and 3,4,5-triphenylisoxazole was obtained.3 The reaction of hydroxy compound 64 is more complex. Dilution of a cone. H2S04 solution of the compound 64 affords 3-hydroxyisoxazolidine. When the... 

The reaction of hydroxy compounds with numerous nucleophiles in the presence of diethyl azodicarboxylate/triphenylphosphine has been investigated . Epimerization with simultaneous O-acylation in the presence of the above reagents, a method initially used in steroid chemistry has been successfully applied to prostaglandin derivatives Recently, this method has been used for the preparation of prim. (lR)[l- Hi]- and -alcohols of high optical purity . 

The thermal decomposition, combustion, and fire retardancy of PU materials have been reviewed. " Upon heating, the polymer decomposes primarily by regenerating the precursor moieties polyols, isocyanates, and amines. Complete volatilization of the resulting products is prevented by the formation of thermally stable isocyanurate rings (produced by trimerization of isocyanates) and the formation of substituted ureas (produced by the reaction of hydroxy compounds with the carbodiimides generated by dimerization of isocyanates). ... 

These rate constants are for the cinnamoylation of hydroxy compounds by cinnamic anhydride catalyzed by A-methylimidazole. The reaction is first-order in each reactant. The kinetics were followed spectrophotometrically in acetonitrile solution. Analyze the data that is, attempt to account for the relationship between structure and reactivity. 

Not only water and alcohols, but also other oxygen compounds, are able to react covalently with acylium ions. In the case of hydroxy compounds the product is stabilized by loss of the proton from the hydroxyl group, but certain ethers give an analogous reaction in which the product is stabilized by loss of a carbonium ion.288 Using acetyl chloride with silver perchlorate in nitromethane as the source of acetyl... 

Depending on the conditions, reactions (I) and (II) can be carried out either concurrently or consecutively. If one works from the outset in alkaline medium, for example, by dropping the desired amount of epichlorohydrin into the mixture of hydroxy compound and the equivalent amount of aqueous alkali hydrox-... 

We wish to report a new approach to condensation reactions of hydroxy compounds related to the Ritter reaction, the Beckmann rearrangement and peptide formation based on easily accessible pentaco-ordinate spirophosphoranes of the type (3) (6 - ). 

A very selective method of oxidizing secondary alcohols is bromino-lysis of tributyltin ethers prepared by the treatment of hydroxy compounds with bis(tributyl)tin oxide. The reaction is regio- and stereospecific and is an important means of oxidizing unprotected glycosides [734]. 

The third group of derivatization reactions of hydroxy compounds for GC analysis includes formation of their alkyl or substituted benzyl ethers... 

Neopentyl tosylate reacts with LiCl in HMPA and gives the chloride with clean inversion without rearrangement (equation 5). Another example of this reaction is the conversion of allylic tosylates to chlorides without rearrangement or reaction of the sensitive acetal (equation 6). Dimethylaminopy-ridine is a useful catalyst for the transformation of hydroxy compounds to chlorides with tosyl chloride. ... 

The only known alternative procedure for the preparation of alkynyl(phenyl)iodonium arylsulfonates, the latest member of the family of polyvalent Iodine compounds, involves the reaction of [hydroxy(tosyloxy)iodo]benzene. PhlOH-OTs, with terminal alkynes as first reported by Koser and elaborated by us. This procedure has a number of shortcomings. Formation of the desired alkynyliodonium salt is usually accompanied by a related vinyl species, R(TsO)C=CHIPh-OTs, that both decreases the yields and causes purification problems. Furthermore, when the alkyl substituent of the starting alkyne is small, such as CH3, n-Pr, n-Bu, etc., this procedure gives either no product or low yields at best. 

On a related front, the reactions of carbonyl compounds with metaliated derivatives of 2-methylthia-zoline furnish adducts (85). Although the initial nucleophilic addition occurs smoothly with a wide variety of aldehydes and ketones, the intermediate P-hydroxythiazolines (85) suffer thermal reversion upon attempted purification by distillation. Moreover, attempted cleavage of the corresponding P-hydroxythia-zolidines, which are readily produced from (85) upon dissolving metal reduction (Al-Hg), leads to the formation of p-hydroxy aldehydes only in simple systems numerous complications arising from dimerization, dehydration and retroaldol processes of the products usually intervene. Consequently it is necessary to protect the initial 1,2-adducts (85 = H) as the corresponding 0-methoxymethyl ether... 

A wide range of nucleophiles has been shown to attack coordinated carbonyl compounds. The products depend upon the fate of the tetrahedral hydroxy intermediate formed. In the reaction of carbonyl compounds and amines the loss of water results in the formation of imines, and this methodology has widespread synthetic application. A novel sexidentate macrocyclic ligand (26) has been prepared by template methods. The formation of the hydrazone from hydrazine and... 

Depending on the conditions, reactions (I) and (E) can be carried out either concurrently or consecutively. If one works from the outset in alkaline medium, for example, by dropping the desired amount of epichlorohydrin into the mixture of hydroxy compound and the equivalent amount of aqueous alkali hydroxide at 50-100°C, then the addition reaction and the HQ elimination occur side by side (Example 4.24). On the other hand, if the hydroxy compound and epichlorohydrin are allowed to react in nonaqueous medium in the presence of acid catalysts, the corresponding chlorohydrin is first formed this can then be transformed into the epoxy compound in a second step by reaction with an equivalent amount of alkali hydroxide. 

Benzenesulfonyl isocyanate is good reagent for the characterization of hydroxy compounds, alcohols and even hindered phenols, for which derivative formation is difficult by other means. The reaction is carried out in benzene or toluene, without heating in the case of alcohols and usually at 80° for 1 hr. with phenols. E. s. J. W. McFarland and J. B. Howard, J. Org. Ghem. 30, 957 (1965). 

An ester interchange reaction occurring when ester is heated in the presence of hydroxy compound (alcoholysis) or acid compound (acidolysis). Since esterification is reversible, the transesterification occurs between mixed esters in the presence of (thermally activated) low concentration of volatile reaction by-products. Ester-amide exchange can also be accomplished by similar (catalyzed) process. 

No further oxidation of the amine products occurs. In the reaction with 2-mercaptoisobutyric acid, there is no evidence for intermediate complex formation and the increase of rate with decreasing [H+] is consistent with the rate law Rate = A z/irh[Co ] [RSH]/[H+] in which the ion CoOH + is the oxidant. The radical character involved in the oxidation of hydroxy-compounds by cobalt has been confirmed by e.s.r. The reductants chosen in this study were glucose, sorbitol, and methyl-a-glucoside. Careful removal of oxygen resulting from the oxidation of water has shown well defined triplets of intensity 1 2 1 g=2.004 0.002) which are consistent with displacement of H from a secondary carbon atom. Thus with glucose the radical (3) is formed. The mechanism of reaction involves an intermediate complex formation,... 

The principal methods used for the derivatization of hydroxy compounds may be classified on the basis of the following types of chemical reactions ... 

The choice of chemical reactions available for the derivatization of hydroxy compounds in aqueous samples (when it is impossible to remove the large excess of water) is relatively limited compared with the whole... 

Other Reactions. Shi and co-workers have reported an unusual reaction of -hydroxy a-diazo carbonyl compounds with compound (1). When the reaction of -hydroxy a-diazo carbonyl compounds and compound (1) is carried out in the presence of EtsN, instead of the desired bisdiazo esters, /3-(/9-tolylsulfonyl) a, -unsaturated carbonyl compounds or /3-(/9-tolylsulfonyl) a-diazo esters are obtained in good to high yields (eq 15). ... 

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