Aminophenol group

Reduction to aminophenol. Reduce about 0 5 g. of o-nitrophenol with cone. HCl and tin as described on p. 385. After a few minutes the yellow molten o-nitrophenol disappears completely, the solution becoming homogeneous and colourless due to the formation of 0-aminophenol (which is soluble in HCl). Cool and add 30% aqueous NaOH solution note that a white precipitate is first formed and then redissolvcs in an excess of NaOH, and that the solution does not develop an orange coloration, indicating that the nitro-group has been reduced. 

Reactive xanthene dyes with P-hydroxyethylsulfonyl groups, as exemplified by stmcture (29), provide brilliant shades and excellent washfastness on cotton (40). The sulfutein derivative (29) is synthesized by condensing 3-aminophenol-P-hydroxyethylsulfone with... 

A group of aminoxanthenes, ie, pyra2oloxanthenes, is used as color formers ia pressure or heat-sensitive imaging papers (43). These compounds are colorless, but, upon contact with acidic electron-accepting material, are converted to resonance forms that are lightly colored. An example is stmcture [58294-05-6] (35), which forms upon the condensation of A[,A/-diethyl-y -aminophenol with phthalic anhydride, followed by addition of 6-hydroxyinda2ole ia 80% sulfuric acid (44). 

The chemical properties and reactions of the aminophenols and their derivatives are to be found in detail in many standard chemical texts (25). The acidity of the hydroxyl function is depressed by the presence of an amino group on the benzene ring this phenomenon is most pronounced with 4-aminophenol. 

The amino group behaves as a week base, giving salts with both mineral and organic acids. The aminophenols are tme ampholytes, with no 2witterion stmcture hence they exist either as neutral molecules (4), or as ammonium cations (5), or phenolate ions (6), depending on the pH value of the solution. 

The aminophenols are chemically reactive, undergoing reactions involving both the aromatic amino group and the phenoHc hydroxyl moiety, as weU as substitution on the benzene ring. Oxidation leads to the formation of highly colored polymeric quinoid stmctures. 2-Aminophenol undergoes a variety of cyclization reactions. 

Acylation. Reaction conditions employed to acylate an aminophenol (using acetic anhydride in alkaU or pyridine, acetyl chloride and pyridine in toluene, or ketene in ethanol) usually lead to involvement of the amino function. If an excess of reagent is used, however, especially with 2-aminophenol, 0,A/-diacylated products are formed. Aminophenol carboxylates (0-acylated aminophenols) normally are prepared by the reduction of the corresponding nitrophenyl carboxylates, which is of particular importance with the 4-aminophenol derivatives. A migration of the acyl group from the O to the N position is known to occur for some 2- and 4-aminophenol acylated products. Whereas ethyl 4-aminophenyl carbonate is relatively stable in dilute acid, the 2-derivative has been shown to rearrange slowly to give ethyl 2-hydroxyphenyl carbamate [35580-89-3] (26). 

Substitution of various groups by amino or hydroxyl functions is industrially unimportant for the production of 2- and 4-aminophenol, but this type of reaction is used for the synthesis of 2- and 4-aminophenol derivatives. However, 3-aminophenol caimot be obtained easily by reduction. It is made by the reaction of 3-aminobenzenesulfonic acid [121 -47-1] with sodium hydroxide under fusion conditions (5—6 h 240—245°C). The product is purified by vacuum distillation (25). 

Acid YeUow 23 (31), commonly known as Tartraziae, stiU maintains sales of nearly 0.5 million /yr ia the United States. It was first discovered ia 1884 and is made by coupling equimolar quantities of diazotized sulfarulic acid to 3-carboxy-l- -sulfophenyl)-5-pyrazolone. Other monoazopyrazolone dyes of commercial importance iaclude Acid YeUow 17 (32) (sulfarulic acid — l-(2,5-dichloro-4-sulfophenyl)-3-methyl-5-pyrazolone and Acid YeUow 40 [6372-96-9] (33) (Cl 18950) (p-aminophenol l-(4-chloro-2-sulfophenyl)-3-methyl-5-pyrazolone) foUowed by esterification of the phenoUc hydroxy group with -toluenesulfonyl chloride. 

Aminophenols. Reaction of chloroformate with aminophenols (qv) also takes place at the more reactive amino group selectively. Thus (9-aminophenol [95-55-6] gives benzoxazolone [59-49-4] by cyclization of the intermediate carbamate (31). 

The employment of non-protic electrophiles for the foregoing type of cyclizations as illustrated in Scheme 8 has the particular merit of leaving a useful point of departure for further transformations. Comparable cyclizations of 2-allyl-3-aminocyclohexenones with mercury(II) acetate are preceded by dehydrogenation to the corresponding 2-allyl-3-aminophenol as shown in Scheme 9 82TL3591). The preferred direction of cyclization depends upon the nucleophilicity of the amino group. 

An important group of colouring matters, known as the rhodamines, is obtained from phthalic anhydride and w-aminophenol and its derivatives. They hai e a constitution sinylai... 

To determine the direction of primary attack at aminobutynones in the presence of competing hydroxyl and amino groups in the benzene ring, the reaction of 4-dimethylaminobut-3-yn-2-one with m-aminophenol has been examined (65-70°C, THF, 20 min). It was found that the hydroxyl group reacts first to form (9,A-ketenacetal of 4-dimethylamino-4-(m-aminophenoxy)-but-3-en-2-one (363) (88ZOR1165). 

The form amido- should be so translated only when it is in combination with an acid group. Usually it is to be translated amino- as, Amidopropion-sdure, aminopropionic acid Amidophenol, aminophenol. The same holds for imido-, anUido-, etc. 

N-substituted phenylhydroxylamine derivatives, e.g. N-acetyl and N-sulphonic acid, also form the para-aminophenol", but more bulky groups prevent reaction, it is thought by steric hindrance to the approach of the hydronium ion. -substituted phenylhydroxylamines, on the other hand form only the ortho product, it is thought via an intramolecular rearrangement, e.g. 

The keto acids (66) having a tertiary amino group at 4-position are successfully prepared by the reaction of 3-ferf-aminophenols (69) with phthalic anhydride in organic solvent such as benzene, toluene, or chlorobenzene at elevated temperature, though each keto acid has its own... 

On the other hand, the reaction of 3-,sec-aminophenols (71) with phthalic anhydride does not give the corresponding keto acids (72). The keto acids (72) having a secondary amino group at 4-position are prepared by the reaction of 3-sec-aminophenols (71) with phthalimide at 150-220°C in the presence of boric acid, followed by hydrolysis of the intermediate carboxamide with aqueous sodium hydroxide (Eq. 3). 

A tridentate N02 donor set complex was formed from 2-pyridinecarboxaldehyde N-oxide and 2-aminophenol and gave mononuclear and trinuclear compounds. The trinuclear zinc complex was structurally characterized and revealed bridging acetate groups, [ZnLZn(OAc)4ZnL].865... 

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