Acetyl reaction + /3-naphthol

Bismuth(III) triflate tetrahydrate can be utilized as a more commercially available catalyst for the Fries rearrangement of PAs to 2-hydrox-yaryl ketones. In the reaction with 1-naphthyl acetate, bismuth triflate (10% mol) gives the best yield in 2-acetyl-l-naphthol, the amount of... 

The studies have been extended to esters that contain condensed polyaromatics in the phenolic substructure. For instance, 1-naphthyl acetate gives 2- and 4-acetyl-1-naphthols [22, 30, 42], whereas in the case of 2-naphthyl acetate, 1-, 3-, 6-, and (marginally) 8-acetyl-2-naphthols are obtained [27, 49-53]. The reaction also works with heterocyclic compounds, such as furan [54], pyridine [55-57], indole [58-60], or chromane [61] derivatives. 

A FI calorimetric biosensor was developed for the determination of dichlorvos (Zheng et al., 2006). The enzyme chicken liver esterase was used as the biorecognition element and acetyl-l-naphthol as the substrate. This enzyme was immobilized on an ion exchange resin, which was then packed in the enzyme reaction cell. The reference cell was filled with the same batch of the resin, but with a completely inactivated enzyme. As a result, the enzymatic reaction occurred in the enzyme reaction cell, but not in the reference cell and there was a temperature difference at the outlets of the two cells. The detection was based on the inhibition of the enzyme by the analyte, measuring the difference of the signal obtained with and without inhibition. 

Also obtained by reaction of propionic acid with 4-acetyl-a-naphthol in the presence of polyphosphoric acid at 100° for 15 min (44%) [7777]. 

Contribution to the overall rate from steps 1 and 3 are approximately equal, and that from 2 is thought to be quite small and although an alternative mechanism such as via (CH3COClH)+ which fits the kinetics may be possible, and indeed may be present, it is probably not as prominent as that via CH3CO+HCl2". Satchell107 found that the reaction of acetyl chloride with 0-naphthol was... 

Although in the reaction of acetyl chloride with 0-naphthol (in nitromethane) unionised halide was thought to be implicated, Satchell108 has shown that in the case of acetyl bromide (in acetonitrile) there is strong evidence that reaction proceeds via free and ion-paired acetylium ions, viz. 

The reactions of 0-naphthol and 4-methoxyphenol with acetyl, propionyl, butyryl, 0-chloropropionyl and chloracetyl chlorides in acetonitrile produce some striking kinetic results109. The behaviour of acetyl, propionyl and n-butyryl chlorides fit reasonably well into the pattern for acetyl chloride in nitromethane and acetyl bromide in acetonitrile. However, with chloracetyl chloride the mechanism is essentially a synchronous displacement of covalently bound chlorine by the phenol and this process is powerfully catalysed by added salt with bond breaking being kinetically dominant. When no added salt is present the rate of hydrolysis of chloracetyl chloride is ca. 8000 times slower than that of acetyl chloride. Although, normally, in second-order acylation reactions, substituents with the greatest electron demand have been found to have the fastest rates, the reverse is true in this system. Satchell proposes that a route such as... 

The case of diketonc 66 is more difficult to interpret, as this substrate undergoes a Mannich reaction initially on the acetyl group at position 4 of the 1-naphthol ring and is then further aminomethylated at the acetyl group in position 2. ... 

All types of alcohols and phenols are acylated by anhydrides. The reaction is catalyzed by a small amount of sulfuric acid, zinc chloride, acetyl chloride, sodium acetate, or pyridine. r-Butyl alcohol gives /-butyl acetate in 60% yield. Acetylation of phenols may be accomplished in an aqueous alkaline solution, the acylation proceeding more rapidly than the hydrolysis of the anhydride. The yields are above SX)%. Phenol, dihydroxybenzenes, naphthols, and phenols carrying nitro, amino, halo, carboxyl, or carbomethoxyl groups are acetylated by this procedure. ... 

It was first found that a chiral Yb catalyst, prepared in situ from Yb(OTf)3, (R)-(+)-l,T-bi-2-naphthol [(l )-BINOL], and a tertiary amine, in dichloromethane, was quite effective in enantioselective Diels-Alder reactions [36]. Some additives were also found to be effective not only in stabilizing the catalyst but also in controlling enantiofacial selectivity in the Diels-Alder reaction. When 3-acetyl-l,3-oxazolidin-2-one was combined with the chiral catalyst as an additive, the (2S,3R) form of the endo adduct was obtained in 93 % ee. When, on the other hand, 3-phenylacetylacetone was mixed with the catalyst as an additive, the (2R,3S) form of the endo adduct was obtained in 81 % ee [37]. 

Alkenes add photochemically to naphthalenes, normally to give products from 1.2 addition to the ring. In a report which appears to be a further example of this reaction Chow and co-workers reveal that Irradiation of mixtures of naphthols. or their methyl ethers, and acetyl acetone yield products derived from 1,2 addition of the enol form of the diketone to the naphthalene ring. Thus 1-naphthol gives the cyclobutanol (109) which retro-aldolises to the isolated product (110). However, the authors show that the excited state involved is In... 

The other part of the diaminonaphthol dihydrochloride solution is treated with acetic anhydride and then sodium acetate the reaction in aqueous solution effects selective acetylation of the amino groups and affords 2,4-diacetylamino-l-naphthol (4). Oxidation of 4 by Fe " and oxygen from the air is attended with cleavage of the acetylamino group at the 4-... 

Montmorillonite KIO and KSF are highly efficient for the O-acetylation of phenols and naphthols (equation 48). The reaction can be achieved in solvents such as CH2CI2 or under solvent-free conditions. 

Acetylation of naphthalene gives methyl naphthyl ketone, and sulfonation followed by alkaline fusion gives naphthol (Scheme 4.60). The methyl and ethyl ethers of naphthol are prepared from naphthol by reaction with the corresponding alkyl sulfate under basic conditions. These ethers are usually known by the shorter names of yara and nerolin, respectively. Yara, nerolin and methyl naphthyl ketone possess floral odours and are moderately important perfume ingredients. 

As well as phase 1 reactions, phase 2 reactions also show sex differences. Thus glucuronic acid conjugation of 1-naphthol (figure 4,4) is greater in male than female rats and this difference is also found in microsomes in vitro. The acetylation of sulphanilamide (figure 4.64) is also greater in male than female rats. Sex differences in metabolism depend on the substrate, however. For example, the hydroxylation of aniline or zoxazolamine shows little difference between the sexes, in contrast to the three-fold greater metabolism of hexobarbital or aminopyrine in male compared with female rats. 

The acetylation of alcohols and phenols with acetic anhydride and HSZ-360 zeolite at 60oC used no solvent. The acetate of 1-dodecanol was obtained in 98% yield, and the acetate from 1 naphthol in 100% yield.183 The acylation of anisole with acetic anhydride at 100oC without solvent using zeolite H-/8 gave 4-methoxyacetophenone (6.30) in 98%yield.184 The catalyst could be recovered, regenerated, and reused with no decrease in yield. These reactions show that not all zeolites are used at high temperatures in the vapor phase. 

Heptakis 6-0-t-butyldimethylsilyl-P-cyclodextrin, on reaction with 4-chloro-methyl-A -methyl-2-nitroaniline, affords the mono-3-substituted benzyl ether. P-Cyclodextrin carrying a 2-(naphthylmethyl) group at 0-6 exists with the aromatic rings within the cavity to an extent which is very temperature dependent. Temperature can therefore be used to control the degree of complexing of the aromatic system with a fluorescent naphthalene compound. Heptakis-[2,3-di-0-acetyl-6-deoxy-6-iodo]-P-cyclodextrin treated with 6-methoxycarbonyl-2-naphthol allowed access to the compound having naphthoic acid substituents at all of the primary positions, and this forms a very stable 1 1 complex with a merocyanine laser dye which is a mimic of the antenna function in photosynthesis and shows promise as a photochemical microreactor. Mono-[6-0-(8-qui-nolyl)]-P-cyclodextrin has been reported, and the stabilities of inclusion complexes with amino acid guests have been described. ... 

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