4- Tolyl acetate

The 2-chloro-l,2-difluorovinyl ether of furfuryl alcohol also rearranges at — 35l C despite loss of aromaticity. Methanolysis then affords ester 12, which requires heating to 90 C for rearoma-tization. The 2-chloro-l,2-difluorovinyl ether of benzyl alcohol is sufficiently stable to be isolated but rearranges at room temperature methanolysis affords chlorofluoro(2-tolyl)acetic acid ester 13. Apparently, a 1,3-benzyl shift is not favored in this case, as opposed to other fluorine-containing vinyl benzyl ether systems discussed in Section 5.1.3. 

As to the question of intra- or intermolecularity of the rearrangement there are three opinions, one which states that the reaction is completely intermolecular148, another supports a concurrent intra- and intermolecular mechanism149, whilst a third claims that the reaction is completely intramolecular150. Evidence for the intermolecular mechanism is based on trapping experiments such as the reaction of meta-tolyl acetate (CVIII) in the presence of we/a-chlorobenzoyl chloride (CIX) when the acylation product (CX) is formed rather than the products of... 

Simultaneous inter- and intramolecular reaction have been suggested on the basis153 of the varying yields of the ortho and para isomers and also of the acetyl-ated product of added diphenyl ether as the dilution was changed 5-fold in the reaction of meta-tolyl acetate in the presence of diphenyl ether. In particular it was noted that as the dilution increased the amounts of acetylated diphenyl ether and the para product both decreased whilst that of the ortho product rose very slightly. 

The pH dependence of the reaction of m-tolyl acetate with cyclohexa-amylose implies a pAa of 12.1 for the catalytically active secondary hydroxyl group (Van Etten et al., 1967b). Although this pK at first appears low for the ionization of an aliphatic alcohol, it is consistent with the value of 12.35 determined thermodynamically for the ionization of the secondary hydroxyl groups of the ribose moiety of adenosine (Izatt et al., 1966 Christensen et al., 1966), and with the value of 12.2 reported by Lach for the... 

Ethyl 2-fluoro-2-(4-tolyl)acetate (15) Typical Procedure 30... 

A solution of mixed A. jV-diethyl-l,l,2,3,3,3-hexafluoropropanamine (10) and 11 (2.2 g, 10 mmol) in CH,C12 (15 mL) was added dropwise to a solution of ethyl 2-hydroxy-2-(4-tolyl)acetate (14 0.78 g, 4 mmol) in CH2C12 (20 mL) at rt. After stirring for 24 h, the mixture was poured into H20 and was extracted with i-Pr20. The combined organic layers were washed with H20, dried (Na,CO,) and concentrated. The residue was subjected to column chromatography (silica gel, hexane/EtOAc 9 1). The first elution gave ethyl 2-fluoro-2-(4-tolyl)acetate (15) yield 0.47 g (60%). 

Methylbenzyl Acetate FEMA No. 3072 o-Tolyl Acetate 164.20/Ci0Hi2O2/ ch2oocch3 ch3 colorless liq/ sweet, nutty s—most fixed oils ss—prop glycol ins—gly 1 mL in 2 mL 70% ale remains clear on dilution... 

SYNS ACETIC ACID-4-METHYLPHENYL ESTER p-ACETOXYTOLUENE 4-ACETOXYTOLUENE p-CRESOL ACETATE p-CRESYL ACETATE (FCQ FEMA No. 3073 4-METHYLBENZOIC ACID METHYL ESTER p-METHYLPHENYL ACETATE NARCEOL PARACRESYL ACETATE O p-TOLYL ACETATE p-TOLYL ETHANOATE... 

C9H5CIN203 3>chloro-4 nitroquinoline-1-oxide 14100-52-8 405.90 34.922 2 16003 C9H7F302 a,a,a-trifluoro-p-tolyl)acetic acid 32857-62-8 476.15 41.597 2... 

C9H10O3 2-hydroxy-2-(m-tolyl)acetic acid. .. 520.33 45.841 2 16890 C9H11N 2,3-dihydro-1 H-inden-5-amine 24425-40-9 521.15 45.920 1.2... 

That the reaction is not an intramolecular rearrangement has been shown by the fact that a mixture of products is obtained when aluminum chloride is added to a solution of o-chloro-p-tolyl acetate and p-tolyl benzoate.66 Evidence for a common intermediate in this reaction and... 

The negative effect of sulfolane on the formation of o-HAP, already observed during the transformation of pure PA, could be explained by a competition between sulfolane and PA for adsorption on the acid sites. However, if this were the case, sulfolane would also decrease the initial rates of p-HAP and p-AXAP formations which involve adsorbed PA species (for the acylation of P or of PA). The initial rates of production of p-HAP and p-AXAP in sulfolane and in dodecane are less easy to compare than the rates of o-HAP production. Indeed the apparent greater production of p-HAP and p-AXAP in sulfolane could be due to the greater catalyst stability in this solvent. However, from the two experiments with H-BEA-10 (lOOmg and 500 mg) and from the experiment with H-BEA-70 it can be concluded that the initial production of p-HAP and p-AXAP is faster in sulfolane than in dodecane. Moreover, the same conclusion can be drawn from acylation of anisole with phenyl acetate or p-tolyl acetate the initial rate of formation of p-methoxyacetophenone is higher in sulfolane than in dodecane. Therefore sulfolane would have, besides a negative effect on the reaction rates due to its... 

The rate of anisole acylation depended on the acetate (Table 2). Initially it was about 1.5 times greater with p-tolyl acetate and with 2-methoxyphenyl acetate than with phenyl acetate, slightly lower with 2-methoxyhydroquinone diacetate, 2.5 times lower with the hydroquinone diacetate and very low with 2,4,6-trimethylphenyl acetate. The low reactivity of this latter acetate can be related to limitations in the rate of diffusion of this bulky compound in the BEA zeolite pores. Furthermore, a greater reactivity of this acetate was found with HFAU zeolites whose pore size is greater. Curiously, with hydroquinone diacetate (but not with the 2-methoxyhydroquinone acetate), there was a quasi immediate deactivation. We are carrying out additional experiments so as to understand how the reactivity of aromatic acetates changes with their nature and the zeolite acidity and porosity. 

With p-tolyl acetate, in which the position in para to the acetate group is blocked by the methyl group, no intermolecular reaction is observed and only 2-hydroxy-... 

Beilstein Handbook Reference) Acetic acid, 4-methylphenyl ester Acetic acid, p-tolyl ester 4-Aoetoxytoluene p-Acetoxytoluene AI3-01266 BRN 1908125 p-Cresol acetate p-Cresyl acetate Cresyl acetate Cresyl acetate, p- Cresylic xetate, P- EINECS 205-413-1 FEMA No. 3073 4-Methylbenzoic acid methyi ester 4-Methylphenyl acetate p-Methylphenyl acetate Narceol NSC 43244 Paracresyl acetate p-Tolyl acetate 4-Tolyl acetate p-Tolyl ethanoate. A synthetic perfume. Liquid bp = 212.5° d = 1.0512 Xm = 265, 271 nm (e = 446, 406, MeOH) slightly soluble in H2O, soluble in EtOH, EtzO, CCI4, CHCI3. 

Bromination of m-tolyl acetate in CC14 under irradiation by a 500 W lamp gives a 75 % yield of 3-acetoxybenzylidene bromide, which is converted in 70% yield into m-hydroxy-benzaldehyde by sodium formate in alcohol.431... 

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