Catechol diethyl ether

Catechol diethyl ether Catechol dimethyl ether >240 153,328... 

Catechol diethyl ether 22 47 32 — blue-grey dark red... 

Obtained by reaction of propionyl chloride with catechol diethyl ether in the presence of aluminium chloride in refluxing benzene for 40 min (49%) [6850]. Also refer to [6851-6854]. 

To a solution of chiral sulfide catalyst (9.5 mg, 0.05 mmol) and catechol (1 mg, 1 pmol) in t-BuOH (450 pL) was added the benzaldehyde (26 pL, 0.25 mmol), benzyl bromide (60 pL, 0.5 mmol) and n-Bu4NI (92 mg, 0.25 mmol). The resulting mixture was vigorously stirred at r.t. for 15 min (20-24 °C), and an aqueous solution of NaOH 28.5% (52 pL, 0.5 mmol, giving a 90 10 ratio of -BuOH water) was subsequently added. After 24 h of reaction, water (6 mL) was added, the two phases were separated, and the aqueous layer was extracted with diethyl ether (2x5 mL). The combined organic layers were dried over MgSC>4 and concentrated in vacuo. Purification by silica gel column chromatography afforded the two diastereoisomeric epoxides. 

Benzo-1,2-quinone (11) is prepared by the oxidation of 1,2-dihydrox-yhenzene (catechol) with silver(I) oxide in diethyl ether. This compound is not very stable and is also an oxidizing agent. 

The aluminium oxide was separated from the reaction mixture by filtration and thus a reaction liquid was obtained. The aluminium oxide separated by filtration was washed with 20 mL. of a 1 N aqueous solution of sodium hydroxide and the washing was added to the reaction liquid. The reaction liquid was adjusted to pH 6 by the addition of a 12 N hydrochloric acid and then the unaltered catechol was extracted three times with 50 mL. portions of diethyl ether. From the extract was recovered 1.61 g of catechol. 

The migration of oxygen from a quaternary center in a cyclohexadienone may be preferred to a carbon shift, when present as an ether or ester function rather than free hydroxy. Thus the p-quinol acetate (117) yields the orcinol monoacetate (118 79%) on treatment at room temperature with trifluoroacetic anhydride, and the p-quinol ether (119) forms the resorcinol diethyl ether (120 71%) in ethanolic sulfuric acid. In the second case, hemiketalization must intervene also some methyl shift (12%) is observed. With the quinol (121), treatment with acetic anhydride-sulfuric acid leads to the lactone (122) acetylation or lactonization probably precedes oxygen shift. A number of related examples can be found in the steroid area. - Thermal 1,3-shifts of p-quinol acetates can also be induced acetate (117) yields catechol acetate (123 50-60%, 45 °C) by way of isomerization of the first-formed acetate (124). In the o-quinol acetate series, 1,2-acetoxy shift is seen in (125) (126 92%) and in (127) (128 90%), both in... 

Methods involving LLE were developed for determination of phenol and other phenolic compounds. For example, for simultaneous determination of phenol, hydroquinone (66) and catechol (42) in urine, the samples were subjected to acid hydrolysis, saturation with sodium sulfate and LLE with diethyl ether. End analysis was by RP-HPLC on a Ci8 column, elution with sodium acetate-acetic acid buffer-acetonitrile gradients, and ELD. The recovery and reproducibility were generally over 90%. The method appears to be more sensitive than GC or HPLC with UVD. It is proposed for cigarette smokers and refinery workers exposed to low benzene concentrations. Good recoveries of these metabolites was attained at 0.1 to 50 mgL concentrations, with coefficients of variation of a few percent, both for within a day and between day determinations. ... 

Racemic 2,3-butanediol was converted to the racemic ditosy-late, which was then treated with catechol under the influence of NaOH in dimethylformamide (DMF) to yield the desired compounds, cis- and trans-2,3-dimethyl-l,4-benzodioxane [3] and [4]. The solid trans isomer [4] was obtained by repeated recrystallization from methanol. Column chromatography of the mother liquid using AloOj as adsorbent and petroleum ether and diethyl ether in a 1 1 ratio as eluent, gave pure liquid cis isomer [3]. By comparison with the PMR spectra (8) of pure trans- and cis-2,3-dimethyldi-oxane, the solid isomer was identified as trans, and the liquid isomer as cis. The compounds were further characterized by IR, NMR, CMR and elemental analyses. The CMR spectral data for 2 and 4 are summarized in Table I. 

Dimeth.y1-l,4-benzodioxane [3] [41. Into a stirred solution of 62 g (1.1 mole) K0H, 55 g (0.5 mole) catechol and 1.5 1 DMF in a flask, equipped with mechanical stirrer, pressure-equalizing addition funnel and condenser with drying tube, was added a solution of 2,3-butanediol ditosylate in 500 ml DMF. After stirring at room temperature for 24 hours and refluxing 24 hours, it was mixed with twice the volume of water and extracted with twice the volume of diethyl ether. The extract was dried over anhydrous MgS04 and condensed in a rotary evaporator. Fract. dist. (vac) gave 24 g mixture of cis- [3] and trans-2,3-dimethyl-1,4-benzodioxane [4]. Yield 29.23%. b.p. 96-100°C/6 mm. Anal. Calcd. for C-.H. O, C, 73.12 H, 7.36. Found C, 73.27 H, 7.40. u c c... 

Diisopropyl ether, which is occasionally used in the laboratory as a higherboiling ether, is especially liable to peroxide-formation.16 It is advisable to purify it by filtration through aluminum oxide, as for diethyl ether, and to store it over sodium wire or to stabilize it by addition of 0.001% of pyro-catechol, resorcinol, or hydroquinone.17... 

The reaction of methyllithium with the 4-methoxyphenylimine of 1-naphthaldehyde in the presence of a chiral ligand derived from a catechol dialkyl ether as an asymmetric controller (A) afforded the corresponding 1,2-addition product as an optically active amine in 70% ee (ref.93). A solution of methyllithium (R Li) (2.0 mmol) in diethyl ether was added at -tOO C to a solution of the imine (R = 1-Naph 1.0 mmol) and ligand A (2.6 mmol) in toluene and the reaction mixture was then stirred for 1 hour at the same temperarture and finally quenched with water. 

The reaction of resorcinol with prenyl halides in ethereal solution containing alkali metals or alkaline earth metals or their hydroxides has been instanced among a range of other compounds (ref. 11). By contrast the reagent, isoprene-magnesium-diethyl ether (ref.4) with either resorcinol (R = OH,R = H) or catechol (R = H, R = OH) only afforded chroman products. 

Simpson and Currell [32] used butanol - glacial acetic acid (97 3) as the mobile phase and sprayed the developed plate with catechol violet solution followed by irradiation of the plate for 10 minutes with UV radiation and a respray with catechol violet solution to detect the separated compounds as blue spots. This procedure can be applied to the detection of organotin compounds in PVC using a preliminary extraction of the additives from 5 g polymer with diethyl ether for eight hours. Ether is removed by evaporation and ethanol added to precipitate polymer which is then filtered off. If more accurate quantitative results are required it is necessary to perform an extraction additional to the diethyl ether extraction by using an azeatrope of carbon tetrachloride - methanol (2 1) for a further four hours. 

Numerous compounds can be separated successfully on 250 (xm-silica gel GF254 or HF254 layers, prepared in the usual way and with benzene as solvent (Fig. 106) (cf. also [282]). Pastuska and Petrowitz [191a], Fishbedst and co-workers [63] and Fiori and Marigo [62] have recommended equipolar solvents like petrol ether (BP 50—75° C)-diethyl ether (85 + 15) or n-hexane-ethyl acetate (95 -j- 5). Catechol and the other di- and triphenols then remain at the start point (Table 31). They can, however, be separated with more polar solvents [70]. 

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