Ozonolysis of olefins VIII. Synthesis of phenoxyacetaldehydes by ozonolysis of allylphenylethers

Synthesis of aryloxyacetaldehydes and N-(aryloxyethyl)cyclohexanamine hydrochloroides

“…However, the yields are not high, and they rarely exceed 50%. For example, Sakurai et al [3] described the reaction of substituted phenoxyacetaldehydes with primary and secondary amine hydrochlorides in methanol in the presence of triethylamine, followed by reduction with NaBH 4 , which afforded 11-31% of the corresponding 2-phenoxyethanamines.Aryloxyacetaldehydes necessary for the synthesis of aryloxyethanamines according to [3] can also be prepared in several ways: by catalytic oxidation of 2-phenoxyethanol [7], by alkylation of phenols with bromoacetaldehyde acetals and subsequent hydrolysis [2,8], by ozonolysis of allyl phenyl ethers [9], and by oxidation of glycerol monophenyl ether with lead tetraacetate [10]. The most appropriate procedure seems to be oxidation of 2-(aryloxymethyl)oxiranes with periodic acid in aqueous medium or aqueous dioxane, which was proposed in [11] for the synthesis of phenoxyacetaldehyde.…”

“…Aryloxyacetaldehydes necessary for the synthesis of aryloxyethanamines according to [3] can also be prepared in several ways: by catalytic oxidation of 2-phenoxyethanol [7], by alkylation of phenols with bromoacetaldehyde acetals and subsequent hydrolysis [2,8], by ozonolysis of allyl phenyl ethers [9], and by oxidation of glycerol monophenyl ether with lead tetraacetate [10]. The most appropriate procedure seems to be oxidation of 2-(aryloxymethyl)oxiranes with periodic acid in aqueous medium or aqueous dioxane, which was proposed in [11] for the synthesis of phenoxyacetaldehyde.…”

Parallel Synthesis of Prostaglandin E1 Analogues

“…The solution was allowed to warm to room temperature over 1 h, the layers separated, and then the aqueous layer was extracted with CH 2 Cl 2 (4×). The combined organic layers were then washed with 1 N HCl (5×), brine (2×), and saturated aqueous NaHCO 3 (3×), dried over MgSO 4 , and concentrated at 30 °C to a pale brown oil (26.5 g, 97%) that matched the literature compound …”

“…The combined organic layers were then washed with 1 N HCl (5×), brine (2×), and saturated aqueous NaHCO 3 (3×), dried over MgSO 4 , and concentrated at 30 °C to a pale brown oil (26.5 g, 97%) that matched the literature compound. 21 Stored at -15 °C as crude mixture.…”

Fields of Ozone Applications

“…The easily available allylphenyl ethers are ozonized at 233 K, treated with DMS giving solutions of the corresponding phenoxyacetaldehydes which are purified by column chromatography. Their reaction with 1-methyl-1phenylhydrazine yields the corresponding hydrazones [85].…”