CS248939B1 - Substituted 5-phenoxy-2-furaldehydes and their method of preparation - Google Patents

Abstract

The solution relates to the field of organic chemistry and deals with the preparation of new compounds of substituted 5-phenoxy-2-furaldehydes. The essence of the method for the preparation of 5-phenoxy-2-furaldehydes is that 5-bromo- or 5-nitro-2-furaldehyde is treated with substituted sodium or potassium phenolate in dimethyl sulfoxide at a temperature of 25 to 90 °C. Substituted 5-phenoxy-2-furaldehydes according to the solution are characterized by the formula R-0 CH=O can serve for the preparation of new heterocyclic compounds with a condensed furan core.

Description

248939 2

The invention relates to substituted 5-phenoxy-2-furaldehydes and to a process for their preparation. A suitable method for their preparation is the reaction of substituted phenolates with 5-bromo or 5-bromo, respectively. 5-nitro-2-furaldehyde in dimethylsulfoxide as solvent. In Literature / Koreňová A., Krutošíková A., Kováč J .: Chem. rumors in print describe the preparation of 5- (2-nitrophenoxy) -2-furaldehyde by reacting sodium 2-nitrophenolate with 5-bromo-2-fural-dehyde in dimethyl sulfoxide at 90 ° C with very good yield compared to work / Tanaka A , Usui T., Shimadzu M .: J. Heterocycl. Chem. 18, 1241 (1981).

StUdium literature has shown that 5-aryl-2-furaldehydes wherein aryl is 2,4,5-trichlorophenyl, 3,4,6-trichloro-2-nitrophenyl and 4-chloro-2-methylphenyl have not yet been prepared.

S-5-aryl-2-furaldehydes of formula n-o

CH = O / 1 wherein R is 2,4,5-trichlorophenyl, 2-chloro-4-nitrophenyl-3,4,6-trichloro-2-nitrophenyl, 4-chloro-2-methylphenyl and a method for their preparation.

The principle of the preparation of 5-phenoxy-2-furaldehyde is that it is treated with a substituted sodium or potassium phenolate of formula II e 9 R-O Me / 11 /

wherein Me is Na or K and R is as defined above for 5-bromo-2-furaldehyde or 5-nitro-2-furaldehyde of formula III X-

CH = O / 111 / where X 1 Br, NO 2 in dimethyl sulfoxide at 25 ° C to 0 ° C. The advantages of the process for preparing the compounds according to the invention are, inter alia, that the reaction of the substituted phenolates with 5-bromo or 5-nitro-2-furaldehyde is carried out in one step under good conditions with good yield. The best yields were obtained using sodium or potassium 4-chloro-2-methylphenolate.

The attached substituted 5-phenoxy-2-furaldehydes with good crystallization of the compound. Example 1 5- (2,4,5-Trichlorophenoxy) -2-furaldehyde 2,4,5-trichlorophenyl (19.7 g, 0.1 mol), sodium / 2.3 g, 0.1 gm / sec. react with dimethyl sulfoxide (50 ml) at 50 ° C. To the 2,4,5-trichlorophenate prepared in this way, molten 5-bromo-2-furalehyd (17.5, 0.1 mol) is added so that the temperature does not exceed 90 ° C. The reaction mixture is maintained at 90 ° C with stirring for 7 h. It is poured onto ice (700 g). 3 248939

The precipitated precipitate is filtered off with suction and the unreacted 5-bromo-2-furaldehyde is iodo-distilled. The residue was cooled, the precipitate was filtered off with suction and recrystallized from ethanol. Note: Commercial 2,4,5-trichlorophenol was crystallized before use from n-heptane. EXAMPLE 2 5-4-Chloro-2-methylphenoxy-2-furaldehyde (Id) 4-Chloro-2-methylphenol (14.2 g, 0.1 mol), potassium (3.9 g, 0.1 gm) and does not react. dimethyl sulfoxide (50 ml) at 40 ° C. 5-Bromo-2-furaldehyde (17.5 g, 0.1 mol) was added to the 4-chloro-2-methylphenol-potassium salt thus prepared so that the temperature did not exceed 80 ° C. The reaction mixture is maintained at 80 ° C with stirring for 7 h. It is poured onto ice (500 g) and treated similar to Example 1. Compounds Ib and Ic are similarly synthesized.

Spectral Measurement 1 H NMR spectra were recorded on an 80 Hz spectrophotometer! BS 487 C Tesla using etrtetramethylsilane as internal standard. Extracts, i.e., elemental analysis and 1 H NMR are shown in Table 1. I and II.

Taboo sludge

Substituted 5-phenoxy-2-furaldehydes

Zlúč.čís. Sumar Formula Calculated / Found% N m.p. [° CJ / TX. [i] / MH /% c% H% Cl Ia C 11 H 5 Cl 3 3 45.32 1.73 36.47 - 110 to 111 / 291.5 / 45.42 1.75 36.35 / 75 / Ib CUH6C1NO5 49, 37 2.26 13.25 5.23 100 to 105 / 267.6 / 49.40 2.30 13.28 5.42 / 30 / Ic C11H4C13N ° 5 39.26 1.20 31.61 4.16 125 up to 127 / 336.5 / 39.24 1.22 31.60 4.20 / 8 / Id C12H9ClO3 60.92 3.82 14.98-46 to 47 / 236.6 / 60.88 3.80 14, 86/92 /

Table II: 1 H NMR data (5 ppm, 1 Hz) 5-phenoxy-2-furaldehyde synthesized

Compound H3 H4 CH * = OH arom Other signals Ia 7,60d 5,97d 9,36s 7,94s 8, 10s Ib 7,59d 6,00d 9,38s Ic 7,59d 6, O8d 9,40 8,49s Id 7.56d 5.73d 9.35 7.45m 7.10-7.42 2.12 CH3

Claims (2)

SUBSTITUTE 5-Phenoxy-2-furaldehydes of Formula I RO- (V-CH-O-O) (1) wherein R is 2,4,5-trichlorophenyl, 2-chloro-4-nitrophenyl, 3, 4,6-trichloro-2-nitrophenyl, 4-chloro-2-methylphenyl. 2. A process for the preparation of 5-phenoxy-2-furaldehydes of the general formula I according to claim 1, characterized in that it is substituted with a sodium or potassium phenolate of formula II 6 & R-OMe / 11 / wherein Me is Na or K and R is as defined above for 5-bromo-2-furaldehyde or 5-nitro-2-furaldehyde of formula III X CH = O / 111 / where X x Br, NC> 2 in dimethyl sulfoxide at 25 to 90 ° C. Severografia, n. P., MOST Price 2,40 Kčs i *