SU436825A1 - The method of obtaining asymmetric diine derivatives of ferrocene - Google Patents

Description

one

A method is proposed for producing new ferrocene derivatives, in particular asymmetric DIIN ferrocene derivatives of the formula

ferrocene cyclodentadienyl ring, in the region of 2151-2130 cm for communication, in the region of 1260 cm for C-O-C communication.

Example 1. Getting 6- (p-fe | rrocenylphenoxy) -2,4-hexadium: n- (o-chlorophenol) -.

In a three-necked flask equipped with an auto-stirrer, a gaseous water tube and an addition funnel, 0.632 g (0.002 mol) of p-phproprocenyl ester, ilphenol, 5 ml of methanol, 10 ml of DMF, 20 ml of diethyl ether, 0.2 g of copper ortrichloride, 5 ml of n-butylamine and 0.1 g of hydroxylamine hydrochloride.

A raspvor of 0.491 g (0.002 mol) of 3-bromopropargyl ester of o-chlorophenol in methanol was introduced through a dropping bottle for 45 minutes. At room temperature B, nitrogen atmosphere, the reaction mixture is stirred for 1 hour. After termination of the reaction, the mixture was poured into cold distilled water, acidified with a 10% hydrochloric acid solution and extracted with diethyl ether. The ether extracts are combined and washed several times with 5% alkali solutions and distilled water.

After evaporation of the ether, the dry residue is purified by thin layer chromatography on (heptai: chloroform 1: 1). The resulting 6- ((g-ferrocene. Phenyl) -2,4 - hexadiine (o-chlorophenol) -1 has so pl. 69-7GS (heptane), yield 85.9% of theoretical.

Found,%: C 69.41; 69.08; H 4.19; 4.62; Fe 11.74; 11.98; C1 7.43; 6.98.

CasHsiOaFeCl.

Calculated,%: C 69.69; H 4.34; Fe 11.65; C1 7.39.

The product is not described in the literature.

Example 2. Getting 6- (d-ferrocenylphenoxy) - 2,4 - hexadiine - (2,4 - dichlorophenol) -1.

In a three-necked flask equipped with an automixer, a gas-intake tube and a dropping funnel, 0.632 g (0.002 mol) of p-ferrocenylphenol nopargyl ester, 6 ml of methanol, 12 ml of DMF, 24 ml of diethyl ether, 0.2 g of copper chloride, 5 ml of n- butylamine and 0.1 g of hydroxylaedine hydrochloride. A solution solution of 0.560 g of 3-bromo propargyl ester of 2,4-dichlorophenol in methanol is introduced via an addition funnel over 45 minutes. At room temperature IB under a nitrogen atmosphere, the reaction mixture is stirred for 50 minutes. After completion of the reaction, the mixture is poured into cold distilled water, acidified with 10% hydrochloric acid and extracted with diethyl ether. The ether extracts are combined, then washed several times with a 5% alkali solution and water. After distilling off the solvent, the dry residue is purified by thin layer chromatography on ABOZ (hexane: ethyl alcohol 1: 1).

6- (-Ferrocenylphenoxy) -2,4-hexadiene (2,4-dichlorophenol) -1 is melted at 90-9GS (hexane).

The yield of 75.7% of theoretical

Found,%: C 65.84; 65.02; H 3.62; 3.52; Fe 10.32; 10.94; C1 14.22; 14.06.

C28H2oFeCl2.

Calculated,%: C 65.25; H 3.88; Fe 10.88; C1 13.79.

The product is not described in the literature.

P131 3. Preparation of 6- (l-ferrocenylphenoxy) -2,4-hex1-cadiin- (2,4,5-trichlorophenol) -1.

In a three-necked flask equipped with an azto-stirrer, a gaseous inlet tube and an addition funnel, 0.632 g (0.002 mol) of “-ferrocenylphenol propargyl ester, 8 ml of methanol, 16 ml of DMF, 32 ml of diethyl ether, 0.2 g of copper-chloride, 5 ml of n- butylamine and 0.1 g of hydroxylamp hydrochloride. A solution of 0.629 g of 2,4,5-tr, and chlorophenol in methanol was introduced through an addition funnel over 45 minutes.

At room temperature under a nitrogen atmosphere, the reaction mixture is stirred for 1 hour. Extract and purify the synthesized compound as in Example 2.

Get 6- (ha-ferrocenylphenoxy) -2,4-hexadiene- (2,4,5-trichlorphenol) -1 with so pl. 94-95 ° C (hexane). The product yield of 72.7% of theoretical.

Found,%: C 60.20; 61.02; H 3.12; 3.02; Fe 10.61; 10.58; C1 19.21; 19.12. C28Hi9O2FeCl3.

Calculated,%: C 60.98; H 3.45; Fe 10.18; C1 19.19. The product is not described in the literature.

Example 4. Getting 6- (ha-ferrocenylphenoxy) -2,4 - hexadiene- (2,4,6 - trichlorophenol) -1.

In a three-necked flask, filled with an aiBTOMe scraper, a gas inlet tube and an addition funnel, 0.632 g (0.002 mol) of p-ferrocenylphenol propargyl ether, 8 ml of methanol, 16 ml of DM.F, 32 ml of diethyl ether, 0.2 g of copper chloride, are placed. 5 ml of n-butylamine and 0.1 g of hydroxylamine hydrochloride. A solution of 0.629 g of 2,4,6-trichlorophenol 3-bromiropargyl ether in methanol was introduced through an addition funnel over 40 minutes.

At room temperature under a nitrogen atmosphere, the reaction mixture is stirred for 1 hour. P1, the synthesized compound is purified and purified analogously to Example 2. 6- (p-Ferrocenylphenoxy) -2,4 - hexadiine - 1- (2,4,6-11-chlorochlorophenol) - has so pl. 138-140 ° C (alcohol). The product yield of 79.8% of theoretical.

Found,%: C 60.20; 60.12; P 4.06; 4,10; Fe 10.42; 10.54; C1 19.84; 19.98.

C28Hi9O2FeCl3.

Calculated,%: C 60.98; H 3.45; Fe 10.18; C1 19.19.

The product is not described in the literature. The physico-chemical characteristics of the obtained asymmetric diine derivatives of ferrocene are given in the table. The method of obtaining

ABOUT

) "С С-CsC-iCH2 n-Y-f

R

BUT

where R iR-СНз, СгНз; - halogen; , Se, Te; ,

starcharyl ether p-fer, rocenylpheiol is reacted with zchbrompropinyl ether

substituted phenol in an environment of a suitable organic solvent or mixture of solvents in the presence of a complexing agent, for example n-butylamine, a reducing agent — hydroxylamine hydrochloride — and a catalyst, nalEmer of copper chloride, with isolation of the target product by known methods. the subject of inventions asymmetric diene derivatives of ferrocene formula