SU410626A1 - METHOD OF OBTAINING PHENYLODIONIUM BETAINOVINDANDIONS-1,3 - Google Patents

Description

one

The invention relates to a method for producing substituted indandnones-1,3 and phenyldionium betains of indandiones-1,3, which are widely used as intermediates for the synthesis of various organic compounds, such as ninhydrins, used in analytical chemistry.

A known method of producing phenyldionium betaine indanedione-1,3 from phenyloiodo-diodiacetate and indanedione-1,3. The reaction is carried out in a solution of alkaline methanol at a temperature of from -5 ° C to 0 ° C for 2 hours. The yield of the target product is 70%. However, this method is characterized by a relatively low yield of the target product, as well as the need to maintain a low temperature.

The aim of the invention is to reduce the reaction time and increase the yield of the target product.

The goal is achieved by carrying out the reaction at 5-20 ° C. in a mixture of chloroform, ethanol and ether, preferably at a ratio of 1: 1: 2.5, respectively.

The proposed method is simple to implement. The duration of the reaction according to this method is 5 min. The yield of the target product 80-98%.

Example 1. 3, 22 g (0.01 mol) of phenyl iodosodium diacetate are dissolved in 15 ml of chloroform

and 15 ml of ethanol, -the resulting solution is filtered and 40 ml of ether are poured into it, then cooled to 7-12 ° C and 1.46 g (0.01 mol) of finely ground indanedione (not containing bindone) are added. The mixture was stirred vigorously for a minute, the precipitated yellow precipitate was sucked off on a filter, washed with ether, and dried for 1 hour at room temperature. Yield 2.80-3.0 g (80-85%); m.p. 119 ° C (with decomp.).

Found%: I 36.50.

CisHgOal.

Calculated,%: I 36,45.

IR (NaCl): 1662 (45), 1605 (50), 1560 (74).

An analytical sample is obtained by reprecipitation of the product from chloroform with cyclohexane. The product is suitable for further syntheses without special purification; it should be used immediately after synthesis. This substance can be stored at 0 ° C in the dark for several days.

Example 2. The experiment was carried out as in Example 1, but after cooling the solution to 7-12 ° C, 1.91 g (0.01 mol) of finely ground 4-nitroindandion-1,3 (not containing bindone) was added to it. The mixture was vigorously stirred for 2-5 minutes, the precipitated yellow precipitate was filtered off with suction on the filter, washed with ether (5 ml), hot ethyl acetate (5 ml).

again with ether and dried for 1 hour at room temperature.

Yield 3.30-3.70 g (85-95%); m.p. 135 ° C (with decomp.).

Found,%: I 32.14.

C, 5HsN04l.

Calculated,%: I 32,28.

IR spectrum (NaCl): 1644 (60), 1597 (55),

1533 (52).

An analytical sample is obtained by reprecipitation of the product from methyl ethyl ketone with cyclohexane. The product is suitable for further syntheses without special purification. Suspended matter can be stored at 0 ° C in the dark for several months.

Example 3. The experiment was carried out as in Example 1, but after adding 40 ml of ether, the solution was cooled to -5 ° C and 1.77 g (0.01 mol) of finely rubbed 4-chloroandendiol-1, 3 (not containing bindone ). The mixture was vigorously stirred for a minute and at the end of the reaction, more 20 ml of ether was added. The precipitated yellow precipitate is filtered off, washed with ether and dried for 1 hour at room temperature. Yield 2.86– 3.05 g (75–80%); m.p. 124-125 ° C (with decomp.).

Found,%: I 33.01.

CisHgOzICl.

Calculated,%: I 33,17.

IR (NaCl): 1626 (86), 1590 (60).

The obtained material can be re-precipitated from acetone by cyclohexane, but it is sufficiently pure for further transformations and without re-precipitating. Phenylodionium betaine 4-chlorindandio and 1,3 should be used

immediately after synthesis. It can be stored at 0 ° C in the dark for several hours.

Example 4. 4.02 g (0.0125 mol) of phenyl iodo-disodium diacetate are dissolved in 25 ml of chloroform and 25 ml of ethanol, 50 ml of ether are poured, filtered and, stirring vigorously, added in parts of 2.84 g. mole) finely ground 4, 5,6,7-tetrachloroan dianed1, 3. After 5 minutes, the yellow precipitate is filtered off, washed with acetone and ether, and dried for 1 hour at room temperature. Yield 4.61-4.85 g (95-100%); m.p. 150-15GS (with decomp.).

Found,%: 125.94. CisHsOzICU.

Calculated,%: I 26,12.

IR (NaCl): 1624 (49), 1548 (27).

The resulting material can be redeposited.

of dioxane cyclohexane, but it is sufficiently pure for further transformations and without

redeposition It can be stored at 0 ° C

in the dark for several weeks.

Subject invention

Claims (2)

1- A method of producing phenyldionium betains of indandion-1,3 by reacting phenyl iodo-disodium diacetate with indandion-1,3 with isolation of the target product by known techniques, characterized in that process intensification, the reaction is carried out in a mixture of chloroform, ethanol and ether and at 5-20 ° C. 2. The method according to claim 1, characterized in that the mixture of chloroform, ethanol and ether take in the ratio of 1: 1: 2.5.