DD146295A1 - PROCESS FOR THE PREPARATION OF SALIZYLANILID-O-GLYCOSIDES - Google Patents

Abstract

The invention relates to a process for the preparation of salicylanilide-O-glycosides of the general formula I. The invention aims to provide new agents in the field of crop protection. According to the invention, either salicylanilide with protected glycosyl halide is dissolved in dry acetone, the solution with the addition of anhydrous potassium carbonate and a water-binding agent, preferably Drierit, heated to reflux for 25 to 35 h and then entazyliert the formed acylated salicylanilide O-glycoside, (Compounds a to e of the general formula I) or salicylanilide with hepta-O-acetyl * cellobiosyl bromide in acetone / potassium hydroxide reacted within 25 h at room temperature and the resulting salicylanilide O - * - cellobiosidhepteazetat subsequently entacetylated (compound f of the general formula I). a) X = * - D-glucopyranosyl; b) X = * - D-xylopyranosyl; c) X = * - L-arabinofuranosyl; d) X = * - D-ribopyranosyl; e) X = * - D-mannopyranosyl or f) X = * - cellobiosyl.

Description

215 923 - / -

Dr ₀ K. Schwabe. ,

Dr. B. Tschiersch ·

Process for the preparation of salicylanilide glycosides

Field of application of the invention

The invention relates to a process for the preparation of salicylanilide-O-glycosides of the general formula I, .OX

CO-NH

in which a) X = β-D-glucopyranosyl;

b) X = β-D-xylopyranosyl;

c) X = O-L-arabinofuranosyl; , ·

d) X = β-D-ribopyranosyl;

e) X = β-D-mannopyranosyl or

f) X = β-cellobiosyl,

The invention lies in the field of pesticides «

Characteristic of the Known Technical Solutions The synthesis of these compounds, with the exception of the compound a of the formula I, has not yet been described. Compound a of formula I was prepared by reaction of salicylanilide with acetobromo glucose in a mixture of acetone and aqueous potassium hydroxide solution (BN Stepanenko and LV Zhukova: Dokl. Akad. Wai ^ k-SSSR J ^. (1971), 115 -116). The usability of this compound as a crop protection agent is not known. Also described is the synthesis of glycosides of 5-bromo-3-allyl-4'-chloroanilide, which can be obtained by reacting the S-bromosalicyl-1'-chloroanilide.

in dry acetone with the addition of anhydrous potassium carbonate (Ko Schwabe, B. Tschiersch, W, Wohlrab '., J. Redslob: WP C07 H / 214030).

Object of the invention

The aim of the invention is to find a process for the preparation of glycosides of the salicylanilide of the formula I in good yields, which can be used as a plant protection agent.

Explanation of the essence of the invention . ,

According to the invention, this object is achieved by, in order to prepare the compounds a to e of the general formula I salicylanilide of the formula II

OH

II

dissolved with protected Glykosylhalogenid in dry acetone and the solution with the addition of anhydrous potassium carbonate and a water-binding agent, preferably Drierit, 25 35 hrs. Heated under reflux - and from the resulting compounds of general formula III, in the

PY

a) Y = tetra-O-acetyl-.beta.-D-glucopyranosyl;

b) Y = tri-O-acetyl-β-D-xylopyranosyl;

c) Y = _{Tri-0-benzoyl-L-v} Y. .arabinofuranosyl;

d) Y = tri-O-acetyl-.beta.-D-ribopyranosyl or

e) Y = tetra-0-acetyl-β-D-mannopyranosyl

means that the protecting groups are cleaved off by treatment with sodium methylate in absolute methanol. According to the invention, the compound of the general formula is represented by f. Salicylanilide in aqueous potassium hydroxide solution

-3- 2

and adding a solution of hepta-O-acetyl-K-cellcbiosylbromide in acetone. and allowing the mixture to stand at room temperature for 24 hours.

Aus.der in this case formed compound of general formula III, in the

f) Y = hepta-O-acetyl-β-cellobiosyl

The acetyl groups are cleaved by treatment with sodium methylate in absolute methanol. The novel compounds are characterized by fungicidal effects and can be used to control plant pests.

If necessary, they can be split into the highly active active form (aglycone) and the corresponding sugar by means of the presence of fungal enzymes (glycosidases). This selective activation leads to a preferential damage of the fungal cells and a diminished effect on the host cells. Therefore, the newly prepared compounds transport forms of fungistatic substances in the sense of the "method for the development of fungicides and other pesticides" claimed by B ₀ Tschiersch, K »Schwabe, E. Kluge and H. Lyr in WP 130 126. In WP 130 126 be z. B. the low phytotoxic effects of salicylanilide cellobioside with good fungicidal activity in Erysiphe graminis / barley highlighted. Similarly good results are achieved with the compounds presented here. The invention is illustrated by the following examples:

1st example . , , ·

A solution of 14.4 g (67.5 ml vial) of salicylanilide and 10 g (33.9 ml of ole) of tri-O-acetyl-γ-D-xylopyranosyl chloride in 200 ml of dry acetone is added 8,19 g (59s3 mmol) of potassium carbonate and 20 g of drierite (calcium sulfate) under exclusion of moisture refluxed for 30 hrs. »Then it is filtered from the insoluble and with. Washed acetone. From the Fil.trat the acetone is removed i Vako and the remaining oil is taken up in ice-cold chloroform. The chloroforraic solution is shaken five times with ice-cold 5% sodium hydroxide solution to

  - 4 -

to remove excess salicylanilide. Subsequently, the organic. Mit'Wasser phase washed until neutral and Ge, dried (Wa ₀ SO.) _A laughing evaporating the chloroform i. Vak.

c. H-

the oily residue is recrystallized from isopropanol _β Smp. 132-132. -5 ° (isopropanol) ... Yield: 9.6 g (60 % yield of theory, based on xylose derivative)

Bo To a solution of 9.6 g (20.3 mmol) of salicylanilide-O-.beta.-D-xylopyranoside triacetate obtained in A in 19 ml of absolute methanol is added 2.9 ml of a 0.092 molar absolute. Methanolic sodium methoxide solution Add and leave for 1 hr. At room temperature. The course of the deacetylation is monitored by thin-layer chromatography (silica gel plate, eluent chloroform / methanol 9: 1) »After complete deacetylation is neutralized with Amberlit IR120 and the filtrate i. Vak. evaporated to dryness, recrystallization from a little water gives salicylanilide O-.beta.-D-xylopyranoside.

Mp 88.5 - 91 ° C (H ₂ O) -

Yield: 5.76 g (82 % of theory).

2 «EXECUTIVE SUMMARY

A. In 50 ml of water, 2.63 g (46.8 mmol) of potassium hydroxide and 5 g (23.4 mmol) of salicylanilide are dissolved successively. To this solution is added a solution of 16.36 g (23.4 mmol) of hepta -0-acetyl-f) [- cellobiosylbromide in 4 l of 6 ml acetone and shake. The mixture remains at room temperature for 24 hours and is then poured into a salt-saturated ice-water mixture with stirring. To complete the precipitation, leave to stand for 12 hours in the cold, filtered and washed with water. The product is dissolved in 150 ml of chloroform, the solution is cooled down, extracted four times with ice-cold 5% strength sodium hydroxide solution, extracted by shaking, washed neutral with water and the organic phase, dried, isobutane. The chloroform is i. Vak. evaporated and the

215 923

syrupy residue is recrystallized from isopropanol to give mp 194-196 ° (isopropanol). ,

Yield: 10.5 g (54 % yield of theory, based on Cellobios ederi vat)

B ₀ To a solution of 10.5 g (12.6 mmol) of salicylanilide O-β-cellobioside heptaacetate in 300 ml of absolute methanol is added 32 ml of a 0.092 molar absolute methanolic solution of sodium methoxide and the mixture is shaken for 2 hrs room temperature. The course of the deacetylation is monitored by thin-layer chromatography (silica gel plate, eluent chloroform-methanol 9: 1). After complete deacetylation is neutralized with Amberlit IR 120 and the filtrate i. Vak. evaporated to dryness. Recrystallization from water gives salicyl-O-β-cellobioside. . Mp 147-149 ⁰ C (water) Yield: 5.5 g (81% of theory)

Claims (1)

E rf indussprucb. Process for the preparation of salicylanilide-O-glycosides of the general formula I, - '.. a in which a) X = β-D-glucopyranosyl; b) X = β-D-xylopyranosyl; · c) X = C 1-k-arabinofuranosyl; d) X = β-D-ribopyranosyl; e) X = β-D-mannopyranosyl or. , f.) X = β-cellobiosyl means, characterized in that for the preparation of the compounds a to e of the general formula I salicylanilide. with estimated glycosyl halide dissolved in dry acetone, refluxed with the addition of anhydrous potassium carbonate and a water-binding agent, preferably Drierite ', for 25-35 hours, to give the compound f of general formula I salicylanilide with hepta-O-acetyl - ^ - Cellobiosylbromid in acetone / potassium hydroxide within 24 hours, reacted at room temperature and then entazyliert the, each formed azylated salicylanilide O-glycoside then »