SU1384586A1 - Method of producing alkoxyisoxazolidines - Google Patents

Abstract

The invention relates to heterocyclic compounds, in particular to the preparation of alkoxyisoxazolidines of the formula RjCH-CH -CHRj-NR; -0, where benzocl or para-substituted by a halogen atom with a benzoyl or alkyl group; one of the radicals R and RJ is an alkoxy group, and the other is a hydrogen atom or lower alkyl which can be used in the preparation of functional cyclic hydroxylamines. The goal is to develop a method for obtaining new compounds. Their preparation is carried out with a compound of the formula R CH — CH —CHRj—, where R is the indicated values, one of the radicals R and R, is a hydroxy group, and the other is a hydrogen atom or lower alkyl, and an alcohol of the formula where R is lower alkyl , in the medium of an organic solvent in the presence of an acid catalyst, which is mixing the solvent. with S (L

Description

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The invention relates to organic chemistry, namely to a new method of producing new compounds, specifically alkoxyisoxazolidines with an aroyl substituent in position 2,

The invention can be used in chemical and medical industry to obtain functional derivatives of cyclic hydroxylamines, as well as in the development of new methods for the synthesis of biologically active compounds.

The purpose of the invention is to develop a new method of obtaining new compounds - alkoxyisoxazolidines.

The invention is illustrated by the following examples.

Example. Preparation of 2-benzoyl-3-methoxyisoxazolidine.

To a solution of 0.98 g (5 mmol) of 2-ben-3-hydroxyisoxazolidine in 50 ml of benzene, 2-3 drops of concentrated sulfuric acid and 3 drops of methanol are added and stirred at room temperature for 5-10 minutes, then the solution is passed through a layer of alumina and remove the solvent in vacuo. The residue is recrystallized from hexane. Obtain 0.82 g (79%) of substance with so pl. 72-75 C.

IR spectrum: 1660 (); 1230 (OCH)

Spectrum of PNR (CpClS) g 1.9 (2H, m, 4-H); 2.5 and 3.5 (ZN, s, Z-OSN); 3.05 (1H, m, 5-H); 4.0 (1H, m, 5-H); 4.7 (1H, m, 3-H); 7.2 (5H, m, SeN) ppm

Found: C, 63.70; .H 6.50.

With „H ,, NO ,.

Calculated,%: C 63.76; H 6.28.

PRI mme R 2. Preparation of 2-p-nitrobenzoyl-3-methoxyisoxalidine.

To a solution of 1.19 g (5 mmol) of 2-p-nitrobenzoyl-3-hydroxyisoxazolidine in 40 ml of methyl iodide, 3 drops and 0.2 ml of methanol are added. The mixture is stirred for 10 minutes, passed through a thin layer of alumina and the solvent is evaporated. The residue is recrystallized from 1: 1 ether-hexane. Obtain 1.04 g (83%) of substance with so pl. .

IR spectrum: 1675 (); 1280 (OCHj).

 PMR (CDCl); 1.9, (1H, m, 4-H); 2.3 (W, m, 4-H); 3.5 (1H, m, 5-H); 4.4 (1H, m, .5-H) .; 5.07 (1H, m, 3-H); 8.05 (4H, m, SbN4); 2.9 and. 3.35 (ЗН, с, З-ОСН,) ppm

Found,%: C 52.18; H 4.80.

C ,, H, N, 0,

Calculated,%: C, 52.38; H 4.76.

PRI me R 3. Preparation of 2-p-toluyl-5-ztoxyisoxazolidine.

0.3 ml of ethanol and 2-3 drops of concentrated sulfuric acid are added to a solution of 1.03 g (5 mmol) of 2-p-toluene-1-5-hydroxyisoxazolidine in 30 ml of methyl iodide. The mixture is stirred for 20 minutes, then passed through an alumina pad and the solvent is removed. The residue is chromatographed on a silica gel 40 column. UOmesh in the heptane – ethyl acetate system 4: 1, collecting the fraction with Rf 0.83 (in the petroleum ether – ethyl acetate system 2: 1). The substance of 0.67 g (57%).

IR pattern: 1670 (), 1260 () cm-.

PMR spectrum (CDCi,): 1.2 (3N, t, Hz, SI,); 1.9 (3N, s.); 2.2 (2H, m, 4-H); 3.6 (2H, q, J 8 Hz, SNg); 5.6 (1H, m, 5-H); 7.0 (4H, m, SbN4) ppm

Found,%: C 66.52; H 7.48.

С, Н „ЁОэ.

Calculated,%: C, 66.38; H 7.23.

g

EXAMPLE 4 Preparation of 2-p-bromo benzoyl-3-isopropoxy-5-methylisoxazolidine.

To a solution of 1.43 g (5 mmol) of 2-p-bromobenzoyl-3-hydroxy-5-methylisoxazolidine in 50 ml of methylene chloride is added Oj4 ml (5 mmol) of isopropanol and 3 drops of concentrated sulfuric acid. The mixture was stirred at room temperature for 20 minutes, then passed through an alumina pad and the solvent was evaporated. The residue is chromatographed on a 40100 mesh silica gel column in the 4: 1 heptane-ethyl acetate system, collecting a fraction with Rf 0.42 (in the heptane-ethyl acetate system 3: 1). Yield: 1.04 g (63%)

M-fP (CDCl,) spectrum: 0.9 and 1.2 (3N, d, J 5 Hz, 5-CH,); 1.3 (6H, m, (CH,) CH); 2.4 (2H, m, 4-H); 3.5 (1H, m, 5-H); 4.4 (1H, m, .CH); 5.1 and 5.5.3 (1H, m, 3-H); 7.4-7.9 (4H, m, CgH4) ppm (mixture of diastereomers).

Found,%: C 51.64; H 5.32.

C ,, H, 8NO, Br

Calculated,%: C, 51.22; H 5.49.

Thus, this method allows to obtain the desired products with high yields.

Claims (1)

Invention Formula A method for producing alkoxyisoxazolidines. general formula HS /  “I. where R, is benzoyl or para-substituted by halogen, nitro group or lower alkyl benzoyl; . R and R - are one of the alkoxy radicals, and dsrggoy is hydrogen or lower alkyl, Similarly, hydroxyisoxazolidine of the general formula f / o p / R2 -N. About R. Where has the indicated meanings. R and R is one of the hydroxy groups, and the other is hydrogen or lower alkt, subjected to interaction with the alcohol of the General formula R40H, where R is lower alkyl, in the environment of an organic solvent in the presence of an acid catalyst that is not miscible with the solvent.