SU1726475A1 - 1, 12-diaza-2, 5, 8, 11, 15-pentaoxacycloheptadecane and a method of its synthesis - Google Patents

Abstract

The invention relates to heterocyclic substances, in particular the preparation of 1,1,12-diaza-2,5,8,11,15-pentaoxacycloheptadecane, which can be used as complexing agents and phase transfer catalysts. The goal is to create a new heterocyclic system in a new way. It is carried out by the reaction of 1,8-diamino-3,6-dioxoctane with 1,5-ditosyloxy-3-oxapentane in acetonitrile in the presence of sodium carbonate. Yield 39.87%. Bf CioH22N20s. 2 sec. f-ly;

Description

This invention relates to organic chemistry, namely to 1,12-diaza-2,5,8,11,15-pentaoxacycloheptadecane of the formula

about / sn2s-: 2 sn2sn2 sn2sn2h0

CFYCH /

CK2CH2Coronanda, the closest in structure to the proposed compound, i.e. containing nitrogen and oxygen atoms in the cycle, have found application in organic synthesis, analytical chemistry and biochemistry as complexing agents and phase transfer catalysts.

The aim of the invention is a new seven-membered heterocyclic system containing two nitrogen atoms and 5 oxygen atoms, and the development of a preparative method for producing this system. Connection can find

use as a catalyst for phase transfer in organic synthesis.

This goal is achieved by the fact that 1,12-diaza-2,5,8,11,15-pentaoxacyclohep-tadecane is obtained by reacting 1,8-diamino-oxy-3,6-dioxaoctane with 1,5-ditosyloxy-3- oxapentane in acetonitrile in the presence of sodium carbonate. The reaction mixture was heated in a sealed ampoule at 117-123 ° C for 38.5 hours. The product was isolated by standard methods.

EXAMPLE 1 1,8-Diphthalimidooxy-3,6-dioxaoctane.

A solution of 35.8 g (220 mmol) of M-hydroxyphthalimide and 27.6 g (100 mmol) of 1,8-dibromo-3,6-dioxooctane in 100 ml of DMF was kept at 60 ° C for 40 h, then distilled off Do DMF in a vacuum of 10 mm Hg, the residue was washed with 100 ml of water. 2x100 ml of 10% aqueous solution of HNCO3, 100 ml of water, dried and recrystallized from 165 ml of n-propanol. Received 14.6 g

cl

with

XI th o VB

cl

(32.7%) 1,8-diphthalimidooxy-3,6-dioxoxane, white crystals, m.p. 138-139 ° C. Found,%: C 60.21; H 4.57; N 6.26.

C22H20N208

Calculated,%: C 60.00; H 4.57; N 6.36.

PMR spectrum (100 MHz,, DMF-d, d, ppm); 3.19 (s, OCH2CH20, 4H); 3.35-3.56 (t, NOCH2CH20, 4H); 3.94-4.00 (t, NOCH2, 4H); 7.52-7.54 (t, ss, 8H).

Example 2 1,8-Diaminooxy-3,6-dioxa octane.

A solution of 1.0 g (20 mmol) of NaH4-H20 in 10 ml of n-propanol was added to a boiling solution of 3.8 g (8.64 mmol) of 1,8-diphthalimidoxy 3,6-dioxoctane in 30 ml of n-propanol stirring and boiling. After 2-3 minutes, a white precipitate fell. The reaction mixture was boiled with stirring for 1.5 hours, then cooled to 15 ° C, the white phthalhydrazide precipitate was filtered off, washed with 15 ml of n-propanol. The alcoholic filtrate was evaporated in a vacuum of 5-3 mm Hg. The residue was sequentially extracted with 35 ml abs. Et20 and 30 ml of dichloromethane, the extracts were evaporated under a vacuum of 5 mm Hg. 1.0 g (64.0%) of 1,8-diaminooxy-3,6-dioxaoctane from dichloromethane extract was obtained from the ether extract - 0.5 g (32.0%). The overall yield of 1,8-diaminooxy-3.6-dioxaoctane is 96%. colorless liquid, so kip. 101-103 ° C (2 mm Hg).

Found,%: C 39.91; H 8.87.

SbN1b№04

Calculated,%: C 39.99; H 8.95.

PMR spectra (80 MHz:, d, ppm): 3.66 (S, OCH2CH20, 4H); 3.60-3.90 (t, NOCH2CH20, 8H); 5.35 (S, ONH2, 4H).

Mass Spectrum (C.L. isobutane, m (Z) relative. Int.,%): 181 / M + H / + (62.27); 167 (7.26); 166 (100); 151 (7.73), 89 (11.22); 60 (22.68); 45 (52,12).

Dipicrate 1,8-diaminooxy-3,6-dioxane-octane, yellow crystals, so pl. 140-142 ° C.

Found,%: C 33.92 H 3.54; N 17.32.

Cl8H22NsOl8

Calculated,%: C, 33.87; H 3.47; N 17.55.

PMR spectrum (100 MHz. DMF - d7, .d, ppm); 3.30 (s, OCH2CH20, 4H); 3.40-3.54 (t, NOCH2CH20, 4H): 3.96-4.10 (t, NOCH2, 4H): 8.33 (S, CbH2.4 H).

PRI me R 3. 1.12-diaza-2,5,8,11,15-pentaoxacycloheptadecane.55

five

0

5 0 5 0

five

0

five

A mixture of 0.543 g (3,017 mmol) of 1,8-diaminooxy-3,6-dioxaoctane, 1.243 g (3,017 mmol) of 1.5-ditosyloxy-3-oxa-pentane, 0.9 g of sodium carbonate and 20 ml of abs. Acetonitrile in a sealed ampoule was kept for 38.5 hours at 117-123 ° C. Then the ampoule was opened, the precipitate was filtered, washed with 15 ml. abs acetonitrile. The combined filtrate was evaporated in vacuo (3 mm Hg), the residue was separated by column chromatography (A1203, eluent-abs. Benzene). Obtained0.301 g (39.87%) of 1,12-diaza-2,5,8,11,15-pentaox-cycloheptadecane, a colorless liquid.

Found,%: C 47.78; H 9.06.

C10H22N205

Calculated,%: C, 47.98; H8.86.

PMR spectrum (200 MHz,, d, ppm): 2.52-2.70 and 3.02-3.16 (m, NCH2, 4H); 3.40-3.91 (t, NCH2CH20 and NOCH2CH20, 12H); 3.58 (S, OCH2CH20, 4H).

Mass spectrum (C.I., isobutane, M / Z / OTH. Int.,%): 252 (10.81); 251 / M H / + (89.56); 181 (9.07); 130 (7.24); 100 (10.05); 88 (7.43); 87 (17.75); 86 (100); 72 (7.83); 60 (25.56); 45 (28.69).

PRI me R 4. To a stirred mixture, 198 g (1.65 mol) of chloroform, 80 ml of 50% aqueous solution, NaOH solution and 1.2 g (0.0048 mol) of 1.12-diazo-2, 5,8,11,15-pentaoxacyclodeptadecane added dropwise 23.0 g (0.5 mol) abs. ethanol, not allowing the temperature of the mixture to rise above 15 ° C, Stir the reaction mixture for 1 hour at 20 ° C, separate the organic phase, extract the aqueous phase with 2x50 ml of chloroform. The combined organic extract was dried over magnesium sulfate, chloroform was distilled off, and the residue was fractionated in vacuo. 10.6 g (43%) of triethyl orthoformate obtained by GLC analysis were obtained.

Claims (2)

Invention Formula 1.1,12-Diaza-2,5,8,11,15-pentaoxacyclo-heptadecane of the formula ABOUT Hn. -CHoCHov 0 sn2sn2 sn2sn2x CH2CH2 NH 2. A method for producing 1,12-diaza-2,5,8,11,15-pentaoxacycloheptadecane, which is characterized by the fact that 1,8-diaminooxy-3,6-dioxaoctane is reacted with 1,5- ditosyloxy-3-oxapentane in the medium of acetonitrile and in the presence of sodium carbonate.