SU1752734A1 - 3,4-dihydroxyfurazane as an intermediate product for synthesis of compound, containing dioxafurazanyl moiety, reagents, used in analytical chemistry, and method of its synthesis - Google Patents

Abstract

The invention relates to heterocyclic compounds, in particular, to the preparation of a furazan derivative, 3,4-dihydroxyfurazan, a semi-product for the synthesis of analytical chemistry reagents. The goal is to create a new method of obtaining a new intermediate. The synthesis is carried out by the reaction of a tetryacetyl derivative of oxalyl dihydroxamic acid with sodium acetate crystal hydrate in glacial acetic acid with heating. Yield 9–11%, m.p. 189-190 ° C, brutgo-formula CaH2 Oz 2 sp f-ly.

Description

The invention relates to organic chemistry, specifically to a new derivative of furazan - 3,4-dihydroxyfurazan of the formula HO-y ~ -. N (1) and the method for its preparation.

Compound I can be used as an intermediate in the synthesis of various compounds containing a dioxafurazanyl fragment of the formula

Μ _χ N (54) 3.4 DIHYDROXYFURAZANE AS AN INTERMEDIATE PRODUCT IN SYNTHESIS OF COMPOUNDS CONTAINING A DIOXAFURASANESY FRAGMENT. OF REAGENTS IN ANALYTICAL CHEMISTRY ° AND METHOD FOR ITS PRODUCTION (57) The invention relates to heterocyclic compounds, in particular to the preparation of a furazan derivative - 3,4-dihydroxyfurazan - an intermediate for the synthesis of analytical chemistry reagents. The goal is to create a new way to obtain a new intermediate. The synthesis is carried out by the reaction of a tetraacetyl derivative of oxalyl dihydroxamic acid with crystalline sodium hydrate in glacial acetic acid with heating, Yield 9 - 11%, mp. 189 - 190 ° С, gross formula C2H2N2O3. 2 s.p. f-ly.

“• On the basis of (I) it is possible to obtain both linear, for example (VI) and polycyclic derivatives, for example (lll) - (V), which can find application in analytical chemistry:

NON 04

ΜΟΝΟΙ _ ("Oh

(Vi) / w ^λ ο ce ΝαΟΗ o V.

V

0 N (V)

1752734Al

Polycyclic compounds (III) - (V) are new previously unknown heterocyclic systems.

A compound is known in the literature in the molecule of which at the same time 5 a furazan cycle and two hydroxyl groups are present, namely 3,4-bis (hydroxymethyl) furazan of the formula non ₂ s - ^ - ^ sn., He (VII)

Since the hydroxy group in compound (VII) is separated from the furazan cycle by a methylene fragment, it cannot serve as the starting point for the synthesis of substances containing a structural fragment of formula (II),

Also known are compounds containing a hydroxyl group directly bonded to the furazan ring of the general formula

NN (VIII) \ / 25 where R-Rh, CH ₂ COOR (COR * Het.

However, these compounds also cannot be the starting materials for the synthesis of the compounds of formula (II), since they have only one hydroxy group in the furazan ring. thirty

A compound is known which is a derivative of 3,4-dihydroxyfurazan, namely 3,4-dimethoxyfurazan, of the formula ^N 4 ₀ z ^N о *)

This compound also cannot be the starting point for the synthesis of a group of compounds of formula (II), since it lacks 40 active hydroxy groups, which are non-existent centers of the reactivity of compound (I).

A known method of producing derivatives (I), which is based on the reaction of a derivative of azoxifurazan 45 with alcoholates o

+

HjCO-ot-N = N-77V ^0CH 3 CH ₂ ONq NN MN —— *

V ® '' O ''

AXIS, (fX)

It is not possible to obtain compound 55 (I) in this way, since the corresponding azoxifurazan (ie, 3,3-dihydroxyazoxyfurazan) is unknown.

The aim of the invention is a new derivative of furazan for the synthesis of compounds _ containing dioxafurazanilny Fragment, and the development of a convenient preparative way to obtain it.

The goal is achieved in that the compound 3,4-dihydroxyfurazan of formula (I) is obtained according to the method consisting in the fact that the tetraacetyl derivative of oxalyl dihydroxamic acid (XI) is reacted with sodium acetate crystalline hydrate in glacial acetic acid at 70 - 80 ° C subsequent processing of the reaction mixture with concentrated hydrochloric acid and solvent extraction of the product.

Yield (I) is 9-11%.

AcO _h ^ OAc f NaOAc-SH ^ + AcOH „„, p. / L

AcON NOAc N, Ν (Xj). ⁰

For the obtained substance according to the data of elemental analysis, IR, mass, NMR ¹³ C-spectra, taking into account the method of its preparation, only one variant of the structure of formula (I) is possible.

The method is based on the thermal cyclization of a hydroxamic acid derivative in the presence of acids. It is known that the thermoreaction of hydroxamic acid derivatives with acid reagents leads to a Lossen rearrangement:

0R

R - C f 7 — R - N = C - 0,, ^ NO-R where R ', R-H, Ac, ToS.

A well-known example of the cyclization of hydroxamic acid derivatives to the hydroxyfurazan derivative is based on alkaline dehydration:

NH ₂ 0H honh _s ROC-CH ₂ CC-OR --- ₀ ^ С he * —NOOSSI ₂ - £ Г ^ ОН _{x Z} N .о

It should be noted that the use of an anhydrous salt or dilute (even .96%). Acetic acid in the reaction instead of sodium hydrate crystalline hydrate, as well as lowering or raising the temperature from this interval, does not lead to the desired product.

Attempts to alkaline cyclization (X1) in (I) did not succeed.

Only the totality of the conditions taken for the synthesis of (I) and the selected starting compound made it possible to obtain a new multifunctional compound of interest as an intermediate for synthesis / OH

GN, -C-C ^z // and substances containing a dioxafurazanyl fragment.

PRI me R 1. Obtaining 3.4-dihydroxyfurazan (I).

A. 5.76 g (20 mmol) of oxalyl dihydroxamic acid tegraacetate (X) and 5.44 g (40 mg mol) of sodium acetate crystalline hydrate are stirred in 10 ml of glacial acetic acid at 70 ° C. for 20 hours and poured into 25 ml of concentrated hydrochloric acid acids. The resulting mixture was left overnight and then extracted with ether (5 x 50 ml). The extract was dried over calcined MgSCH, filtered and the solvent removed. The residue was recrystallized. Obtain 0.18 g (9%) of the product in the form of white crystals, so pl. 189 - 190 ° С (decomp., SSC / EA).

IR spectrum, cm '¹; 3570 s; 3400 s; 3300 2800 (wide band); 2700 - 2400 (wide band); 1595 s; 1420 s; 1290 cf. 1270 s; 1210 cl; 1020 s; 950 cl; 910 cl; 880 s

Mass spectrum, m / z: 102 (M ⁴ ); 72 (M ⁺ - O); 45; 44; 43: 42; 32; thirty.

NMR ³ C (acetone-ёb) dmd: 158,38.

Found,%: C 23.34; H 1.88; N, 26.98. S2M2N2O3

Calculated,%: C 23.52; H .1.96; N, 27.45.

B. Carry out analogously to item A using 15 ml of glacial acetic acid at a temperature of 80 ° C for 20 hours. Yield (1) 10%.

B. Carry out analogously to item A using 20 ml of glacial acetic acid at 75 ° C for 30 hours. Yield (I) 11%.

PRI me R 2. The use of 3,4-dihydroxyfurazan in the synthesis.

A. Preparation of 2, 3. 11, 12-difurazano-1, 4, 7, TO, 13, 16-hexaoxacyclooctadecadiene-2, 11 (V).

1.02 g (10 mmol) of compound (I) is dissolved in a mixture of 20 ml of n-butanol and 0.5 ppm of water and 0.4 g (10 mmol) of NaOH is added, heated to 60 ° C and a solution of 0.71 g (5 mmol) of dichlorodiethyl ether in 10 ml of n-butanol.

Then a solution of 0.4 g (10 mmol) of NaOH in 1 ml of NgO is added and a solution of 0.71 g (0.5 mmol) of dichlorodiethyl ether in 10 ml of n-butanol is added dropwise and the reaction mixture is heated to boiling. After cooling, add 1-2 ml of concentrated acid and evaporate to dryness in a vacuum of a water-jet pump. The product is recovered from the residue by extraction. 0.12 g (7%) of the expected product are obtained,

IR spectrum, cm '¹;2980;1610;1575;1450;1400;1340;1290;1185;1160;1120; 1030: 910.

Mass spectrum, τ / ζ: 344 (M ⁴ ), calculated 344.

PMR spectrum, ppm : 3.7 - 4.4.

B. Preparation of substance (VI).

To a solution of 0.25 g (2.4 mmol) of compound (I) in 5 ml of absolute CH3CN, 0.5 g (4.8 mmol) of triethylamine are added dropwise. The resulting solution was stirred for 5 min and 0.44 g (2.4 mmol) of 4,5-dichlorfurazano [2, 3-c] pyrazine was added 10 to it. After stirring for 1 h at room temperature, the reaction mixture was diluted with 20 ml of НГО and the product was filtered off, washed with water, and dried in air. Obtain 0.25 g (54%) of a substance which sublimates at 260 ° C. T.razl. 283 ° C. ... ,

IR spectrum (KBr), g ^ cm ’; 3500-3400; 3300; 3000; 3000-2980; 1620; 1580; 1520; 1470; 20 1325; 1180; 1060; 840 /

Mass spectrum, m / z; 238 (M ⁴ ), 153 (M ⁺ ~ / rm ^

OH), 152 (M ⁴ - 'OH-H).

V

Found,% C, 30.41; H O, 04; N, 35.21. C6H2N6O5

Calculated.%: C 30.25; H O, 06; N, 35.29. B. Preparation of substance (III).

To a solution of 0.51 (5 mmol) of compound (I) 30 and 3.4 g (10 mmol) of tetrabutylammonium hydrosulfate in 20 ml of NgO is added a solution of 0.8 g (20 mmol) of NaOH in 5 ml of H2O, diluted with 50 ml of alcohol and cooled to 10 ° C. Sediment IAGZOG; filtered off, washed with 35 alcohol and the filtrate evaporated to dryness in vacuo. The remaining oil is dissolved in 30 ml of abs. CH3CN, filtered from Na2SO4 residues, the filtrate was evaporated to dryness and the remaining oil was dried in vacuo (60 ° C / 1 mm 40 Hg). 3.3 g of ditetrabutylammonium salt (I) are obtained in the form of a thick yellow oil. The resulting salt is dissolved in 40 ml of abs. CH3CN, add 1.09 g (5 mmol) of 2, 3, 5, 6-tetrachloropyrazine and stir at 50 ° C for 1 hour. Evaporate from the rotor to dryness, fill in the residue with 20 ml of НГО, filter the precipitate, wash with water and dry. The resulting substance (1.4 g) was dissolved in 75 ml of a mixture of CHCI3 / CCI4 1/1 and passed through a column of silica gel (10 g, silica gel 100 / 160μ), eluting with the specified solvent mixture. Collect 120-130 ml of eluate and evaporate. Obtain 0.95 g (77%) of compound (III), so pl. 206 - 207 ° C (in a sealed capillary).

Mass spectrum, m / z: 246 (M ⁴ ); 178 (M ⁺ -68) (CI2). ,.

IR spectrum, cm ⁴ : 1550: 1445; 1370; 1230; 1230; 1165; 1135; 1005; 980; 880; 860.

¹³ C NMR spectrum (acetone-D) d, ppm: 139.17; 142.07; 153.58.

Found,%: C 29.29; N, 22.78; CI 28.22. C6CI2N / 1O3

Calculated,%: C29.90; N22.73: CI 28.73. 5

D. Preparation of substance (IV).

Diethrabutylammonium salt (I) (3.3 g, obtained according to item B) is dissolved in 50 ml of abs. CH3CN and 0.78 g (3.6 mmol) of 2, 3, 5, 10 6-tetrachloropyrazine was added and stirred at 60 ° C for 1 h. The reaction mixture was evaporated to dryness, the residue was poured into 20 ml of water, the precipitate formed was filtered off, washed with water and are dried. The resulting mixture of (III) and (IV) was stirred for 10 min in 50 ml of a mixture of CHCI3 / CCI4 1/1, the insoluble residue, which is (IV), was filtered off (0.23 g, 33%). After recrystallization from CHC1z> mp, 154-155 ° C. 20

Mass spectrum, m / z: 276 (M ⁺ ); 246 (M ⁺ O); 208 (M ⁺ -68); 202; 190.

l4K-cneKTp _z cm ' ¹ : 1570; 1480; 1400: 1260; 1200: 1035: 985.

Found,%: C 34.67; N30.07. 25

SAMBOb

Calculated,%: C 34.80; N, 30.44.

Thus, the use of sodium acetate crystalline hydrate in glacial acetic acid to treat the tetraacetyl derivative of oxalyl dihydrooxamic acid makes it possible to obtain 3,4-dihydroxyfurazan, which is a valuable intermediate for the synthesis of new heterocyclic systems.

Claims (2)

Claim 1. 3,4-dihydroxyfurazan formula BUT it is 77 as an intermediate in the synthesis of compounds containing the dioxafurazanyl fragment, reagents in analytical chemistry. 2. A method for producing 3,4-dihydroxyfurazan, as an intermediate in the synthesis of compounds containing a dioxafurazoyal fragment, reagents in analytical chemistry, characterized in that the tetraacetyl derivative of oxalyl dihydroxamic acid is reacted with crystalline sodium hydrate in glacial acetic acid under heating.