SU1085979A1 - Complexes of copper with 4,4-dialkoxy-2-oxybenzalaniline as liquid crystal paramagnetic spin probes and 4,4-dialkoxy-2-oxybenzalaniles - Google Patents

Description

This invention relates to novel complex copper compounds, specifically to copper complexes with 4,4-dialkoxy-2-hydroxybenealaniline of the general formula

OR

where ,, CgH which can be used as liquid crystal paramagnetic spin probes, for example, to determine the value of the parameter of the order of liquid crystal ((LC) matrices).

The complex of metals with Schiff bases flj of the general formula

R is alkyl, aryl;

Where

Me - Sc, Co, Re,

and copper complexes with benalaniline 2 formula

Ro4OVHcl N- (oVoT

HE

where ,,,,,

R ,, With,

9, which possess liquid crystal, but do not exhibit paramagnetic properties.

Known copper complex formula

С 1оНг1н (ОУ- (н (ОУ 1оНг1

    / V- /

o-du-o

/ I / i

joHji QX- (iH-ci -. (gy dioH2, o

which exhibits both paramagnetic and liquid crystal properties 4.

However, the use of this compound for the study of LCD matrices is unknown.

The aim of the invention is new copper complexes with both paramagnetic and liquid crystal properties, which can be used as liquid crystal paramagnetic spin probes for studying LCD matrices.

5 New copper complexes with 4,4-dialkoxy-2-hydroxybenzalaniline of the general formula (I) are described, which are brown shiny crystals, soluble in four carbon tetrachloride, benzene, hot than n-heptane, insoluble in water.

Compounds of general formula (D) are obtained by boiling in anhydrous ethanol of equivalent amounts of copper acetate and the corresponding Schiff base — 4,4-dialkoxy-2-oxybenzalaniline of the general formula

; O) N- {OXOR {n

he

which exhibit para-parasitic properties due to the presence of paramagnetic metals in them.

A disadvantage of the known compounds is their lack of liquid crystal properties, which makes it difficult to use them to study liquid crystal arrays.

The Schiff basis of the general formula is also known.

where ,, CgH,.

Schiff bases of the general Formula I) are new compounds representing yellow crystals, well soluble in chloroform, benzene, acetone, hot ethanol,

practically insoluble in water. They are obtained by heating in ethanol equivalent amounts of the corresponding substituted 4-alkoxy-2-oxybenzalaniline and 4-alkoxybenzaldehyde according to the scheme

KO

HE

01 - “- VOCHOU N-b1- (p) oK + NgO OH where,., CgH .. Example 1. 4,4-Digeksilok-2-hydroxybenzal ANILINE. A solution of 1.3 g (o, 007 mol) of 4-hexyloxyaniline in 8 ml of hot ethanol is poured into 1.5 g of 0.007 mol) 4-hexyl-2-oxybenzaldehyde in 10 ml of hot ethanol. The mixture is warm for 30 minutes. Upon cooling, a yellowish crystalline residue precipitates, which is filtered and recrystallized from alcohol. 1.9 g of 4,4-dihexyloxy-2-oxybenzalaniline are obtained. Yield 73%. Calculated,%: C 75.58; H 8.88; N 3.51. Found,%: C 75.60; H 8.90; N 3.43. Phase transition temperatures; T, T2 127 ° C; dT r-59 ° C (.T is the transition of the substance from the solid-crystalline region to the liquid-crystal region; 1/2 the transition from the liquid-crystal region to the isotropic liquid. The type of mesophase is smectic. In the IR spectrum of this benzalaniline, x-ray the absorption bands of the azomethine groups (CH N) 610 cm and the hydroxyl group bound by an intramolecular hydrogen bond (oi 3030 cm. Example 2.4,4-Dioctyl si-2-oxybenzalaniline. K 1,6.g (o, 0065 mol) 4-octyloxy si-2-hydroxybenzaldehyde in 10 ml of hot ethanol, the solution is poured into 10 ml of ethanol 1.43 g (0.0065 mole of 4-octyloxyaniline. Yellowish crystals precipitated after half-hour boiling and subsequent cooling are filtered and recrystallized from ethanol. 2.5 4.4-dioctyloxy-2-hydroxybenzalhayline are obtained. Exit 84.7%. Calculated: C 76 , 84; H 9.48; N 3.09. C2; Found,%: C 76.90; H, 58; M 3, Temperatures of phase transitions: T,,, 5 ° C; l,. The type of mesophase is smectic The absorption bands in the IR spectra in the region of 1610 cm correspond to the oscillations of m p in the region of 3030 cm to the oscillations (U linked by an intramolecular hydrogen bond. Example 3. Copper complex with 4, 4-dioctyloxy-2-hydroxybenzalaniline. To 1.02 g (0.002 mol) of 4,4-dioctyloxy-2-hydroxybenzalaniline in 50 ml of hot ethanol was added 0.233 g (0.001 mol) of copper acetate in 50 ml of ethanol. The mixture is heated; 1 h. The precipitated brown precipitate is filtered off, washed with water, alcohol and recrystallized from N-hexane. Obtain 0.89 g of the copper complex. Yield 80%; Calculated,%: C, 71.90; H 8.68; M 2.89; C.6, 61. Found,%: C 71.40; H 8.72; N 3.01; C 6.72. Temperatures of phase transitions: Т Т2 163С; . Type of mesophase - disk. In the infrared spectrum of this complex, a characteristic absorption band in the region of 1600 cm is observed, corresponding to oscillations -} (a lower absorption band in the region of 3030, corresponding to m-O vibrations (d disappears. Parameters of the EPR spectrum: g-factors, 21610,003, j 2.049iO, 005; constants of the hyperfine interaction (loi).) Example 4. Copper complex with 4,4-dihexyloxy-2-hydroxybenzo71B aniline. To 1.074 g (o, 0027 mol) of 4,4-dihexyloxy-2-hydroxy-alaniline in 50 ml 0.27 g (0.0013 mol) of copper acetate in 50 ml of ethanol is added to hot ethanol. The mixture is heated for 1 hour. The precipitate is filtered off and washed watered with water, alcohol, and recrystallized from n-hexane to obtain 0.99 g of the copper complex., Yield 86%. Calculated,%: C, 70.01; H, 7.94; N, 3.27; Cu, 7.47. C 70.85; H 7.52; N 3.07; Cu 7.25. Phase transition temperatures: T, T, 164 ° C.; Mee-phase type is disk, in the IR spectrum of the complex the absorption band in the 1600 cm region corresponds to oscillations of MP (o, n) the band of the associated-3 (o) disappears, the parameters of the EPR spectrum: -f factors, –2,216iO, 003,, 04i 10.005, constants of hyperfine interaction (1 A FOm) 1 3-13 (lg). PRI me R 5. The most important characteristics of the LCD matrices that determine their use in electro-optical devices on the LCD / are the dielectric (aE - 6 |,) and optical Lc and I, Id) anisotropy fs. These values are determined, in turn, by the degree of orientation / orientational ordering of molecules) LC - (lp-in i0E-p5 where p is the density of the medium). When, u4g) 0, i.e. the substance is an ordinary liquid. The higher the S value in the LCD matrix, the more suitable it is for various LCD optoelectronic devices. Usually, for liquid cocrystalline matrices 6 d O, 8. In the LCD matrix-p-methoxyboneylidene-P-butylanrshin (MBBD), compounds of the general formula (1) are introduced at a concentration of 10 mol, the EPR spectra are measured, the degree of orientation of the LCD matrix is calculated according to 6. A value of 5 is obtained, equal to 0.78. In the case of the use of a complex of copper with benzalaniline as a paramagnetic probe. W-- ocho; get an underestimated value of S, equal to 0.67. Thus, the proposed compounds of the general formula (l), when used as liquid crystal paramagnetic spin probes, provide reliable information on the orientational support of the LCD matrix molecules.

Claims (1)

In case of use as paramagnetic probe of a complex of copper with benealaniline get an underestimated value of 5 equal to 0.67. 15 Thus, the proposed compounds of the general formula (Ϊ), when used as liquid crystal paramagnetic spin probes, make it possible to obtain 20 information on the orientational ordering of LC matrix molecules.