SU1467054A1 - Derivatives of o-sulfobenzoic acid as intermediate compounds for producing soluble polymers electrically conducting upon doping with iodine - Google Patents

Abstract

The invention relates to sulphonic acids, in particular, to o-sulfobenzoic acid formulas, COR Ol where SOjNQ which can be used as intermediate compounds for the synthesis of monomers used in the preparation of soluble polymers having electrical conductivity after doping . The goal is to detect new compounds of the indicated class with useful properties. Their preparation is carried out by the reaction of Friedel-Crafts acylation of various bi-cal aromatic hydrocarbons (diphenyl, fluoren) with o-sulfobenzoic acid anhydride in the presence of anhydrous aluminum chloride. Output 50-70% of theoretical. 1 tab. W (L

Description

The invention relates to the synthesis of new chemical compounds, specifically to derivatives of o-sulfobenzoic acid of the general formula ^CH 2

which can find application as intermediate compounds for the synthesis of monomers. used in the preparation of soluble polymers having electrical conductivity after doping. The goal is to identify new compounds of this class that have useful properties. Their preparation is carried out by the Friedel-Crafts acylation reaction of various binuclear aromatic hydrocarbons (diphenyl, fluorene) with o-sulfobenzoic acid anhydride in the presence of anhydrous aluminum chloride. The yield of 5O-7OZ is theoretical.

t abl.

which can find application as intermediates for the synthesis of monomers used in the preparation of soluble polymers having electrical conductivity after doping.

The aim of the invention is the search for derivatives of o-sulfobenzoic acid, which can be used as intermediates in the synthesis of monomers used to obtain soluble and ₉ > SU. 1467054 A1 polymers - polyarylene sulfophthalides having electrical conductivity) after doping with iodine.

Example 1. Sodium salt of 2 (4-phenylbenzoyl) sulfobenzoic acid.

20 g (0.1086 mol) of o-sulfobenzoic acid anhydride, 66.7 g (0.43 mol) of diphenyl, 37.6 g (0.28 mol) without aqueous chloride are charged into a flask equipped with a hydraulic shutter mixer aluminum. After stirring, the mixture in the flask is heated to 90 ° C (in the bath), after 4 hours the resulting homogeneous solution is unloaded in 800 ml of chilled water and left for 10 hours. After that, the suspension is filtered, the filtrate is treated with 20% NaOH solution. The precipitated (finely dispersed precipitate containing aluminum) is filtered off, the filtrate is evaporated by half, cooled. The precipitated crystals of the sodium salt of 2- (4-phenylbenzoyl) sulfobenzoic acid are filtered off, washed with a small amount of cold water. After drying in an oven (80 C, 10 h), twice crystallization from ethyl alcohol, washing with sulfuric ether and drying (80 ° C, 10 h), 29 g (75% of theory) of the expected product are obtained in the form of a white crystalline powder with a mp of 296-298 ° C.

Found,%: C 63.19; H 3.59;

S 8.67; Na 6.26.

CH ₄₈ SO ₄ Na "

Calculated,%: C 63.3; H 3.6;

8.9; Na 6.38.

IR, cm '”': 1200, ^ _s _ _o = 1675.

EXAMPLE 2 Sodium salt of 2- (2-fpuorenoyl) sulfobenzoic acid

In a flask equipped with a stirrer with a hydraulic shutter; 10 g (0.055 mol) of o-sulfobenzoic acid anhydride and 20 g (0.15 mol) of anhydrous aluminum chloride are charged.

The mixture is stirred and then 36 g (0.216 mol) of fluorene are added and the synthesis is carried out at 90 ° C for

h. The product is discharged into chilled water. Further, similarly to example 1. After drying (80 ° C, 10 h), twofold recrystallization from ethyl alcohol, washing with sulfur dioxide, drying (80 ° C, 10 h), 10 g (50% of theoretical) of the desired product are obtained in the form of white amorphous substances with so pl. 330-332 ° C.

Found,%: C 63.7; H 3.65; S 8.2; Na 5.94.

C _{2 °} H S0 ₄ Na

Calculated,%: C 64.5; H 3.48;

S 8.6; Na 6.18.

IR, cm ^-1 : Э _5Ог = 1205.9 _С _ _О = 1670.

Example Z. Monomer production

2.1- benzoxatzol-3-chloro-3-diphenylyl-

1.1-dioxide.

5 g (0.014 mol) of sodium salt of 2- (4-phenylbenzoyl) sulfobenzoic acid, 15.0 ml (0.208 mol) of thionip chloride, 25 mp benzene, 0.02 mp (0.000248) are charged into a flask equipped with a reflux condenser. mol) of pyridine, heated at 90 ° C for 3 hours. The hot solution was filtered off from sodium chloride, the filtrate was evaporated to 15 ml, and cooled. The precipitated crystals are filtered off, washed with hexane and dried in vacuo (50 ° C, 6 h). After drying, 4.3 g (86.8% of theory) of the expected product are obtained in the form of a white crystalline powder with a melting point of 168-170 ° C.

Found,%: C 63.38; H 3.64;

S 8.10; C1 9.73.

C ₄₉ H „SO, Cl

Calculated,%: C 63.95; H 3.59;

S 8.97; C1 9.95.

IR, see “: ίsol = 1200; ^ ₅₀ " ⁱⁿ = 1365.

The monomer 2,1benzoxathiol-3-chloro-3-fpuorenoyl-

1.2-dioxide, mp 162-164 ° C.

Found,%: C 64.57; H 3.9;

S 8.06; C1 9.5.

Calculated,%: C 65.10; And 3.52; S 8.68; C1 9.63.

IR, cm '': -? ^ = 1205; · Ί οξ ₅ ⁵ = 1368.

PRI me R 4. Obtaining a polymer.

In a three-necked flask, equipped with a stirrer with a hydraulic shutter, an air cooler, 8 g (0.0224 mol) are charged in an argon stream

2.1- benzoxathiol-3-chloro-3-diphenyl-

1.1-dioxide, 11.17 ml (2 mol / l) nitrobenzene, 0.14 ml (5 mol%). SbCl ₅ and carry out the synthesis at 100 ° C (in the bath) for 10 hours. Next, the polymer is dissolved in dimethylformamide and precipitated.

in ethanol, the polymer is filtered off, washed with sulfuric ether and dried (90 ° С, 10 h) in an oven. After drying, 7.0 g (97% of theory) of the polymer in the form _of white amorphous powder with a given viscosity hydrochloric · ^ _"e ^c = about 84 dl / g measured in tetrahporetane.

Found,%: C 70.60; H 3.91; S'9.54.

Calculated,%: C 71.25; B 3.75; S 10.0.

PRI me R 5. Preparation of electrically conductive material.

0.5 g of the polymer prepared as described above is dissolved in 5 cd of tetrachloroethane and the resulting solution is poured onto a horizontally mounted plate with an area of 50 cm * After evaporation of the solvent at room temperature, a transparent, uniform film of 90-100 microns thick is obtained. After saturation of the film at 40 ° C with iodine, the electrical conductivity is 4.2 · 10 ' ⁴ Ohm * cm ~ ¹ .

Similarly, a polymer is prepared using 2,1-benzoxathiol-3-chloro-3-fluoroenoyl-1,1-dioxide as a monomer. Their physicochemical properties and structural evidence are given in the table.

The advantages of electrically conductive polymers - polyarylene sulfophthalides obtained on the basis of intermediate compounds - derivatives of o-sulfobenzoic acid over polyphenylins described in the literature are as follows.

Polyarylene sulfophthalides have an electrical conductivity after doping with iodine equal to 4.2 · 10 “ ⁴ 0m ~ cm ~.

Polyarylene sulfophthalides are soluble> 1 in common organic solvents (tetrachloroethane, dimethylformamide, cyclohexanone). At room temperature. This makes it possible to obtain electrically conductive materials in the form of films by the method of irrigation from a solution, which ensures reproducibility of characteristics, as well as the possibility of plasticizing and obtaining electrically conductive compositions.

Known polymers - p-polyphenenes have an electrical conductivity after saturation with iodine equal to 1 ·. 10 Ohm cm, they are not soluble in organic solvents and cannot be obtained in the form of films from a solution by irrigation.

Claims (1)

Claim Derivatives of o-sulfobenzoic acid of the general formula as intermediates for the synthesis of monomers used in the preparation of soluble polymers,. having electrical conductivity after doping with iodine. N.R. - insoluble, P - soluble.