SU476748A3 - The method of obtaining bis-stilbene compounds - Google Patents

Description

RT is hydrogen, alkyl;

RS and Rg are the same or different, hydrogen, halogen, Ci-C18-alkyl, cycloalkyl, phenylalkyl, phenyl, alkenyl, hydroxy, alkoxy, aral, coxy or phenoxy, CN, cyanalkyl, carbonyl or its function- major derivative, such as eff or a-mid, carboxy or carbalkoxy alkyl, sulfo group or its functional derivative, such as ether or amide, aminogrunine, and Re and Rg / together with two adjacent carbon atoms of the benzene ring form a six-membered cycle;

RIO is hydrogen or NO3 alkl-yl;

Rii is a —N — A— group, in which A is lower alkyl, alkenyl or hydroxyalkyl or aralkyl.

The proposed method for the preparation of compounds of formula I is that the substance of the general form

is treated with a compound of the general formula RI-X2 or R2-X2, where R, Ri and R2 are as defined above; one of Xi and X2 means 1group 0 CH-, and the other is a residue of the general formula

Y

ABOUT

ABOUT

-CH, -P- OY, SNg-P-OY Jflu

 Y

I

Oy

where Y is unchanged or substituted alkyl, aryl, cycloalkyl or aralkyl, in the presence of strong bases in a polar solvent, followed by separation of the target product by a known technique.

Upon receipt of symmetric bms-stilbene compounds, the ratio between the starting reagents usually | BUT is 1: 2.

IB hydroxides are most commonly used as strong bases, and alkali metal alcohols and alcohols containing up to 25% water are most often used.

Among the solvents, toluene, xylene, chlorobenzol, alcohols, ethanol glycol, ethylene glycol monomethyl ether, preferably .M-methylpyrrolidone, dimethylformamide (DMF), diethylformamide, dimethyl acetone or dimethylsulfonic oxide (DMSO) can be used.

The reaction temperature is 10-180 ° C, preferably 30-60 ° C.

As strong bases, it is better to use lithium, sodium or potassium hydroxides, amides and alcohols of C-C4-primary alcohols. In some cases, it is possible to use alkali metal sulfides and carbonates, aralkyl | Derivatives, for example, phenyl lithium, or strongly basic amines, including ammonium bases, for example, hydroxy |

The resulting compounds of formula I, when dissolved or finely dispersed, have noticeable fluorescence and can be used as optical brighteners for various high molecular weight and low molecular weight organic materials or materials containing organic substances.

Example 1. To a suspension of 60 g of tert-butyl potassium in 125 ml of anhydrous DMF with stirring and 40-50 ° C, a solution of 32.7 g of benzaldehyde-2n sulfonic acid sodium salt containing 70% of free sulfonic acid is added dropwise over 40 min. and 22.7 g of 4,4-b "c- (diethoxyphoofonmethyl) -difenil in 50 ml of anhydrous DMF, was observed

 the formation of a red-brown suspension, stirred for 1 hour at 40-50 ° C and poured into 2.5 liters of cold water. The resulting light yellow solution is heated to boiling, filtered, treated with hot

5 filtrate 375 g of sodium chloride, cool, the separated light yellow product is recrystallized twice from a mixture of 900 ml of water and 90 ml of acetic acid with the addition of 18 g of sodium chloride, once from

0 mixtures of 100 ml of DMF and 1000 ml of water with the addition of 150 g of sodium chloride and twice from 900 or 500 ml of ethanol. . Output 4.0 g (14.2%). To obtain the starting 4,4- (5ms- (diethoxyphosphonomethyl) diphenyl, to 420 g of triethylphosphite at 142-il46 ° C for 3 hours, 301 g of 4,4-bischloromethyldiphenyl in 1200 ml of xylene are added and boiled for 20 hours cooler, the solvent is distilled off, 410 ml of triethylphosphite are added, boil

20 hours under reflux, Excess triethyl phosphite is distilled off, the mixture is cooled to 12: 0 ° C, 500 ml of toluene is added, cooled to room temperature, filtered, the precipitate is recrystallized from toluene and

5 get 361.5 g (66.3%) 4,4-bis- (diethoxyphosphonomethyl) diphenyl

ABOUT

o e gndo ii

II OS, N

Z-TiS

/

sn, -

.P-CH.

-os., n

C, N50gP5

in the form of a white crystalline powder, so pl. 108-110 ° C.

Example 2. To well mixed

89% suspension of 126.5 g of powdered potassium hydroxide in 500 ml of anhydrous DMF in a stream of nitrogen slowly add a homogeneous mixture of 113.5 g of 4,4-by- (diethoxyphosphonomethyl) diphenyl and 129 g of sodium benzaldehyde-2-sulfonic acid, containing 86% free sulfonic acid, maintaining the temperature at 40-45 ° C, stirring for 3 hours at this temperature and pouring into 3.5 l of distilled water with a temperature of 70 ° C.

1.5 kg of sodium chloride and 1.5 kg of ice, 37% hydrochloric acid is added to pH, stirred for 1 hour at room temperature, the precipitate is filtered off, washed with 23% sodium chloride solution, dried and receive 158 g raw product containing 21% sodium chloride and 125 g (89%) of the disodium salt. After recrystallization of the wet precipitate from ethanol, g (72%) of pure product containing 13% sodium chloride is isolated. Further recrystallization from ethanol gives the desired product, which does not contain sodium chloride.

Calculated,%: C 59.78; H 3.58; S 11.40.

С28Н2о№Об52.

Found,%: C 59.62; H 3.54; S 11.19.

When replacing 113.5 g of 4,4-by-b- (diethoxyphosphanmethyl) diphenyl by 99.6 g of 4,4-by-b- (dimethoxyphosphate methyl) diphenyl and using 116 g of sodium benzaldehyde-2 sulfonic acid containing 88% free sulfonic acid, and The reaction time of 5 hours gives 163 g (87%) of a crude product containing 24.5% sodium chloride. The crude product is dissolved in 1600 ml of boiling distilled water, filtered, washed

O N O °

NQll:, S- V-r: H S0, a

in the form of thin yellow needles.

Calculated,%: C, 48.87; H 2.37; S 16.73.

C28Hi8Na40l2S4.

Found,%: C 48.39; H 2.67; S 16.17.

Prymme 4. 22.7 g of 4,4-bis- (diethoxyphosphonomethyl) diphenyl and 14.4 g of i-toluyl aldehyde are dissolved in 100 ml of anhydrous DMF, cooled to 20 ° C, added drop by drop over 15 minutes 20 g

 a form of pale yellow shiny scales, m. pl. 300 ° C

Calculated,%: C 93.22; H 6.78.

SzoN26 Found,%: C 92.98; H 6.64.

At measure 5. 22.7 g of 4,4-b "c- (diethoxyphosphone. Methyl) -diphenyl and 15.7 g of l-ciadbenzaldehyde at 40 ° C and stirring were dissolved in 100 ml of anhydrous DMF, for 20 minutes 20 g of 30% is added dropwise.

(

6

400 ml of boiling distilled water, 400 g of sodium chloride are added to the clear filtrate, cooled, filtered, dried, crystallized and 147 g are obtained.

(86%) of the pure product, which is 18% iatri chloride.

When using instead of caustic potash an equivalent amount of 98% caustic soda, the yield of raw and pure product is 73% 70%, respectively. Besides

in addition, DMSO can be used instead of D. MFA.

EXAMPLE 3. Analogously to example 2 of

113.5 g of 4,4-by-b- (diethoxyphosphonomethyl) diphenyl, 222 g of benzaldehyde-2 disodium salt, 4-di-sulfonic acid containing 70% free sulfonic acid, 800 ml of anhydrous DMF and 126 g of powdered potassium hydroxide after 1 hour get a thick reactive the mixture, which is poured into 1.4 l of distilled water with a temperature of 80 ° C, filtered, cooled to 15 ° C, treated with 5 l of ethanol, the crystals are filtered off, kept in vacuum and get 113 g (59.3% in tetrasodium salt a) product.

After non-recrystallization from a water-methanol mixture, treatment with ion exchange resin and neutralization with caustic soda, pure tetrasodium salt is obtained.

I sojka

(63.3%) 4.4 - bbs - (/ g-methylstyryl) -liphenyl zero, observed temperature increase to 48 ° C and formation of a pale yellow thick suspension, stirred for 1 hour, dispensed 50 ml methanol, neutralized with glacial acetic acid, the precipitate is filtered off, recrystallized from a mixture of 600 ml of DMF and 1200 ml of trichlorobenzene and 12.2 g (63.3%) of 4,4-bg of c- (and methylstyryl) -biphenyl are obtained

“-GU

he.

a solution of sodium methylate in methanol, maintaining the temperature at 50 ° C, the resulting orange suspension is stirred for 5 hours at 45-50 ° C, cooled to room temperature, the precipitate is filtered off, washed well with methanol, recrystallized from a mixture of 500 ml of trichlorobelzole n 250 ml of DMF or 500 ml of trichlorobenzene with the addition of bleaching earth and get 4.2 g (20.6%) 4,4-b "c- (-cyanostryl) -piphenyl

crystalline powder

yellow

in Appleg

7-7 ° I t. Pl. C 88.21, H 4.94; N 6.86.

%:

Calculated

SsoNaoHgFound,%: C 88.08; H 5.15; N 6.92.

Example 6. To a suspension of 13.2 g of potassium greg-butylate in 200 ml of anhydrous DMF at 40-50 ° C and stirring is added in x; ;; lm solution of 3.9 g of methyl ether bin: -f H, C001

CH-CBB as a yellow crystalline powder, so pl. 300 ° C

51.6 g of the obtained diester in 1500 ml of methyl cellosolve and 60 g of a 30% aqueous solution of caustic acid are stirred for 5 hours at 95-100 ° C, cooled, filtered, acidified, washed with aqueous hydrochloric acid, the free dicarboxylic acid is separated washed with water and dried.

 (с-с1

in the form of yellow shiny plates, so pl. 281-283 ° C

Calculated,%: C 75.54; H 4.17; C1 14.67.

SZoNZIOa.

Found,%: C 74.72; H 4.17; C1 14.50.

4.85 g of the obtained hloran.pidridav 200 lgl

H, C

in the form of yellow-green thin needles, so pl. 300 ° C, which is recrystallized from o-dt1-chlorobenzene or DMF.

PRI me R 7. To a suspension of 25.5 g of powdered potassium hydroxide in 120 ml of DMF containing 12% water is added dropwise with stirring and a 40-45 ° C solution of 22.7 g of 4.4- & y- (diethoxyphosphonomethyl) diphenyl and 14.4 g p-toluyldehyde in 50 ml DMF, the resulting yellow suspension is stirred for 2.5 hours at 40-45 ° C, 500 ml of water is added, filtered, the precipitate is washed with water and With Mbanol, 18.1 g (93.8%) of 4,4-b “c- (l-methylstyryl) -DIFE1NYL are obtained in the form of a yellow powder, m.p. 300 ° C. After recrystallization from 1500 ml of trichlorobenzene with the addition of bleaching earth or from a mixture of 750 ml of trinchlorobenzene and 750 ml of DMF, 8.6 g (44.6%) of yellow crystals are obtained, so pl. 300 ° C

In a similar way, bbc-stilbene compounds of the formula I are prepared, where R1 and L are hydrogen listed in the table.

zaldehyde-4-carboxylic acid and 5.0 g 4.4-15 and 1 :- (dieth, xyphosphonomethyl) -diphenyl with 20 ml of DMF, the resulting yellow gusset is stirred for 4 hours at 40-45 ° C, cooled, filtered, and the precipitate is recrystallized from a mixture of 1000 ml of trichlorobenzene and 500 ml of DMF or from 500 ml of DMF and obtain 1.0 g (19-20%) of diester

to 13.4 g of the obtained dicarboic acid in 200 ml of chlorobenzene and 0.5 ml of DMF are added 20 ml of thonyl chloride, heated to 950 ° C, 1 mixture is stirred at 95-100 ° C for 3 hours, cooled, the precipitate is recrystallized twice from o-dichlorobenzene and 7.3 g (50.3%) of acid chloride is obtained

chlorobenzene is refluxed for 6-7 hours at 55-60 ° C, skip the current of dry dimethylamine, cool, filter, wash with methanol, inject and get 4.8 g (96%) of the compound

- (SOOK

300