RU1816762C - Method of selenopyrilium salts synthesis - Google Patents

Abstract

SUMMARY OF THE INVENTION: Product: 2,6-diphenylseleno-pyrilium chlorocincate BF Szd Has CUSe2Zn, 63% yield, mp. 232-234 ° C. 2,6-Dipheny-4-methyl-selenopyrilium chlorcinate BF C36Hi5Cl4Se2Zn. yield 65%, mp. 188-190 ° C. 2-Phenyl-5,6-tetramethylene selenopyrilium chlorzincate BF SzonZoSM5e22p, yield 65%, mp 160-161 ° C. 2,6-Diphenylselenopyrilium tetrafluorobarium BF Ci7Hi3BF4Se, 96% yield, mp. 168-140 ° C, 2,6-Diphenyl-4-methyl-selenopyrilium tetrafluorobarium BF CieHiaBfySe, 90% yield, mp. 172-175RS. 2-Phenyl-5,6-tetramethylene-selenopyrilium tetrafluoroborate BF CisHisBFaSe, yield 98%, mp. 137-140 ° C. 2,6-Diphenyl-selenopyrilium perchlorate BF Ci7Hi3Cf04Se, yield 94 ° C, mp. 187-188 ° C. 2,6-Diphenyl-4-methyl-selenopyrmlium perchlorate BF CieHmCiO4Se, 95% yield, mp. 195-196 ° C. 2-Phenyl-5,6-tetramethylene selenopyrilium perchlorate BF Ci5HisCI04Se, yield 99%, mp. 137-140 ° C. Reagent 1: 0 CR-CHRi-CHR2-CH2-C (R3) 0. where R.Ra-Ph, Ri H, R2 H, CH3, RRi СCH2) 4. Reagent 2: zinc selenide and 12-14 n. a solution of hydrogen chloride in absolute methanol or ethanol. Subsequently, selenopyril chlorozincates are converted by treatment with boron trifluoride etherate, hydrofluoric acid or perchloric acid into the corresponding tetrafluoroborates or selenopyril perchlorates. (L c oo VI O y

Description

conductors; photosensitive materials for electrophotography, etc.

quite complex and do not give good yields of the target product.

The known method based on the interaction. Several methods are known for the preparation of diacetylene ketones with hydroselenide or selenopyril salts, which, however, are 5 sodium followed by a series of transformations.

DgS5SS02n HAG. A.-С.С-ЗНМеЪ

-78 ° C R OH W & X HX

Se + NaB (C2H5) 3H has significant drawbacks: a labor-known method for producing the inaccessibility and high cost of the starting salts of selenopyril based on hydrodiacetylene ketones, multi-stage, as well as selenium derivatives of selenocyclohexa, low yields of target products. 10 on

 A.-С.С-ЗНМеЪ

-78 ° C R OH W & X HX

CH3, C2Hb. X- PF6, BF / i NaHSE + B (C2H5) s

zinc selenide. The reaction time is 2 hours. Yield (V) 2.68 g (65%). Mp 188-190 ° C.

Found,%: C 52.1; H 3.7; CI 17.2.

(Ci8Hi3SeCI) 2ZnCl2

Calculated,%: C 52.24; H 3.65; C117.13.

PMR spectrum: SRzSOOD / (SDz) 250 1: 1; 8.68 ppm (s, 2H, cat), 8.07-7.65 ppm. (m, UN. 2Ph); 2.66 ppm (s, 3H, CH3).

EXAMPLE 12 2-Phenyl-5.6-tetramethylene-selenopyril chloride (VI).

The process is carried out as in Example 1, using 2.3 g (0.01 mol) of 3- {2-oxo-cyclohexyl) -1-phenyl-propan-1-one (II). 40 ml of a 12N solution of hydrogen chloride in abs. Methanol. The reaction time is 2 hours. Yield (IV) 2.4 g (65%), mp. 160-161 ° C.

Found,%: C 47.01; H 3.98; CI 19.05.

(CisGi5SeCI) 2ZnCl2.

Calculated,%: C 47.68; H 4.00; CI 18.76.

PMR spectrum (СД2С 2 / СрзСООД 1: 1) 2.04-2.23 ppm (m. 2H. / 3-CH2), 299-3.43 ppm. (m, 4H, a-CH2), 7.25-7.54 ppm. (m, 5H, Ph), 8.32 ppm. (s, 2H, cat).

Example 13. 2, 6-Diphenylselenopyril tetrafluoroborate (VII) 2.59 g (0.005 mol) of chlorzincate 2,6-diphenylselenopyril (IV) was dissolved in a mixture of 1QO ml conc. hydrochloric acid and 50 ml of hydrofluoric acid when heated to 70-80 ° C. After cooling the reaction mixture, the precipitated crystalline reaction product was separated, washed with ether, dried. Yield (VII) 2.37 g (95.6%). Mp 1b8-170 ° C.

Found,%: C 52.99; H 3.40.

Ci Hi3SeBF4.

Calculated,%: C 53.31; H 3.42.

PMR spectrum (SRzSOOD) 7.11-7.46 ppm (m. UN. Ph). 8.06-8.34 ppm (m. ZN, cat).

Example 14. 2,6-Diphenyl-4-methyl-selenopyril tetrafluoroborate (VIII) 1 g (0.002 mol) of chlorozincate 2,6-diphenyl-4-methyl-selenopyril (V) is heated in a mixture of 50 ml of benzene and 10 ml of boron trifluoride etherate until the salt is completely dissolved (5-7 minutes), after which the reaction mixture that has cooled to room temperature is poured into 300 ml of abs. Ether. The salt is filtered off, washed with abs. ether, dried. Yield (VIII) 0.94 g (90%, mp 172-175 ° C.

Found,%: C 54.38; H 3.02.

CieHi3SeBF4.

Calculated,%: C 54.72; H, 3.32.

PMR spectrum (SDsbM) 2.93 ppm (C. ZN. CHz); 7.66-8.01 ppm (M .. 1, H, Ph), 8.54 ppm. (S., 2H. Cat).

Example 15.2-Phenyl-5-tetramethylene-selenopyril tetrafluoroborate (IX). 0.13 g (0.0003 mol) 2-phenyl-5,6-tetramethylene-selenopyril chlorozincate is heated at 50

ml of 40% hydrofluoric acid in a water bath to 80-90 ° C for 3-5 minutes. The precipitated salt, after cooling the reaction mixture, is separated, washed with ether, and dried. Yield (IX) 0.11 g (98%). Mp 137-140 ° C.

Found,%: C 49-34; H 3.95.

CisHiBSeBF.

Calculated. %: C 49.90; H, 4.19. PMR spectrum (SRzSOOD) 1.74-1.80 ppm (m. 4H, a-CH2), 2.93-3.13 ppm. (m, 4H, Ј-CH2), 7.37-7.50 ppm. (m, 5H, Ph), 8.20 ppm. (s, 2H, cat),

Example 16.2.6-Diphenylselenopyril perchlorate (X). 1 g (0.0025 mol) of 2,6-diphenylselenopyrilyl (IV) chlorozincate is heated with 40 ml of 57% perchloric acid until the starting salt is completely dissolved (3-5 minutes). The crystals precipitated after cooling the reaction mixture were separated, washed with water, and dried. Yield (X) 0.9 g (94%). Mp 187-188 ° C. Literature data: so pl. 187-188 ° C.

Example 17. 2,6-Diphenyl-4-methylselenopyril perchlorate (XI). 2 g (0.004 mol) of Chlorozincate 2, b-diphenyl-4-methylselenopyril (V) is dissolved in a mixture of 10 ml of a 1N solution of sodium methylate prepared from 0.023 g of sodium metal and 10 ml of methyl alcohol and 25 ml of dioxane, then the solution is filtered, poured into 20 ml of 57% perchloric acid. The precipitated salt crystals are separated, washed with water, ether and dried. Yield (XI) 1.89 g (95%). Mp 195-198 ° C.

Found,%: C 51.86; H, 4.02.

CieHi8SeCI04

Calculated,%: C 52-38; H, 4.39.

Literature data: so pl. 195-196 ° C. Example 18 2-Phenyl-5,6-tetramethylene-selenopyril perchlorate (XII). 0.13 g (O., 0003 mol) of 2-phenyl-5.6-tetramethylene-selenopyril chlorine zinc (VI) is heated with 5 ml of 57% perchloric acid in a water bath (3-4 minutes). After the reaction mixture was cooled to room temperature, the precipitated salt crystals were separated, washed with ether, and dried.

Yield (CI) 0.11 (99%). Mp. 137-140 ° C. Found,%: C 47.75; H 3.96.

CisHisSeClO / j.

Calculated,%: C 48.21; H, 4.05.

1 H-NMR spectrum (SRzSOOD / SD2C12 1: 1) 1.87-1.99 ppm (s, 4H,), 3.20-3.43 ppm. (m, 4H, I-CH2); 7.72-7.84 ppm (m, 5H, Ph), 8.56 ppm. s, 2H, cat).

Claims (1)

The claims The method of producing salts of selenopyrilum of the general formula Where R, Ri, Ra, H3 have the above values / 2, ) hydrogen selenide in an acidic medium, which requires that, in order to increase Se. 3 targeted product exits and simplifications .-process, interaction with 1,5-diketone hydrogen selenium is subjected at the moment of its recovery: R, Ra Ph, RI H, Ra H, CH3; the divisions obtained in the course of the reaction selery Rj-RI - (CH2) 4-; zinc niZ with 12-14 n chloride solution And SG 1/2 ZnCl2, BF4, CI04, 10 hydrogen, in absolute methanol or by the interaction of 1,5-diketones with a total zero direct molar ratio of 1,5-dikoformuliton: zinc selenide equal to 1.0: 1.05-1.10,  subsequent transformation I form R Y X L their treatment with trifluoride 00 Rabora, hydrofluoric acid or   , perchloric acid to the corresponding tetrafluoroborates or perchlorates of selenopyri.