SU789524A1 - Pyrazolo(1,5-a)pyrimidinium derivatives as intermediate products in synthesis of polymethyn dyes - Google Patents

Description

Calculated,%: CE 9.7, N 11.5.

The dye distyril. A mixture of 0.18 g (0.5 mmol) of perchlorate, 0.16 g (1.1 mol) of p-dimethylamino-hexaldehyde and 2 ml of acetic anhydride boil for 15-20 minutes. After cooling, the precipitated dye crystals are filtered off, washed with ether (0.26 g, 84%) and recrystallized from acetic anhydride, mp 7350.

(e-10 -) nm: 518 (3.6), 622 (6.3).

Found,%: С С 5.9.

. Nzb C

Calculated,%: С С 5.7.

PRI mme R 2. 2,3-dimethyl-g1-phenycyclopenta (3,4) pyrazolo (1,5-a) pyrimidinium perchlorate. A mixture of 1.5, g (7.5 mol). 3-anilino-4,5-trimethylenepyrazole, 1.5 ml of 13 mol of 3-chloro-2-methyl butene-2-al and 2 ml of trifluoroacetic acid are heated in a water bath for 20 minutes and left to stand for 24 hours at room temperature. The resulting solution was then diluted twice with ether and 1 ml of 57% perchloric acid was added. The precipitate is filtered off, washed with ether and receive 2.52 g (54%) of a mixture of 2,3 - and 3,4-dimethyl derivatives in a 1: 1 ratio. After four recrystallizations from methanol, 2,3-dimethyl isomer was isolated in pure form. M.p. 249252. PMR: 2.23 and 2.32 (2- and 3-CH). 1.5-3.0 (methylene groups), 7.3 (wide phenyl peak), 8.95 (4: H). UV: 249 (1.1), 252 (1.1), 262 (1.0), 394 (0.13).

Found,%: 019.9.

 .

Calculated%: CE 9.7.

Dye styryl. A mixture of 0.15 g (0.4 mol) of perchlorate, 0.1 g (0.7 mol) of p-dimethylaminobenzaldehyde and 2 ml of acetic anhydride is boiled for 5 minutes. After treatment as in example 1, the dye was obtained with a quantitative yield. M.p. 238-241 ° (from ethanol). PMR: 2.37 (W-CH) / 3.03 (dimethylamino group).

Found,%: C g 7.3.

S2bNa.7SEM404

Calculated,%: C 2 7.2 578 / 8.0 (in ethanol).

Prima rz. 2,4-dimethyl-1-phenyl-7, 8,9,10-tetrahydropyrimido (1,2-b) indazolium trifluoroacetate, iodide and perchlorate. A mixture of 3.2 g (15 mol) of 3-anilino-4,5-tetramethylene pyraeol, 1.8 g (18 mol) of acetyl-acetone and 2.05 g (18. Mol) of trifluoroacetic acid is heated on a water bath for 20 minutes. After cooling, the viscous brown mass is triturated with ether, the precipitate of trifluoroacetate (3.6 g 61%) is filtered off and the ethyl acetate is recrystallized. M.p. 110-111. PMR: 2.34 (2-CHO,), 2.87 (4-CHg), 1.2-2.8 (methylene, groups), 7.22 (3-H), 7.3-7.9 (aromatic protons). Found,%: N 10.9.

-20 go z g

Calculated: N 10.7.

J Perchlorate was obtained from trifluoroacetate and 571 in an alcohol solution. M.p. 162-163 (from ethanol).

Found,%:, 6

C.eHj-oCFN O Q Calculated: C 2 9.4.

Iodide is obtained from trifluoroacetate and KE in an alcohol solution. M.p. 192195 ° (from ethanol). Found,%: M 10.2.

C g N 20 3 N ,,

5 Calculated,%: N 10.4.

Symmetric carbocyanin. A solution of 0.39 g (1 mol) of trifluoroacetate and 0.3 ml (2.2 mol) of triethylorthoformate in 1 ml of acetic anhydride is boiled for 10 minutes. After cooling, 0.2 g (1.4 mol) of NaCEC-H O is added and the precipitated precipitate is recrystallized from ethanol. Yield 0.25 g (75%).

G4

T.PL. 282-284 °, A (.10): 608

11.3 ethanol.

Found,%: Cit 5.5j N 12.9.

Calculated,%: Cg 5.3, N 12.6.

PRI me R 4. 2,4-dimethyl-1-fe0nylpyrimido (1,2-c) indazolium perchlorate. A mixture of 2.1 g (10 mmol of 3-anilinoindazole, 6 ml of trifluoroacetic acid and 1.2 ml (12 mol) of acetylacetone) is boiled for 20 minutes. The excess of tri5 fluoroacetic acid is distilled in

vacuum water jet pump when heated in a water bath. The dark yellow thick oil is dissolved in 3-4 ml of ethanol and 1.25 ml of 57% is added.

0 NSEO. The precipitate (1.7 g) is filtered off and another 0.3 g of product is isolated from the filtrate by precipitation with ether. Total yield 2.0 g (54%). M.p. 243-245 with razl. (from ethanol). PMR: 2.65 (2-CH), 3.15 4-CHj, 5.85 (10-n, d

  Hz), 6.3-7.3 (aromatic prototypes)

Found,%: Ct 9.5. C.gH. Calculated,%: C 9.5.

0 Dye stiril. A mixture of 0.37 g (1 mol) of perchlorate, 0.15 g of 1 mol) p-dimethylaminobenzaldechga. Yes, and 2.5 ml of acetic anhydride is heated in a water bath. 20 minutes.

5 A precipitate is formed from the blue-violet solution, which after cooling is filtered, washed with alcohol and ether. 0.45 g (90%) of green crystals are obtained,

Q T. 350 (from a mixture of muranoic and acetic acids). CR: 2.50 (2-CH) 3.13 (dimethylamino group), 5.85 (10-H, d, Hz) 6.6-7.4 (ethylene and aromatic protons). L. / vvciicc

5 (f-lO--): 610 (6.3).

Found,%: C t 7.0.

CgT H,

Calculated,%: Cl 7.0.

The dye distyril. A mixture of 0.1 g (0.27 v1ol) perchlorate, 0.1 g (O, 7 mol) p-dimethylaminobenzaldehyde and 2 ml of acetic anhydride was boiled for 15 minutes. After cooling, brown-green crystals (0.15 g, 90%) are filtered off and recrystallized from a mixture of acetic and formic acids (4: 1). T. 350 °. Lmax (f 10): 620 (6.1), 560570 (4.0) ethanol.

Found,%: C I 5.7.

, 04

Calculated,%: C 5.6.

EXAMPLE 5 2-methyl-1,4-dipheniprimido (1,2-b) indazolium perchlorate A mixture of 0.63 g (3 mol) of 3-anilinoindazole, 0.55 g (3.4 mol) of benzoylacetone and 2 ml of trifluoroacetic acid is heated in a water bath for 1 hour and then refluxed for another 40 minutes. The orange-red solution, when cooled, solidifies into a crystalline mass, which is dissolved in an ethanol-ether mixture (1: 2), 0.4 years of 57% HC 204 is added, and 0.82 g of brick-red powder is filtered off (59%) . M.p. 298 (from acetic acid), PMR: 2.50 (2-CF), 5.83 (10-6. Hz), 6.7-7.8 (aromatic protons).

Found,%: Cr 8.2.

.dSgMzO

Calculated: C 8.1.

Dye styryl. Obtained by boiling perchlorate with a 1.65-fold excess of p-dimethylaminobenzaldehyde in acetic anhydride for 15 min with a yield of 89%. M.p. 275-277 (of acetic anhydride)): 597 6.9 in ethanol.

Found,%: C 6,1.

Calculated: C 6.3.

PRI me R 6. 7-anilino-2,4-dn methyl-1-phenylpyrazolo (1,5-a) pyrimidine perchlorate. A mixture of 0.50 g (2 mol) of 3,5-dianinopyrazole, 0.5 ml (5 mol) of acetylacetone and 1 ml of trifluoroacetic acid is heated on a water bath for 0.5 hour. After cooling, ether O is precipitated, 75 g of a yellow-orange substance, which is dissolved in 10 MP of ethanol and added with 0.55 ml of 57% HCifQ-obtained

0.65 g (60%). T. 253-255 (from ethanol). PMR: 2.03 (2-CH) 2.52 (4-CH ,,) 5.20 (8-H), 6.53 (3-H), 6.6-7.4 aromatic protons.

Symmetric carbocyanin. Obtained similarly to the dye of example 3 with the release of 60%. M.p. 350 (from ethanol) .L, ks (MO): 640 (4.6). Found,%: C 4.8, N 15.3, C H jCFNgO

Calculated,%: C 4.8; N 15.2.

Claims (1)

Invention Formula Pyrazolo derivatives (1; 5-a) pyrimidini of the general formula ss, „IV | in -5 Ya .N. jt where R-CHj; R-CHj HfB -CHj, R fy 35 together with k- (CH)} (S,}, CH CH-SISN) R-Seo, y, as intermediates for the synthesis of polymethine dyes. Sources of information taken into account in the examination l.W.Ried.R.P. Peuctier-t, -Ann 1965, 682, p.141.