CS221362B1 - Diaralkylidenmalondialdehydes and method of preparation of the same - Google Patents

Description

The present invention relates to dlaralkylidene malion dialdehydes and a process for their preparation. These substances are new and not yet described. It is useful in two ways. The first field of application is synthetic organic chemistry, since diaralkylidene malonialdehydes are reactive materials that can be converted by cycloaddition and cyclocondensation reactions to a variety of hitherto inaccessible heterocyclic compounds. The second aspect of its possible further use arises from the biological activity - both the substances themselves and the prepared heterocyclic compounds. This group of substances is closest to the aralkylidene malonium aldehydes which have already been described (Z. Arnold, V. Král, author's certificate no. 217 376).

The present invention relates to diaralkylidene malonium dialdehydes of formula I

R1 CHO

CHO (I) wherein R 1 is phenyl, substituted phenyl wherein the substituents are halogen, CH 3 -,

CH 3 O-, -NO 2, -N (CH3) 2, furthermore naphthyl and heterocyclic nucleus with five and six membered ring - 2-thienyl, 2-furyl, 2-pyridyl, 3-pyridyl and 4-pyridyl, and R ² is phenyl, a substituted phenyl, or a heterocyclic ring having a 5- or 6-membered ring, or when the R ¹ and R ² phenyls can be linked at the 3 and 3 'positions by a chemical bond either directly or via a carbionyl -CO- or vinylene group - CH — CH—. A process for the preparation of these compounds consists in that the geminal dihal derivative of the general formula II

Ri \

CX2

R ² / (II) wherein X is Cl, Br, I and R, and R ² is as defined above, is reacted with trimethiniovou salts III t 4 ^N ~ CH ~ CH H _C = -NR CIO _S; din where R ³ is C 1 -C 4 alkyl, in the presence of anhydrous silver perchlorate, aluminum chloride or mercuric acetate221362 in absolute nitromethane, nitrobenzene, 1,2-dimethoxyethane or methylene chloride under cooling, then 8 hours to 3 days at temperature of the compound of formula IV

4-7 * \ _D = □ / \ 'IJN = HO »wherein R ^1, R ^2, R ³ has the abovementioned meaning, is converted to the final product hydrolýziou. Preferably, 1,3-hisdimethylaminotrimethinium perchlorate in absolute intromethane is used as the compound of formula III. Preferably, anhydrous silver chloride was used to generate carbonate ions, resulting in a rapid and unambiguous reaction; aluminum chloride and mercury (II) acetate may also be used.

The reaction is usually carried out by dissolving 1 equivalent of the type III trimethinium salt in absolute nitromethane, adding two equivalents of silver perchlorate and calcium carbonate to neutralize the acid formed. While cooling, 1 equivalent of the appropriate dichloro derivative is added. The reaction is further carried out with stirring, usually for several hours at room temperature. During the reaction, a type IV intermediate is formed which is soluble in nitromethane. The reaction is worked up by filtering off the resulting silver chloride and the remaining calcium carbonate. The solvent was evaporated, the residue was stirred 3X with dry ether. The desired diaralkylidene malonialdehyde is obtained by hydrolysis in a slightly acidic medium, the product is extracted into benzene or benzene-methylene chloride. Very pure products were obtained by silica gel chromatography, crystallization and sublimation.

The present invention is illustrated in more detail by the following non-limiting examples.

[‘.Y; He did

Diphenylmethylenemalondialdehyde

0.497 g (2.2 mM) of 1,3-bisdimethylaminoitrlimethinium perchlorate was dissolved in 15 ml of absolute nitromethane, added 0.829 g (4 mM) of silver perchlorate and 0.5 g of calcium carbonate. Cooled to -35 ° C, then a solution of 0.474 grams (2 mM) of diphenyldichloromethane in 5 mL of absolute nitromethane was slowly added dropwise. The mixture was then stirred in the absence of moisture and light at normal temperature for 6 hours. Then, the intermediate 3X was washed with dry ether (magnetic stirrer 3X20 X). This is followed by hydro-lysis with 150 ml of water, 1 ml of HCl and 5 g of sodium chloride. Extraction into benzene - first stirring 4 hours, then 2X after · 2 hours. Combined benzene extracts dried over magnesium sulphate overnight, solvent evaporated on rotary evaporator. 0.41 g of crystalline substance was obtained. Chromatography in methylene chloride (removal of benzophenion contamination), sublimation (100 ° C / 25 Pa) afforded 0.31 g (66%) of diphenylmethylene malondlaldehyde, m.p. 140-141 ° C.

For: C16H12O2 (236.3)

Calculated ·:

% C, 81.34;% H, 5.12;

Found:

81.12% C, 5.14% H. 1 H-NMR spectrum (CDCl 3, δ):

9.57 (s, 2H, CHO);

7.17-7.60 (m, 10H, 2 * CeH5).

IR spectrum (CHCl 3, cm ^-1) :

p (C = H) CHO 2747 w, 2856w; v (C = O) CHO 1727 m, 1696 m, 1664 m; v (ring) 1597 w, 1580 w, 1490 vw, 1445 m,

1079 watts, 1032 watts; d (C = C) 1553 m, 1539 m, sh.

Mass Spectrum: 236.

Example 1 a d 2

Phenyl-1-naphthylmethylene-maliondialdehyde

0.497 g (2.2 mM) of 1,3-bistrimethinium perchloirate and 0.829 g (4 mM) of silver perchlorate were dissolved in 15 ml of absolute nitromethane, further suspended in 0.5 g of calcium carbonate. Cooled to -35 ° C, nitromethane solution (0.574 g, 2 mM) of phenyl-1-naphthyldichloromethane was slowly added dropwise so that the color of the reaction mixture remained yellow. Allow to warm to room temperature spontaneously, stir for 4 hours, then allow to stand overnight. Aspirated through diatomaceous earth, nitromethane evaporated on a rotary evaporator. The intermediate was stirred 3X with 20 mL dry ether. The hydrolysis was carried out with 150 ml of 3% sodium chloride with the addition of 1 ml of 80% perchloric acid. Extraction of the product into benzene. Stir vigorously for 4 hours (50 mL of benzene), then 2X for 2 hours (2X 50 mL of benzene). The combined benzene extracts were dried with magnesium sulfate, the solvent was removed by rotary evaporation. Yield of crude product 0.45 g. Chromatography in methylene chloride, sublimation (90 ° C / 25 Pa), crystallization (pet5

221382 nalether). Yield: 0.37 g (65%) of phenyl-1-naphthylmethylene-malion-dialdehyde, m.p. 113-114 ° C.

For C20H14O2 (286.3]

Calculated:

83.90% C, 4.93% H;

Found:

83.53% C, 4.87% H. 1 H-NMR spectrum (CDCl 3,,):

9.34 (d, 1H, CHO, I = 2.5),

9.77 (d, 1H, CHO, J = 2.5);

7.21 - 8.0 (m, 12H, anom.

IR spectrum (CHCl3, cm ^-1) :

in CH (CHO) 2746 w, 2859 m;

v (C = O) 1703 ws, 1731 sec, sh, 1669 sec;

H (ring) 1595 m, 1580 m, 1555 m, 1511 m,

1455 m.

Mass Spectrum: HR 286.0993; theory 286.0994.

Example 1 and d 3

9-Fluorenylidenemalondialdehyde

0.5 g of calcium carbonate was added to a solution of 0.497 g (2.2 mM) of 1,3-bisdimethylaminotrimethinium perchlorate and 0.829 g (4 mM) of silver perchlorate in 15 ml of absolute nitromethane. Cooled to -35 ° C, at this temperature a 0.470 g (2 mM) 9,9-dichlorofluorene nitromethane solution was added dropwise with stirring. Allow to warm slowly to room temperature, continue stirring for 8 hours. Carboraffin is added to the reaction mixture, aspirated through diatomaceous earth, and nitromethane evaporated. Intermediate stirred 3X with dry ether, hydrolyzed with 100 mL of 5% sodium chloride solution with 1 mL of perchloric acid. Extraction into benzene - after 5 min. in the organic phase, 9-fluorenone, then hydrolyzed overnight, extracted into benzene with 5% methylene chloride. The combined extracts were dried over magnesium sulfate, the solvent was removed by rotary evaporation. Pure product obtained

a): chromatography on benzene - methylene chloride and subsequent sublimation first at 50 ° C / 25 Pa (residual fluorenone), then pure product at 85 ° C / 25 Pa. 0.22 g (47 percent) of 9-fluorenylidenemalondialdehyde was obtained,

mp 137-138 ° C;

b) crude product dissolved in benzene, shaken with 3X 5 ml of 2N NaOH, combined alkaline fractions shaken with petroleum ether, then acidified to pH 2 with hydrochloric acid, shaken into ether (3X), then sublimated to give analytically pure product.

For C16H10O2 (234.3)

Calculated:

% C, 82.04;% H, 4.30;

Found:

81.93% C, 4.24% H.

@ 1 H-NMR Spectrum (CDCl3, .delta.):

10.5 (s, 2H, CHO);

7.05 - 7.9 (m, 8H, arOm.).

IR spectrum (CHCl 3, cm -1 ⁾ :

vCH (CHQ) 2743 v, w, sh, 2775 w, 2865 w;

ν (0 = 0) 1704, 1664 s;

H (C = C) + H (ring): 1613 sh, 1602 m, 1584 m, 1554 m, 1509 vw, 1450 m.

Mass Spectrum: 234.

Example 4

9.10- ϋϋιγάΓθ-10-οχο ^ 9-Ηηΐ1ΐΓ3ηγΜβηιη3ΐοηdialdehyde

0.497 g (2.2 mM) of 1,3-bisdimethylamino-trimethinium perchlorate and 0.704 g (2 mM)

10.10-dibriimanthron was dissolved with stirring in 25 ml of absolute nitromethane, 0.5 g of calcium carbonate was added, cooled to -30 ° C, and a solution of 0.829 g (4 mM) of silver perchlorate was slowly added dropwise with cooling. overnight, worked up as in Example 1. Chromatography in methylene chloride afforded 0.16 g (31 percent) of the product.

For C17H10O3 (262.3)

Calculated ·:

% C, 77.86;% H, 3.84;

Found:

% C, 77.71;% H, 3.80.

¹ H-NMR spectrum (CDCl 3, δ):

9.83 (s, 2H, CHO).

8.3 (m, 2H, aryl),

7.8 (m, 6H, anom, b).

IC spectrum (CHCl3, cm -1 ⁾ :

v (C = O) CHO 1753w, sh, 1712s, 1677s, v (C = O) (CO) 1677s, 1666s, sh, (ring) (C = C) 1596m, 1588m, 1564 w,

1558 w., Sh.

Mass Spectrum: 262.

Example 5

Bis (4,4‘-dimethylaminophenyl) methylenemalondialdehyde

To 1.073 g (4 mM) of 4,4'-bis (dimethylamino) benzophenone in 10 ml of absolute chloroform was added 0.4 ml of phosphorus oxychloride, allowed to stand for half an hour, then a solution of 0.994 g (4.4 mM) of 1, 3-bisdimethylaminotrimethinium perchlorate in 10 ml absolute chloroform and refluxed for 20 h The solvent was evaporated, hydrolyzed with 20% potassium carbonate solution overnight with vigorous stirring Extraction of the product into 3: 1 benzene-methylene chloride (5X). The solvent was evaporated, chromatographed in methylene chloride-acetone 8: 1 to give 0.06 g of product, mp 75-76 ° C.

For C20H22N2O2 (322.4)

Mass Spectrum 322.

Example 6

Phenyl-4-methoxyphenylmethylene malonialdehyde

0.497 g (2.2 mM) of 1,3-bisdimethylaminotrimethinliumperchlorate and 0.829 g (4 mM) of silver perchlorate were dissolved in 15 ml of absolute nitromethane, 0.5 g of calcium carbonate was added and 0.534 g of nitromethane was added dropwise while cooling to -35 ° C. (2 mM) phenyl-4-methoxyphenyldlchloromethane. Stirred in the absence of moisture and light 6 rods. at room temperature, then do not stand overnight. Work up analogously to Example 1. After hydrolysis, 0.68 g of crude product was obtained, chromatographed 10 in methylene chloride; 0.48 g (90 percent) of phenyl-4-methoxyphenylmethylenedialdehyde was obtained, m.p. 35 ° C.

For C17H14O3 (266.3)

Calculated:

76.68% C, 5.30% II;

Found:

76.59% C, 5.27% H. 1 H-NMR spectrum (CDCl 3, δ):

9.57 (d, 1H, CHO, J = 2.0),

9.54 (d, 1H, CHO, J = 2.0),

6.87 - 7.67 (m, 9H, aroma,

3.87 (s, 3H, CH 3 O).

IC spectrum (CHCl 3, cm ^-1) :

v (ring) 1603 sec., 1575 m, 1444 m, 1077 w, 100W;

v (- OCH 3) 2849 m (CH), 1463 m (£ _as CH 3), 1261 vs (C - O), 1032 m (O - CH 3).

Example 7

Phenyl-4-methylphenylmethylene malonialdehyde

0.829 g (4 mM) of silver perchlorate and 0.5 g of calcium carbonate were added to a solution of 0.497 g (2.2 mM) of 1,3-bisdimethylaminotrlimethinium perchlorate. Cooled to -35 ° C, then a solution of 0.502 g (.2 mM) of phenyl-4-methylphenyldichloromethane was added dropwise. Reaction overnight at room temperature. Work up in the same manner as in Example 1. After crystallization from hexane-carbon tetrachloride, 0.39 g (78%) of the product was obtained, m.p. 125-126 ° C.

For C17H14O2 (250.3)

Calculated:

% C, 81.58;% H, 5.64;

Found:

% C, 81.64;% H, 5.55.

1 H-NMR spectrum (CDCl 3, ,S):

9.48 (d, 1H, CHO, J = 1.8), 9.46 [d, 1H, CHO, J = 1.8), 7.0-7.63 (m, 9H, arom.), 2.42 (s, 3H, CH 3).

IR spectrum (CHCl3, cm ^-1) :

v (C-H) CHO 2747 vw, 2857 w, p (C = O) 1731 m, sh, 1697 s, 1662 m; p (ring) 1609w, 1577w, sh, 1445w, 1077w, 1000w

Mass Spectrum: 250.

Example

Phenyl-4-halophenylmethylene-malonialdehydes

0.994 g (4.4 mM) of 1,3-bisdimethylaminotrimethinium perchioliate was 'dissolved' in 25 ml of absolute nitromethane, 1.658 g (8 mM) of silver perchlorate was added and 4 mM of the appropriate dichloro-derivative (phenyl-4-) was added while cooling to -35 ° C. halo.phenyldichloromethane). Reaction overnight at ambient temperature. Treated analogously to Example 1.

Yield of phenyl-4-chlorophenylmethylene-malonialdehyde 0.56 g (52%) mp 36-38 ° C.

v (C-H) CHO 2747 vw, p (C = O) 1729 m, sh, br, 1695 s, 1661 s;

Prio C16H11CIO2 (270.7)

Calculated:

% C, 70.99;% H, 4.10; Found:

H, 4.02; H, 12.96. 1 H-NMR spectrum (CDCl 3, δ):

9.64 (d, 1H, CHO 2) = 1.6),

9.55 (d, 1H, CHO, J = 1.8),

7.20-7.67 (m, 9H, arom.).

IR spectrum (CHCl3, cm ^-1 ):

v (C-H) CHO 2750 vw; 2860 w;

v (C = O) 1732m, sh, br, 1710m, br, 1668m;

h (ring) 1591 m, 1492 m, 1445 m, 1001 vw.

Yield of 4-bromophenylmethylenemalondaldehyde 0.76 g (60%), mp 69-71 ° C, For C 16 H 11 BrO 2 (315.2)

Calculated:

% C, 60.98;% H, 3.52;% Br, 25.35; Found:

% C, 60.69;% H, 3.48;% Br, 25.12.

@ 1 H-NMR Spectrum (CDCl3, .delta.):

9.66 (d, 1H, CHO, J = 1.8),

9.57 (d, 1H, CHO, J = 1.8),

7.20-7.75 (m, 9H, aram.).

IR (CHCl3, cm ^-1 ):

v {C — HJCHO 2749 vw, 2860 w;

»(C = O) 1732m, sh, 1716m, sh, 1706m, 1696m, sh, 1667m;

v (ring) 1587 W, 1487 W, 1445 W, 1072 W, 1000 W

Mass Spectrum: 314.

Example 1 9

Phenyl-4-nitriophenylenethylenemalondialdehyde

0.994 g (4.4 mM) of 1,3-hisdimethylaminotrimethinium perchlorate and 1.658 g (8 mM) of silver perchlorate were dissolved in 25 ml of absolute nitromethane. After addition of 1 g of calcium carbonate cooled to -35 ° C and with stirring, a nitroimethane solution of 1.132 g (4 mM) of phenyl-4-nitriophenyldichloromethane is added dropwise. The reaction was stirred overnight, worked up in the usual manner (Example 1). Yield of pure product after chromatography in methylene chloride 0.42 g (37%); 1.1. 40-42 ° C.

Prio CieHiiNOá (281,3)

Calculated:

68.33 ο / p C, 3.94% H, 4.98% N;

Found:

68.11% C, 3.79% H, 4.93% N 1 H-NMR spectrum (CDCl 3,?):

9.80 (d, 1H, CHO, J = 1.3);

9.54 (d, 1H, CHO, J = 1.3),

7.20 - 7.70 (m, 9H, arom.),

8.25 (dd, 2H, 8.0, 1.5).

IR (CHCl3, cm ^-1 ):

v (C — HJCHO 2748 w, 2864 m; v (C = 0) 1729 s, sh, 1708 s, 1674 vs; v (ring) 1619 m, 1602 s, 1580 m, 1444 m,

1078 in, 1000W;

v _as (NO2) 1533 s, 1541 s, sh; in _s (NO2) 1350 vs, 1329 s.

Example 10

4-Methoxyphenyl-4-nitrophenylmethylenemondialdehyde

0.994 g (4.4 mM) of 1,3-bis-dimethylaminotrimethinium chloride and 1.658 g (8 mM) of silver perchlorate were dissolved in 30 ml of absolute nitromethane. After addition of 1 g of calcium carbonate cooled to -35 ° C, a 1.256 g (4 mM) of 4-methoxyphenyl-4-nitrophenyldichiomethane was added dropwise at this temperature overnight at room temperature.

1). Chromatography in methylene chloride, yield 0.62 g (50% / o) of product, mp 46-48 ° C.

For C17H13NO5 (311.3)

Calculated ::

C, 65.59; H, 4.21; N, 4.50;

Found:

65.66% C, 4.25% H, 4.46% N. 1 H-NMR spectrum (CDCl 3, δ):

9.80 (d, 1H, CHO, J = 1.1),

9.65 (d, 1H, CHO, J = 1.1),

7.0 - 7.60 (6H, m, arom.),

8.30 (dd, 2H, arom.), (M-NO 2),

3.90 (s, 3H, CH ₃ O).

iC spectrum (CHCl 3, cm ^-1 ):

v (C-H) CHO 2750 vw, 2860 w; v (CH 3) OCH 3 2850 w; v (G = 0) 1732 m, sh, 1703 m, 1669 m; h (ring) 1603 sec, 1573 m, 1491 w, sh, 1442 w;

in _{as (NO2),} 1532 m, 1542 m, SH;

_S (N%) 1349 s, 1333 m;

OCH3: and _As (CH3) 1,463 watts;

v (C-O) 1261 s, v (O-CH 3) 1030 m.

Example 11

Phenyl-X-pyridylmethylenemalondialdehydes (X = 2,3,4)

0.994 g (4.4 mM) of 1,3-bis-dimethylaminotrimethinlumperchlarate and 1.658 g (8 mM) of silver perchlorate were dissolved in 25 ml of absolute nitromethane and 1 g of calcium carbonate was added. Cooled to n, and -35 ° C, a nitriomethane solution of 0.952 g (4 mM) of phenyl-X-pyridyldichloromethane (X = 2,3,4) is added dropwise. Reactions at room temperature, stirred for 48 hours. Aspirate through diatomaceous earth, evaporate nitromethane, stir the intermediate 3X with dry ether. Hydrolyzed with 100 mL of 5% NaHGO 3 solution, with the addition of sodium chloride. Extracted into benzene-methylene chloride 5: 1, 5X for 2 h at vigorous; stirring. The combined extracts were dried over magnesium sulfate. Then the solvent was evaporated on a rotary evaporator; the crude product is chromatographed in methylene chloride.

Yield of phenyl-2-pyridylmethylene-malondialdehyde 0.48 g (51%), mp 70-72 ° C. Pro.CisHiiNOa (237.3)

Calculated:

75.94% C, 4.67% H, 5.90% N;

Found:

% C, 75.76;% H, 4.62;

¹ H-NMR spectrum (CDCl 3, SS):

9.67 (s, 1H, CHO);

9.53 (s, 1H, CHO);

8.88 (ddd, 1H, aroma, 5.0 1.0, 1.0),

7.05-7.82 (m, 8H, arom.).

IR spectrum (CHCl 3, cm ^-1 ):

u (C-H) CHO 2735 vw, 2763 vw, 2858 m; v (0 = 0) 1717 w, sh, 1670 sec; v (ring) 1605w, sh, 1597w, 1583m, 1572w, sh, 1444w, 1077w, 1030w.

Mass Spectrum: 237.

Yield of phenyl-3-pyridylmethylenemalondialdehyde 0.56 g (59%), distillation 110 ° C / 25 Pa.

Prio C15H11NO2 (237.3)

Calculated:

75.94% C, 4.67 θ / ο H, 5.90 θ / ο N;

Found:

75.81% C, 4.59% H, 5.79%;

1 H-NMR spectrum (CDCl 3, δ):

9.64 (d, 1H, CHO, J = 1.3);

9.78 (d, 1H, CHO, J = 1.3);

J.2

8.50 (bs, 1H, pyridine),

8.78 (dd, 1H, pyridine, 4.5, 2.0),

7.08-7.72 (m, 7H, ariom).

IR (CHCl3, cm ^-1 ):

, in (C-HJCHO 2748 vw, 2862 w;

(C = O) 1729 .mu.m, 1705 m, 1670 s; v (ring) 1615 m, 1584 m, 1557 m, 1478 m,

1445w, 1078w, 1026m, 100lw.

Yield of phenyl-4-pyridylmethyl-malondialdehyde 0.75 g (79%), mp 59-60 ° C. Prio C15H11NO2 (237.3)

Calculated:

75.94 θ / ο C, 4.67 θ / ο H, 5.90 θ / ο N;

Found:

75.79 θ / ο C, 4.63 θ / ο H, 5.79 θ / ο N. 1 H-NMR spectrum (CDCl 3, δ):

9.75 (d, 1H, CHO, J = 1.5);

9.66 (d, 1H, CHO, J = 1.5);

7.05-7.72 (m, 9H, arom.).

IR (CHCl3, cm ^{@ -1} ):

v (C-H) CHO 2750 vw, 2862 w; v (C = O) 1729m, sh, 1710m, 1673m; in (ring) 1596 w, 1581 w, 100Ovw.

Example 12

Phenyl-2-thienylmethylenemallondialdehyde

0.497 g (2.2 mM) of 1,3-bisdimethylaminotrimethinium perchlorate and 0.829 g (4 mM) of silver perchlorate were dissolved in 15 ml of absolute nitromethane, 0.5 g of calcium carbonate was added; and cooled to -35 ° C. At this temperature, a nitriomethane solution of 0.486 g (2 mM) of phenyl-2-thienyldichloromethane is added dropwise. The reaction was worked up analogously to Example 1. After chromatography in methylene chloride, 0.38 g (78%) of the product was obtained, m.p. 123 ° C.

For C14H10O2S (242.3)

Calculated:

69.40 θ / ο C, 4.16 θ / ο H, 13.23 θ / ο S;

Found:

69.52 θ / ο C, 4.18 θ / ο H, 13.11 θ / ο S.

¹ H-NMR spectrum (CDCl 3, δ):

9.80 (d, 1H, CHO, J = 1.8),

9.46 (d, 1H, CHO, J = 1.8),

7.08 - 7.68 (m, 7H, arom.),

7.8 (dd, 1H, thiophene, 5.0 1.5).

IR spectrum (CHCl 3, cm ^-1 ):

(C-H) CHO, 2748 vw, 2865 w;

v (0 = 0) 1722m, 1694s, 1694s, 1661m; in (ring) C4H3S-1540 m, 1414 s; v (ríng) C6H5— 1597 W, 1445 W, 1078 W,

1030 Vw, 1000 VW.

Example 13

Bis (2-thienyl) methylene malondiialdehyde

0.497 g (2.2 mM) of 1,3-bisdimethylaminothylmethylium pentochloirate and 0.829 g (4 mM) of silver hypophosphite dissolved in 15 ml of absolute nitroxnethane, added! 0.5 g of calcium carbonate and cooled to -35 degrees Celsius; 0.37 g (2 mM) of his (2-thienyl) dichloromethane was added dropwise at this temperature. Reaction 24 hours at normal temperature. Treated in the usual manner (Example 1). Obtained. 0.25 g (50%) of product, m.p. 168-169 ° C.

for C12H8O2S2 (248.3)

Calculated:

58.04% C, 3.25 θ / ο H, 25.82 θ / ο S;

Found:

58,12 "/ o C, 3.21 _0/0 H 0 25.53 / ₀ s.

¹ H-NMR spectrum (CDCl 3, δ):

9.65 (s, 2H, CHO);

7.83 (dd, 2H, thiophene, 5.0 1.4),

7.23 (t, 2H, thiophene, 5.0),

7.47 (dd, 2H, thiophene, 5.0, 1.4).

IR spectrum (CHCl 3, cm ^-1 ):

v (C-H) CHO 2749 vw, 2850 w; ν (0 = 0) 1721 m, 1691 s, 1658 s; in (ring) C4H3S-1523 m, br, 1414 s, 1351 w, 1234 m.

The process of the present invention is useful for the preparation of a variety of diaralkylindemailondialdehydes (starting material geminal dichloro derivative and 1,3-bisdimethylamine trimethinium perchlorate). A great advantage of the process according to the invention is that, in a simple experimental setup with readily available raw materials, the hitherto unwritten diaralkylidenemaldehyde dialdehydes are obtained as very pure products in high yields. Further, these compounds can be used in organic synthesis to prepare a variety of potentially biologically active heterocyclic compounds.

Claims (2)

the subject of the invention What is claimed is: 1. A diaralkylidene malonialdehyde of the formula I < CH 2 (R) wherein R ¹ is phenyl, substituted phenyl, wherein the substituents are halogen, CH 2 -, CH 2 O-, -NNO 2, -N (CH 3) 2, 1-naphthyl and a 5-membered heterocyclic ring and a 6-membered ring, 2-thienyl, 2-furyl, 2-pyrldyl, 3-pyrldyl and 4-pyrldyl, and R ² is phenyl, substituted phenyl, or a heterocyclic ring having a 5- or 6-membered ring, optionally if R ¹ and R ^{The 2-} phenyls may be linked at positions 3 and 3 'by chemical bonding either directly or via carbones 1 -CO- or a vinylene group -CH = CH-. 2. A process for the preparation of the diaralkylidene malondialdehydes of the general formula I according to claim 1, characterized in that the geminal dihallogenderivative of the general formula II Rl \ CX2 z R2 wherein X is Cl, Br, I, and R ¹ and R ² is as defined above, is reacted with trimethiniovou salts III rIn-CH = CH-CH = NR ₃ ClO ³ (III) wherein R ³ is C 1 -C 4 alkyl in the presence of silver perchlorate, aluminum chloride, or mercuric acetate, in absolute nitromethane, nitrobenzene, 1,2 ^L dimethoxyethane, or methylene chloride under cooling and at room temperature and thereafter the resulting intermediate of formula (IV) is CH 2 ^{+ 2} C 10 C = c 2, / \ 3 Rc = CH-NR1 L- ¹ (iv) wherein R ¹ , R ² , R ³ is as defined above, by hydrolysis to convert to the final product.