Manufactoring process of aldehydes of polyméthines unsaturated

MINISTRY OF COMMERCE AND INDUSTRY. DIRECTION OF THE INDUSTRIAL PROPERTY. * 4 *PATENT. Gr. 14.-Cl. 1. [...] 823,384

Society said: g. [...] I. AKTIENGESELLSCHAFT residing in Germany. Demanded 28 October 1937, to 14^{m h 50,} to Paris. .-Published 17 May 1938 Issued 7 February 1988.

The Requester has been found that a ob- aldehydes of polymethines holds non- saturated valuable, by treatment of colo- agents of the general formula R * Pf fl? R³Lc-= Cj " - 0 = vf X = acid radical R " h⁴wherein R1, R_{3 =} = [...] ; R_2, R = 4" alkyl, R_{ls R2 and}R_3, R_{4 capable of forming a} nuclear system simple or substituted; X = = acid radical any, by example halogen, acid radical [...], acid radical-aryl sulfonic; N = un integer 1, 2, 3, with h alkalis in the presence of a- [...]attitude. The strong alkali are used in smaller- molecular [...], the low alkali can excess also be used. The reaction is performed, preferably, to the heat boiling. Therefore, it can, by example, distilling water vapor, as a pre- presence of alkaline agents, solutions-point its-alcoholic dye of the pro- starting said. A molecule of the base aromatic secondary is then removed and replaced by oxygen. The Acid released during the reaction is combined with the alkaline agent in the presence. Dyes of polymethines g_{0 as starting materials} can be made, for example, by reacting secondary and primary amines with furfural or its peers of upper [...] and acylating or [...] the hydroxyl compound 35 obtained, according to the method of French patent application filed on October 1987 [...] the name of the Requester for: "A method for the preparation of dyestuffs to the [...]". ko Since starting materials, also can utilize dyes which are substituted in the chain polymethine, for example with a halogen, alkyl or a [...]. The substituent appears then also, well [...] 5 tensioned, in the molecule of the aldehyde. As alkaline agents, may be used alkali hydrates, hydrates [...] alkali, alkaline carbonates or other inorganic bases, further 5o organic bases. The novel aldehydes of polymethines are distinguished by high reaction. They may be employed, by! example, for the synthesis of dyes of polymethines 55. The aldehyde with three! [...] conduit groups, after reaction Price the booklet: 10 francs. with salts of [...] of heterocyclic bases, to [...], the aldehyde with 7 [...][...] and groups to the aldehyde with 9 leads to the methine groups [...]. Example 1.-iso of the yellow dye gr. (obtained by utilizing tetrahydroquinoline, of [...] and hydrochloric acid after Claisen) are dissolved in 600 cm^{3 of}[...] ; the hot solution is added to 600 cm^{3 of} hot water; the yellow solution is added with intensive 2,0 gr. magnesium oxide, very finely powdered; is then introduced water vapor slightly superheated. Methanol is first evacuated by distillation and, later, the separate tetrahydroquinoline (molecule 1) passes in distilled. When it is no longer removed from amine, the aldehyde is ether extract or benzol at of the liquid become almost colourless. The remover is almost completely evaporated from the dried solution of the aldehyde; there remains a thick yellow liquid which, after cooling (optionally after grinding with the glass rod or by seeding) is solidified at the crystalline state. The mass is washed with a little absolute ether and is pressed onto _AOE280A2AO>-clay or [...]. The new aldehyde of formula likely: shape of the crystals well shaped. color very slightly yellowish. The solution in the methanol is almost colourless. The melting point is to 8i °. Example 2. - io gr. of the violet dye likely the formula: GH" Ch^{2/v \}H^{2 ch 2 c}₍H? d N-CH CH-GH = = CH-CH = CH ~ CH = N\Br ' produced by French patent application aforesaid, are dissolved in 100 cm^{3 of} hot methanol, the solution is added to 100 cm^{3 of hot water and 45} 2 gr. magnesium oxide; is then introduced into the composition of the water vapor (as indicated in the example 1); after removal of the amine, added methanol, and then extracts at 5o benzol; benzyloxycarbonyl the extract is dried and evaporated. Abundant There is a crystallization of the aldehyde of formula likely following: Properties of the aldehyde: small needles fine brown-red, soluble in methanol, benzol, the vinegar glacial, with a color of an intensive yellow. Melting point 159°. 60.-level i Example 8 gr of the violet dye. Ch^{2 [...]} ' ch , I^CH 2 H^{2 Ci}ICH^{2 H} |^{2 d} N-CH = CH-CH CII-C = = = N CH-CH of [...] and tetrahydroquinoline is dissolved in 16 cm^{3 of} hot methanol, [...] 5 cm^{3 is added hot water} and o, has gr. 65 of [...] ; the mixture is then boiled until the water vapor escaping no longer contains a tetrahydroquinoline. Optionally, there is further added a little borax and water. The cooled liquid, which yo the aldehyde is already separated substantially, is extracted with a mixture of methanol and a portion of two parts of benzol; after drying " with sodium sulfate, the solution is evaporated intensive yellow. y5 likely The aldehyde of formula: CH " CO-CH^{3 [}[...]* i- [...] N-CH = CH-CH = CH-C = CH-GH = 0 crystallizes in fine needles reddish; it e ' is soluble with a yellow color intensive in alcohol, methanol, benzol; 8o it is