JPS602336B2 - Method for producing coumarin compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides that one of the resonant limit structural formulas has the general formula is H or OCH3, Y is or, An is a colorless anion, RI is H or C ratio, Z and Z2
is OH, CN, C, ~C2 alkoxy, C ratio COO, S
C, ~C4 optionally substituted with QH or phenyl
It relates to a method for producing coumarin compounds corresponding to an alkyl group, in which ZI and Z may be taken together or may form a bran fused to a benzene nucleus with neighboring carbon atoms.

The difference in the resonance limit structure produced by the compound of formula 1 can be expressed as formula 1 (
The aldehyde of x=-CH=○) is shown in relation to this as follows. Equivalently, compounds of formula 1 can occur in different tautomeric forms depending on the range in which they themselves find themselves.

This is the protonated form (
Ane represents an anion).

Possible alkyl radicals ZI and Z2 are, in particular, those having 1 to 4 carbon atoms, such as methyl, ethyl, n
-propyl, 8-methoxyethyl, 3-ethoxyethyl, n-butyl and isobutyl.

C, to C4 alkyl groups can be further substituted with one substituent, such as hydroxyl; nitrile; C, to C2 alkoxy, acetoxy and sulfo. Possible aralkyl radicals Z and Z2 are, in particular, phenyl-C, to C4-alkyl radicals, the benzyl, Q-phenylethyl, 8-phenylethyl and phenyl-n-propyl radicals being particularly preferred.

Preferred heterocycles, which may be formed with ZI and Z and the N atom to which they are bonded, and which may be fused with a benzene ring, include a 6-membered N-double ring structure, such as piveridine, and a benzene ring-fused dotted ring. The structure is a two- or three-membered alkylene chain in which ZI is directly bonded to the 6-position of the coumarin ring, and/or an alkyreso chain in which Z is bonded to the 8-position.

Alkyl RI is preferably hydrogen or methyl.

In addition to aldehydes, X is characterized by alkyl- or aryl-substituted hydrazones, in particular oximes, azomethyl and the group -CH=N-NH-Y, where Y represents an electron-withdrawing group that imparts acidic properties to the vicinal NH group. It is a special hydrazone.

Azomethine and azomethinium salts to be mentioned in particular are those having one or two methyl groups or optionally substituted phenyl groups on the azomethine nitrogen.

A preferred substituent on such a phenyl group is a methoxy group. A particularly preferred azomethine is anyl, and a particularly preferred azomethinium salt is Willsmeier (V
ilsmeier) reaction, i.e. before hydrolysis to aldehydes (OA),
In particular, the formula 1 = ☆ノCH3Ane\CH3 where An8 is an anion such as P02CI2e or CIe.

The electron-withdrawing group Y, which imparts acidic properties to the vicinal NH group of the hydrazone group -CH=N-NH-Y, can be cationic, anionic, ionic, or nonionic.

In a narrower sense, Y is a lattice-attracting group, which is an unsaturated triple or quadruple group that imparts acidic properties to the vicinal NH group and can also be a member of a ring in a polycyclic system. It is bonded to the NH group by a telo-oriented C atom or by a phosphorus atom at the 8-position 5 of the acid. A systematic view of the heterosteering orientation C atoms selected here is provided by J.

umal of Chemical DM dish menta
tion 10, 128-1 (1970). By heteroorientation of the C atom is meant a direct single or multiple bond of the C atom to a nonmetallic heteroatom of Group 5, 6 or 7 of the Periodic Table, preferably oxygen or nitrogen. Nitrogen atoms can also be ring atoms. Groups Y with an unsaturated triple hetero-oriented C atom are formally derived from carboxylic acids, those with a quadruple hetero-oriented C atom from carbonic acid, and those with a bound phosphorus atom from phosphorus. Of course, the oxygen atoms derived from acids and of these acids in the sense defined above can also be replaced by other nonmetallic atoms, such as nitrogen. Y can be acyclic or cyclic. The cyclic group Y is preferably connected to the adjacent NH group by a fourfold heterooriented unsaturated ring C atom and is formally a cyclic carbonic acid derivative. Preferably the group Y is -W-(V)m-Q or U where W is carbonyl, carboimino or phosphonyl, V is 101, or, R2 is hydrogen or methyl and R3 is hydrogen or optionally substituted alkyl, Ane is a colorless anion, m is the number 0 or 1, Q is hydrogen, alkyl, aryl or a double cyclic group, U is imidazoline or 4 - 5-dioxoimidazoline, and Q corresponds to a cation, anion, Zwitter ion, or nonionic group of which may further have a substituent.

In the present invention, the anion Ane is a colorless organic or inorganic anion which is common in dye chemistry, such as chloride ion, bromine ion, iodine ion, sulfate ion, hydrogen sulfate ion, amidosulfonate ion, phosphate ion, phosphorus ion. Acid hydrogen ion, nitrate ion, chlorozincate ion, methylsulfate ion, ethylsulfate ion, p-toluenesulfonate ion, benzenesulfonate ion, methylsulfonate ion, acetate ion, formate ion, lactate ion,
Tartrate ion or succinate ion.

The alkyl group Q preferably has 1 to 2 carbon atoms.

Preferred aryl groups Q belong to the benzene group.

The rear ring Q is preferably a 6-membered double aromatic ring, such as pyridine. Examples of suitable substitutions on the double cyclic group Q are:
It is a methyl group.

The N-compound is preferably in the form of a quaternary cycloammonium salt, with possible anions as defined above (
(as value e). A preferred group of compounds within the coumarin compounds of formula 1 is where h is unsubstituted C, to C4 alkyl, 8-cyanoethyl, 8-methoxyethyl, 8-ethoxyethyl, 8-hydroxyethyl, 8-acetoxy Ethyl, benzyl, Q-phenylethyl, 8-phenylethyl, y-phenyl-n-propyl, or an ethylene or 1,3-propylene group bonded to the 6-position of the coumarin ring.

r is unsubstituted C, to C4 alkyl, 8-cyanoethyl, 8-methoxyethyl, 8-ethoxyethyl, 8-hydroxyethyl, 8-acetoxyethyl, benzyl, 3
-phenylethyl, y-phenyl-n-propyl or ethylene group bonded to the 8-position of coumaric acid.

X′ is the formula -CHi Maru 4 Here M is =.

・:N. day, =N-C6day5.=(C鴇)2Ane or =N-NH-Y', and Ane and Y
is defined above, and corresponds to . Coumarin compounds of formula 1 can be prepared, for example, by the Vilsmeier reagent, in which compounds of the formula Z1, Z, RI and A are as defined above.
The product thus obtained is optionally hydrolyzed to form a free aldehyde compound (X=1CH=○), and optionally are prepared by reacting the main reaction product or free aldehyde compound with an "aldehyde reagent" in a manner known per se.

The Vilsmeyer reagent is used in a wide range of applications using known methods [e.g., Hou n-Weyl, “Method.
refer to "Dender Omanischen Chemie" (Methods of Organic Chemistry), Vol. 1, p. 29 et seq.]
in which carboxylic acid amides are treated with special acid halides,
It refers to compounds prepared, for example, by treatment with POC13, SOC12 and COC12, which transfer carbonyl groups.

In particular, compounds considered to be Vilsmeyer's reagents are more particularly known as
v. Chim. acta, 42, 1959 (1959)
of the general formula where Z is C, ~C4 alkyl, benzyl or phenyl;
C4 alkyl or Z3 and Z are those which, together with the N atom to which they are attached, can form morpholine, piveridine or pyrrolidine.

Suitable carponamides for the preparation of this reagent include N-methylformamide, N-ethylformamide, and di-N.N.
-butylformamide, N-phenyl-N-methylformamide, N-benzyl-N-methylformamide, N
-formylpiveridine, N-formylmorpholine, especially N.N-dimethylformamide.

The use of the Vilsmeier reagent obtained from dimethylformamide and POC13 has proven particularly advantageous.

Accordingly, a suitable procedure involves treating a compound of formula V with at least one equivalent of a Willsmeier reagent of formula, resulting in a compound of formula corresponding to formula 1, where Z1, Z, Z3, Z4. , RI and A are as defined above, by hydrolyzing the reaction product of X;
a free aldehyde compound of formula oa corresponding to formula 1, where -CH=0, and optionally skin or o
a with the formula M'-N ratio W where M is optionally substituted phenyl, hydroxyl or -NH-Y, and Y is an enteric ion, anion,
Zwitterion or non-ionic group, which is attached to the vicinal NH group by an unsaturated triple or quadruple hetero-oriented C atom, which can also be a ring member of the post-atomic system, or by a phosphorus at oxidation level 5. by condensation with an aldehyde reagent to which it is attached, depending on the atom, or by reacting with sodium bisulfite to form a bisulfite adduct.

A suitable reaction medium for the Vilsmeyer reaction is in particular an excess of a carboxylic acid amide, ie preferably dimethylformamide, but other anhydrous inert solvents, such as chlorobenzene or acetonitrile, are also suitable.

The reaction is carried out at 30-100 qC, preferably 40-90°C.

When RI=hydrogen, a temperature of 40-70<0>C is preferred; when RI=alkyl, a temperature of 70-90<0>C is preferred. Specifically, a compound of formula V is dissolved or suspended in dimethylformamide and added slowly to a Willsmeier reagent of formula V, optionally with gentle cooling of the reaction vessel; The compound is gradually introduced in solid form into the Vilsmeier reagent at the reaction temperature.

Reaction times are generally 1 to 18 hours, about 1 to 1 infant hour when RI=day, and about 6 to 1 anchor hour when RI=alkyl.

To obtain the free aldehyde (0, 1 with X=CH=○), the reaction mixture is preferably poured onto ice water and stirred until the oa is completely separated.

Examples of suitable compounds of formula V are: 7-diethylaminocoumarin, 7-dimethylaminocoumarin, 7-di-n-propylaminocoumarin, 7-di-n-butylaminocoumarin, 7-di-8-cya/ethylaminocoumarin, 7-8-cyanoethyl- Penzylamino-coumarin, 7-di-8-hydroxyethylamino-coumarin, 7-di-3-methoxyethylamino-coumarin, 7-di-8-ethoxyethylamino-coumarin, 7-dibenzylamino-coumarin, 7-n -butylbenzylamine/-coumarin, 7-Q-phenylethylmethylaminocoumarin, 7-di-8-phenylethylaminocoumarin, 7-di-phenyl-n-bropylaminocoumarin, 7-di-phenylmethylaminocoumarin, -8-acetoxyethylami/-coumarin, 71B-sulfoethyl-methylaminocoumarin, 71N-piveridinylcoumarin, and compounds of the formula.

Further condensation with aldehyde reagents such as skin or sodium bisulfite generally does not require complete hydrolysis of the reaction mixture to Da; instead, in most cases small amounts of water, methanol or ethanol are added. It is sufficient to destroy the excess Vilsmeyer reagent by slow dropwise addition and then react the acidic reaction solution with the aldehyde reagent without intermediate isolation.

Examples of suitable aldehyde reagents are: Aniline, toluidine, anisidine, chloroaniline and sulfanilic acid; hydroxyamines; acylhydrazines such as penzoylhydrazine, isonicotinic acid hydrazide, 2-methyl-isonicotinic acid hydrazide, aminoguanidine carbonate, ethyl carbonate ester hydrazide, and diphenyl phosphate Ester hydrazide; 2
- hydrazinoimidazoline hydrobromide; and sodium bisulfite. This reaction can be carried out at room temperature or elevated temperature, approximately 3
The temperature is 0 to 100°C, preferably 40 to 8°C.

When one wishes to avoid using strongly acidic reaction media for this reaction, the mixture is first neutralized with a base such as sodium hydroxide solution or ammonia, during which time the skin is already partially or completely hydrolyzed. oa, followed by condensation with an aldehyde reagent without any intermediate monomerization.
The condensation of the isolated aldehyde (roa, corresponding to formula 1 with Preferably it can be carried out at 40 to 90 qo.

Possible organic solvents are polar or non-polar immutable solvents; when water-immiscible solvents are used, the water formed in the reaction is preferably removed from the reaction mixture by co-distillation. Examples of solvents used are: Alcohols such as methanol, ethanol, isopropanol, n-propanol, n-butanol, glycols, glycomonomethyl or monoethyl ether, and amides such as formamide, dimethylformamide, dimethylacetamide and N-methylpyrrolidone; dimethylsulfoxide; ice acetic acid, acetonitrile, dioxane and tetrahydrofuran; and water-immiscible solvents such as benzene, toluene,
xylene or chlorobenzene. The reaction with sodium bisulfite can advantageously be carried out in a 30-40% strength aqueous sodium bisulfite solution at about 70-95°C, preferably at 90°C. The starting components of formula V are partially known. These starting components are, for example, Betiman (Pech
ma blood) reaction, the following reaction equation (where Z1, Z, A
and RI are as defined above).

The starting component can also be prepared by condensing an aldehyde with ethyl malonate to form a coumarine ester, followed by acid saponification with decarboxylation (e.g., boiling
treatment with 8% strength hydrochloric acid for 5 hours), in which case the cold solution is subsequently neutralized with sodium hydroxide to give Axis 5, compound V precipitates in the form of pure crystals. .

Hydrolytically labile groups in the groups ZI and Z (wherein Z1, Z and A are as defined above), such as carboxylic acid esters, urethanes and ureas, can be prepared using esterification methods known per se. Alternatively, groups that should be introduced later by an acylation method and are modified under the conditions of the Willsmeyer synthesis, such as groups that are converted to hydroxyl groups or chloroalkyl groups, should first be introduced using known methods if such changes are to be avoided. , should be protected, for example by acetylation.

Under Vilsmeyer conditions the carbamoyl group is converted to a nitrile group and can be converted back to the carbamoyl group by subsequent acidic saponification, for example with 90% strength 2S04 at room temperature. In the hydrolysis of the Willsmeier reaction mixture, it is possible, if appropriate, to work up under particularly mild conditions by pouring the mixture onto a solution of ice and sodium acetate.

Compounds of formula 1 containing quaternary ammonium or cycloammonium groups can advantageously be prepared by subsequent quaternization of tertiary bases based on these groups.

The quaternizing agents that can be used are those common in basic dye chemistry, examples of which are: dimethyl sulfate, jetyl sulfate, p-toluenesulfonic acid C,
~C4 alkyl esters, C, ~ alkyl halides such as ethyl chloride, n-butyl bromide, 8-cyanoethyl chloride, 8-methoxyethyl chloride, 3-ethoxyethyl chloride and 1-k. rho-2-iodoethane; phenyl-C, to C3 alkyl halides, such as penzyl chloride and Q-1 or 8-phenylethyl bromide; allyl bromide; and alkylene oxides, in the presence of acids such as glacial acetic acid, hydrochloric acid or sulfuric acid. Ethylene oxide, propylene oxide and C, to C4 alkoxypropylene oxide; and acrylates,
For example, acrylic acid, alkyl esters or acylamides of acrylic acid C, -C4. The novel coumarin compounds of formula 1 are valuable dyes and/or valuable intermediates for coumarin dyes.

Compounds of formula 1 which are x 1 CH = ○ or modified and which retain the double bond character, such as oximes, hydrazones or azomethine, are valuable dyes in their own right and contain free aldehyde groups. Offal is especially preferred.

Moreover, these compounds are intermediate products in the production of coumarin dyes of hitherto unknown value; such dyes can be prepared by methods known per se, e.g. analogously to the procedure described above, by condensation with methylene-active compounds of the type malodinitrile or ethylthia/acetate. These dyes can be used in oils and polymeric organic materials, such as lacquers, films, sheets, fibers and moldings, such as polyolefins, such as polyethylene and polypropylene, polystyrene, polyamides, polyurethanes,
It can be used to dye materials made of polyester and acrylic polymers, such as polyacrylonitrile.
Dyes of formula 1 without anionic and ionic groups are particularly useful for this purpose. The preferred fields of application are:
Dyeing and dyeing of natural, semi-synthetic and synthetic fiber materials and fabric materials. Dyes containing sulfo groups are particularly effective in the dyeing and dyeing of polyamide, polyurethane and wool fibers, while enteric ionic dyes are particularly effective in dyeing and dyeing fibers containing acid groups, such as polyacrylonitrile, acid-modified polyester and acid-modified polyamide fibers. Coumarin dyes of formula 1, which are particularly suitable and do not contain ionic groups imparting water solubility, are suitable for dyeing and dyeing polyester, polyamide, polyurethane, cellulose 21/2 acetate, cellulose acetate, polypropylene and polyacrylonitrile fibers. It is a disperse dye. Using the dyestuffs of the formula 1 according to the invention, the fibers and fabrics mentioned above have excellent application fastness properties and very clear dyeings of yellow to orange color are obtained.

Coumariso dyes of the formula 1, in which X represents an aldehyde, an aldehyde oxime or an aldehyde hydrazone group -CH=N-NH-Y, further exhibit an intense green-yellow to yellow poppy, luminescent color under UV light or sunlight. .

Particularly vivid dyeings of the aforementioned materials are therefore obtained with these dyes. Furthermore, these dyes are suitable for dye laser devices. Such dye laser devices consist of a container containing a solution of these poppy, photodyes and a transport source coupled thereto, capable of exciting the dye solution to produce radiation. For this purpose, the dye has a concentration that emits laser fin radiation in a solvent that does not interfere with the radiation.
Preferably it is used at a concentration of 10-2 to 10-4 mol/its. In this way, the device is capable of producing traversal laser radiation of 450 to 56 dish wavelengths. Examples of solvents that do not interfere with or impede the stimulated radiation are: water, monohydric or polyhydric alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol and ethylene glycol monoethyl ethers, ring ethers such as dioxane and tetrahydrofuran, aromatic compounds such as benzene, toluene, phenol, resorcinol and Cresols, as well as cyclohexane, decalin, chloroform, dimethyl sulfoxide, acetonitrile, ketones such as acetone, butanone (21) and cyclohexanone, esters such as ethyl acetate, malonjetyl ester and glycol diacetate, and fluorinated alcohols such as hexafluoro Isoprobanol.Coumarin dyes of the formula 1, which do not contain ionic groups imparting water-drop properties and are sublimable, are particularly suitable for transfer processes such as those described, for example, in French Patent Specification 12 Paper 30 and 1334829. As is known, this method consists of dye transfer, i.e. sublimation of the dye from a temporary support printed with a special printing ink under the action of heat and, if necessary, pressure, onto the support to be printed. Examples of possible substrates to be printed on are polyester, polyamide,
polyacrylonitrile, acid-modified polyester and acid-modified polyamide fiber materials. The temporary support used is preferably paper, but also cellophane, cellulose fibrous materials, metals, etc. The dye to be transferred is generally not directly applied to a temporary support, but rather as a printing paste,
It is applied to the temporary support by methods known per se (gravure printing or flexography) in the form of spray solutions, dyeing solutions, preferably anhydrous neutral printing inks. This printing ink comprises at least: (a) a dye of formula 1 defined as above and which sublimes at 160-240°C; b) an organic solvent commonly used in printing inks; and (c) a resin soluble in the solvent. Contains.

Generally, the dye is present in the printing ink in the form of a solution. Examples of suitable solvents are: Hydrocarbons such as benzene, toluene and xylene; chlorinated hydrocarbons such as chlorobenzene, ethylene chloride, trichloroethylene and tetrachloroethylene; alcohols such as methanol, ethanol, isopropanol,
butanol and pendyl alcohol; ketones such as methyl ethyl ketone and cyclohexanone, and various ethers and esters; examples of suitable resins are:
Ketone resins, such as Ku Tharz AFS, and cellulose ethers, such as ethyl cellulose. In order to improve the sharpness of the contours of the printed products produced according to the invention, an auxiliary support printed with a new printing ink can be used, if necessary, with OB2110
9101, it can be coated with a layer of colorless binder or resin.

For certain purposes, for example for printing paper on rotary presses, it is preferred to use water-based printing inks which, in addition to the sublimable dye of formula 1, contain binders, thickeners,
and fillers customary in printing technology and, if necessary, surfactants and/or organic water-miscible solvents.

So-called highly filled inks with a binder to filler weight ratio of 1:6 to 1:8 are suitable for this purpose. Suitable supports for absorbing the dye during the transfer process are preferably woven materials consisting of fibers of the type mentioned above, as well as corresponding polymeric non-woven materials.

Dye migration is from 160 to 240 °C, preferably from 200 to 2
Occurs in 15-6 sand at 20°C.

Heat transfer can be accomplished by direct contact of heated plates, heated air, heated steam, or infrared radiation.

Dyeings and prints which exhibit excellent fastness in use, such as fastness to washing, rubbing and light, are obtained on the material used as support. Sublimable dyes of formula 1 which are particularly suitable for transfer processes are those of the formula where LI and L
2 is a C, to C4 alkyl group optionally substituted with nitrile, hydroxyl or acetoxy; a 2- or 3-membered alkylene group bonded to the 6 or 8 position of coumarin and optionally substituted with a methyl group; or together with the N atom to which they are attached can form a piverizine ring, L3 is hydrogen or methyl, L is =NH-NH-Y0, =NOH or =○,
Y0 is -CO-R0, 1C(=NH)-NH2 or imidazo1'-2-yl, and R0 is phenyl, pyridyl or ethoxy, without ionic groups imparting water solubility. , is a compound.

Next, the present invention will be specifically explained with reference to Examples.

Among these, the characteristic values of the compounds in the main examples are as shown in the table below. Example 1 100 ml of dimethylformamide is added dropwise to 200 ml of phosphorus oxychloride at 20-50°C.

The mixture is stirred at 50:00 for 48 minutes in the absence of moisture. 217 in dimethylformamide at 240
The evening suspension of 7-di-ethylaminocoumarin is added to the "Vilsmeyer reagent" thus prepared, and the mixture is flooded at 60 DEG C. for 2 hours.

Hydrolyze the azomethinium salt of formula and excess Weilsmeier reagent, pour the reaction solution onto 4k9 ice water, and stir the mixture for 2 hours. The crystalline precipitate of the dye of formula '11 is washed with water, well pressed, and dried under vacuum at 7 p.m. A 7-diethylaminocoumarin-3-aldehyde of the formula <·> is obtained.

Due to special purity requirements, this dye can be recrystallized from ethylene glycol monomethyl ether.

It shows a strong green poppy light, especially in non-polar solvents,
It is excellent as a transfer dye and dyes polyester a bright greenish-yellow color with excellent light fastness. 7-jethylamino-coumarin used as a starting material is obtained as follows. The 7-jethylaminocoumarin-13-carboxylic acid ethyl ester of 578 mg in 18% strength hydrochloric acid of 2350 was triturated under reflux for 5 hours, resulting in its saponification and decarboxylation, resulting in the formation of the 7- Jethylaminocoumarin dissolves as the hydrochloride salt to form a dark brown solution.

After cooling, add 450' of saturated sodium acetate solution,
Adjust the multiplication value to 4-5 with cooling with a 45% strength sodium hydroxide solution of about 700. The crystalline precipitate is filtered, thoroughly washed with water, and dried under vacuum at 50°C. The yield is about 42
It is 0 evening. The dyes shown in the table below are prepared in the same way as compound [1'] from the appropriate starting compounds.

Example number Z′
Z〃 Color for polyester (transfer)
2 n-QH9- n-QH
9- Bright greenish yellow 3 NC
-CH2-CH2- NC-CH2-CH
2- 〃4 530-Earth-CH2- 530-Town 2-Earth-
〃5 C2 day 50-CH2-CH2-
C2 day 50-CH2-CH2- City Hall 6 CH3C-○-CH2-qH2-
CH3-C-○-CH2-CH2- 〃7
10> days.

-CH2-CH2- Day.・CH2-CH2-
〃8 NC-CH2-CH
2-CH3
〃10) Example 9 of acid hydrolysis of compound 10 at 80°C. 30 minutes of dimethylformamide was added dropwise to 30 hours of phosphorus oxychloride at 20 to 50°C, and this mixture was added to 50q.
A suspension of 7-dibenzylaminocoumarin in dimethylformamide at 80° C. was added, the mixture was warmed to 70° C. for 12 hours, poured into ice water at 400° C., and water was added. The multiplier value is adjusted to 7 with cooling with sodium oxide solution, the whole is briefly warmed to 8.0, and then cooled.

Filter the crystalline precipitate, wash well with water, press well,
Vacuum dry at 0°C. 7-dibenzylaminocoumarin-3-aldehyde of formula (9) is obtained after 35.5 minutes.

In non-polar solvents such as dioxane, this compound exhibits a strong green-yellow fluorescence, and when used in the dyeing of polyester it gives bright green-yellow dyeings with excellent lightfastness. The 7-dibenzylaminocoumarin used as the starting material is obtained as follows. 272.5 ml of m-aminophenol was dissolved in 1500 ml of dimethylformamide under nitrogen atmosphere, 200 ml of sodium bicarbonate and 730 ml of penzyl chloride were added, and the mixture was heated to 100° C. for 6 hours. During this time, a small amount of aqueous liquid comes out.

After cooling, the crystalline precipitate was filtered, washed with ethanol,
Vacuum dry at °C. The mother liquor is stirred with 800' concentrated hydrochloric acid. The crystalline precipitate was filtered and suspended in 1000' ethanol, filtered and washed with ethanol.
Dry at 0. A total of 661.5 m-dibenzylaminophenol hydrochloride (containing sodium chloride) are obtained. 5 minutes of m-dibenzylaminophenol hydrochloride (containing sodium chloride) was gradually stirred at 50 degrees Celsius and 350 degrees of phosphorus oxychloride and 400 degrees of dimethylformamide were heated to 50°C for 30 minutes. Stir the mixture at 5 to 0 degrees Celsius, pour into 4K9 ice water, add 40% strength sodium hydroxide dropwise with cooling and adjust the multiplication value to 5. do.

The aqueous phase is washed with water, the water is washed with water, and the water is extracted with 2 times of methylcyclohexane. - Cool the combined methylcyclohexane solution, filter the crystalline precipitate, wash with methylcyclohexane and dry under vacuum at 50°C. Yield: 200 evenings 41N・N
-Dibenzylaminosalicylaldehyde. 8M piveridine and 3' glacial acetic acid in 700 molar toluene.
In addition to 0.41N-N-dibenzylaminosalicylaldehyde and 105.0% diethyl malonate,
This mixture is heated for one hour while the toluene-ethanol-water mixture is distilled off from the column.

The solvent is then distilled off in vacuo (the mixture is heated in a water bath).
The 7-dibenzylaminocoumarin-3-carboxylic acid ethyl ester obtained as a residue is saponified and decarboxylated without intermediate monomerization. For this purpose, 500 parts of triacetic acid and 500 parts of concentrated hydrochloric acid were added to this ester and the mixture was heated to 110° C. under reflux with stirring.
Heat for 1q hours. After cooling, this solution is added to ice water and the mottling value is adjusted to 4-5 by adding dropwise 40% strength sodium hydroxide solution. Filter the crystalline precipitate, wash with water,
Recrystallize from toluene. 112 hours of 7-monobenzylaminocoumarin is obtained.

Further reaction with 56 hours of pendyl chloride in 230 degrees of dimethylformamide (6 hours at 100°C) gave 130 hours of pendyl chloride.
7-Dibenzylaminocoumarin is obtained.

The dyes shown in the table below are prepared analogously to compound (1) from the appropriate starting compounds. Dye Example 14 30 minutes of dimethylformamide was added dropwise to 30 minutes of phosphorous oxide at 20-50°C, the mixture was kept at 50°C for 3 minutes, and 23°C in 40 minutes of dimethylformamide The suspension is added and the mixture is heated to 90°C for 18 hours, poured onto 400ml of ice water and the whole is stirred for 3 hours.

A strongly acidic aqueous solution is obtained that is stable for several days of a red-yellow azomethine dye of the formula.

Example 15 A solution of 123 p-anisidine in 30% strength acetic acid of 60' is added to the acid dye solution made according to Example 14 and the mixture is stirred at room temperature for 4 hours to form a red-yellow acidic dye of the formula Azomethine dye is formed, then 20%
It can be isolated in crystalline form by salting out with strong sodium chloride solution.

When this dye is dissolved in 5% acetic acid and neutralized with sodium bicarbonate, neutral azomethine of the formula is obtained in the form of red-yellow crystals.

Example 16 The acid dye solution prepared according to Example 14 was reacted with hydroxylamine hydrochloride for 1 hour and 7 minutes at 50° C. while the mixture was brought to pH with sodium acetate.
5 and a crystalline yellow oxime of the formula is thus obtained.

Example 17 The acid dye solution prepared according to Example 14 is reacted with 13.6 hours of aminoguanidine carbonate at 50° C. for 5 hours to obtain yellow guanylhydrazone hydrochloride of the formula as a crystalline precipitate.

Example 18 100 ml of dimethylformamide was added dropwise to 200 ml of phosphorous oxychloride at 20 to 50 ml.

The mixture is stirred at 50° C. for 48 minutes in the absence of moisture. A suspension of 189 mm of 7-dimethylamino coumarin in 240 mm of dimethylformamide was added, the mixture was flooded to 60 Qqo for 2-5 hours, poured onto 5K9 ice water, and the whole was heated at room temperature for 8 hours. Stir, filter the crystalline precipitate, wash with water until almost neutral, and dry at 50:00.

7-dimethylaminocoumarin-3-aldehyde of formula 145 is obtained.

This dye can be purified by recrystallization from ethylene glycomonomethyl ether. In non-polar solvents such as dioxane, this dye exhibits a blue-line color. The compounds listed in the table below are obtained analogously from the appropriate starting compounds. Example 21 24.5 hours of 7-diethylaminocoumarin-3-aldehyde and 200 hours of 14 hours of penzoylhydrazine are heated under reflux for 5 hours.

After cooling, the crystalline pulvinar was filtered, washed with ethanol, and
It is recrystallized from 0' ethylene glycol monomethyl ether, washed with ethanol, and dried under vacuum at 60°C. A diethylaminocoumarin-3-aldehyde benzoylhydrazone of the formula 33 was obtained as a greenish-yellow dye, which turned greenish yellow in dimethylformamide and showed light;
It exhibits a bright greenish-yellow color with excellent fastness against polyester. The dyes listed in the table below are prepared in a similar manner from the appropriate starting compounds.

Dye Example 25 12.3 7-diethylaminocoumarin-3-aldehyde and 14.5 phosphoric acid diphenyl ester hydrazide in 100' ethanol
(Produced from phosphate diphenyl ester chloride and hydrazine hydrate according to 12.5 total pages)
Stir for 1 hour at room temperature.

The crystalline precipitate was filtered, washed with ethanol and recrystallized from 120' ethylene glycol monomethyl ether.
Wash with ethanol and vacuum dry at 4×. The formula is obtained.

This dye exhibits a strong greenish-yellow poppy glow in dimethylformamide and dyes polyesters in bright yellow with excellent fastness. Example 26 24.5 ml of 7-diethylaminocoumarin-3-aldehyde, 200 ml of aminoguanidine carbonate and 7 ml of glacial acetic acid are heated under reflux for 5 hours, during which time carbon dioxide is evolved.

After cooling, this crystalline precipitate was filtered, washed with ethanol,
Suspend in 250ml of water at 75°C, adjust to feed 7 with saturated sodium bicarbonate solution, filter while warm, recrystallize from 200ml of dimethylformamide, wash with ethanol, and vacuum dry at 50°C. A dye of formula 20.5 is obtained.

The dye can be applied in non-acidic organic solvents such as dioxane, dimethylformamide, chlorobenzene, pyridine or chloroform, or on non-acidic textile materials such as polyester, polyamide or cellulose acetate.
It shows a deep bright yellow color, but the poppy shows no light. In acidic solvents, such as glacial acetic acid, and 0.5% strength hydrogen chloride in ethanol, and on textile materials containing acid groups, such as polyacrylonitrile, acid-modified polyesters and acid-modified polyamides, the dye is very Strong greenish-yellow poppy, showing light.

Example 27 A dye of formula (1) in 100 g of oxalic acid diethyl ester is boiled for 5 minutes with stirring and cooled.

The crystalline precipitate is washed with ethanol, recrystallized from 400% ethylene glycol monomethyl ether, washed with ethanol, and dried under vacuum at 70°C. A dye of formula 7.2 is obtained.

This dye exhibits a very strong green-yellow poppy glow in dimethylformamide. This dye is completely soluble in hot water. Example 28 Dye 7 of formula (1) is suspended in 90' of acetone.

A solution of 2.1 ml of amidosulfonic acid in 10 ml of water is added at room temperature. The mixture is stirred at room temperature for 1 hour. The crystalline precipitate is filtered, washed with acetone and dried at 60°C. A dye of formula 6.8 is obtained.

This dye exhibits a green poppy glow in dilute aqueous solution. For polyacrylonitrile, it gives a vivid greenish-yellow poppy, light dyeing of excellent fastness. Flooding the product with an equal amount of o-phenyldiamine in glacial acetic acid gives the corresponding imidazoquinoxaline dye. Example 29 Suspend the dye next to the 5-day formula in acetone and add 1
A solution of 2.1 ml of aminosulfonic acid in 0.0 ml of water is added at room temperature with stirring.

The mixture is stirred at room temperature for 1 hour, and the crystalline precipitate is filtered, washed with acetone and dried under vacuum at 70°C. Yield is 5.1 units of dye of formula.

In dilute aqueous solution, this dye shows a green fluorescence and on polyacrylonitrile it gives greenish-yellow poppy, light dyeings of excellent fastness. Example 30 The dye on the side of the 9-day ceremony was dyed with 60' of anhydrous black.

Suspend in benzene, add 3.2 hours of dimethyl sulfate and warm the mixture at 660 for 6 hours. The crystalline precipitate is then filtered, washed with toluene and dried under vacuum at 50 oo. The yield is 10.2 days. This dye corresponds to the formula. This dye exhibits a very intense green poppy glow in dimethylformamide. This dye dyes polyacrylonitrile a bright greenish-yellow color with very good fastness properties.
Dyes of relatively valuable properties can be substituted for dimethyl sulfate by using equimolar amounts of jetyl sulfate (at 80°C), n-butyl bromide (9yo), pendyl chloride (at 125°C), allyl bromide (
110o, autoclaved), B-chloropropionitrile (125o), 8-koo propionic acid amide (
125 o'clock), shrimp chlorohydrin (120 o, autoclaved), ethylene oxide or propylene oxide (in glacial acetic acid, 50 °C), 2-ethoxy-1-bromoethane (100 o'clock), 1-chloro o-2-iodethane (
When using 95qo) or chloroacetic acid (13pi○),
can get.

Example 31 A compound of formula {11 of 9.82 and 2-hydrazinoimidazoline hydrobromide in 60' of ethanol is boiled at reflux for 5 hours and then cooled.

The crystalline precipitate is filtered, washed with ethanol, and dried under vacuum for 50 minutes. A compound of formula 15 is obtained.

Claims (1)

[Claims] 1 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Here, X is CH-Z, Z is O, =NOH, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or = N -NH-Y, R^2 is H or OCH_3, Y is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and An is a colorless anion , R^1 is H or CH_3, Z^1 and Z^2 are OH, CN,
C_1-C_2 alkoxy, CH_3COO, SO_3
C_1 to C_ which may be substituted with H or phenyl
It is a 4-alkyl group, and Z^1 and Z^2 may be taken together to form ▲ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or may form a ring fused to the benzene nucleus with neighboring carbon atoms, In producing coumarin compounds,
Formula ▲Mathematical formulas, chemical formulas, tables, etc.▼ Here, Z^1, Z^2 and R^1 are as defined above.
ilsmeierreagent), and the product thus obtained is optionally hydrolyzed to form a free aldehyde compound (X=-CH=O),
and, if necessary, a process characterized in that the main reaction product or the free aldehyde compound is reacted with an "aldehyde reagent" in a manner known per se.