JPH10204070A - Sulfonamide compound and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound useful as a coupling component for producing azo dyes for optical recording media, liquid crystals, heat-sensitive transfer, fibers, plastic coloring, etc. SOLUTION: This compound is represented by formula I [X is H, a (substituted)alkyl, a (substituted)alkoxy or a halogen; Y is an alkyl having >=2 fluorine atoms; R<1> and R<2> are each a (substituted)alkyl; R<1> and R<2> or X together may form a ring] or its salt., e.g. 3-(N,N-diethylamino)- trifluoromethanesulfonanilide or trifluoromethanesulfonic acid salt. The compound of formula I is obtained by reacting of a compound of formula II with an alkylsulfonyl halide or an alkylsulfonic acid anhydride having >=2F atoms bonded to an alkyl.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel sulfonamide compound and a method for producing the same. The sulfonamide compound according to the present invention is useful as a dye intermediate for optical disks. Further, the sulfonamide-based azo compound of the present invention is also useful as a colorant for plastic colorants, dyes for fibers, dyes for optical filters, printing inks, dyes for thermal transfer, and metal ion indicators.

[0002]

2. Description of the Related Art Various types of optical discs have been proposed, one of which includes an organic dye in a recording layer. Various organic dyes have been studied, but none of them are satisfactory. An object of the present invention is to provide an intermediate useful for synthesizing an azo dye suitable for an optical disk, particularly an optical disk having a metal reflective layer and using a short-wavelength semiconductor laser.

[0003]

An intermediate according to the present invention comprises:
A sulfonamide compound represented by the general formula (7) and an azo compound having a sulfonamide group represented by the general formula (8).

[0004]

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In the formula (4), X represents a hydrogen atom, an optionally substituted alkyl or alkoxy group, or a halogen atom. Y represents an alkyl group having at least two fluorine atoms. R ¹ and R ² each independently represent an optionally substituted alkyl group, or R ¹ may be bonded to X or R ² to form a ring.

Preferably, X is a hydrogen atom, a methyl group,
Tyl, methoxy, ethoxy or methoxyethoxy
Y is a carbon having at least two fluorine atoms
An alkyl group of the number 1 to 3, especially a trifluoromethyl group or
A 2,2,2-trifluoroethyl group;¹And R
^TwoAre each independently a carbon which may have a substituent
It is an alkyl group having a prime number of 1 to 6. Number of carbon atoms as a substituent
1 to 6 alkoxy groups, phenyl groups, cyclohexyl
And vinyl groups. Also, R¹Is R ^TwoOr
When bonded to X to form a ring, the ring is oxygen
It is preferably a 6-membered ring which may contain atoms and the like.
And a ring having 1 to 4 carbon atoms such as a methyl group or an ethyl group.
May be substituted.

[0007]

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In the formula (8), D represents an aromatic ring,
X, Y, R ¹ and R ² are the same as in the formula (7).
Examples of the aromatic ring of D include aromatic compounds such as a homocyclic ring such as a benzene ring and a naphthalene ring, and a heterocyclic ring such as a thiophene ring, a thiazole ring, an imidazole ring and a thiadiazole ring. As the heterocycle, Dyes and Di
gments 3 (1982) p81 to 121 are preferably used. Some of the sulfonamide compounds according to the present invention are illustrated in Table 1 below.

[0009]

[Table 1]

[0010]

[Table 2]

[0011]

[Table 3]

The sulfonamide compound according to the present invention is obtained by reacting an aniline represented by the following formula (5) with an alkylsulfonyl halide or an alkylsulfonic anhydride having at least two fluorine atoms in an alkyl group. , Can be manufactured.

[0013]

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(Wherein X, R ¹ and R ² have the same meanings as in formula 4.) This reaction is generally carried out at −20 to 80 ° C., preferably at 20 ° C. or lower, particularly at 0 ° C. or lower. Start, 20-3
The reaction should be terminated at 0 ° C. This reaction is preferably performed in a solvent, and various solvents such as benzene, toluene, xylene, n-hexane, and methylene chloride can be used. Preferably, methylene chloride or toluene is used.

When trifluoromethanesulfonic anhydride is used as the alkylsulfonic anhydride, a trifluoromethanesulfonic acid salt of a sulfonamide compound is obtained. The desired free sulfonamide compound can be obtained by reacting an alkali such as sodium acetate or sodium bicarbonate in a suitable solvent such as methanol, ethanol or N, N-dimethylformamide. . In the diazotization coupling in the next step, trifluoromethanesulfonic acid salt may be used as it is.

[0016]

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The compound of the formula (5) can be produced by various known methods. For example, a compound in which X is a hydrogen atom and R ¹ and R ² are each an optionally substituted alkyl group is a compound which can be easily obtained on the market.
It can be easily produced by alkylating aminoacetanilide followed by hydrolysis. Also, X
In which R ¹ and R ¹ form a ring, for example, N in Table 1
o. The compound corresponding to 9 can be prepared by alkylating tetrahydroquinoline with an alkylating agent such as n-butyl bromide, followed by nitration and reduction. A compound in which R ¹ and R ² combine to form a ring,
For example, in Table 1, No. The compound corresponding to 7 can be produced by nitrating and reducing N-phenylmorpholine.

The sulfonamide compound according to the present invention is used as a coupling component when producing an azo dye. The azo dye obtained here can be used for various uses such as for optical recording media, liquid crystals, thermal transfer, fibers, and plastic coloring. For example, a nickel-containing azo dye obtained by the following reaction is useful as a dye for laser light absorption of an optical recording medium. In the formula, E represents an alkyl group having 1 to 3 carbon atoms.

[0019]

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Some of the azo group-containing sulfonamide compounds according to the present invention are illustrated in Table 2 below.

[0021]

[Table 4]

[0022]

[Table 5]

[0023]

[Table 6]

[0024]

[Table 7]

[0025]

EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples. Example 1 3-N, N-diethylaminoaniline having a purity of 93%
8 g (0.05 mol) was dissolved in 20 ml of toluene. Under a nitrogen stream, 20 g of trifluoromethanesulfonic anhydride was kept at 20 ° C. or lower while stirring, and the above toluene solution was added dropwise thereto over about 30 minutes. 0-5 continuously
After stirring at 1 ° C. for 1 hour, the mixture was left overnight. 200 ml of ice water
The reaction solution was poured thereinto, and the aqueous layer was removed by decantation. 50 ml of n-hexane was added to the toluene layer in which a white precipitate was formed, to obtain pale brown crystals. This was collected by filtration, washed with water and dried. 3-N, N-diethylamino-trifluoromethanesulfonanilide trifluoromethanesulfonate 1
5.21 g were obtained. The results of elemental analysis are as shown in Table-3,

[0026]

[Table 8]

It was in agreement with the calculated value. In addition, the mass spectrum of this product was M ⁺ 296, and it was detected in a form in which trifluoromethanesulfonic acid was removed. Its IR spectrum is shown in FIG. Next, 5 g of trifluoromethanesulfonate of 3-N, N-diethylamino-trifluoromethanesulfonanilide obtained by the above method was used.
Was dissolved in 10 ml of methanol at 20-25 ° C.
To this, 5 g of sodium acetate was added, and the mixture was stirred at 20 to 25 ° C. for 1 hour, and then 20 ml of water was added.
Extracted in ml. After the obtained extract was washed three times with 100 ml of water, sodium sulfate was added and dried. Column chromatography purification was performed using a column packed with "Wakogel C-200" (silica gel manufactured by Wako Pure Chemical Industries), and toluene was distilled off from the main fraction under reduced pressure.
1.82 g of off-white crystals of 3-N, N-dimethylamino-trifluoromethylsulfonanilide which is compound 1
I got The results of elemental analysis of this product are as shown in Table-4,

[0028]

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The calculated value was consistent.

[0030]

Table 9 Table - 4 C H N Calculated _{44.6 5.1 9.5 (C 11 H 15} F 3 N as ₂ O ₂ S) analysis 44.7 5.0 9.4

FIG. 2 shows the IR spectrum of this product. Example 2 In N-methylpyrrolidone in the presence of potassium carbonate, 3
-Aminoacetanilide was reacted with n-butyl bromide to synthesize 3-N, N-di-n-butylamino-acetanilide. This was added to and dissolved in a 10% (by volume) aqueous sulfuric acid solution, and the mixture was stirred under reflux for 4 hours. Then, the mixture was neutralized with sodium hydroxide and extracted with toluene to obtain 3-N, N-di-n-butylaminoaniline.

In the same manner as in Example 1 except that this aniline compound was used, No. 1 in Table 1 was used. 2-compound 3-
N, N-di-n-butylamino-trifluoromethanesulfonanilide trifluoromethanesulfonate was obtained. When the mass spectrum was measured, M ⁺ 352 in which trifluoromethanesulfonic acid was removed was detected. Its IR spectrum is shown in FIG.

Example 3 The procedure of Example 1 was repeated, except that 3-N, N-diethylamino-4-methoxyaniline was used instead of N, N-diethylaminoaniline.
o. 3-N, N-diethylamino-4
The trifluoromethanesulfonate salt of -methoxy-trifluoromethanesulfonanilide was obtained. When the mass spectrum of this product was measured, it was found that M ⁺ 326 in the form of trifluoromethanesulfonic acid was removed. FIG. 3 shows the IR spectrum.

Example 4 4.08 g (0.025 mol) of 3-N, N-diethylaminoaniline and 6.29 g (0.062 mol) of triethylamine were dissolved in 100 ml of dichloromethane at room temperature. A solution prepared by dissolving 5.0 g (0.027 mol) of 2,2,2-trifluoroethylsulfonyl chloride in 30 ml of dichloromethane was added dropwise thereto. After stirring at room temperature for 30 minutes, 50 ml of water was added, and the mixture was further stirred for 30 minutes. The reaction solution was extracted with dichloromethane, and from the extract, No. 1 in Table 1 was extracted. Thus, 3-N, N-diethylamino (2,2,2-trifluoroethyl) sulfonanilide, which is the compound of No. 5, was obtained. Its molecular weight was confirmed by mass spectrum to be 3-N, N-diethylamino- (2,2,2-trifluoroethyl) sulfonanilide. Example 5

[0035]

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2.00 g of 2-amino-4,5-dicyanoimidazole represented by the above structural formula (10) was added to 60 m of water.
1, 10% of 35% hydrochloric acid and diazotized at 0-5 ° C. by dropwise addition of 4.5 ml of an aqueous solution of 1.14 g of sodium sulfite. The obtained diazo solution was added to 65 ml of methanol.
-N, N-diethylaminotrifluoromethanesulfonanilide / trifluoromethanesulfonate 5.33
g, 0.6 g of urea and 6.0 g of sodium acetate were dropped at 0 to 5 ° C., stirred for 3 hours, and left overnight. The precipitated crystals were separated by filtration and dried to obtain the following structural formula (1)
5.23 g of red crystals shown in 1) were obtained.

[0037]

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Absorption λ of this compound in a methanol solution
The max was 487 nm. Fig. 5 shows the absorption spectrum.
Shown in Example 6 6.6 g of the compound of the present invention represented by the structural formula (11) synthesized according to the formulation of Example 5 was dissolved in 150 ml of methanol, and 2.0 g of dimethyl sulfate was added thereto while stirring at 20 ° C.
In minutes. At this time, the reaction temperature was 24 ° C due to heat generation.
Up. After stirring at 24 to 25 ° C for 1 hour, 2.2 g of potassium carbonate was added, and the mixture was stirred at 24 to 25 ° C for 5 hours. The generated crystals were separated by filtration and dried to obtain 2.56 g of red crystals represented by the following structural formula (12). Λmax in a methanol solution of this compound is 513.5 n
m. FIG. 6 shows the absorption spectrum.

[0039]

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Example 7 4.4 g of the compound of the present invention represented by the structural formula (11) synthesized by the formulation of Example 5 was dissolved in 35 ml of N, N-dimethylformamide (hereinafter abbreviated as DMF), and potassium carbonate 1 Add .38 g. While stirring at 15 to 25 ° C, 1.87 g of ethyl iodide was added dropwise over 10 minutes. This is heated to 60 to 63 ° C and reacted for 3 hours.
After cooling, 25 ml of demineralized water was added dropwise over about 15 minutes. After standing overnight, the crystals were filtered off and washed with water. The obtained crystals were dispersed in 100 ml of methanol, stirred at 15 ° C. to 25 ° C. for 1 hour, filtered, washed with methanol, and dried to obtain a red compound represented by the following structural formula (13). 87 g were obtained.

[0041]

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This compound was treated with DMF-methanol (5: 9
5) λmax in the mixed solution was 517.5 nm. FIG. 7 shows the absorption spectrum. Examples 8 to 10 Journal of American Chemi
cal Society Vol. 73 p4606-
4608 (1951) with reference to the following structural formulas (14) to (14).
Compound (16) was synthesized. The absorption λmax in the methanol solution was 459 nm for (14) and 476 n for (15).
m, (16) was 485 nm.

[0043]

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Embodiment 11

[0045]

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1.15 g of 2-amino-5-methyl-1,2,4-thiadiazole represented by the above structural formula (17)
Was dissolved in 10 ml of acetic acid and 5 ml of propionic acid, and 1 ml of sulfuric acid was added dropwise at 0 to 5 ° C with stirring.
At 55 ° C., 3.55 g of 43% nitrosylsulfuric acid was added dropwise to perform diazotization. The obtained diazo liquid was added to 30 ml of methanol 3-
A solution of N, N-dibutylaminotrifluoromethanesulfonanilide, 5.0 g of trifluoromethanesulfonate, 0.4 g of urea and 4.0 g of sodium acetate was added dropwise at 0 to 5 ° C., and after stirring for 3 hours, Left overnight. The precipitated crystals were separated by filtration and dried to obtain 1.6 g of a reddish-brown compound represented by the following structural formula (18).

[0047]

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Λmax in the methanol solution is 523 nm
Met. FIG. 8 shows the absorption spectrum. Example 12 Amino-trifluoromethy-1,2,2
Synthesis of 4-triazole Zh. Obshch. Khim Vol. 53 198
4 (1983). 23.1 g of trifluoroacetic acid was added to 25 g (0.184 mol) of aminoguanidine bicarbonate, and the mixture was stirred at 20 to 25 ° C. for 30 minutes. To this was added 500 ml of toluene, and the mixture was stirred under reflux for 15 hours while distilling off water and toluene generated by the reaction. After standing overnight, the precipitated crystals were separated by filtration to obtain 14 g of white crystals represented by the following structural formula (10). The structure of this compound is represented by the molecular ion peak 1 in the mass spectrum.
52 was confirmed.

[0049]

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The structural formula (10) obtained as described above
Is dissolved in a mixture of 7.5 ml of acetic acid and 2.5 ml of propionic acid, and cooled to 5 ° C. or lower while stirring. At 3-5 ° C 43 of nitrosylsulfuric acid
3.6 g of a weight% sulfuric acid solution was added, and the mixture was further stirred at 0 to 5 ° C for 2 hours. This reaction solution was prepared in advance,
Methoxy-5-Trifluoromethyl
sulonylamino-N, N-diethyl
anilinetrifluoromethanesu
5.24 g of lfonic Acid salt, 0.4 g of urea,
4 g of sodium acetate was added to a mixture dispersed in 40 ml of methanol at a temperature of 5 ° C. or lower for about 20 minutes. At this time, ice and a 20% aqueous sodium acetate solution were appropriately added so that the temperature of the reaction solution did not become 5 ° C. or more so that the pH of the reaction solution did not become 2 or less. The obtained reaction solution is further cooled at 5 ° C.
After stirring for an hour, the mixture was left overnight. 2. The reaction solution was filtered to obtain a red crystal represented by the following structural formula (20).
62 g were obtained.

[0051]

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Λmax in methanol solution of this compound
Was 519.5 nm. FIG. 9 shows the absorption spectrum. Example 13 3.42 g of the azo compound represented by the structural formula (20) synthesized according to the formulation of Example 12 was dispersed in 20 ml of DMF, and 0.97 g of potassium carbonate was added with stirring.
In this, 1.31 ethyl iodide at 20-25 ° C.
g in 5 ml of DMF was added dropwise over about 3 minutes. After stirring the reaction solution at 20 to 25 ° C for another 2 hours, the mixture was cooled to 20 ° C or lower, and 30 ml of water was added dropwise over about 10 minutes. The precipitated crystals were filtered to obtain 3.0 g of red crystals represented by the following structural formula (21).

[0053]

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Absorption λm of this compound in methanol solution
ax was 521 nm. FIG. 10 shows the absorption spectrum.
Shown in Example 14 4.89 g of the azo compound represented by the structural formula (20) synthesized by the formulation of Example 12 is dissolved in 50 ml of DMF, and 1.27 g of allyl bromide is stirred at 15 to 20 ° C.
Was added dropwise. After stirring at 15 to 20 ° C for 3 hours, water 50 was added.
ml was added and the mixture was further stirred for 2 hours. The generated crystals were separated by filtration, washed with water, and dried to obtain 4.0 g of red crystals represented by the following structural formula (22). Its absorption λmax in a methanol solution was 528 nm. FIG. 11 shows the absorption spectrum.

[0055]

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Embodiment 15

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0.98 g of 3-amino-5-methylisoxazole represented by the above structural formula (23) was added to 10 m
l, dissolved in 5 ml of propionic acid, sulfuric acid 1m at 0-5 ° C
of nitrosyl sulfate 3.55 at 0-5 ° C.
g was added for diazotization. The obtained diazo solution was added to a solution prepared by dissolving 3.91 g of 3-N, N-diethylamino-4-methoxy-trifluoromethanesulfonanilide, 0.4 g of urea and 4.0 g of sodium acetate in 40 ml of methanol at 0 to 5 ° C. The mixture was added dropwise, stirred for 3 hours, and left overnight. The precipitated crystals were separated by filtration and dried to obtain 2.95 g of red crystals represented by the following structural formula (24).

[0058]

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The absorption λma of this in a methanol solution
x was 455.5 nm. FIG. 12 shows the absorption spectrum.
Shown in

[Brief description of the drawings]

FIG. 1 is an IR spectrum of a trifluoromethanesulfonate of 3-N, N-diethylamino-trifluoromethanesulfonanilide obtained in Example 1.

FIG. 2 is an IR spectrum of 3-N, N-diethylaminotrifluoromethanesulfonanilide obtained in Example 1.

FIG. 3 IR of 3-N, N-di-n-butylamino-trifluoromethanesulfonanilide obtained in Example 2
It is a spectrum.

FIG. 4 is an IR spectrum of 3-N, N-diethylamino-4-methoxy-trifluoromethanesulfonanilide obtained in Example 3.

FIG. 5 is an absorption spectrum of a substance obtained in Example 5 in a methanol solution.

FIG. 6 is an absorption spectrum of a substance obtained in Example 6 in a methanol solution.

FIG. 7 is an absorption spectrum of a substance obtained in Example 7 in a solution with DMF-methanol (5:95).

FIG. 8 is an absorption spectrum of a substance obtained in Example 11 in a methanol solution.

FIG. 9 is an absorption spectrum of a substance obtained in Example 12 in a methanol solution.

FIG. 10 is an absorption spectrum of a substance obtained in Example 13 in a methanol solution.

FIG. 11 is an absorption spectrum of a substance obtained in Example 14 in a methanol solution.

FIG. 12 is an absorption spectrum of a substance obtained in Example 15 in a methanol solution.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07D 249/14 502 C07D 249/14 502 261/14 261/14 277/58 277/58 277/82 277/82 295/12 295 / 12 Z 333/36 333/36 G11B 7/24 516 G11B 7/24 516

Claims (7)

[Claims] 1. A sulfonamide compound represented by the general formula (1) and a salt thereof. Embedded image [In the formula, X represents a hydrogen atom, an alkyl group or an alkoxy group which may be substituted, or a halogen atom. Y
Represents an alkyl group having at least two fluorine atoms. R ¹ and R ² each independently represent an optionally substituted alkyl group, or R ¹ is X or R
^It may combine with ² to form a ring. ] 2. Y is a trifluoromethyl group or 2,2,
The sulfonamide compound according to claim 1, which is a 2-trifluoroethyl group. 3. X is a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group or a methoxyethoxy group,
R ¹ and R ² each independently represent 1 to 6 carbon atoms
The sulfonamide compound according to claim 1, wherein the compound is an alkyl group. 4. A compound represented by the general formula (2), which is reacted with trifluoromethanesulfonic anhydride, trifluoromethanesulfonyl chloride or 2,2,2-trifluoroethanesulfonyl chloride. A method for producing the sulfonamide compound represented by (3). Embedded image [In the formula, X represents a hydrogen atom, an alkyl group or an alkoxy group which may be substituted, or a halogen atom. R
¹ and R ² each independently represent an alkyl group which may be substituted, or R ¹ may be bonded to X or R ² to form a ring. [Chemical formula 3] [Wherein, X, R ¹ and R ² are the same as those in the formula (2). Z represents a trifluoromethyl group or a 2,2,2-trifluoroethyl group. ] 5. An azo compound having a sulfonamide group represented by the general formula (4). Embedded image [In the formula, D represents an aromatic ring, and X, Y, R ¹ and R ² are the same as those in the formula (1). ] 6. An azo compound having a sulfonamide group represented by the general formula (5). Embedded image [Wherein, R ³ represents an alkyl group having 1 to 6 carbon atoms which may be branched, and X, Y, R ¹ and R ² are the same as those in the formula (1). ] 7. An azo compound having a sulfonamide group represented by the general formula (6). Embedded image [Wherein, R ⁴ represents an alkyl group having 1 to 6 carbon atoms;
Y, R ¹ and R ² are the same as in the formula (1). ]