JPH09143129A - Production of 4-aminophenylacetylene compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To realize a method for producing a 4-aminophenylacetylene compound useful as a halation-inhibiting agent used for thermally developing photosensitive materials or as its synthetic intermediate in short processes in a good yield by using inexpensively available raw materials. SOLUTION: This method for producing the 4-aminophenylacetylene compound of formula III comprises reacting a 4-aminoacetophenone compound of formula I (R<1> , R<2> are am each H, formyl, an acyl, an alkoxycarbonyl, an aryloxycarbonyl, carbamoyl, or R<1> and R<2> form a five-membered ring together with N) with a reacting agent obtained from triphenylphosphlne and an active chloride compound, reacting the obtained α-chlorostyrene compound of formula II with a base. The active chloride compound is used in an amount of approximately 0.5-3 moles based on the triphenylphosphine. The reaction temperatures of the first and second processes are -20 to 140 deg.C and -20 to 150 deg.C, respectively. The compound of formula I can easily be synthesized by acylating p- aminoacetophenone as a starting raw material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fog inhibitor used in silver halide photographic light-sensitive materials, particularly heat-developable light-sensitive materials, and a process for producing 4-aminophenylacetylene compounds which are synthetic intermediates thereof.

[0002]

2. Description of the Related Art A technique for easily and quickly obtaining an image by changing the re-image processing method of a light-sensitive material using silver halide from a conventional wet processing using a developing solution or the like to a dry processing using heating or the like. Has been developed. Photothermographic materials are known in the art, and the photothermographic materials and their processes are described in US Pat. Nos. 3,152,904 and 3,30.
1,678, 3,392,020, 3,457,075, British Patents 1,131,108, 1,167,777 and Research Disflower, June 1978, pages 9-15 (RD-1702
9). Phenylacetylenes having an acylamino group at the p-position are useful as compounds that suppress fogging. There are many known methods for synthesizing phenylacetylenes (for example, S. Pa
tai Ed., "The chenistry of the carbon-carbon trip
le bond "p. 755, John Wiley & Sons (1978)), this method has a large number of steps, and many synthesis methods are disadvantageous in terms of cost.

On the other hand, in recent years, a coupling reaction between an aryl halide and an acetylene compound using a palladium catalyst has been developed as a method having a small number of steps as shown below (for example, Synthesis 198).
0 , 627; ibid., 1981 , 364, ibid, 1984, 728; Organom
et allics 12 , 263 (1993); J. Org. Chem., 59, 5818 (1
994) etc.).

[0004]

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[0005]

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According to this synthesis method I, 4-nitrophenylacetylene and 4-nitrophenylacetylene which are precursors of the target compound, a phenylacetylene compound having an acylamino group at the p-position, are used.
Aminophenylacetylene is synthesized, but the 4-nitrophenylacetylene compound is an explosive compound and is not suitable for large-scale synthesis. In contrast, synthetic method II
However, when p-iodoaniline itself is reacted with acetylene alcohols in the presence of a Pd catalyst, the conversion rate is low. Therefore, synthesis of 4-aminophenylacetylene by protection and deprotection with a trifluoroacetyl group is proposed. However, the cost is not satisfactory. On the other hand, the following method is known as a method for converting methyl ketone to acetylene, but the reaction operation is complicated and the yield is low. Further, when phosphorus pentachloride is used, improvement is desired such that a large amount of ice must be used for post-treatment.

[0007]

[Chemical 6]

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method capable of producing a desired p-aminophenylacetylene compound with a high yield in a shorter process than a raw material which can be obtained at a low cost.

According to the present invention, a specific p-aminoacetophenone compound is reacted with triphenylphosphine dichloride or a reaction agent obtained from triphenylphosphine and an active chloride compound to obtain an α-chlorostyrene compound. Then, it was made based on the finding that the above problems can be efficiently solved by reacting with a base. That is, the present invention provides a compound represented by the general formula (I):

[0009]

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(Where R is¹And R^Two, Hydrogen atom, holmi
Group, acyl group, alkoxycarbonyl group, aryl group
A oxycarbonyl group or a carbamoyl group or a group represented by R¹
And R ^TwoAre bonded to form a 5-membered ring with the nitrogen atom
Good. ) 4-aminoacetophenone compound
With triphenylphosphine dichloride or trif
Reactions obtained from phenylphosphine and active chloride compounds
General formula (II)

[0011]

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An α-chlorostyrene compound represented by the formula (wherein R ¹ and R ² have the same meanings as those in the general formula (I)) is prepared and reacted with a base to give the general formula (II
I)

[0013]

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(Wherein R ¹ and R ² have the same meanings as in the general formula (I)) to obtain a 4-aminophenylacetylene compound, which is a process for producing a 4-aminophenylacetylene compound. Provide a way.

BEST MODE FOR CARRYING OUT THE INVENTION Next, the manufacturing method of the present invention will be described in detail. R ¹ and R ² in the general formulas (I) to (III) each represent a hydrogen atom, a formyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group or a hydrogen atom. Here, the acyl group includes
The alkylcarbonyl group and the arylcarbonyl group are included, and the carbamoyl group includes a substituted or unsubstituted carbamoyl group. R ¹ and R ² in the general formulas (I) to (III) are preferably a hydrogen atom or a formyl group, preferably an alkylcarbonyl group having 2 to 18 carbon atoms (eg, acetyl, palmitoyl), preferably 7 to 7 carbon atoms. 18 arylcarbonyl groups (for example benzoyl), preferably alkoxycarbonyl groups having 2-18 carbon atoms (for example methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl), preferably 7-carbon atoms.
18 aryloxycarbonyl groups (eg phenoxycarbonyl), preferably substituted or unsubstituted carbamoyl groups having 1 to 18 carbon atoms (eg carbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl).
And R ¹ and R ² may combine with each other to form a 5-membered ring together with the nitrogen atom. Examples of the 5-membered ring that may be formed include substituted or unsubstituted phthalimide, succinimide, maleimide, hydantoin, and urazole. Particularly preferred is phthalimide.

R ¹ particularly preferably represents a hydrogen atom.
R ² is more preferably a C 2-18, particularly preferably a C 2-8 alkylcarbonyl group, and a C 7-
It is an arylcarbonyl group having 18 carbon atoms, a C2-18, particularly preferably an alkoxycarbonyl group having 2-8 carbon atoms, and an aryloxycarbonyl group having 7-18 carbon atoms. Furthermore, it is particularly preferable that R ¹ in the general formula (III) is a hydrogen atom, and R ² is an alkylcarbonyl group having 2 to 18 carbon atoms, a C ^{2 to} 8 special carbon atom or an arylcarbonyl group having 7 to 18 carbon atoms. Groups are preferred.

Next, the step of synthesizing the α-chlorostyrene compound represented by the general formula (II) will be described. The compound represented by the general formula (I) can be easily synthesized by acylation using p-aminoacetophenone as a starting material.
Examples of the active chloride compound used together with triphenylphosphine include carbon tetrachloride, hexachloroethane,
Trichloroacetonitrile, trichloroacetic acid ester,
N-chlorosuccinimide, 1,3-dichloro-5,5
-Dimethylhydantoin, trichloroisocyanuric acid can be mentioned. More preferred are N-chlorosuccinimide, 1,3-dichloro-5,5-dimethylhydantoin and trichloroisocyanuric acid. These compounds are used in an amount of 0.5 to 3 mol, preferably 0.9 to 1.5 mol, based on triphenylphosphine. Triphenylphosphine dichloride, or triphenylphosphine used together with an active chloride compound is preferably used in an amount of 0.5 to 5 mol, more preferably 0.9 to 2.5 mol, based on 1 mol of a 4-aminoacetophenone compound. Is. Examples of the reaction solvent used include aliphatic hydrocarbon solvents such as hexane and heptane, aromatic hydrocarbon solvents such as benzene and toluene, ether solvents such as tetrahydrofuran, and acetonitrile.
Reaction temperature is -20 to 140 ° C, preferably 0 to 120 ° C
It is.

Next, the step of synthesizing the 4-aminophenylacetylene compound represented by the general formula (III) will be described. As the base, sodium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide. Are used. These are preferably used in an amount of 0.5 to 5 mol, more preferably 0.9 to 3 mol, based on the compound of the general formula (II) which is a reaction substrate. Examples of the reaction solvent include alcohol compounds such as methanol, ethanol and tert-butanol, ether solvents such as tetrahydrofuran, amide solvents such as N, N-dimethylacetamide and dimethylimidazolidinedione (DMI), benzene and toluene. Aromatic hydrocarbon solvent, dimethyl sulfoxide (DMSO), etc. are used. The reaction temperature is-
20 ° C to 150 ° C, preferably -20 ° C to 100 ° C, particularly preferably 0 to 100 ° C. Next, specific examples of the compounds of the general formulas (I) to (III) in the production method of the present invention will be shown, but the present invention is not limited thereto.

[0018]

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[0019]

[Table 1] Compound No.R ¹ R ² (I)-1 HH (I)-2 H COCH ₃ (I)-3 H COC ₃ H ₇ (i) (I)-4 H COC ₁₅ H ₃₁ (I) -5 H CO-Ph (I) -6 H CO ₂ CH ₃ (I)-7 H CO ₂ C ₂ H ₅ (I)-8 H CO ₂ C ₄ H ₉ (t) (I)-9 H CO ₂ -Ph (I) -10 H CON (CH ₃ ) ₂ (I) -11 COCH ₃ COCH ₃ (I) -12 CO-Ph CO-Ph (I) -13 CO ₂ C ₂ H ₅ CO ₂ C ₂ H ₅ Ph Represents a phenyl group, CO-Ph represents a benzoyl group, and CO ₂ Ph represents a benzoyloxy group (hereinafter the same).

[0020]

[Table 2]

[0021]

[Table 3]

Compounds (II) -1 to (II) -26 are compounds represented by the following general formula (II) -A in which R ¹ and R ^{2 are the same.}
Is a compound having the same R ¹ and R ² as the corresponding compounds (I) -1 to (I) -26 in the above table. In addition, the compound (I
In II) -1 to (III) -26, R ¹ and R ² in the compound represented by the following general formula (III) -A are the corresponding compounds (I) -1 to (I) -in the above table. 26 is a compound having the same R ¹ and R ² as 26.

[0023]

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[0024]

According to the present invention, p- which can be obtained at a low cost
P-Aminophenylacetylene can be synthesized in a shorter time and with a higher yield than aminoacetophenone. Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

[0025]

【Example】

Example 1 Compound (I) -1 was acylated to give compound (I) -3 and then chlorinated to give compound (II).
-3, and then treated with a base to give compound (III) -3. Compound (I) -1 (p-aminoacetophenone) 135.
0 g (1 mol) was dispersed in 500 ml of acetonitrile, 81 ml of pyridine was added thereto, and 105 ml of isobutyric acid chloride was added dropwise at an internal temperature of 5 to 10 ° C under ice cooling. After reacting for 2 hours, 2 liters of water was added, and the precipitated crystals were filtered to obtain 166.0 g of compound (I) -3 as colorless crystals.
(Yield 81%) was obtained.

Next, 20.5 g (0.1) of compound (I) -3
Mol) was dissolved in 300 ml of toluene, and 73.3 g (0.22 mol) of triphenylphosphine dichloride was added to this, and a calcium chloride tube was attached, and the mixture was heated under reflux for 6 hours. After the solvent was distilled off, the residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 2/1) and crystallized as n-hexane to give compound (II).
-3 was obtained as colorless crystals (15.0 g, yield 67%). Next, the compound (II) -3 11.2 g (0.05 mol) was added to tert.
-Dispersed in 50 ml butanol, to which potassium tert-
Butoxide (6.6 g, 0.05 mol) was added, and the mixture was heated under reflux for 3 hours under a nitrogen atmosphere. After cooling, add 100 ml of water,
The precipitated crystals were filtered to obtain 7.77 g (yield 83%) of compound (III) -3 as colorless crystals.

Example 2 Compound (I) -1 was acylated to give compound (I) -9 and then chlorinated to give compound (II) -9, which was then treated with a base to give compound (III).
Synthesis example for obtaining -1 Compound (I) -1 (p-aminoacetophenone) 135.
0 g (1 mol) was dissolved in 1 liter of acetonitrile,
Add 81 ml of pyridine and add phenyl chlorocarbonate under ice cooling.
126.0 ml was added dropwise. After dropping, the mixture was further reacted for 1 hour, the precipitated crystals were filtered, washed thoroughly with water, and then washed with a small amount of acetonitrile to obtain 245.0 g (yield 96%) of compound (I) -9 as colorless crystals. Obtained.

Next, 25.5 g (0.1 mol) of the compound (I) -9 was dissolved in 300 ml of toluene, 36.7 g (0.11 mol) of triphenylphosphine dichloride was added thereto, and a calcium chloride tube was attached. The mixture was heated under reflux for 9 hours. Purification was performed by silica gel chromatography (n-hexane / ethyl acetate = 3/1), and crystallization was performed using n-hexane to give compound (II) -9 as colorless crystals.
2.7 g (yield 46%) was obtained.

Next, 13.7 g (0.05) of compound (II) -9
(Mol) was dissolved in 70 ml of methanol, and 8.42 g (0.15 mol) of potassium hydroxide was added thereto, and the mixture was mixed under nitrogen atmosphere for 3 times.
Heating and stirring were performed for hours. The mixture was returned to room temperature, 150 ml of water was added, and the precipitated crystals were filtered to obtain 4.80 g (yield 82%) of compound (III) -1 as pale brown crystals. Compound (II
I) -1 is a known compound (Helv chim Acta 54 , 2060 (197
1)), and the structure was confirmed by ¹ H-NMR.

Reference Example 1 Synthetic Example in which Compound (I) -9 is Chlorinated to Compound (II) -9 (Conditions Different from Example 2 are Used) Compound (I) -9 2.55 g (0.01 mol) ) Was dissolved in 30 ml of toluene, and 2.62 g (0.01 mol) of triphenylphosphine and 1,3-dichloro-5 were added thereto while cooling with ice.
5-dimethylhydantoin 1.08 g (0.0055 mol)
Were sequentially added, and the mixture was heated under reflux for 3 hours. The remaining starting compound (I) -9 was removed by silica gel column chromatography, and crystallization was performed from n-hexane.
0.80 g of Compound (II) -9 as colorless crystals (yield 29
%)Obtained. Reference Example 2 Synthesis of Compound (II) -9 by Chlorination of Compound (I) -9 (Adopting Conditions Different from Example 3) N-chlorosuccinimide instead of 1,3-dichloro-5,5-dimethylhydantoin The reaction and post-treatment were carried out under the same conditions as in Example 3 except that 1.34 g (0.01 mol) was used to obtain 1.30 g (yield 47%) of compound (II) -9.

Example 3 Compound (I) -1 was acylated to give compound (I) -7 and then chlorinated to give compound (II) -7, which was then treated with a base to give compound (III)-.
Synthesis example 1) Compound (I) -1 (p-aminoacetophenone) 135.
300 ml of ethyl acetate, 60 g of sodium hydroxide and 500 ml of water were added to 0 g (1 mol), and 95 ml (1 mol) of ethyl chlorocarbonate was added dropwise at 5 to 10 ° C under ice cooling. After further stirring for 1 hour, separating the layers, washing with saturated saline,
After distilling off the solvent, crystallization from acetonitrile was carried out to obtain 197.3 g (yield 95%) of compound (I) -7 as colorless crystals.
%)Obtained. Then, under almost the same conditions as in Example 2, chlorination and base treatment were carried out, and compound (III) -7 was passed through compound (III) -7 to give compound (III) -7 at a yield of 40%. Got 1.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07C 233/92 9547-4H C07C 233/92 271/26 9451-4H 271/26 C07D 207/404 C07D 207/404 207/448 207/448 233/74 233/74 249/12 508 249/12 508 G03C 1/498 504 G03C 1/498 504 8/40 506 8/40 506

Claims (1)

[Claims] 1. A compound of the general formula (I) (In the formula, R ¹ and R ² represent a hydrogen atom, a formyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group or a carbamoyl group, or R ¹ and R ² are bonded to each other to form a 5-membered ring together with a nitrogen atom. A 4-aminoacetophenone compound represented by the general formula (II) embedded image may be reacted with triphenylphosphine dichloride, or a reaction agent obtained from triphenylphosphine and an active chloride compound. (In the formula, R ¹ and R ² have the same meanings as in formula (I).) An α-chlorostyrene compound represented by the formula (I) is prepared and reacted with a base to give a compound represented by formula (III): (In the formula, R ¹ and R ² have the same meanings as in formula (I).) A method for producing a 4-aminophenylacetylene compound, characterized by obtaining a 4-aminophenylacetylene compound.