JPS5865261A - Synthesis of hydrazone compound - Google Patents

Abstract

PURPOSE:To prepare the titled compound useful as a charge transfer material for organic photosensitive material of electrophotography, rapidly, in high yield, by reducing a nitroso compound in an organic acid, and carrying out the condensation reaction of the resultant hydrazine compound with a carbonyl compound simultaneously or successively in the same organic acid. CONSTITUTION:A nitroso compound (e.g. the compound of formulaI) is reduced with a reducing agent (e.g. powder of metal such as Mg, Ca, Al, etc.) in an organic acid (e.g. acetic acid, formic acid, propionic acid, etc.) to obtain a hydrazine compound. The compound is condensed with a carbonyl compound (e.g. the compound of formula II) simultaneously or successively to the above reduction to obtain the objective hydrazone compound. The process is advantageous since the reduction of the nitroso compound and the condensation of the reaction product can be carried out simultaneously in the same organic acid, and the separation of the nitroso compound is not necessary. The nitroso compound is preferably prepared by nitrosating an amine compound such as the compound of formula III in an organic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for synthesizing a hydrazone compound, and more particularly to a method for synthesizing a hydrazone compound by reacting a hydrazine compound and an aldehyde compound in an organic acid.

Traditionally, hydrazone compounds reduce nitroso compounds,
It can be obtained by first forming a hydrazine compound, isolating it, and then subjecting it to a condensation reaction with an aldehyde compound in a solvent. As the solvent, alcohols such as methanol and ethanol, acetic acid, etc. are often used.

On the other hand, since the above-mentioned nitroso compound can be obtained by dropping an aqueous solution of nitrous acid into an aqueous solution of the hydrochloride of the L1 amine compound, the condensation reaction, which dislikes moisture, and this nitroso reaction can be carried out in the same solvent. It was difficult to carry out the system.

Therefore, in the conventional method for synthesizing hydrazone compounds, after isolating the hydrazine compound from the reaction solution as described above,
A method of conducting a condensation reaction between this and a carbonyl compound in the presence of an acid catalyst was known.

However, many hydrazine compounds are very unstable and easily oxidized, and when the nido μso compound is reduced and isolated as a hydrazine compound, it may not be possible to derive the hydrazone compound or the yield will be quite low. It had become.

An object of the present invention is to provide a method for synthesizing hydrazone compounds that eliminates the above-mentioned drawbacks.

Another object of the present invention is to provide a method for synthesizing hydrazone compounds with high yield.

This object of the present invention is achieved by simultaneously or sequentially carrying out the reduction of the nitroso compound and the condensation reaction with the hydrazine compound and the carbonyl compound in an organic acid.

In the synthesis method of the present invention, a carbonyl compound and a nitroso compound are made to coexist in an organic acid such as acetic acid, formic acid, propionic acid, butyric acid, malonic acid, cono-phosphoric acid, etc., and then magnesium, calcium, aluminum tram, zinc ferrite, etc. By adding the metal powder (reducing agent), 2) reduction of the pso compound and condensation reaction of the hydrazine compound and carbonyl compound produced thereby can be carried out simultaneously to obtain the desired hydrazone compound. can.

However, in another specific example, a nitroso compound, a carbonyl compound, and a metal powder such as those described above are combined with a lower alcohol such as methanol or ethanol, a cyclic ether such as 1,4-oxane or tetrahydrofuran, methyl alcohol,
The desired hydrazone compound can be obtained by coexisting in a cellosolve such as ethylsolve and an organic solvent such as N,N-dimethylformamide, and then adding the above-mentioned organic acid thereto.

In another specific example, a nitrone compound may be dissolved in an organic acid as described above, and an organic solvent mixture of a carbonyl compound and a metal powder as described above may be added thereto to achieve the desired purpose in a high yield. A hydrazone compound can be obtained.

In another embodiment, a carbonyl compound is dissolved in an organic acid as described above, and a mixture of a nitrone compound and a metal powder as described above in an organic solvent as described above is added to this solution. The desired hydrazone compound can be obtained in high yield.

However, in the synthesis method of the present invention, it is also possible to add the carbonyl compound after converting the nitroso compound into a hydrazine compound using the metal powder as described above. At this time, it is desirable to add a carbonyl compound to the pore where the hydrazine compound is oxidized in the air.

In the synthesis method of the present invention, it is preferable to obtain the above-mentioned nitroso compound by nitrosating an amine compound in the above-mentioned organic acid. For example, by dispersing or dissolving an amine compound in an organic acid such as acetic acid, formic acid, propionic acid, butyric acid, malonic acid, succinic acid, etc., and adding a nitrite such as sodium nitrite to this solution or dispersion, A nitroso compound is present in the above-mentioned actual acid, then a carbonyl compound is added to the organic acid containing the nitrone compound, and then a metal powder such as magnesium, calcium, aluminum, zinc, or iron is added. By simultaneously carrying out the reduction of the compound and the condensation reaction between the hydrazine compound and carbonyl compound produced thereby, the desired hydrazone compound can be obtained in high yield.

The above-mentioned synthetic method allows the nitronation, reduction, and condensation reactions to be performed in the same organic acid, and there is no need to isolate the nitroso compound, so the hydrazone compound can be obtained quickly and in an extremely high yield. There is an advantage that it can be done.

In another specific example, an amine compound is nitrosated in an organic acid as described above, and an organic solvent mixture of a carbonyl compound and a metal powder as described above is added to the organic acid containing the nitrone compound. Also, hydrazone compounds can be obtained in high yield. Examples of the organic solvent used in this case include lower alcohols such as methanol and ethanol, cyclic ethers such as 1,4-dioxane and tetrahydrofuran, cellosolves such as methylsolve and ethylsolve, and N,N-dimethylformamide.

As mentioned above, in the synthesis method of the present invention, during the condensation reaction, an organic solvent such as the one described above can be added to boric acid.
You don't have to add it yet.

The carbonyl compound that can be used in the synthesis method of the present invention can be represented by the following general formula (1), for example.

General formula (1) In the formula, R1 and tortoise are hydrogen atoms; aryl groups such as phenyl, naphthyl, anthryl, and pyrenyl which may have substituents; heterocyclic residues such as pyridyl and furyl; carbazole, Indicates an aromatic residue containing a heterotetracycle such as fetchavazine, phenoxazine, and indole. However, R1 and bird cannot become hydrogen atoms at the same time. Substituents for Y and R2 include alkyl groups such as methyl, ethyl, propyl, and butyl; aryl groups such as phenyl and naphthyl; alkoxy groups such as methoxy, ethoxy, and propoxy; halogen atoms such as chlorine, bromine, and iodine; dimethyl Examples include dialkylamino groups such as amino, diethylamino, dipropylamino, and dibutylamino.

As a specific carbonyl compound, if it is clear (7) α
DCHO C! H5 CzHda 07) 08) 09) ■) h can be listed.

However, the amine compound that can be used in the present invention has the general formula (2)-! or (3).

General formula (2) General formula (3) 11)NH 7 In the formula, R4 is an alkylene group such as methylene, ethylene, propylene, butylene which may have a substituent; a phenylene group; naphthylene M, etc. f.

R3, Rs, IL, and 几 represent an alkyl group such as methyl, ethyl, propyl, butyl, etc., which may have a substituent; an aryl group such as phenyl, naphthyl, etc.; Examples of the substituent include alkoxy groups such as methoxy, ethoxy, and proxy; halogen atoms such as chlorine, bromine, and iodine; and dialkylamino groups such as dimethylamino, diethylamino, diethylamino, and dibutylamino.

Specific examples of the amino compound include Riba and the like.

However, the nitroso compound used in the present invention has the general formula (4
) or (5).

General formula (4) General formula (5) 111, -N-N.

12 In the formula, R9 represents a noalkylene group such as methylene, ethylene, propylene, and phethylene which may have a substituent; a phenylene group; a naphthylene group, etc.; H4, RIO, R1
1 and R12 are methyl which may have a substituent,
Alkyl groups such as ethyl, propyl, butyl; phenyl,
The nine devices representing aryl groups such as naphthyl include alkyl groups such as methyl, ethyl, propyl, and butyl; aryl groups such as phenyl and naphthyl; alkoxy groups such as methoxy, ethoxy, and propoxy; Halogen atom; examples include dialkylamino groups such as dimethylamino, diethylamino, 7-fluoroylamino, and dibutylamino.

Examples of specific nitroso compounds include the following.

The various hydrazone compounds obtained by the synthesis method of the present invention are extremely useful materials as charge transport materials for Ig-Ko electrophotographic photoreceptors, electron donating substances for charge transfer complex type electrophotographic photoreceptors, and the like.

Hereinafter, the present invention will be explained according to its implementation.

Example I 847 g of P-diethylaminobenzaldehyde (4,7
8/100 mol) and ethano-A = 100 ml, zinc 30
g (0,459 mol) were coexisting in a 300 ml beaker and cooled to 10°C in an ice water bath.

Next, 10 g of a nitroso compound represented by the formula (2,39/1008
) was dissolved in 100 ml of acetic acid. This liquid was dropped into the PIil cooling liquid and maintained at 20°C or lower. After the dropwise addition was completed, the zinc was distributed from door to door, and the P solution was further stirred by an amount of SO.

A yellow precipitate was obtained by adding f'E to water to this reaction solution. This was crystallized from methyl ethyl ketone (11), and mp
229.5~230.0°0 bright colored crystals 11.9 g
(Yield 35 (easy)!

35 g (0.14 mol) of the nitroso compound represented by is dissolved in 230 ml of acetic acid and cooled at 10°01.

Next, 87.5 g (1.14 mol) of zinc and 24.81 g (0.14 mol) of P-diethylaminobenzaldehyde coexisted in 110 ml of ethanol and were added dropwise to the coolant. After the dropwise addition was completed, zinc was poured from door to door, stirring was continued for 30 minutes, and the reaction solution was poured into water to obtain a yellow precipitate. This precipitate was recrystallized from methyl ethyl ketone mp 120.
26.5 g of yellow crystals (yield: 449%) at 5-121.5°C
) was obtained.

Example 3 (Synthesis of the same hydrazone compound as in Example 2) Example 2
253 g (1.14 mol) of the nitroso compound used in
77 in acetic acid, and 202 g (1.14 mol) of P-diethylaminobenzaldehyde was added thereto at 10 °C.
250 g (3.82 mol) of zinc at 20° C.
added so as not to exceed. Furthermore, this reaction solution was filtered,
The p solution was poured into water to obtain a yellow precipitate.

This yellow precipitate was reconsolidated with methyl ethyl ketone, and mpl 2
183 g of yellow crystals (yield: 40
．． 8%).

Comparative Example 1 (Synthesis of the same hydrazone compound as in Example 2) Example 2
35 g (0.14 mol) of the nitrone compound used in 1 was dissolved in 230 ml of acetic acid, cooled to 10.
7. sg (t, x+ moles) was added in portions.

This liquid was then filtered and poured into water to isolate the hydrazine compound. Next, this hydrazine compound was mixed with ethanol 11
0 ml of P-diethylaminobenzaldehyde 24. slg (o, 14 mol) was added and stirred for 30 minutes, and the reaction solution was poured into water to obtain a yellow precipitate. This precipitate was recrystallized from methyl ethyl ketone and the mp was 120.0 to 121.
．． 10.23 g (yield 18.8%) of 5°0 yellow crystals were obtained.

2,7-C N-phenylaminonaphthalene 10
g (3.22/100 mol) was dissolved in 100 ml of acetic acid, and 4.89 g (7.08/100 mol) of sodium nitrite was slowly added to nitrosate. Next, 11.42 g of P-jethylaminobenzaldehyde (6,44/1
00 mol) was added and cooled to 10"C. 20g (0.31 mol) of zinc was added to this solution in such a way that the liquid temperature exceeded 20°C. After the reaction was completed, the zinc was removed from door to door, and the p solution was Poured into water to obtain a yellow precipitate.

Furthermore, it was recrystallized from methyl ethyl ketone, and the mp 1
8.18 g of eclipse of 47.5-1500°0 was obtained. (Yield of amine paste: 38.5%) 2 sog (x,
mol) was added for nitrosation. 202 g (1.14 mol) of P-diethylaminobenzaldehyde was added to this solution and cooled to 10''O.

To this solution was added 25 og (3, sz moles) of zinc not to exceed 20°. The solution was then filtered and the p solution was poured into water to obtain a yellow precipitate. This yellow precipitate was reconsolidated with methyl ethyl ketone, mpl 28.5-129.5°C
2139 g of yellow crystals (amine base yield Ei 4.4%)
) was obtained.

Comparative Example 2 250 g (1.14 mol) of N-β-naphthylaniline was dissolved in a 35% hydrochloric acid aqueous solution, and nitrous acid was added to this.
87 g (1.26 mol) of IJum was added to effect nitrosation. 202 g (1.14 mol) of P-diethylaminobenzaldehyde was added to this solution, and the mixture was heated at 10°0
cooled down to. 250 g (3.82 mol) of zinc were added to this solution, not exceeding 20°.

Next, this solution was filtered and the p solution was poured into water, but the desired precipitate was not obtained.

Comparative Example 3 (Synthesis of the same hydrazone compound as in Example 5) N-β-
250 g (1.14 mol) of naphthylaniline in 35
Dissolved in 51% hydrochloric acid bath solution, and added 88% sodium nitrite to this.
7 g (1.26 mol) was added to effect nitrosation. This anti-chloride solution was cooled to 10°C, and 87.5g (1,
14 mol) was added little by little.

Next, this liquid was filtered and water was injected to isolate the hydrazone compound. Next, this hydrazone compound was dissolved in ethanol 11, and P-diethylaminobenzaldehyde 2
02 g (1,14 mol) was added, cooled to 10'0, and 250 g (3,82 mol) of zinc was added so as not to exceed 20'0.Furthermore, this reaction solution was filtered, and the p solution was diluted with water. Ebetsu and Huangshin were obtained.

This yellow precipitate was reconsolidated with methyl ethyl ketone, and mp127
．． 73 g of yellow crystals (amine base yield: 16.3) were obtained with a temperature of 0 to 128.0°C.

Example 6 (Synthesis of the same hydrazone compound as in Example 1) Example 1
10 g of the nitroso compound used in (2,39/100
mol) in 100 m/ml of acetic acid, cooled to 10°C in an ice-water bath, and then added 100 m/mol of ethanol to this solution.
30 g (0,459 mol) of zinc dispersed in P-diethylaminobenzaldehyde was added dropwise, and immediately 8.4 g of P-diethylaminobenzaldehyde was added.
7 g (4.78/100 mol) was added and stirred for 30 minutes. Next, the reaction solution was filtered and poured into water to obtain a multicolored precipitate.

This was recrystallized from methyl ethyl ketone, and the mp229.
11.5 g (34%) of yellow crystals with a temperature of 5-230.0°C were obtained.

[Brief explanation of drawings]

Fig. 1 is a characteristic diagram showing the infrared absorption spectrum of the hydrazone compound synthesized in Example 1, Fig. 2 is a characteristic diagram showing the infrared absorption spectrum of the hydrazone compound synthesized in Example 2, and Fig. 3 is a characteristic diagram showing the infrared absorption spectrum of the hydrazone compound synthesized in Example 2. 3 is a characteristic diagram showing an infrared absorption spectrum of a hydrazone compound synthesized in Example 4. FIG. Procedural amendment (spontaneous) 112, 1980 1, Indication of case 1981 Patent Application No. 163613 2, Title of invention Method for synthesizing hydrazone compounds 3, Person making the amendment Relationship with the case Patent applicant Location Tokyo 3-30-2 Shimomaruko, Ota-ku Name (100) Canon Co., Ltd. Representative Ryu Kaku Sanbe 4, Agent Address 146 Tokyo Metropolitan University) (3-30-2 Shimomaruko, Ward 1)
Canon Co., Ltd. (Telephone: 758-2111.) 5, Subject of amendment (1) Detailed description of the invention column 6 of the specification, Contents of amendment (1) Page 25 of the specification, lines 2 to 6 ""hydrazone" was corrected to "hydrazine". (2) Same as above, page 25, line 3, “hydrazone” was corrected to “hydrazine”.

Claims (2)

[Claims] (1) A chemical reaction in which a nitroso compound is converted into a hydrazine compound in the presence of a reducing agent in an organic acid, and a chemical reaction in which the hydrazine compound is condensed with a carbonyl compound to form a hydrazone compound are carried out simultaneously or continuously. Synthesis method of hydrazone compounds. (2) A chemical reaction in which an amine compound is converted into a nitroso compound in an organic acid, a chemical reaction in which the nitrone compound is converted into a hydrazine compound in the presence of a reducing agent, and a chemical reaction in which the hydrazine compound and a carbonyl compound are condensed to form a hydrazone compound. A method for synthesizing hydrazone compounds, which is characterized by simultaneous or continuous synthesis.