JPH06145118A - Production of aminonitro derivative of condensed carbon multicyclic or heterocyclic ketone - Google Patents

Abstract

(57) [Summary] [Structure] A process for producing an aminonitro compound (II), in which a dinitro compound (I) of a condensed carbon polycyclic or heterocyclic ketone is partially reduced in a water-containing organic solvent in the presence of a sulfide. [Chemical 5] (In the formula, X is a single bond, —CH ₂ —CH ₂ —, and —CH═C.
H-, -C (= O)-, -O-, -S-, -N (-R)
Represents -or -C (= C (CN) ₂ )-, and Y represents -C (=
O)-, -C (= O) -C (= O)-, -N (-R)-
Represents C (= O)-or -OC (= O)-, and Z is = C.
H- or = N- is represented, and R represents a hydrogen atom, an alkyl group or an alkoxyl group. [Effect] An aminonitro compound (II) can be selectively produced.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a condensed carbon polycyclic compound or a heterocyclic ketone useful as an intermediate raw material for producing an azo compound useful as a drug, an agricultural chemical, a dye, a pigment, an electrophotographic material, or the like. The present invention relates to a method for producing an aminonitro compound.

[0002]

2. Description of the Related Art In the field of electrophotographic materials, azo organic photoconductive materials having a condensed carbon polycyclic or heterocyclic ketone skeleton have been receiving attention. Such a compound is produced by first subjecting an amino group of a condensed carbon polycyclic aminonitro compound to a diazo coupling reaction, then aminating the remaining nitro group, and further performing a diazo coupling reaction. Therefore, how to produce an aminonitro compound of a condensed carbon polycyclic or heterocyclic ketone with high purity and high yield has been a major problem.

[0003] In the reduction of the dinitro-form of the condensed carbon polycyclic or heterocyclic ketone by the conventional method, the diamino-form is by-produced together with the aminonitro-form since there is no reaction selectivity. When a raw material containing such a diamino compound is subjected to a diazo coupling reaction, it is difficult to separate and purify only the desired monocoupling compound.

Therefore, in order to produce a nitro form of a condensed carbon polycyclic or heterocyclic ketone, the condensed carbon polycyclic or heterocyclic ketone (III) is mononitrated, and the mononitro form (IV) is further reduced to form a monoamino form. A method is known in which (V) is followed by nitration to obtain an aminonitro derivative (II) [GW Gray et al., JCS 2686 (1955)].

[0005]

[Chemical 2]

(In the formula, X and Y are the same as above.) However, even by this method, it is difficult to selectively obtain a mononitro derivative of a fused carbon polycyclic or heterocyclic ketone. Further, there is a problem in that a nitration reaction in which a monoamino compound is converted to an aminonitro compound can obtain only a position where a nitro group is introduced. Furthermore, since this method involves a multi-step reaction, the total yield of the aminonitro compound is lower than that of the starting material.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides a method for producing an aminonitro compound conveniently and in good yield by selectively partially reducing the dinitro compound of a fused carbon polycyclic or heterocyclic ketone. Especially.

[0008]

The present invention has the general formula [I]
A method for producing an aminonitro compound represented by the general formula [II], which comprises partially reducing a dinitro compound of a condensed carbon polycyclic or heterocyclic ketone represented by: in the presence of a sulfide in a water-containing organic solvent. Is.

[0009]

[Chemical 3]

(In the formula, X is a single bond, --CH ₂ --CH ₂
-, -CH = CH-, -C (= O)-, -O-, -S
Represents-, -N (-R)-or -C (= C (CN) ₂ )-, and Y represents -C (= O)-, -C (= O) -C (= O).
-, -N (-R) -C (= O)-or -OC (= O)
Represents-, Z represents = CH- or = N-, and R represents a hydrogen atom, an alkyl group or an alkoxyl group).

As the aminonitro compound of the general formula [II],
For example, the following compounds can be mentioned, and these compounds are known.

[0012]

[Chemical 4]

Examples of the sulfide used in the present invention include sodium sulfide, sodium hydrosulfide, sodium dithionite, ammonium sulfide and the like, but sodium sulfide is preferable.

When sodium sulfide is used, the reaction molar ratio is preferably 1.5 to 2.0 mol, and more preferably 1.6 to 1 mol based on 1 mol of the dinitro compound of the condensed carbon polycyclic or heterocyclic ketone. 0.8 mol is preferred.

As the water-containing organic solvent, any solvent can be used as long as it is inert to the reaction and has appropriate solubility, but a mixed solvent of water-alcohols is preferable. Examples of this alcohol include methanol, ethanol, propanol, isopropanol, butanol, hexanol and the like, with methanol and ethanol being preferred.

The mixing ratio of the water-alcohol mixed solvent is preferably 30 to 95% by volume of alcohol, and 55 to 7 by volume.
0% is particularly preferred. If the amount of alcohol is more or less than this range, the amount of by-products other than the intended product such as a diamino compound is increased, which is not preferable. The amount of the water-containing organic solvent is 1 part with respect to 1 part of the dinitro body of the condensed carbon polycyclic or heterocyclic ketone.
It is preferably 0 part by weight or more, and particularly preferably 30 to 50 parts by weight.

The reaction temperature is preferably the reflux temperature of the water-containing organic solvent. The reaction time varies depending on the reaction temperature, but is 30 minutes or longer. It is preferably 2 to 6 hours, particularly preferably 3 to 5 hours.

After completion of the reaction, the suspension obtained is filtered,
The obtained crystals can be sufficiently washed until the washing liquid becomes neutral and dried to obtain an aminonitro compound of a condensed carbon polycyclic or heterocyclic ketone.

[0019]

EXAMPLES The present invention will be specifically described with reference to the following examples.

Example 2 Preparation of 2-amino-7-nitro-9-fluorenone 50 g (0.18) of 2,7-dinitro-9-fluorenone
5 mole) was added to a mixed solvent of 1300 ml of ethanol and 540 ml of water, and sodium sulfide nonahydrate 71.1 was added thereto.
An aqueous solution prepared by dissolving g (0.296 mole) in 200 ml of water was added dropwise over 20 minutes. The mixture was reacted under stirring under reflux for 3 hours. After cooling after cooling, the obtained crystals were washed with water and dried at 60 ° C. for 10 hours to obtain 35.4 g of crystals of 2-amino-7-nitro-9-fluorenone having a purity of 97%. The crystals were recrystallized from chlorobenzene to give 2-amino-7-nitro-9.
-A pure fluorenone is obtained.

Melting point 279-280 ° C. ¹ H-NMR (DMSO) spectrum is shown in FIG. In mass spectrum and elemental analysis, m / e = 240 (molecular weight 240) elemental analysis value (%) measured value C: 65.23 H: 33.45 N: 11.73 calculated value C: 65.00 H: 33.57 N: 11.66.

Comparative Example The same procedure as in Example was repeated except that 1800 ml of water was used instead of the mixed solvent of 1300 ml of ethanol and 540 ml of water in the example to obtain 34.2 g of a product. As a result of analyzing this product by liquid chromatography, 2,7
-Diamino-9-fluorenone 25 wt%, 2-amino-
It was a mixture of 50 wt% 7-nitro-9-fluorenone and 25 wt% 2,7-dinitro-9-fluorenone.

[0023]

When the reaction is carried out in the water-containing organic solvent of the present invention, the aminonitro compound can be selectively produced.

[Brief description of drawings]

FIG. 1 is a ¹ H-NMR spectrum diagram of a compound obtained in an example.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C07D 219/08 221/06 221/16 311/80 7252-4C 311/86 7252-4C 335/16 (72) Inventor, Mariko Kobayashi, 8-3-1 Chuo, Ami-machi, Inashiki-gun, Ibaraki Mitsubishi Petrochemical Co., Ltd. Tsukuba Research Institute (72) Eiji Taniyama 3-3-1, Chuo, Ami-cho, Inashiki-gun, Ibaraki Yuka Co., Ltd., Tsukuba Research Institute (72) Inventor Takamasa Ueda 2-3-3 Azuchi-cho, Chuo-ku, Osaka-shi, Osaka, Osaka International Building Minolta Camera Co., Ltd. (72) Inventor Hideaki Ueda, Chuo-ku, Osaka-shi, Osaka 2-3-3 Azuchicho Osaka International Building Minolta Camera Co., Ltd.

Claims (1)

[Claims] 1. A general formula [II] characterized by partially reducing a dinitro form of a condensed carbon polycyclic or heterocyclic ketone represented by the general formula [I] in a water-containing organic solvent in the presence of a sulfide. The method for producing an aminonitro compound represented by. [Chemical 1] (In the formula, X is a single bond, —CH ₂ —CH ₂ —, and —CH═C.
H-, -C (= O)-, -O-, -S-, -N (-R)
Represents -or -C (= C (CN) ₂ )-, and Y represents -C (=
O)-, -C (= O) -C (= O)-, -N (-R)-
Represents C (= O)-or -OC (= O)-, and Z is = C.
Represents H- or = N-, and R represents a hydrogen atom, an alkyl group or an alkoxyl group)