JP2507773B2 - Method for producing fluorene compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention provides a compound represented by the general formula (I): (In the formula, R _{1 to} R ₄ represent a hydrogen atom, an alkyl group or an aryl group, and may be the same or different from each other. The benzene nuclei A and B contain a halogen atom, an alkyl group or an alkoxy group as a substituent. Sometimes, it is represented by
The 3,3′-diaminodiphenyl derivative is represented by the formula Q-CHO (wherein Q is a benzene ring or a naphthalene ring, and as a substituent, a lower alkyl group, a lower alkoxy group, a carboxyl group, a halogen atom, an amino group, or a lower alkyl group. Group and / or an phenyl group-substituted amino group) may be condensed with an aldehyde derivative represented by the general formula (II) (Wherein R _{1 to} R ₄ , A, B and Q represent the above-mentioned atoms and groups) and a method for producing the fluorene compound.

The field of application of the present invention is a color-forming recording material, particularly a color-forming recording material in which the optical absorption wavelength of a color-forming material is in the near infrared region.

[Conventional technology and its problems]

In recent years, with the development of semiconductor lasers that emit light in the near infrared region, the use of compounds having absorption in the near infrared region has made remarkable progress. An example is the major advancement of optical disc audio, video or recording fields. In particular, as a field in which the near-infrared absorption of a color-forming material is used, there is a post label that prints a barcode label with a recording material using this type of material. It has a remarkable feature that it can be simplified.

Examples of the coloring material used for such an application include:
Regarding phthalide compounds, Yamamoto Chemical Synthesis Co., Ltd. (JP-A-60-226871) and Kanzaki Silk Co., Ltd. (JP-A-60-36)
468), etc., all of which are compounds having a fluorene nucleus. However, in the case of synthesizing the fluorene skeleton, both applications use the reaction of the following Pscholl, but this reaction has a drawback in complexity of synthesis of the intermediate or in yield.

On the other hand, Journal of Chemical Society (1954) p. 870, nitration, reduction of fluorenone,
Acetylation, re-nitration, deacetylation, deamination,
Although a method of finally leading to 3,6-diaminofluorene by reduction of a nitro group and Wolf-Kisner reduction is described, it is unsuitable as an industrial production method even though it is a complicated and low-yield means for research. .

[Means for solving the problem]

The present inventors dimerized m-nitroiodobenzene, which is obtained in a better yield than m-nitroaniline, in a good yield,
It was confirmed that 3'-dinitrodiphenyl was obtained and 3,3'-diaminodiphenyl was obtained in good yield by reducing this, but in the same manner, alkyl of m-nitroiodobenzene,
A homolog of 3,3'-diaminodiphenyl was synthesized by dimerization and reduction with a substituted product such as alkoxy, and an alkylated product of 3,3'-diaminodiphenyl was obtained by N-alkylation of these homologs. It was found that the fluorene derivative of the general formula (II) can be obtained easily and in a good yield by using it as a compound, and as a result of detailed study, the present invention was completed. The authors of the above-mentioned Journal of Chemical Society stated that it was unsuccessful to obtain 3,6-diaminofluorene from 3,3'-diaminodiphenyl, and the present invention is not expected from this finding.

Examples of the 3,3'-diaminodiphenyl derivative of the general formula (I) used in the present invention include 3,3'-diaminodiphenyl, 3,3'-bismethylaminodiphenyl, 3,3'-bisdimethylaminodiphenyl, 3,3'-bisdiethylaminodiphenyl, 3,3'-bisbutylaminodiphenyl,
3,3'-bismethylbenzylaminodiphenyl, 3,3'-
Diamino-4,4'-ditolyl, 4,4'-dimethyl-3,3 '
-Bismethylaminodiphenyl, 3,3'-diamino-4,
4'-dimethoxydiphenyl, 3,3'-bismethylamino-4,4'-dimethoxydiphenyl, 3,3'-bisdimethylamino-4,4'-dimethoxydiphenyl, 3,3'-bisdiethylamino-4, 4'-diethoxydiphenyl, 3,3'-
Diamino-4,4'-diflorodiphenyl, 3,3'-diamino-4,4'-dichlorodiphenyl, 3,3'-bismethylamino-4,4'-dichlorodiphenyl, 3,3'-bisethyl Amino-4,4'-dichlorodiphenyl, 3,3'-bismethylamino-4,4'-dibromodiphenyl, 3,3'-bisphenylaminodiphenyl, 3,3'-bismethylphenylaminodiphenyl, 3, 3'-bis-p-tolylaminodiphenyl, 3,3'-bis-o-tolylaminodiphenyl, 3,3'-bis-p-chlorophenylaminodiphenyl or 3,3'-bisphenylamino-4,4 ' -Ditolyl and the like can be mentioned.

Aromatic aldehydes that react with this amine to form fluorene derivatives include various substituted or unsubstituted aldehydes such as benzaldehyde, tolualdehydes, chlorobenzaldehydes, alkoxybenzaldehydes, substituted or unsubstituted aminobenzaldehydes, and naphthaldehydes. Many aldehydes in which an alkyl group, a carboxyl group or the like is further substituted on the compounds or their substitution products or these aldehydes are mentioned.

To react these aldehydes with the diaminodiphenyls of general formula (I), it is generally preferred to heat them in an acidic medium. And as a reaction medium,
Either water or an organic solvent can be used, but it is usually convenient to boil it in an aqueous solvent. The reaction temperature does not proceed even at room temperature, but the higher the temperature, the faster the reaction. However, it is not necessary to heat to a special high temperature, and heating to the boiling point of the solvent under normal pressure is sufficient.

The molar ratio of the reaction between the diamine (I) and the aldehyde Q-HCO is preferably an equimolar ratio, but a slight excess or deficiency does not affect the reaction. The concentration of the reactants in the reaction solution is in the range of 1 to 20% by weight, and the result is not so different. The amount of acid used to acidify the reaction medium is sufficient to neutralize the amine, and no particular excess is required. The reaction time varies depending on the substrate, but in an aqueous solvent, about 24 hours is often sufficient. Crude yields are almost quantitative, but most often require purification.

Generally, it is preferable to remove the volatile components by steam distillation after the reaction. When the crude reaction product thus obtained is purified by an appropriate method, the desired product is usually obtained as pale yellow crystals.

The diamine of formula (I) used in this reaction can be synthesized, for example, as follows.

In addition, the diaminodiphenyl compound used in the present invention can be obtained by alkylation or arylation of various 3,3'-diaminodiphenyl derivatives.

Examples of the fluorene derivative obtained by the method of the present invention include 3,6,4'-tris (dimethylamine) 9-phenylfluorene and 3,6-diamino-4'-dimethylamino-9.
-Phenylfluorene, 3,6-bisethylamino-4 '
-Dimethylamino-9-phenylfluorene, 3,6-bisdibutylamino-4'-dimethylamino-9-phenylfluorene, 2,7-dimethyl-3,6-bismethylamino-4'-dimethylamino-9- Phenylfluorene, 2,
7-Dimethyl-3,6-bisethylamino-4'-diethylamino-9-phenylfluorene, 2,7-dimethoxy-
3,6-bismethylamino-4'-dimethylamino-9-
Phenylfluorene, 2,7-dichloro-3,6-bismethylamino-4'-dimethylamino-9-phenylfluorene, 3,6-bisphenylamino-4'-dimethylamino-9-phenylfluorene, 3,6 -Bismethylphenylamino-4'-dimethylamino-9-phenylfluorene, 3,6-bisdimethylamino-4'-methylphenylamino-9-phenylfluorene, 3,6-bismethylamino-4'-methoxy- 9-phenylfluorene, 3,6,
4'-trisdimethylamino-9-α-naphthylfluorene, 3,6,4'-trisdimethylamino-2'-carboxyl-9-phenylfluorene or 3,6-bisdimethylamino-4'-methoxy-9- Phenylfluorene and the like can be mentioned, but the present invention is not limited thereto.

〔Example〕

Hereinafter, the method of the present invention will be described in detail with reference to examples. In the text, "part" means "part by weight".

Example 1 Synthesis of 3,6-bisdimethylamino-9- (4'-dimethylaminophenyl) fluorene Paradimethylaminobenzaldehyde 3 parts, 3,3'-
Bisdimethylaminodiphenyl 4.8 parts (equimolar ratio) with water 8
The mixture was mixed with 0 parts and 10 parts of concentrated hydrochloric acid, and stirred and boiled under reflux cooling for 24 hours. Then, it was made alkaline with caustic soda, a small amount of hydrosulfite was added, and volatile substances were removed by steam distillation. Upon cooling, a crude material was obtained in a substantially quantitative yield, which was dissolved in hot xylene and stored overnight in an ice chamber, the precipitated solid was filtered, washed with cold xylene and recrystallized from xylene to give about 50 Light yellow crystals having a melting point of 210 to 215 ° C. were obtained in% yield.

 The elemental analysis values were as follows.

Molecular formula C ₂₅ H ₂₉ N ₃ , molecular weight 371.531 Elemental analysis value (%) C H N calculated value 80.82 7.89 11.31 Measured value 80.77 8.12 10.86 It was confirmed by NMR spectrum that the target structure was obtained.

In addition, the reflection spectrum (measured with Shimadzu UV-240 machine) of the image (arbitrary density) formed by coloring this substance with 3-benzylsulfonyl-2,5-dicyclohexyloxycarbonyl-1,4-benzoquinone on the paper surface ) Was as shown in FIG.

Example 2 3,6-bismethylamino-2,7-dimethyl-9- (4'-
Synthesis of dimethylaminophenyl) fluorene paradimethylaminobenzaldehyde 1.5 parts, 3,3′-
Bisdimethylamino-4,4'-ditolyl (3,3'-diamino-4,4'-ditolyl is trienesulfonylated, methylated with dimethylsulfate, and then heated with 80% sulfuric acid to 150-160 ℃ to synthesize) 2.4 parts, concentrated hydrochloric acid 5 parts and water 40 parts were reacted in the same manner as in Example 1, the product was extracted with hot ligroin, the ligroin was distilled off, methanol was added and the mixture was stored in an ice chamber overnight, and the precipitated solid was collected. This was dried intimately and recrystallized from ligroin containing a small amount of xylene to obtain pale yellow crystals with a melting point of 226 to 231 ° C in about 50 yields.

 The elemental analysis value of this product was in good agreement with the calculated value.

Similarly, 3,6-bismethylamino-4,4'-dichlorodiphenyl was reacted with para-dimethylaminobenzaldehyde to obtain 3,6-bismethylamino-2,7-dichloro-9- (4'- Dimethylaminophenyl) fluorene had a melting point of 156-158 ° C.

[Brief description of drawings]

FIG. 1 shows the reflection spectrum of the color image of Example 1.
Here, I ₀ : reflected light intensity of the magnesium oxide white plate I: reflected light intensity of the sample.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C07C 227/16 C07C 227/16 229/52 229/52

Claims (1)

(57) [Claims] 1. A general formula (I) (In the formula, R _{1 to} R ₄ represent a hydrogen atom, an alkyl group or an aryl group, and may be the same or different from each other. The benzene nuclei A and B contain a halogen atom, an alkyl group or an alkoxy group as a substituent. Sometimes, it is represented by
The 3,3′-diaminodiphenyl derivative is represented by the formula Q-CHO (wherein Q is a benzene ring or a naphthalene ring, and as a substituent, a lower alkyl group, a lower alkoxy group, a carboxyl group, a halogen atom, an amino group, or a lower alkyl group. Group and / or an amino group substituted with a phenyl group) may be condensed with an aldehyde derivative represented by the general formula (II). (In the formula, R _{1 to} R ₄ represent a hydrogen atom, an alkyl group or an aryl group, and may be the same or different from each other. The benzene nuclei A and B contain a halogen atom, an alkyl group or an alkoxy group as a substituent. Q is a benzene ring or a naphthalene ring, and an amino group substituted with a lower alkyl group, a lower alkoxy group, a carboxyl group, a halogen atom, an amino group, or a lower alkyl group and / or a phenyl group as a substituent. Which may have a group).