JPH09202793A - New phosphonic ester derivative and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new phosphonic ester derivative, important as an intermediate for reaction with aldehydes and synthesis of a new olefin compound useful as an organic electronic material, etc., by reacting a specific aromatic halomethyl derivative with a phosphorous ester derivative. SOLUTION: This new phosphonic ester derivative is represented by formula I [R<1> and R<2> are each a (substituted) alkyl; R<3> is a lower alkyl] and useful as a synthetic intermediate. etc., for reaction with aldehydes and synthesis of a new dimer type α-phenylstilbene derivative useful as an organic electronic material. The compound is obtained by reacting an aromatic halomrthyl derivative represented by formula II (X<1> and X<2> are each a halogen) with a photosphorous ester derivative represented by the formula P(OR<3> )3 (R<3> is a lower alkyl) at 140 deg.C for 5hr.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel phosphonate ester derivative and a method for producing the same, and more particularly, to a novel olefin compound which is useful as an organic electronic material by reacting with an aldehyde. The present invention relates to a novel phosphonate derivative which is important as an intermediate and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, OPC (Organic Pho)
Research and development aiming at further higher durability of the to tolerator) is being conducted. In particular, from the viewpoint of improving wear resistance, research and development have been focused on polymer charge transporting materials having a donor unit (charge transporting unit) in the main chain or side chain. Until now, various charge transport units and polymer skeletons have been studied for polymer charge transport materials. The charge transporting unit includes triphenylamine, tetraarylbenzidine,
Stilbene and the like and, as the polymer skeleton, polyarylate resin, polycarbonate resin, epoxy resin, polyester resin, polyurethane resin and the like have been studied (for example, US Pat. No. 4,801,517,
US Pat. No. 4,806,443, US Pat. No. 4,80
6444, US Pat. No. 4,937,165, US Pat. No. 4,959,288, US Pat. No. 5,030,5.
32, US Pat. No. 5,034,296, US Pat. No. 5,080.989, JP-A-64-9964, JP-A-3-221522, JP-A-2-304456, and JP-A-4-11627. JP, 4-175337, 4-183719, 4-31404, 4-133605, etc.).

The present inventors set out to incorporate a dimer type α-phenylstilbene derivative (hereinafter referred to as an olefin derivative) into the main chain, and set out to develop a novel highly durable polymer charge transport material. . Therefore, it was necessary to synthesize a new dimer-type phosphonate derivative as an intermediate of the olefin derivative in this novel polymer. Up to now, an unsubstituted phosphonate has been disclosed in JP-A-3-149560 (CA116: 1400).
Although a synthesis example is disclosed in 79), it has been difficult to synthesize an alkoxy-substituted product until now because the halogen compound as a raw material is extremely unstable.

[0004]

DISCLOSURE OF THE INVENTION The present invention is a novel dimer type α-, which is a charge transport material for an electrophotographic photoreceptor.
An object is to provide a novel phosphonate derivative intermediate for synthesizing a phenylstilbene derivative and a method for producing the same.

[0005]

As a result of intensive studies, the present inventors have found that the synthesis of a novel phosphonate ester derivative can be carried out extremely advantageously in the Arbusov reaction, and completed the present invention. It was That is, according to the present invention, a phosphonate derivative represented by the following general formula (A) is provided.

Embedded image (In the formula, R ¹ and R ² represent a substituted or unsubstituted alkyl group, and R ³ represents a lower alkyl group.) According to the invention, the following general formula (B)

Embedded image (In the formula, R ¹ and R ² represent a substituted or unsubstituted alkyl group, and X ¹ and X ² represent a halogen atom), and a general formula (C) shown below.

Embedded image P (OR ³ ) ₃ (C) (wherein R ³ represents a lower alkyl group) is reacted with a phosphite derivative represented by the following general formula (A )

Embedded image (Wherein R ¹ and R ² represent a substituted or unsubstituted alkyl group, and R ³ represents a lower alkyl group), and a method for producing a phosphonate derivative is provided.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The phosphonate derivative represented by the following general formula (A) of the present invention is a novel substance which has not been described in any literature. In particular, it can be used as an organic electronic material by reacting with an aldehyde. It is an important intermediate in the synthesis of useful new olefin compounds.

Embedded image (In the formula, R ¹ and R ² represent a substituted or unsubstituted alkyl group, and R ³ represents a lower alkyl group.)

In the phosphonate derivative represented by the general formula (A) of the present invention, examples of the substituted or unsubstituted alkyl group represented by R ₁ and R ₂ in the formula include direct C _{1 to} C ₅ groups. Chain or branched chain alkyl groups may be mentioned, and these alkyl groups may further contain a phenyl group substituted with a fluorine atom, a cyano group, a phenyl group or a halogen atom or a C _{1 to} C ₅ alkyl group. . Specifically, methyl group, ethyl group, n-propyro group, i-propyl group, t-
Examples thereof include a butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-cyanoethyl group, benzyl group, 4-chlorobenzyl group and 4-methylbenzyl group.

[0008] Examples of lower alkyl group R ₃ is straight chain C ₁ ~ _5, or a branched alkyl group, specifically, methyl group, ethyl group, n- Puropiro group, i −
Examples thereof include propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group and n-pentyl group. Hereinafter, specific examples of the phosphonate derivative of the present invention will be shown in Table 1.
However, the present invention is not limited to these compounds.

[0009]

[Table 1]

As described above, the phosphonate derivative represented by the general formula (A) of the present invention has the following general formula (B).

Embedded image (In the formula, R ¹ and R ² represent a substituted or unsubstituted alkyl group, and X ¹ and X ² represent a halogen atom), and a general formula (C) shown below.

Embedded image A phosphite derivative represented by P (OR ³ ) ₃ (C) (wherein R ³ represents a lower alkyl group) is directly or in an organic solvent such as toluene or xylene. It can be easily produced by heating at. In the halomethyl derivative represented by the general formula (B), which is the starting compound of the present invention, X in the formula
The halogen atom of ¹ and X ² is chlorine, bromine, iodine or the like, preferably bromine or chlorine.

[0011]

EXAMPLES The present invention will be described in detail below with reference to examples.

Synthesis Example 1 Synthesis of a compound represented by the following structural formula (D)

Embedded image M. N. Rybakova et. al. Uch. Za
p. , Perm. Gos. Univ. (1968), N
o. The above compounds were synthesized according to 178, 272-278. That is, dry TH is placed in a reaction vessel that has been sufficiently dried.
F of 150 ml and magnesium pieces of 31.61 g (1.
(3 mol) and charged with argon gas. Magnesium was vigorously stirred with a stirring blade, a small amount of iodine was added as a reaction initiator, and 243.15 g (1.3 mo) of p-bromoanisole dissolved in 500 ml of dry ether was added.
l) was added dropwise over 60 minutes while maintaining 22 ° C. After completion of dropping, stirring was continued for another 4 hours. After leaving the reaction solution for a whole day and night, terephthalaldehyde dissolved in 1000 ml of THF was added dropwise over 60 minutes. At this time, stirring became difficult, and 500 ml of ether was added. After completion of dropping, the solution was refluxed for 3 hours to carry out a Grignard reaction. After completion of the reaction, the reaction vessel was cooled to 7 ° C, and saturated ammonium chloride aqueous solution 5
00 ml was slowly added dropwise. Further, the mixture was stirred for 1 hour for decomposition. Then, it was extracted with ether, washed with water, and dried with magnesium sulfate. After removing the ether, silica gel column chromatography (developing solvent: toluene:
Separation was performed with ethyl acetate = 8: 5 to obtain 105.0 g of the target compound in the form of orange powder (yield 51.25).
%). The infrared absorption spectrum is shown in FIG. In FIG. 1, ν _OH : 3430 cm ⁻¹ , ν _co : 1000c
It showed absorptions at m ^-1 , 1020 cm ^-1 , 1035 cm ^-1 . The results of elemental analysis were as follows.

Synthesis Example 2 Synthesis of halomethyl derivative represented by the following structural formula (E)

Embedded image 105.0 g (0.30 mol) of the compound represented by the structural formula (D) obtained in Synthesis Example 1 and 900 ml of chloroform as a solvent were placed in a reaction vessel and stirred at 5 ° C.
Then, 81.1 g (0.30 mol) of phosphorus tribromide dissolved in 300 ml of chloroform was added dropwise over 120 minutes. Stirring was continued for another 4 hours. About 1 after the reaction
The reaction product was poured into 000 ml of ice water, extracted with chloroform, washed with saturated aqueous sodium hydrogen carbonate solution, and dried with magnesium sulfate. The chloroform solution was filtered and evaporated to dryness to obtain 134.0 g of an orange oil (yield 9
1.4%). This compound was extremely unstable in the atmosphere, and immediately the synthesis of the phosphonate ester of Example 1 shown below was performed.

Example 1 Synthesis of phosphonate ester represented by the following structural formula (F)

[Chemical 6] The compound represented by the structural formula (E) obtained in Synthesis Example 2 was dissolved in 149.5 g (0.9 mol) of triethyl phosphite, and the mixture was heated and stirred at 140 ° C. for 5 hours. During the reaction, generated ethyl bromide was removed from the system. After the reaction,
After removing excess triethyl phosphite and diethyl ethylphosphonate by distillation under reduced pressure, silica gel column chromatography [developing solvent, chloroform: THF = 5: 1 (vol.
urematio)] and further recrystallized with a mixed solvent of toluene and n-hexane to obtain 15.29 g of white powder (yield 8.03%). The melting point of this substance was 145.0 to 163.0 ° C., which was broad. The infrared absorption spectrum of this compound is shown in FIG. The results of elemental analysis were as follows.

[0015]

INDUSTRIAL APPLICABILITY According to the present invention, a novel phosphonate derivative which is important as an intermediate for synthesizing a novel olefin compound useful as an organic electronic material, for example, an olefin derivative represented by the following structural formula (G), and The manufacturing method can be provided.

Embedded image

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum diagram (KBr tablet method) of hydrol obtained in Synthesis Example 1.

FIG. 2 is an infrared absorption spectrum diagram (KBr tablet method) of the phosphonate ester obtained in Example 1.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tomoyuki Shimada 1-3-6 Nakamagome, Ota-ku, Tokyo Stock company Ricoh Co., Ltd. (72) Inventor Chiaki Tanaka 1-3-3 Nakamagome, Ota-ku, Tokyo Stocks Inside Ricoh Company (72) Inventor Nozomu Tamoto 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Inventor Akira Katayama 1-3-6 Nakamagome, Ota-ku, Tokyo In-house Ricoh Company

Claims (2)

[Claims] 1. A phosphonate derivative represented by the following general formula (A): Embedded image (In the formula, R ¹ and R ² represent a substituted or unsubstituted alkyl group, and R ³ represents a lower alkyl group.) 2. The following general formula (B): (Wherein R ¹ and R ² represent a substituted or unsubstituted alkyl group, and X ¹ and X ² represent a halogen atom), and a halomethyl derivative represented by the following general formula (C): (OR ³ ) ₃ (C) (wherein R ³ represents a lower alkyl group) is reacted with a phosphite derivative represented by the following general formula (A): (Wherein R ¹ and R ² represent a substituted or unsubstituted alkyl group and R ³ represents a lower alkyl group).