JPH06263732A - Cyclobutene compound and its production and production of squarylium compound - Google Patents

Abstract

PURPOSE:To obtain a cyclobutene compound serving as an intermediate in the production of a new squarylium compound used as a useful material in a field using various color material and semiconductor laser. CONSTITUTION:A cyclobutene compound of formula I (R<1> and R<2> are each alkyl and may together form a ring; R<3> is alkyl optionally having substituent; ring A is benzene ring or naphthalene ring optionally having substituent). This compound can be obtained by reacting an indorine compound of formula II, e.g. 1,3,3-trimethyl-2-methyleneindorine, with 1,2-dichloro-1-cyclobutene-3,4-dione at 10-25 deg.C and subjecting the obtained intermediate of formula III to acidic hydrolysis. An asymmetric squarylium compound of formula V can be obtained by reacting the compound of formula I with a 2-methyl derivative of heterocyclic compound of formula IV (R<4> is alkyl optionally having substituent; ring B is heterocyclic compound containing N; X<-> is anion).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel cyclobutene compound, a process for producing the same, and a process for producing an asymmetrical squarylium compound using the same, and more specifically, to a dye, a polymeric coloring material, and a liquid crystal compound. In the field of chromatic dyes, electrophotographic photosensitive materials for electrophotographic printers,
The present invention relates to a method for producing a novel asymmetric type squarylium compound, which is useful in a semiconductor laser application field such as a recording material for an optical disc, a non-linear optical material, a material for a near infrared cut filter, and an intermediate for producing the compound.

[0002]

2. Description of the Related Art Squarylium compounds having various structures have been known so far.
ew. chem. 79 581 (1967) and the like. In addition, JP-A-2-224751
The use of the squarylium compound produced in claim 3 of the present application in a photopolymerizable composition is described in the publication, but the production method and intermediates of the present invention are not described.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a cyclobutene compound used as an intermediate in the production of various squarylium compounds used as various dye materials and useful materials in the field of semiconductor laser applications. Another object of the present invention is to provide a method for producing an asymmetric squarylium compound using the intermediate thereof.

[0004]

The present invention provides the above-mentioned claim 1.
In the above, the gist is a cyclobutene compound represented by the general formula [I], a method for producing the same, and a method for producing an asymmetric squarylium compound using the same. The present invention will be described in more detail.

The substituents R ¹ and R ^{2 in the} general formulas [I], [II] and [IV] are alkyl groups, which may be linked to each other to form a ring. Examples of the alkyl group include a linear or branched lower alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, and examples of the ring formed by the connection include cyclopentane, cyclohexane, cycloheptane, and the like. And the hydrocarbon ring having a bridging structure such as norbornane, adamantane, bicyclo [3,3,1] nonane, and the like.

[0006] Formula (I), (II), the substituents R ³ and the general formula (III), substituent R ⁴ in [IV], which may have a substituent alkyl group in (IV) Shows,
More specifically, a methyl group, an ethyl group, an n-propyl group,
C such as n-butyl group, n-hexyl group and n-octyl group
_1-8 alkyl group; an alkyl group having 1 to 4 ether groups such as methoxyethyl group, ethoxyethyl group, methoxypropyl group, and methoxyethoxyethoxyethyl group;
An alkyl group substituted with an aryl group such as a phenyl group which may be substituted such as a phenylethyl group and a phenylpropyl group; An aryloxy group such as a phenoxy group which may be substituted such as a phenoxyethyl group and a phenoxypropyl group Alkyl group substituted with; alkyl group substituted with halogen atom such as fluorine atom, chlorine atom, bromine atom; other ester group, cyano group, nitro group, thioether group, carbonyl group, sulfonyl group, amino group, substituted amino Base,
Amide group, thioamide group, hydroxyl group, thiol group, carboxylic acid ester group, sulfonic acid group, furyl group,
An alkyl group having a tetrahydrofuryl group and the like can be mentioned.

Examples of the ring A in the general formulas [I], [II] and [IV] include a benzene ring and a naphthalene ring which may have a substituent, and preferable substituents include methyl group and ethyl group. A lower alkyl group, a methoxy group,
Examples thereof include a lower alkoxy group such as an ethoxy group, a halogen atom such as chlorine and bromine, and a halogen-substituted alkyl group such as a perfluoroalkyl group such as a trifluoromethyl group and a pentafluoroethyl group.

Ring B'which is a heterocycle containing a nitrogen atom in the general formula [IV]

[0009]

[Chemical 7]

[0010]

[0011]

[Chemical 8]

(R ⁵ and R ⁶ are the above general formulas [I] and [I
I] and [IV] have the same meanings as R ¹ and R ² and ring C
Has the same meaning as ring A in formulas [I], [II] and [IV]. However, in the general formula [IV], R ¹ , R ²
And R ⁵ , R ⁶ , R ³ and R ⁴ , or ring A and ring C each represent a different group. )

[0013]

[Chemical 9]

(The ring D has the same meaning as the ring C) or

[0015]

[Chemical 10]

(The ring E has the same meaning as the ring C.) and the like. Ring B in the general formula [III]

[0017]

[Chemical 11]

Is a group which induces ring B '. As the anion (X ⁻ ) in the general formula [III],

[0019]

[Chemical 12]

Specific examples of the cyclobutene compound of the general formula [I] represented by the general formula [I] of the present invention include those shown in Table 1 below.

[0021]

[Table 1]

Specific examples of the asymmetric squarylium compound represented by the general formula [IV] of the present invention are shown in the following table.
There are two.

[0023]

[Table 2]

The compound of the general formula [I] of the present invention can be synthesized as follows. That is, the 2-methyleneindoline derivative represented by the above general formula [II] is dissolved in an aprotic solvent such as benzene, and an equimolar ratio of 1,2-dichloro-1-cyclobutene-3,4-dione ( Solution in aprotic solvent) is added at reaction temperature 10-25 ° C. The mixture is stirred for 20-40 minutes at the same temperature, and the resulting crystals are filtered and separated and purified by column chromatography to obtain an intermediate monochlorotetracarboxylic acid derivative represented by the following general formula [I ']. .

[0025]

[Chemical 13]

(R ¹ , R ² and ring A have the same meanings as in the above formula [I].) 100
The compound of the general formula [I] can be synthesized by acidic hydrolysis in an aqueous acetic acid solution at 3 ° C. for 3 to 5 hours, and separating and purifying by reversed-phase column chromatography.

A compound of the general formula [IV] can be synthesized by using the cyclobutene compound of the general formula [I] as follows. That is, 4 of the nitrogen-containing heterocyclic compound having methyl at the 2-position represented by the general formula [III] in an equimolar ratio with the cyclobutene compound represented by the general formula [I] is used.
The reaction product is obtained by reacting the primary amine salt in an alcohol-benzene mixed solvent in the presence of a base such as quinoline and under reflux for 3 to 7 hours. The reaction product is separated and purified by silica gel column chromatography (developing solution: methylene chloride-methanol or ethyl acetate) to obtain an asymmetric squarylium compound (compound of general formula [IV]).

The squarylium compound of the general formula [IV] produced by the present invention has an absorption for long wavelength light and is therefore useful as a red-sensitive material for laser plate making and the like. It is a useful technique as a novel intermediate and a production method produced in a yield.

[0029]

The cyclobutene compounds represented by the general formula [I] of the present invention are dyes, polymeric coloring materials, dichroic dyes for liquid crystals, electrophotographic photosensitive materials, recording materials for optical disks, and non-linear optical materials. It is used as a synthetic intermediate for the asymmetric squarylium compound [IV] of the present invention used in the field of utilizing semiconductor lasers such as materials for near infrared cut filters.

The asymmetric squarylium compound [IV] produced by using the general formula [I] of the present invention has excellent solubility and is suitable for the above-mentioned uses.

[0031]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples.

Example 1 No. 1 in Table 1 above. Synthesis of Cyclobutene Compound of 1 1,3-Dichloro-1-cyclobutene-3,4-dione (3.0 g, 20 mmol) was dissolved in benzene (15 ml) to prepare a solution of 1,3,3-trimethyl-2-methyleneindoline ( In the general formula [II], A = benzene ring, R ¹ ,
Benzene solution 1 containing 3.5 g of R ² , R ³ = methyl group 1
Add 5 ml dropwise. After the dropping, the mixture is stirred for another 20 minutes and then at room temperature, and the resulting reaction product is filtered. This is separated and purified by silica gel column chromatography (developing solution: methylene chloride) and recrystallized from chloroform to obtain 2.7 g of a monochlorocyclobutene derivative (yield 47%). 2.2 g (7.8 g) of this intermediate
mmol) in 22 ml of acetic acid-water mixed solvent in 100 ml.
The product is obtained by reacting at 5 ° C for 5 hours and distilling off the solvent. By reverse-phase column chromatography (filler: Cosmo Seal 75C18-OPN: manufactured by Nakarai Task Co., developing solution: water-methanol (2/1), the mixture was separated and purified, and recrystallized from a mixed solvent of methylene chloride / hexane. No. 1 compound of interest (A = benzene ring, R ¹ , R ² , R ³ = methyl group in the general formula [I])
Was obtained (yield 37% based on the amount of monochlorocyclobutene derivative used). The IR spectrum νco, elemental analysis value, ¹ H-NMR spectrum and mass spectrum of this product were as follows.

[0033]

[Table 3]

The chemical shift values obtained by hydrogen nuclear magnetic resonance are shown below. ¹ H-NMR (d ₆ -DMSO) δ: 1.55 (6 H,
s), 3.34 (3H, s), 5.45 (1H, s),
7.01 (1H, t, J = 7.3Hz), 7.11 (1
H, d, J = 7.9 Hz), 7.25 (1H, t, J =
7.3 Hz), 7.38 (1 H, d, J = 6.7 Hz) Mass spectrum: m / z 269 (M +, 41), 19
8 (100), 158 (65)

Example 2 In Table 2, No. 2 above. Synthesis of Asymmetric Squalylium Compound of No. 1 No. 1 obtained in Example 1 0.14 g of the compound of 1 (0.
51 mmol) and 0.15 g (0.51 mmol) of N-methyl-2-methylbenzothiazolium iodide salt were mixed with butanol-benzene mixed solvent (4/1 (v / v)) 5
Dissolve in 0 ml, 0.1 g of quinoline (1.0 mmo
1) is added and the reaction is carried out under reflux (100 ° C.) for 5 hours. After completion of the reaction, the solvent was distilled off, the product was separated and purified by silica gel column chromatography (developing solvent: methylene chloride-ethyl acetate), and recrystallized from a methylene chloride-hexane mixed solvent to give an asymmetric squarylium compound (Table -2, No. 1) was obtained with a yield of 80%. Νco of IR spectrum of this thing, elemental analysis value,
^{The 1} H-NMR spectrum, mass spectrum and UV spectrum were as follows.

[0036]

[Table 4]

¹ H-NMR (CDCl ₃ ) δ: 1.78
(6H, s), 3.47 (3H, s), 3.72 (3
H, s), 5.77 (1H, s), 6.01 (1H,
s), 6.94 (1H, d, J = 7.9 Hz), 7.0
9 (1H, t, J = 7.3 Hz), 7.20-7.33
(4H, m), 7.42 (1H, dt, J = 7.3an
d1.2 Hz), 7.59 (1H, d, J = 7.3H)
z) Mass spectrum: m / z 414 (M +, 5), 129
(100) UV spectrum: 647 nm (log ε = 5.43 in chloroform)

[Example 3] In Table 2, No. Synthesis of asymmetric squarylium compound of No. 2 Table-1, No. 1 obtained in Example 1 Compound of 1 0.14
g (0.51 mmol) and N-propyl iodide-
2,3,3-Trimethylindorhenium salt 0.17 g
(0.51 mmol) was reacted under the same conditions as in Example 2 and recrystallized from a methylene chloride-hexane mixed solvent to give an asymmetric indoline-based squarylium compound (Table 2, No. 2) in a yield of 85%. Obtained in. IR spectrum νco, elemental analysis value, ¹ H-NM
The R spectrum, mass spectrum, and UV spectrum were as follows.

[0039]

[Table 5]

¹ H-NMR (CDCl ₃ ) δ: 1.04
(3H, t, J = 7.3Hz), 1.79 (12H,
s), 1.80-1.91 (2H, m), 3.54 (3)
H, b), 3.99 (2H, t, J = 7.3 Hz),
5.91 (1H, s), 5.98 (1H, s), 7.0
0 (2H, d, J = 7.9 Hz), 7.11-7.18
(2H, m), 7.28-7.38 (4H, m) Mass spectrum: m / z 452 (M +, 31), 43
7 (18), 158 (100) UV spectrum: 634 nm (log ε = 546 in chloroform)

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C07D 405/14 209 7602-4C 417/08 209 9051-4C C09B 57/00 Z 7306-4H // G02F 1/35 504 9316-2K G03G 5/06 384 9221-2H (C07D 401/08 209: 00 215: 00) (C07D 405/06 209: 00 307: 00) (C07D 405/14 209: 00 215: 00 307: 00) (C07D 417/08 209: 00 277: 00)

Claims (3)

[Claims] 1. A cyclobutene compound represented by the following general formula [I]: (R ¹ and R ² represent an alkyl group and may be connected to each other to form a ring. R ³ represents an alkyl group which may have a substituent, and ring A may have a substituent. Indicates a good benzene ring or naphthalene ring.) 2. The following general formula [II]: (R ¹ , R ² , R ³ and ring A have the same meanings as in claim 1.) and an indoline compound represented by
A process for producing a cyclobutene compound of the general formula [I] according to claim 1, which comprises reacting with -dichloro-1-cyclobutene-3,4-dione. 3. The cyclobutene-based compound according to claim 1 and the following general formula [III]: (R ⁴ represents an alkyl group which may have a substituent,
Ring B represents a heterocycle containing a nitrogen atom, and X ⁻ represents an anion. ) A method for producing an asymmetric squarylium compound represented by the following general formula [IV] by reacting a 2-methylheterocyclic derivative represented by [Chemical 4] (R ¹ , R ² , R ³ and ring A have the same meaning as in general formula [I], and R ⁴ and ring B have the same meaning as in general formula [III], provided that And Represent different groups. )