JPH01246285A - 2,3-disubstituted-6,7-dicyano-1,4,5,8-tetraazanaphthalene derivative - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [X1 and X2 are NHR<1> (R<1> is alkyl, alkenyl, aryl, aralkyl or alkaryl), NR<2>R<3> (R<2> and R<3> are alkyl, alkenyl or aralkyl) or formula II-IV]. EXAMPLE:2,3-Di(n-octylamino)-6,7-dicyano-1,4,5,8-tetraazanaphthalene expressed by formula V. USE:A functional coloring matter, curing agent for epoxy resins and monomer for synthesizing functional high polymers. PREPARATION:One mol 2,3,6,7-tetracyano-1,4,5,8-tetraazanaphthalene expressed by formula VI and 2 mol amines expressed by the formula R<1>NH2, NR<2>R<3> or formulas VII-IX are dissolved in a suitable solvent and a base, as necessary, is added as a catalyst to carry out reaction at ambient temperature in the case of the aliphatic primary amines or at 50-80 deg.C in the case of the aliphatic secondary amines.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides novel 2,3-disubstituted-6,7-dicya-2
4.5.8-Tetraazanaphthalene derivatives can be used as functional dyes, epoxy resin curing agents, monomers for the synthesis of functional polymer compounds, and the like.

[Conventional technology]

Percyano compounds or polycyano compounds such as TC'Nα, TCNE, and 2,3,5.6-tetracyanopyrazine have been known for a long time, and their strong electron-withdrawing properties have been used to apply them to charge transfer complexes or to Although dicyanopyrazine, tricyanopyrazine, tricyanoethylene M5, etc. have been synthesized by nuclear substitution reactions, the naphthalene derivative according to the present invention has not been known.

C Problems to be Solved by the Invention] The present invention provides novel industrially useful 2,3-disubstituted-6,7-
Dicyano-1,4,5,8-tetraazanaphthalene m
'211 bodies are provided.

[Means for solving problems]

The present invention is based on the formula [11, where Xl+X may be the same or different<, N
HR', NR A, -(), -QHl-〇 (Here, yen, alkyl, alkenyl, aralkyl, alkaryl
R'', R3 represents alkyl, alkenyl, aralkyl and may be the same or different) It is a naphthalene derivative. Substituent R1゜R1
, and R3 each preferably have 1 to 20 carbon atoms.

The compound represented by the general formula [1] is 2,3,6.7-tetracyano-1,4,5 represented by
, 8-tetraazanaphthalene [hereinafter abbreviated as TCNTAN. The synthesis method is described in Seishang University Engineering Report No. 26 (1978). ) and an appropriate first. It is synthesized as follows by a nucleophilic substitution reaction with a secondary amine.

To describe the reaction mode specifically, for 1 mole of TCNTAN, "'C2 mole R'NH!, Ni2" is 113, (1?
', R'', +13 is above), HC), HQH%HO
The amino group represented by is dissolved in a suitable solvent, a base is added as a catalyst if necessary, and the reaction is carried out at a temperature ranging from room temperature to 50 to 80°C.

The reaction can be carried out by simply mixing 1 mol of tetracyanotetraazanaphthalene and 111 to 4 mol, preferably 2 to 3 mol, of the amine in a solvent, but in order to improve the yield, it may be necessary to dissolve the amine in an amine solution containing a catalyst. A method in which tetracyanotetraazanaphthalene is gradually added dropwise to the solution is preferable. In the reaction, an amine solution is added dropwise to the tetracyanotetraazanaphthalene solution. Tetracyanotetraazanaphthalene becomes excessive, but in this state, Due to the strong electron-withdrawing property of cyanotetraazanaphthalene, it forms a charge transfer complex with amines, which is not preferable because the reaction solution is colored dark brown and the substitution reaction is significantly hindered.

The solvent is not limited as long as it is inert to the reaction reagent and has sufficient dissolving power, but examples include methylene chloride, chloroformacetone, acetonitrile, ethyl acetate, butyl acetate, TIIP, dimethoxyethane, isopropyl alcohol, toluene, xylene. , benzene, DMF,
It is preferable to use DMSO or the like.

The reaction temperature and reaction time vary depending on the type of amine used. When aliphatic primary amines are used, the reaction time may be 1 to 2 hours at room temperature including the dropwise addition time, but when aliphatic secondary amines are used, 1 to 2 hours at 5°C to 80°C is required. When using aromatic primary amines, a base such as triethylamine, pyridine, I) Btl (1,8-diazabicyclo(5,4,0)-7-undecene) is added as a catalyst, and the dropwise addition time is also adjusted at 50 to 80°C. Allow to react for 1 to 2 hours.

The novel naphthalene derivative according to the present invention is also 2,3-dichloro-6,7-dicyano-1,4,5,8
- Tetraazanaphthalene (Chengfan University Engineering Axis N126 (
(1978) disclosed a synthesis method. Below (CC
(abbreviated as NTAN) and 1. It can also be easily synthesized by condensation reaction with secondary amines.

〔Example〕

Next, the present invention will be specifically explained with reference to Examples.

Example 1 2.3-di(rooctylamino)-6,7-dicyatwo 1.4.5° 8-tetraazanaphthalene TCNTAN 2.0 g (8,62 x 10-' mol) and n-octylamine 2.2 g (1,71x 1
When 0-" mole) was dissolved in 100 l of ethyl acetate, the solution was colored black due to the formation of a charge transfer complex. When the solution was stirred at room temperature for 1 hour, the black color almost disappeared and TL
A new spot was generated on C that emitted blue fluorescence to 336 nm Uv light. After drying the product, the product was subjected to silica gel column chromatography using a 1:1 mixed solvent of benzene:ethyl acetate to obtain 0.9 g of yellow crystals (yield: 24%). Request, p, 208~
210℃ [Melting point measuring device MRK N manufactured by Mita Hashira Riken Kogyo
18430 (upper limit of measurement temperature 250℃) and below, same,
) M''-436゜Example 2 2.3-di(n-butylamino)-6,7-dicyatu 1.4,5゜8-tetraazanaphthalene TCNTAN 3.6g (1,55xlO-''mol) was dissolved in acetic acid. Ethyl 350IIIi! Dissolved in 500eg 1
Introduce into dropping funnel No.2. 11 four-bottle flask H
After replacing with 8, 2.27 g of n-butylamine (3
, 11x 10-" mol) and ethyl acetate 250111 were added dropwise at room temperature while stirring. As the droplets of the n-butylamine solution mixed, a charge transfer complex was formed and the mixture turned black, but eventually due to the excess TCNTAN. The complex was consumed in the separation-replacement reaction, so the reaction solution returned to a yellow color.The dropwise addition was carried out at a slow speed that caused the reaction solution to take on a slightly blackish tinge, and it took about 1 hour.Then, it was aged for 1 hour at room temperature. The reaction solution turned yellow and showed 336r++ on TLC.
A new spot was generated that emitted blue fluorescence in response to +υV light. After drying the product, it was recrystallized from acetonitrile/benzene/n-hexane to obtain 2.45 g (yield: 49%) of yellow crystals. m, p, 25
0℃ or higher, M″″-324, elemental analysis C57, 2%, N
32.9%, H6.5%, calculated value C59.3%, N3
4.6%, H6.2%.

Example 3 3.5 g (1,51X 101 mol) of TCNTAN, 8.1 g (3,Ox 10-'' mol) of stearylamine, and 50 ml of chloroform 100-I!ethyl acetate were weighed into 14 300 ml flasks and heated at °C. After reacting for 1 hour, a new spot emitting blue fluorescence was generated on TLC under 336 nm UV light. When column separation was performed using a mixed solvent of benzene: ethyl acetate 2:1 in the same manner as in Example 1, 2.0 g of yellow crystals were obtained. was obtained.Yield 27%
, mp, 144.6℃0M゛-716゜Example 4 Piperidine 1.5g (1,76xlo-"mol),
2.5 g (0.86 x 10-" mole) of TCNTAN and 300 mj! of acetonitrile (100+*jl replaced with Nt) were placed in a flask and reacted for 1 hour at 50°C, and yellow crystals were separated and precipitated. After filtering, washing with a small amount of acetonitrile, and drying, 1.5 g of yellow crystals were obtained. Yield: 50%, M"
=348. up, 250 or more 0 elemental analysis C59,
6%, N34.9%, H5.5%: Calculated value C62.1%
, N32.2%, H5.7%.

Example 5 Morphorif 1.5g (1,72X 10-"-T-/l
), TCNTAN2.0 g (0,86X 10-
"mol)" and 100 m j! of acetonitrile were reacted and treated in the same manner as in Example 3 to obtain 1.6 g of yellow crystals (
When irradiated with 336 nm UV light, yellow fluorescence was emitted.

). Yield 53%, M”=352, mp, 250°C or higher.

Elemental analysis C53.8%, N29.6%, H4.7% Bicalculated values C54.5%, N31.8%, H4.5%.

Example 6 2.5 g (1,08× IF” moles) of CNTAN, 2.0 g (2,15× 10-” moles) of aniline
D8 and P501112 were introduced into a 100m flask and reacted at 50°C for 3 hours and then at 100°C for 1 hour, but no change was observed on TLC.
After adding a catalytic amount of υ and reacting at 50°C for 1 hour, it was observed that a new spot was generated on TLC, so the reaction solution was dried and applied to a silica gel column using a mixed solvent of acetone:n-hexane 1:1. Isolation of the product by chromatography gave 1.8 g of yellow crystals. Yield 46%,
M” -364, a+p, 0 elemental analysis above 250℃ C
64.5%, N32.2%.

H3.5%: Calculated value C65.9%, N30.8%, H
3.3%.

Example 7 CCNTAN 1. Og (3,98X101 mol)
, 0.74 g of aniline (7,97X 10 moles) and '? Setonitrile 50mA 100sj! When the mixture is placed in a fourth flask and stirred at room temperature for 1 hour, yellow crystals begin to separate. After filtering the crystals and dissolving them in ethyl acetate, 0.
Wash with I NKO II aqueous solution.

0.9 g of yellow crystals were obtained by reprecipitation from the ethyl acetate phase. Yield 62% M''-364, mp, 250℃ or higher. Elemental analysis C65.3%, N31.5%, H3.2
%: Calculated value C65°9%, N30.8%, 83.3%
.

Example 8 TCNTAN 4.64 g (2,00xlO-'mol), n-butylamine 1.46g (2,00x 10-'mol)
”mol), n-octylamine 2.58g (2,00x
10-" mol) in 200 liters of acetonitrile. The solution is colored black due to the formation of charge transfer complexes. After stirring for 2 hours at room temperature, UV at 366 nm on TLC.
Three spots that emit blue fluorescence in response to light occur 0
After drying the reaction solution, benzene 7tonitrile = 3:
1 Perform column chromatography using a mixed solvent,
1.82 g (yield 23.!IH) of the target compound was isolated. The structure was confirmed by NMII, M^SS, etc. (
The other two TLC spots are each 2.3-di-
n-butylamino-5,6-dicyano-1,4,5,8
-tetraazanaphthalene and 2,3-di-n-octylamino-5,6-diatwo-1.4,5.8-tetraazanaphthalene. ) mp, 228-230℃, M''=380゜'I
I-NMl? (COCl!・DMSO) Integrated intensity ratio 1. a13.8 H16,4i s, s Example 9 2.3-dichloro-5,6-diami2 1,4,5.8
- Tetraazanaphthalene 5.02g (2,00x 10
mol), n-butylamine 1.46g (2,00X
10-” mol), n-octyl 7mi 72.58g
(2,00X 10-” mole), acetonitrile 200
Mix @1 and stir at room temperature for 2 hours. Thereafter, the same procedure as in Example 8 was carried out to isolate 1.90 g (yield 25%) of the target compound. mp, 228~230'c, M"=38
0゜ [Effect of the invention] The synthesized compounds of Examples 1 to 3 are fluorescent dyes, and the absorption spectra were measured with a Shimadzu photospectrometer tlV-240, the fluorescence spectra and the quantum yield were measured with a Hitachi fluorescence phorosvector meter, Hitachi 850 model. The results of measuring the ratio are shown in Table 1.

Table 1 The polyazaboriacene derivatives synthesized according to the present invention are used in agricultural wavelength conversion films; bulbs, synthetic fibers such as wool, silk, cotton, Tetoron, nylon, and acrylic; optical brighteners for detergents; display sprays; Concentrator for solar cells: In addition to being used as a fluorescent dye in laser dyes, etc., it can also be used as an epoxy resin curing agent, photosensitizer, and monomer for functional polymer synthesis.

Applicant: Nippon Soda Co., Ltd.

Claims (1)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] [In the formula, X_1 and X_2 may be the same or different,
NHR^1, NR^2R^3, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Here, R^1 is Alkyl, alkenyl, aryl, aralkyl, alkaryl, R^2, and R^3 represent alkyl, alkenyl, and aralkyl, and may be the same or different. ] 2,3-disubstituted-6,7-dicyano-1,4,5
, 8-tetraazanaphthalene derivative.