JP2514909B2 - Polymerizable diacetylene compound - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel polymerizable diacetylene compound.

[0002]

BACKGROUND OF THE INVENTION Some diacetylene compounds are known to be unique compounds that polymerize in the crystalline state to form crystalline polymers. Polymer produced (polydiacetylene)
Is a π-donating polymer represented as a resonance hybrid of the following two limiting structures:

[0003]

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Attention has been paid to a new material for electronic materials that utilizes the large mobility of delocalized π electrons in the main chain and the nonlinear polarization. However, the solid-state-polymerizable diacetylene compound often has a large non-conversion side chain substituent in order to achieve a polymerization-active crystal state. Therefore, electronic interaction becomes impossible on the main chain side or between the main chain and the ruled chain, and high conductivity and high-order electrical and optical functions have not been developed.

On the other hand, as a polymerizable diacetylene compound having a substituted phenyl group as a side chain of a donor system, some reported examples have already been reported (G. Wegner).
Others, Pure Upright Chemistry (Pure Ap
pl. Chem) Vol. 49, p. 443 (1977).
Year); G. Wegner et al., Colloid and Polymer Science (coll. Poly)
m. sci. ) Volume 252, 655 (1974)
However, there are drawbacks such as extremely low polymerizability and loss of polymerizability even if the substituents are slightly changed, and a general-purpose molecular design method and compatibility method are still established. The current situation is that there are none.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above points, and provides a polymerizable diacetylene compound having good solid-phase polymerizability and capable of exhibiting high-order electrical and optical functions. The purpose is to do. Therefore, the polymerizable diacetylene compound according to the present invention has the following general formula:

[0007]

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(However, A is any one of benzene, naphthalene, anthracene and pyridine, H is -NHCO-,
Any one of -CONH-, -OCONH-, -NHCOO-, L is an alkyl group having 7 or more carbon atoms or a fluorinated alkyl group having 7 or more carbon atoms, A'is any of benzene, naphthalene, anthracene, pyridine, and H 'Is -NH
CO-, -CONH-, -OCONH-, -NHCOO
-, L'represents an alkyl group having 7 or more carbon atoms or a fluorinated alkyl group having 7 or more carbon atoms. ) Is indicated by.

The polymerizable diacetylene compound according to the present invention comprises a hydrogen bond atomic group (indicated by H and H'in the above formula) and a long chain alkyl group (L in the above formula) for maintaining its orientation. , L ′) is introduced,
There is an advantage that a compounding aromatic ring-substituted diacetylene compound, which has been difficult to obtain solid-phase polymerizability in the past, can be imparted with high polymerizability.

Further, the polymerizable diacetylene compound according to the present invention has a side chain aromatic ring (indicated by A and A'in the above formula).
Since strong interaction between the organic solvent and the main chain is possible, it is expected that the mobility will be high, the doping characteristics will be improved, and the third-order and second-order nonlinear optical effects will be achieved as an optical material. Wide range of applications in the field of materials is possible.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in more detail.

The polymerizable diacetylene compound according to the present invention is represented by the following general formula.

[0013]

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(However, A is any one of benzene, naphthalene, anthracene, and pyridine, H is -NHCO-,
Any one of -CONH-, -OCONH-, -NHCOO-, L is an alkyl group having 7 or more carbon atoms or a fluorinated alkyl group having 7 or more carbon atoms, A'is any of benzene, naphthalene, anthracene, pyridine, and H 'Is -NH
CO-, -CONH-, -OCONH-, -NHCOO
-, L'represents an alkyl group having 7 or more carbon atoms or a fluorinated alkyl group having 7 or more carbon atoms. )

In the above general formula, A and A'represent benzene, naphthalene, anthracene and pyridine which are aromatic or heterocyclic compounds. Further, L and L'represent long-chain alkyl groups, that is, hydrocarbon-based and fluorocarbon-based alkyl groups, both of which have a remarkable polymerization promoting effect when they have 7 or more carbon atoms.

In the present invention, the substituents at both ends of the diacetylene need not be of the same type as long as they do not hinder the packing of the molecular ring, and a molecule represented by the chemical formula below can be polymerized.

[0017]

Embedded image (N is an integer of 7 to 23)

The high solid-state polymerizability of the polymerizable diacetylene compound according to the present invention controls packing of diacetylene monomer --NHCO, --CONH, --NHCO.
O, a hydrogen bonding atomic group of -OCONH (H in the formula,
It is realized by the synergistic action of H ′) and a long chain alkyl group for controlling the orientation.

That is, according to the present invention, a general-purpose synthesis of a polymerizable diacetylene compound having an aromatic ring having an arbitrary structure as a pendant side chain substituent can be carried out, and the polymer has an inter-main-chain or main-chain structure. -It is expected to have a unique electro-optical property based on the charge-transfer interaction between side chains, and it can be widely applied as a novel electronic material material that has never existed before.

[0020]

EXAMPLES Synthesis examples and polymerization examples of the polymerizable diacetylene compound according to the present invention will be described below. Of course, the present invention is not limited to these polymerization and synthesis examples.

[0021]

Synthesis Example 1 Synthesis of 1,3-butadiyne-1,4-bis (o-stearoylanilide). (The synthesis route and yield are shown below as Chemical Formula 6 together with the following synthesis examples and polymerization examples).

First, o-iodoaniline (2.2 g) and trimethylsilylacetylene (1.2 g) were dissolved in dehydrated dimethylamine (30 ml), and this solution was replaced with argon, and then bis (triphenylphosphine) palladium dichloride ( 140 mg) and cuprous iodide (10 mg) were added, and the mixture was stirred at 30 ° C.

After the reaction, the solvent diethylamine was distilled off under reduced pressure, the residue was extracted with benzene, and recrystallized from benzene-methylcyclohexane.

The product was yellowish brown acicular 2- (o-aminophenyl) trimethylsilylacetylene, and the yield was 1.5 g.

After dissolving 1.5 g of the above compound in 20 ml of methanol to obtain a methanol solution, 1N-potassium hydroxide aqueous solution (10 ml) was added with stirring at room temperature.
The reaction was carried out for 2 hours.

After distilling off methanol under reduced pressure, the residue was extracted with ether and recrystallized from methylcyclohexane.

The product was o-aminophenolacetylene in the form of orange needles, and the yield was 0.8 g.

0.8 g of the above compound was dispersed in cupric acetate monohydrate (1.4 g) in pyridine-methanol (1:
1, 10 ml) and reacted at 50 ° C. for 90 minutes. The reaction mixture was poured into ice water and the precipitated yellowish brown powder was collected by filtration.
After drying, it was recrystallized from benzene-methylcyclohexane.

The product was tan needle-shaped 1,3-butadiyne-1,4-bis (o-amylin), and the yield was 0.6.
g.

The above compound (0.4 g) and triethylamine (0.2 g) were dissolved in anhydrous ether, and a solution of stearyl chloride (1.2 g) in anhydrous ether was added dropwise with stirring for 30 minutes at room temperature and the reaction was continued overnight. It was

The reaction solution was heated to 30 ° C. and unnecessary triethylamine hydrochloride was filtered off. The filtrate was cooled, and the precipitated crystals were collected by filtration, thoroughly washed with ether, and dried under reduced pressure. The yield was 0.6 g.

The infrared absorption spectrum and 1 H-NMR spectrum of this compound are shown in FIGS. 1 and 2, respectively.

[0033]

Synthesis Example 2 (a) Synthesis of 1,3-butadiyne-1,4-bis (m stearoylanilide)

(B) Synthesis of 1,3-butadiyne-1- (o-stearoylanilide) -4- (m-stearoylanilide).

(C) Synthesis of 1,3-butadiyne-1,4-bis (o-benzoic acid-N-heptadecanylamide).

(D) 1,3-Butadiyne-1,4-bis (o- (N-phenylcarbamate heptadecanyl))
Synthesis of.

(E) Synthesis of 1,3-butadiyne-1,4-bis (o- (phenyl phenylcarbamate)).

(F) Synthesis of 1,3-butadiyne-1,4-bis (β- (N-steroylnaphthylamine)).

(G) Bis (2-ethyl-3-benzoic acid)
Synthesis of N-heptadecanylamide).

(H) Synthesis of bis (1-ethynyl-2- (N-heptadecanylcarbamate anthracyl)).

(I) Synthesis of bis (2-ethynyl-3- (N-stearoylamino) pyridine).

The above compound of the present invention was synthesized in the same manner as in Synthesis Example 1. The synthesis route and yield are shown below together with Synthesis Example 1.

[0043]

Synthesis Example 1 Synthesis of 1,3-butadiyne-1,4-bis (o-stearoylanilide).

[0044]

[Chemical 6]

[0045]

Synthesis Example 2 (a) Synthesis of 1,3-butadiyne-1,4-bis (m stearoylanilide)

[0046]

[Chemical 7] IR: 1664 cm ^-1 (C = 0 expansion / contraction) 3300 cm ^-1 (NH expansion / contraction)

(B) Synthesis of 1,3-butadiyne-1- (o-stearoylanilide) -4- (m-stearoylanilide).

[0048]

Embedded image IR (KBr)

(C) Synthesis of 1,3-butadiyne-1,4-bis (o-benzoic acid-N-heptadecanylamide).

[0050]

[Chemical 9] IR: 1660cm ^-1 (C = 0 stretching) 3305cm ^-1 (NH stretch)

(D) 1,3-Butadiyne-1,4-bis (o- (heptadecanyl N-phenylcarbamate))
Synthesis of.

[0052]

[Chemical 10] IR: 1700cm ^-1 (C = 0 stretching) 3310cm ^-1 (NH stretch) 1538cm ^-1 (NH bending)

(E) Synthesis of 1,3-butadiyne-1,4-bis (phenyl o- (N-phenylcarbamate)).

[0054]

[Chemical 11] IR: 1700cm ^-1 (C = 0 stretch) 3320 cm ^-1 (NH stretch) 1540 cm ^-1 (NH bending)

(F) Synthesis of 1,3-butadiyne-1,4-bis (β- (N-steroylnaphthylamine)).

[0056]

[Chemical 12] IR: 1700cm ^-1 (C = 0 stretch) 3320 cm ^-1 (NH stretch) 1540 cm ^-1 (NH bending)

(G) Bis (2-ethyl-3-benzoic acid)
Synthesis of N-heptadecanylamide).

[0058]

[Chemical 13] IR: 1638 cm ^-1 (C = 0 expansion / contraction) 3306 cm ^-1 (NH expansion / contraction)

(H) Synthesis of bis (1-ethynyl-2- (N-heptadecanylcarbamate anthracyl)).

[0060]

Embedded image IR: 1700cm ^-1 (C = 0 stretch) 3320 cm ^-1 (NH stretch) 1540 cm ^-1 (NH bending)

(I) Synthesis of bis (2-ethynyl-3- (N-stearoylamino) pyridine).

[0062]

Embedded image IR: 1700 cm ^-1 (C = 0 expansion / contraction) 3320 cm ^-1 (NH expansion / contraction)

[0063]

[Polymerization Example 1] Photo-solid-state polymerization of 1,3-butadiyne-1,4-bis (o-alkaloylanilide).

R in the chemical formula 16 shown below is CH _3- , CH
The photo-solid-state polymerization properties of ₃ (CH ₂ ) ₆ −, CH ₃ (CH ₂ ) ₁₆ − and Ar− were compared.

Each of the above-mentioned four kinds of diacetylene compounds was sandwiched in a quartz plate by 15 mmol, heated and melted, and subsequently cooled to room temperature. The sample produced in this manner was irradiated with ultraviolet rays having a wavelength of 254 nm, and the change in the polymerization yield with time was measured by the decrease in the absorption of the monomer characteristics accompanying the polymerization. The results are shown in Fig. 3.

[0066]

[Polymerization Example 2] Photopolymerization was similarly attempted for other representative diacetylene compounds, and the solid-state polymerizability of each compound was compared from the final polymerization rate.

The results including polymerization examples are shown in Tables 1, 2, and 3.

[0068]

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[0069]

[Table 1]

[0070]

[Table 2]

[0071]

[Table 3] Evaluation of polymerizability: ++ Polymerization yield 70% or more ++ 40 to 70% +> 0 to 40% − Polymerization inactive

[0072]

Industrial Applicability As described above, the polymerizable diacetylene compound according to the present invention has a conventional solid-phase polymerizability by introducing a long-chain alkyl group for maintaining the hydrogen-bonding atomic group and its orientation. There is an advantage that high polymerizability can be imparted to the serving aromatic ring-substituted diacetylene compound, which was difficult to obtain.

Furthermore, since this polymer is capable of strong interaction between the side chain aromatic ring and the serving main chain, in terms of conductivity, higher mobility and improved doping characteristics are achieved, and tertiary and secondary materials are used as optical materials. The following non-linear optical effects are expected, and they can be widely applied in the field of organic electronic materials.

[Brief description of drawings]

1 shows 1,3-butadiyne-1,4 shown in Synthesis Example 1.
Infrared absorption spectrum of bis (o-stearoylanilide).

FIG. 2 1H-NMR spectrum of the above compound.

FIG. 3 is a graph showing the change over time in the photopolymerization rate of each polymerizable diacetylene compound described in Polymerization Example 1.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07D 213/72 C07D 213/72 213/81 213/81 C08F 38/00 MPU C08F 38/00 MPU / / C09K 9/02 C09K 9/02

Claims (1)

(57) [Claims] 1. The following general formula: (However, A is benzene, naphthalene, anthracene,
Any of pyridine, H is -NHCO-, -CONH
-, -OCONH-, or -NHCOO-, L is an alkyl group having 7 or more carbon atoms or a fluorinated alkyl group having 7 or more carbon atoms, A'is any of benzene, naphthalene, anthracene, and pyridine, and H'is -NHCO-, -C
Any one of ONH-, -OCONH-, and -NHCOO-, L'represents an alkyl group having 7 or more carbon atoms or a fluorinated alkyl group having 7 or more carbon atoms. ) The polymerizable diacetylene compound is represented by the formula (1).