JPS6344736B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field of Application of the Invention] The present invention relates to an amino group-containing diacetylene compound, and more particularly to an amino group-containing diacetylene compound having the ability to be easily polymerized by the diacetylene group. [Prior art] In recent years, the synthesis of single-crystalline polymers using topochemical reactions through solid-state polymerization has attracted attention, and attempts have been made to develop various highly crystalline polymers with high elastic modulus using this method. There is. (For example, "Organic Nonlinear Optical Materials" CMC (1985), Micromolecular Chemistry Vol. 134, p. 219, (1970), Journal of
Polymer Science Vol. 89, p. 133 (1971),
Journal of Polymer Science, Polymer Physics Edition Volume 12, 1511
Page, (1974, etc.) [Problems to be solved by the invention] However, the diacetylene compounds with topochemical polymerizability that have been synthesized and studied so far have a hydroxyl group such as HOCH ₂ C≡C—C≡CCH ₂ OH. The progress of research has been hindered because the research has been limited to compounds and derivatives thereof. On the other hand, in materials with nitrogen atoms introduced, the electronegativity and cohesive force of nitrogen atoms can be utilized, and the nitrogen atoms are -NH
-If the diacetylene compounds have bonds, it is possible to utilize the intermolecular force due to hydrogen bonds and the reactivity of the nitrogen atom, which may strengthen the intermolecular interactions between diacetylene compounds and develop various derivatives. There are great expectations for its potential and its practical application. However, few amino group-containing diacetylene compounds that exhibit such topochemical reactivity have been found so far. for example, Although diacetylene compounds containing an amino group in which an aromatic ring is bonded next to a diacetylene bond are already known, this compound has not been recognized to have topochemical properties. The present inventors have conventionally investigated methods for introducing various groups such as alkyl groups next to diacetylene groups and the properties of the resulting compounds. As a result of further intensive research, we have arrived at the present invention. That is, the present invention has the following general formula: (Here, X, Y, X', Y' are one or two selected from hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, or carbonyl groups bonded to the hydrocarbon groups. Indicates the above group or atom, R and R' are
―CH ₂ ―, ―C ₂ H ₄ ―,

At least one aliphatic hydrocarbon group selected from [Formula] or -C(CH ₃ ) ₂ -. ) provides an amino group-containing diacetylene compound. In the present invention, X, X', Y, and Y' are each one or two selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbonyl group bonded to the hydrocarbon group. As a hydrocarbon group that is more than one species or atom and has 1 to 20 carbon atoms,
CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ , C ₅ H ₁₁ , C ₆ H ₁₃ ,
aliphatic hydrocarbon groups such as C ₇ H ₁₅ , C ₈ H ₁₇ , C ₉ H ₁₉ , C ₁₀ H ₂₁ ;

[Formula] represents an alicyclic hydrocarbon group such as [Formula], and the above aliphatic hydrocarbon group, hydrocarbon group, or alicyclic hydrocarbon group is a halogen atom, nitro group, cyano group, carboxyl group, or amide group. , an ester group, a carbonyl group, an ether bond, etc. In addition, the carbonyl group bonded to the hydrocarbon group is a group represented by the general formula Z-CO- (Z represents the hydrocarbon group), and examples include:

【formula】

【formula】

[Formula] etc., preferably,

[Formula] etc. In the present invention, as X, Y, X', Y',
A preferred combination of (X, Y, X', Y') is Particularly preferred is a case in which both X and This is because it is superior in terms of. In the present invention, as R and R', -CH ₂ -, which is easy to synthesize,

【formula】

[Formula] or -C ₂ H ₄ -. The method for producing the amino group-containing diacetylene compound of the present invention includes, for example,

[Formula] (hereinafter referred to as compound ()), as a raw material

Using [Formula], add this with acetic acid, acetyl chloride, acetic anhydride/pyridine system, etc.
N-acetyl derivative, which is oxidized and coupled using a metal catalyst such as copper chloride (2) and oxygen,

It can be synthesized by synthesizing [Formula] and then hydrolyzing it in an acidic aqueous solution such as hydrochloric acid or an alkaline aqueous solution such as an aqueous sodium hydroxide solution. That is, the method for synthesizing the above compound () follows the following reaction formula. On the other hand, the amino group-containing diacetylene compound of the present invention is (hereinafter referred to as compound ()), in the case of
If X, X', Y, and Y' are all not hydrogen at the same time, the raw materials are:

[Formula] and

It can be synthesized by using the following formula and halogenating the ethynyl hydrogen of either of these two types of alkynes, followed by oxidative coupling using a metal catalyst such as copper acetate. That is, the method for synthesizing the above compound () follows the following reaction formula. (Here, Hal indicates a halogen atom) On the other hand, the amino group-containing diacetylene compound of the present invention

In the case of [Formula] (hereinafter referred to as compound ()) (where X, Y are
At the same time, it is not a hydrogen atom), but if we were to describe a synthesis example, as a raw material

[Formula] and HC≡C—R′—NH ₂ was converted by the method used in compound ()

〔Effect of the invention〕

The reactivity of the diacetylene group in the amino group-containing diacetylene compound of the present invention is higher than that of conventionally known diacetylene compounds, and it can easily react with heat, light, pressure, etc. to give a polymer. In addition, the amino group-containing diacetylene compound of the present invention having an -NH- bond is extremely important for synthesizing a new type of diacetylene compound hitherto unknown by utilizing the reactivity of this amino group. It becomes an intermediate. For example, carboxylic acids, carboxylic acid anhydrides, acid chlorides, sulfonyl chloride isocyanates, alkyl halides,
The diacetylene compound synthesized in this way can react with epoxy etc. very easily, and the diacetylene groups can react with each other by solid phase polymerization, and the amino group of the present invention has an -NH- bond at both ends. The diacetylene compound contained therein can be developed into various polymer materials having acetylene groups by utilizing the reactivity of the amino group, and is useful as a raw material for highly crosslinkable materials. [Examples] Hereinafter, the present invention will be explained using Examples in order to further clarify the present invention, but it goes without saying that the scope of the present invention is not limited to these Examples. Furthermore, the reagents used in the examples were purified as necessary. [Example 1] Synthesis of 1,6-diamino-2,4-hexadiyne 100 ml (1.5 mol) of propargylamine was dissolved in acetic acid.
The mixture was heated under reflux in 400 ml for 6 hours. After the reaction, acetic acid was distilled off under reduced pressure, and the temperature was raised to 120°C to 140°C.
A fraction of °C/2 mmHg was collected. This fraction solidified on standing. In this way, 113g (1.3mol yield
79%) of N-acetylpropargylamine was obtained. Distillation is performed two more times to obtain N with a purity of 99% or more.
-Acetylpropargylamine was obtained. (Analysis results) - Melting point 86-87℃ - Infrared absorption spectrum (KBr) 3238cm ^-1 (moderate, narrow, H-C≡C-) 2106cm ^-1 (weak, narrow, -C≡C-) 1647cm ^-1 (Extremely strong, wide, C=0) ・¹ H-NMR (δ, CDCl ₃ ) 1.96 (S, 3H, -CH ₃ ) 2.17 (t, 1H, J=2.6Hz, H-C≡C) 3.96 (dd, 2H, J=4.0Hz, 2.6Hz, - CH ₂
―) 6.3 (bS, 1H, NH) N-acetylpropargylamine 10g
(0.11 mol) was dissolved in 70 ml of pyridine, and this solution was added dropwise to 70 ml of pyridine solution containing 1.1 g (0.01 mol) of copper chloride at 20°C over 10 minutes while blowing oxygen gas at 300 ml/min. did. After the dropwise addition, the mixture was stirred for 3 hours, and the precipitated red solid was isolated by suction filtration. Thus, 5.2 g (0.03 mol yield) of 1,6-diacetylamino-2,4-hexadiyne was obtained.
55%). Furthermore, by recrystallizing in a water-ethanol system, 1, which has a purity of over 99%,
6-Diacetylamino-2,4-hexadiyne was obtained. (Analysis results) - Infrared absorption spectrum (KBr) 3279cm ^-1 (moderate, narrow, H-C≡C-) 1647cm ^-1 (very strong, wide, C=0) ^-1 H-NMR (δ, d6) -dimethyl sulfoxide) 1.83 (S, 6H, -CH ₃ ) 3.97 (d, 4H, J=4.0Hz, -CH ₂ -) 8.3 (bS, 2H, -NH-) 1,6-diacetylamino-2,4 -Dissolve 2g (0.01mol) of hexadiyne in 50ml of concentrated hydrochloric acid,
Heat at reflux for an hour. After the reaction, the mixture was allowed to cool, neutralized with a 5% aqueous sodium hydroxide solution, and further water was concentrated under reduced pressure until about 10 ml remained, and the precipitated black solid was isolated. In this way, 1.1 g (0.01 mol quantitative) of 1,6-diamino-2,4-hexadiine was obtained. Furthermore, we were able to achieve a purity of over 98% using a water-ethanol system. (Analysis results) - Infrared absorption spectrum (KBr) 3500cm ^-1 (medium, wide, -NH ₂ ) 3400cm ^-1 (medium, wide, -NH ₂ ) 1639cm ^-1 (weak, wide, -NH) 1130cm ^{- 1} (weak, narrow, C—N) ・¹ H—NMR (δ, D ₂ O) 3.00 (bS, 4H, —NH ₂ ) 3.97 (S, 4H, —CH ₂ ) [Example 2] 1, 6-bis(N-methylamino)-2,4-
Synthesis of hexadiyne N-methylpropargylamine 7.6g
(0.11 mol) was dissolved in 70 ml of pyridine, and this solution was added dropwise to 70 ml of pyridine solution containing 1.1 g (0.01 mol) of copper chloride at 20°C over 10 minutes while blowing oxygen gas at 300 ml/min. . After the dropwise addition, the mixture was stirred for 3 hours, and the reaction product was poured into 100 ml of water to isolate the precipitated white solid. Thus 1,6-bis(N-methylamino)-2,4-hexadiyne 7.5
g (0.055 mol quantitative) was obtained. Furthermore, the purity could be increased to over 98% by recrystallization with chloroform. (Analysis results) - Infrared absorption spectrum (KBr) 3400cm ^-1 (medium, wide, -NH-) 1640cm ^-1 (weak, wide, -NH-) 1300cm ^-1 (weak, narrow, C-N) - ¹ H-NMR (δ, CDCl ₃ ) 3.52 (S, 6H, -CH ₃ ) 3.97 (S, 4H, -CH ₂ ) 8.0 (dS, 2H, -NH) [Example 3] 1,6-bis ( N,N-dimethylamino)-
Synthesis of 2,4-hexadiyne N,N-dimethylpropargylamine 9.1g
(0.11 mol) was dissolved in 70 ml of pyridine, and this solution was added dropwise to 70 ml of pyridine solution containing 1.1 g (0.01 mol) of copper chloride at 20°C over 10 minutes while blowing oxygen gas at 300 ml/min. . After the dropwise addition, the mixture was stirred for 3 hours, and the reaction product was poured into 100 ml of water to isolate the precipitated white solid. In this way, 9.0 g (0.055 mol quantitative) of 1,6-bis(N,N-dimethylamino)-2,4-hexadiine was obtained. Furthermore, by recrystallizing with ether, the purity could be increased to over 98%. (Analysis results) - Infrared absorption spectrum (KBr) 1300cm ^-1 (weak, narrow, C--N) - ¹ H-NMR (δ, CDCl ₃ ) 3.59 (S, 12H, -CH ₃ ) 3.97 (S, 4H , ―CH ₂ ―)

Claims (1)

[Claims] 1. General formula (Here, X, Y, X', Y' are hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, or carbonyl groups bonded to the hydrocarbon groups
represents a species or two or more groups or atoms, and R, R' are
At least one aliphatic hydrocarbon group selected from --CH ₂ --, --C ₂ H ₄ --, [Formula], or --C(CH ₃ ) ₂ --. ) Amino group-containing diacetylene compound.