JPH02246A - Chiral diatylene - Google Patents

Abstract

NEW MATERIAL: Compd. represented by formula I (wherein R₁ and R₂ each are an org. group containing amino acid part having at least one chiral center).

EXAMPLE: Hexa-2,4-diynylene-bis-(N-benozylalanate).

USE: This new material exhibits useful electro-optical properties and polymerized already in a solid state to form a polydiacetylene net having chriral carbon on its molecularly cyclic crystal or semi-crystal side chain group.

PROCESS: A compd. represented by formula III is coupled with a compd. represented by formula III to obtain the compd. represented by the formula I. In reaction, it is desirable to avoid strong acidic and weak basic conditions and high temp. and, especially, it is pref. to avoid the use of ultrasonic waves in an oxidative coupling stage.

COPYRIGHT: (C)1990,JPO

Description

Detailed Description of the Invention [Field of Industrial Application] This invention relates to chiral diacetylenes. More specifically, this invention relates to chiral diacetylenes.
- centrosymmeLric) Non-crystalline chiral diacetylenes, their production methods, their polymers and their polymerization methods.

[Conventional technology]

Certain diacetylene compounds form large, virtually defect-free single crystals, and these diacetylenes can be topochemically polymerized in air while retaining the visual and microscopic morphology of the crystals. It is known to produce polydiacetylenes that are stable and exhibit very good resistance to both radiation and mechanical damage. Polydiacetylene crystals have a fixed polyene backbone and necessarily have a highly anisotropic morphology. Therefore, this anisotropy has many properties that can be exploited to obtain technological advantages. Specifically, research has begun on whether polydiacetylene crystals have useful electro-optical properties, particularly susceptibilities χ1 and χ3, such as second harmonic generation (St-IG) and frequency mixing. A study was conducted to see if the effects depended on non-zero values.

However, SHG is found only in asymmetrically centered crystals, and many polydiacetylenes to date have yielded symmetrically centered crystals even when their molecular structure exhibits an inversion. Therefore, S I-I G ability was not demonstrated.

[Description of the invention]

The purpose of this invention is to provide diacetylenes and polydiacetylenes that exhibit useful electro-optical properties.

According to this invention, a compound of the formula (R, -C45C-C-C-R1 (1) [wherein R1 and R1 are the same or different, each is an organic group containing an amino acid moiety having at least one chiral center] However, when rj + = IZ*, the groups R1 and R8 have the same handedness as each other.] A compound represented by the following is provided.

The molecules of the compounds of this invention are chiral (!ll images cannot be superimposed) and asymmetrically centered. Of course, they are preferably R3=II, forming crystals that do not span the center of symmetry, in which case the symmetrically substituted molecules are asymmetric.

Suitable compounds according to the invention are those in which R1 and 111 represent an amino acid ester moiety, preferably an alpha amino acid ester moiety, especially an alpha-amino acid ester moiety.

Preferred compounds of this invention are those of formula (It) [wherein R3
and It, the same or different, substituted or unsubstituted hydrocarbon radicals which may be aromatic or non-aromatic, respectively; +1. and R6 are the same or different, each a hydrogen atom or a substituted or unsubstituted hydrocarbon group (which may be aromatic or non-aromatic, different from R3 and R6, respectively), Zl, Z2, Z, and Z are , same or different,
The amino group-protecting functional group, a substituted or unsubstituted hydrocarbon group which may be aromatic or non-aromatic, or the hydrogen atom, Q, and Q, respectively, are the same or different and represent the carboxylate and diacetylene groups, respectively. represents a divalent intervening group containing an integer number of atoms between.

Suitable amino-protecting functional groups include unsubstituted or substituted (eg, nitro-substituted) acyl (eg, acetyl, benzoyl, nitrobenzoyl), alkoxycarbonyl, pendyloxycarbonyl, phenylsulfonyl.

At least one of Ql and Q, respectively, has the formula (CI+
1) nt or (CII t) nt (nt and n,
are the same or C4, respectively, and are integers, e.g. 1
-20) is preferred.

R and R6 are preferably each unsubstituted or hydroxy-, mercapto-, ether-thioether,
It represents an amino- or carboxy-substituted alkyl or aralkyl group, and R4 and R5 preferably both represent a hydrogen atom.

Zl and Z preferably both represent a hydrogen atom.

Z and Z preferably each represent a hydrogen atom or an acyl group (
For example, it represents an acedel group, or a substituted (eg, nitro-substituted) or unsubstituted benzoyl group), an alkoxycarbonyl (eg, 1ark-butoxycarbonyl) group, a substituted or unsubstituted phenyl group, or a benzyloxycarbonyl group.

When Zl-Z4 are all hydrogen atoms, the compound having the general formula (2) may be in the form of an acid addition salt.

The most preferred compounds according to the invention have the general formula! I: (1■) (wherein, all R groups are the same and are substituted or unsubstituted alkyl or aryl groups, and R1 groups are all the same and are amino-protecting groups, substituted or unsubstituted carbonized It is a compound having a hydrogen group or a hydrogen atom).

Compounds of general formula I are "optically active" and compounds of general formula It has 61 carbon atoms. That is, each terminal end contains at least one chiral center. Preferably, the alpha carbon atom of the amino acid moiety h<R1 and a chiral center of ntM. Furthermore, 11, = 11
, the two end groups must have the same handedness. The compounds according to the invention are stereomerically pure and non-ceramic.

Compounds according to the invention include compounds having the general formula 1v: 1, -C==C1l (IV) and general formula ■: R, -C3Cl-1(V) (wherein [tl and Ilt are (same as above) can be produced by reacting with a compound having U.

It is clear that this process is the easiest to prepare compounds having the general formula I, in which R1 and R8 are the same. In this case, a compound having the general formula r can be obtained by dimization of a compound having the general formula 2: It, -C==011 (IV), or by a suitable oxidative dimization. Importantly, the conditions for preparing the compounds of this invention are such as to avoid racemization of the chiral group. That is, care must be taken not only in the binomial reaction but also in the preparation of the starting materials to avoid conditions that would cause ceramization. That is, it is desirable to avoid strongly acidic or weakly basic conditions and high temperatures. It is also preferable to avoid the use of ultrasound, especially during the oxidative coupling step.

A more preferred compound according to the invention is the dimerization of a compound having the general formula (1): 21 N Zl 1Is CC00Qt CEC1-1 (Vl) (wherein R1, R6, Zl, Zco and Ql are the same as above) It can be manufactured by

A more preferred oxidative coupling step is according to the method of Hay [Journal of Organic Chemistry (J.

Org, Chem,) Volume 27, Page 3320 (196
2 years)]. The use of ultrasound causes side reactions of amino acid esters.

After the dimemization reaction, the compound having the general formula I can be converted into another compound having the general formula I if desired.

For example, a compound having the general formula 111 (wherein 11S represents alkoxycarbonyl JtC) reacts with an acid and then an alkali to form the general formula 1v: Further, the compound having the general formula (1) (in the formula, each nl represents a hydrogen atom) can be reacted with halonitrobenzene to lead to the compound of the general formula (1) (in the formula, R1 is a nitrobenzene group).

Other compounds according to the invention have the general formula ■: 110-Ql-CEmi C+-+
A compound having the formula (■) was converted into a compound having the general formula ■: 110-Q, -C-=C-CEC-Ql-Of-1 (■
) and then esterifying this with an N-substituted amino acid. Generally speaking, however, this is an undesirable method using diyne di]-oles which undergo polymerization/decomposition which makes process operations difficult.

The diacetylene according to the present invention generally has a distance between C(2) and C(2°) atoms of diacetylene groups of adjacent molecules in the solid state of not more than 4X10-''m, and therefore has a Schmidt reactive group size of ll' (Schmidt, G.M.J., 1967, “Reactivities of Excited Organic Molecules”)
Excited Organic Molecule
s) p. 227, New York, John Wiley).

These compounds are already polymerized in the solid state and the molecular periodic crystal or semicrystalline side! Forms a poldiacetylene network with chiral carbons at II&.

[Example] The invention is further illustrated in the following examples.

Example! Reflux in 200 ml of benzene (13D I-1) for 72 hours in the presence of 12.8 g of p-toluenesulfonic acid!hydrate (Aldrich).
1 g of alanine (Sigma) and 1 G, 34 ml of propargyl alcohol (Full Power) were reacted.

The resulting salt was isolated by adding petroleum ether (boiling point 60-80°C) to the solution at room temperature.

This addition produced an oil which, after washing with petroleum ether (boiling point 60-80°C) produced a solid and was recrystallized from ethyl acetate/petroleum ether (boiling point 60-80°C).

Then, 0°213 in ethyl acetate (nDH)
The obtained propargyl L-alanine tosylate ( 0.5 g) was benzoylated.

Next, we followed High's method (Journal Op Organic), except that the reaction solvent was stirred without sonication.
Chemistry (J, Org, Ches, ), 2
7, p. 3320 (1962)) to oxidatively couple benzoylated amino acid esters. (Sonication can cause side effects on amino acid esters.) The coupling method used is as follows.

While passing oxygen through the green solution, add propargyl N-benzoyl-thi-alanine ester (6.0 Og), cuprous chloride (1.93 g), and tetramethylethylenediamine ('1' MDA, 2, 94 ml). O upper (F7
The mixture was stirred (80 ml). The reaction was observed by R layer chromatography (observed with silica, ethyl acetate:petroleum (70:30), UV light (wavelength 254 ns) and iodine) and was complete in 2.374 hours.

The mixture was concentrated to an oil. Add hydrochloric acid (approximately IM),
The resulting semi-solid product was extracted with ethyl acetate (2 x 30 ml), dried over M g S OA, and
Filtered. Concentration gave an oil, which from ethyl acetate/petroleum ether gave a colorless solid (3.19 g, 54%).
It crystallized as Melting point 182°C, ν (KBr, disk), 3300 (NH), 3050 (C-1-1),
2940 (C-1-1), 2140 (C=C), 1?
50 (C=C), 1630 (C=C), 715.68
5 (C-1-1) ca+''''1 Examples 2 to 9 The following were produced by a method similar to the production of hexa-2,4-diynylene-bis-(N-benzoylalanate) described in Example 1. was manufactured.

phenylalanate) *Disassembly Yields are based on protected propargyl ester.

Example tO The above example! Propargyl, L-alanine tosylic acid was prepared from monoalanine, propargyl alcohol and p-toluenesulfonic acid monohydrate as described in .

Benzyl chloroformate (1,05 equivalent rf1) at 0°C,
The crude salt (10.0 g), ethyl acetate (150 ml) and aqueous sodium carbonate solution (3 equivalents) were added with vigorous stirring.
was added to form propargyl N-carbobenzoxyalanate. The reaction was observed by thin layer chromatography (silica, butanol:water; acetic acid 4:I
:l).

The obtained organic layer was mixed with a saturated sodium bicarbonate 12 aqueous solution, 1
Washing was performed using M hydrochloric acid solution and saturated aqueous sodium chloride solution. After drying the organic layer over magnesium sulfate,
Concentrated. The residual ester was recrystallized from ethyl acetate/petroleum ether (boiling point 60-80°C).

After that, High's method (Journal of Organic Chemistry (J, Org, Chew, ), 2
7, p. 3320, 1962) to oxidatively couple propargyl N-carbobenzoxyalanate. The ester (5 g), acetone (GO ml), cupric chloride (0,5
Oxygen was bubbled through the molar mixture of ff1). The reaction was monitored by thin layer chromatography (silica, stone 411 ether: ethyl acetate 50:5o). The solvent was evaporated and the residue was shaken with 1M hydrochloric acid. The product was taken up in ethyl acetate and washed with 1M hydrochloric acid, saturated aqueous sodium bicarbonate and saturated sodium chloride. After drying the layers over magnesium sulfate and concentration, the residue was recrystallized from ethyl acetate/petroleum ether (boiling point 60-80 DEG C.).

Thereby, hexa-2,4-diynylene bis(
N-carbobenzoxyalanate) was obtained.

Yield: 58%, melting point: 100-102°C.

Examples II and I2 By a method similar to Example 10, the following 6 were prepared.

Example Noacetylene yield
Melting point (%) (℃) I2 Hexa-2,4-diynylene-bis 56
(Tocarbobenzoxypare-1,) 102-105 Example 13 As described in Example 1 above, propargyl L-alanine tosylic acid was prepared from L-alanine, propargyl alcohol and p-toluenesulfonic acid monohydrate. produced salt. To the crude salt (lOg), with vigorous stirring, was added ethyl acetate (150 ml) and sodium carbonate (3 equiv).
and ditertiary butyl dicarbonate-1-(1,05
ff1) was added to form N-tert-butoxyluponylalana-1.

The reaction was monitored by thin layer chromatography (silica, butanol:water:acetic acid 4:I:I).

The Fir I8 layer was separated, washed, dried, and concentrated as described in Example IO. Residual esters can only be obtained as bends.

Later, High's method (Journal of Organic Chemistry (J, Org, Chew, )),
27, p. 3320, 1962),
Pargyl N-carbobenzoxoalana-1. was oxidatively coupled. Oxygen was bubbled through the mixture of ester (5 g), acetone (400n+1), cupric chloride (ff1 per 1,5 moles) while the mixture was vigorously stirred for 1°. The reaction was monitored by thin layer chromatography (silica, petroleum ether: ethyl acetate 50:50). Example! After evaporating the solvent and removing and washing the residue, drying and concentrating the six layers, the residue was dissolved in dichloromethane/Ishiura (boiling point GO~80
℃).

Thereby, hexa-2,4-diynylene bis(
N-tertiary butoxycarbonyl alaner!・) was obtained.

Yield 5G%, melting point -80°C, [α]'' = -63,0
'(cO, 81 (i, acetone), v (K Brs disk) 3370 (NH), 2975 (C-1-
1), I750 (C=0), I510 (C-1-1
1-1) 'Examples 14 and 15 The following were produced by a method similar to Example 13.

Example diacetylene yield (melting point phenylalanate) Hexa-284-diynylene bis(N-tertiary butylene phenylalanate
2.4g), 4-toluenesulfonic acid monohydrate (2,
02g) and acetic acid (glacial acetic acid, 201g) were stirred together. The reaction was monitored by thin layer chromatography (silica, butanol:acetic acid:water 4:1:I) and was complete within 3 hours.

The mixture is condensed to an oil, then heated with boiling petroleum (2X
It solidified when washed with 25 ml). The solid was dried on the filter.

Thereby, hexa-2,4-diynylene bis(
4-1-luenesulfonic acid alanate) was obtained. Yield 1
00%, ν (K11r disk) 3080-2900
(NH+C-1-1), 1750 (C=0), 1.6
10 (N-H), 810 (C-H) cm-'Example 1
7 and 1B The following were prepared by a method similar to Example 16.

Example Diacetylene Yield (%) phenylalanate) No further purification of these was performed.

Example 19 Hexa-2,4-diynylenebis- under nitrogen atmosphere
(N-tertiary butoxycarbonylbara-1.(5,06
g) and trifluoroacetic acid (2.85 g) (from Aldrich) were refluxed together. The reaction was monitored by thin layer chromatography (silica, butanol:acetic acid:water 4:1:l). After 23 hours, another m of trifluoroacetic acid (0,570 g) was added. The reaction was fully completed in 3 hours.

The mixture was concentrated to an oil. A crude solid was obtained by trituration with ether. After that, the obtained hexa-
2,4-diynylene-bis(trifluoroacetic acid barate) was dissolved in 10 liters of a saturated aqueous sodium bicarbonate solution and stirred for 30 minutes.

The mixture was filtered and the filtrate was extracted with 2×25 ml of ethyl acetate.

Wash the organic solution with saturated sodium chloride (10 ml), dry over magnesium sulfate (BDI-1),
After filtering, it was concentrated. 8.8 ml of 1M hydrobromic acid was added and the solution was concentrated to dryness. Ethanol (10
0 ml) was added and the solution was again concentrated to dryness.

Crystallization from butanol/ether produces a white solid (0,
(180 g, 19%) provided hexa-2,4-diynylene-bis-hydrobromide barate.

Melting point=180.5℃, [α]*o=-17,2(c1,
OO1 water), ν (KBr disk) 2940~2 B
20 (N-1-[+C-H), l 730 (C=0),
1560 (N-1-1), 1480 (C-1-1), 1
380 (C-1-Seal), 1 3 4 0 (C-1
-1) c+s-' Examples 20 and 21 The following were manufactured by a method similar to Example 19.

Example Diacetylene yield
Melting point (%) (°C) Example 22 5g of L-alanine, 7.9 at 50°C under nitrogen atmosphere
2 g of 1-fluoro-4-nitrobenzene and 19.
41 g of potassium carbonate were refluxed together with stirring.

Thin layer chromatography (silica, butanol:acetic acid:
The reaction was monitored with water (4:1:l) and completed within 2 days.

Pour the mixture into 100 ml of deionized water and add IM HCI
The crude product was precipitated using a solution, and then allowed to stand at 4°C overnight.

The semi-solid was collected by filtration and dissolved in 50ml ethyl acetate.

The solution was dried over magnesium sulfate, filtered, and concentrated to an oil.

Thereafter, the obtained N-4-nitrophenylalanine (5
g), propargyl bromide (ff1 per 5 mol), 4 g of sodium bicarbonate and 40 ml of dimethylformamide were stirred at room temperature. The reaction was monitored by thin layer chromatography (silica, ethyl acetate:petroleum:acetic acid 69:29:1) and was complete within 24 hours.

Pour the mixture into 40 ml of deionized water and add 2 x 100 ml
Extract the product using ethyl acetate.

The organic solution was washed with saturated aqueous sodium bicarbonate, IM hydrochloric acid and saturated sodium chloride, then dried over magnesium sulfate, treated with Celite and Calcol, and then filtered. Concentration gave an oil.

Then, High's method (Journal of Organic Chemistry (J, Org, Cheta, )),
27, p. 3320, 1962), the obtained propargyl N-4-nitrophenylalanine was oxidatively coupled. Ester (2,98 g), cuprous chloride (1,25 mol equivalent m) and tetramethyl ether L/7 ('rM) in acetone (200 ml).
Oxygen was bubbled into the mixture containing ED8, 1.25% J and M) while stirring the mixture vigorously. Thin layer chromatography (Silippha ethyl acetate:petroleum 40:6
The reaction was observed according to 0) and completed within 1.5 hours.

The solvent was evaporated and the residue was taken up in ethyl acetate (150ml) and washed twice with IM hydrochloric acid, saturated aqueous sodium bicarbonate and saturated aqueous sodium chloride. The solution was dried over magnesium sulfate, treated with Celite and Calcol, then filtered. Concentration gave an oil which was crystallized from chloroform/petroleum to give yellow crystals (1.78 g, 60%).

Melting point = 86-87℃, ν (KBr disk) 3350 (
N-H 〇-to ■), I 7 4 0 (C
=O), 1 600 (N-0), l 320 (N-
0), 820(C-Ll)cm-', δ(90Mtlz
%CDe13) 1, 56 (3!4, d,
J6. 8l-1z, CHs), 4
, 28 (III, q, J 6.8Hz, a-
C-H), 4.83 (211, sSCI-1g (C=
C)), 6.55 (21-1, dS J9゜2Hz, 8rl-1), 8.07 (21-L dSJ 9.2H
z, Art-1).

Examples 23 and 24 The following were produced by a method similar to Example 22.

Example diacetylene effi
Melting point (%) (℃) Alanate) 24 Hexa-2,4-diynylenebis-451
Example 25 Hexa-2,4-diynylene bis-(4-toluenesulfonic acid alanate) (Example + (iX2, 386 g) and !-fluoro2.
4-Dinitrobenzene (1,488 g, from Aldrich) was dissolved and then 2.543 g of sodium carbonate (from IIDI-1) in 20 ml of water was added with vigorous stirring. Thin layer chromatography (silica, butanol; acetic acid:water 4:1:■)
The reaction was observed using a 100% sterilizer and completed within 4 hours.

The organic layer was separated, diluted with 6011 ethyl acetate, 2 x 30 ml saturated sodium bicarbonate, 2 x 30 ml
IM of aqueous hydrochloric acid and 30 ml of saturated hydrochloric acid. The solution was diluted with magnesium sulfate (nDI
-1), filtered and concentrated to an oil. - Crystallization from butanol/petroleum (60-80°C) is hexa-2°4-diynylene-bis(N
-2,4-dinitrophenylalana-1.) was provided as a yellow solid (!.

0 (3g 148%). Melting point = 46-47℃, [α]”
= +46.8° (cl, 00, acetic acid), ν (Knr disk) 3300 (N-1-1), 1745 (C=O
), I 510 (N-0), +330 (N-0), 83
0 (C-1-11-1) 'Examples 2G and 27 By a method similar to Example 25, the following 6 were produced.

Phenylalanate) [Polymerization of diacetylene] Polymerization of monomeric materials can be easily carried out by various methods. This example illustrated polymerization occurring by heat, pressure, ultraviolet light, and gamma radiation polymerization. Some of the materials polymerize easily in sunlight.

! , thermal polymerization by heating in the dark for 6 hours, Example 2.3.
The products of 4 and 8 were subjected to thermal polymerization.

The temperatures used are as follows.

Example number Temperature ('C) 4
1! 08
For other cases, temperature range 30” to 250°
Thermal polymerization was investigated using differential scanning calorimetry.

If polymerization occurred, a colored product was obtained which was insoluble in organic solvents.

2. Pressure polymerization Samples of the products of the examples shown below were pressurized under the conditions shown below.

Product Conditions Example No. I K11r disc pressure, 16 hours, l! ,
3 metric tons/c-12KBr disk pressurization, 16 hours, l I II' 3 metric tons/as'3
K +1 r disc pressure, 16 hours, 11.3
Metric tons/c-14Kflr disk pressurization, 16 hours, l! , 3 metric tons/cs”5 K1
1r disk pressurization, 16 hours, 11.3 metric tons/
cm"G K mouth"Disk pressurization, 16 hours,
19.1 metric tons/cm”7 K [1
r disk pressurization, 16 hours, 11.3 metric tons/c
yh”8 10 meter injection container 9 KBr disk pressurization, 16 hours, 11.
3 metric tons/C-kai 10 K [1r disk pressurization, 22 hours, 10.1 metric tons/cm@11
KIlr disc pressurization, 22 hours, 10.1
Mettleton/C is 12 K [1r disc pressure, 22 hours, 10.1 meterton/cm"13~1
5 K [1r disk pressure, 4 hours, 11.3 metric tons/am"16-27 KBr disk pressure, 5 hours, 11.3 metric tons/e+a" When polymerization occurs, an insoluble colored product is produced. I got something.

3.Using an ultraviolet polymerization crusher and a vessel, crush a sample of each of the products shown below into a fine powder, and then apply ultraviolet light (wavelength 254 nm) until the color does not change even after further crushing and re-irradiation. , 5
5 watt lamp).

4. Gamma Radiation Polymerization A sample of the product shown below was irradiated with 50 M rad of gamma radiation for 71 E. In all cases, except Examples 13 and 14, which produced water-soluble polymers, 50+ sl of solvent was used, i.e. for the polymer obtained using the product of Example 8, nitromethane was used and Polymerization samples were extracted using extraction U7 form in the case of polymers obtained from the products and acetone for the other test products. The water insoluble product was collected.

[Result] Heat Pressure UV Gamma of product
Line appearance example number 1, 02.3, 11.946.6 red 2 3.03.
313.948.5 Red 3 99.013.537.096.6 Red 4 19.6
2.43.621.1 Red 5 G 19.6 23.8
3.0 Orange/Red G O2+, 9
2.8 20.0 Orange 7 0
3.2 <Supervise 1 Orange 8 2.
2 3.2 9.512.0 Red 9 0 3
．． 6 ＜+ 37.4 Orange/Brown 1
0 <1 4.3 6.11 4
Red l Orange II <1 1.
1 3.0 Ne Red/Pink +2
<1 2. ．． 9 3.4 *
Red/pink 13. 0 <l <s 3
7.1 red 14 0 <1
<1 16.6 Akane 0<! *0<1 *O<1 0 0 Q o 0 0 0 0 Q Not measured, but color change was observed, but not measured.

No polymerization yellow Red tea light brown ^V tea The formation of polymer is

Claims (1)

[Claims] (1) Formula (I) R_1-C≡C-C≡C-R_2 (I) [In the formula, R_1 and R_2 are the same or different,
Indicates an organic group containing an amino acid moiety, each having at least one chiral center. However, in the case of R_1=R_2, the groups R_1 and R_2 have the same handedness.] A compound represented by the following. (2) The compound according to claim 1, wherein R_1 and R_2 are the same, including handedness. (3) The compound according to claim 1 or 2, wherein the amino acid moiety is an L-amino acid ester moiety. (4) Formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_3 and R_6 are the same or different,
aromatic or non-aromatic, each substituted or unsubstituted hydrocarbon group; or may be non-aromatic), Z_1, Z_2, Z_3 and Z_4 are the same or different and are each an amino group-protecting functional group, an aromatic or non-aromatic substituted or unsubstituted hydrocarbon group, or a hydrogen atom, Q_1 and Q_2 are the same or different and each represent a divalent intervening group containing an integer number of atoms between the carboxylate group and the diacetylene group. Compounds described. (5) At least one of Q_1 and Q_2 is expressed by the formula (CH_2)n_1 or (CH_2)n_2[n_
5. The compound according to claim 4, wherein 1 and n_2 are the same or different and each means an integer. (6) The compound according to claim 4 or 5, wherein R_3 and R_6 are the same or different and each is an unsubstituted or hydroxy-, mercapto-, ether-, thioether-, amino- or carboxy-substituted alkyl or aralkyl group. . (7) The compound according to any one of claims 4 to 6, wherein both R_4 and R_5 are hydrogen atoms. (8) The compound according to any one of claims 4 to 7, wherein both Z_1 and Z_2 are hydrogen atoms. (9) Any one of claims 4 to 8, wherein Z_3 and Z_4 are the same or different and each is a hydrogen atom, an acyl group, a substituted or unsubstituted phenyl group, an alkoxycarbonyl, a benzyloxycarbonyl, or a phenylsulfonyl group. Compounds described. (10) Propargyl N-acetyl-(L)-alanine, Propargyl N-acetyl-(L)-phenylalanine, Propargyl N-acetyl-(L)-valine, Propargyl N-benzoyl-(L)-alanine , propargyl N-benzoyl-(L)-phenylalanine, propargyl N-benzoyl-(L)-valine, propargyl N-(4-nitrobenzoyl)-(L)-alanine, propargyl N-(4-nitro benzoyl)-(L)
-phenylalanine, propargyl N-(4-nitrobenzoyl)-(L)
-valine, propargyl N-t-butoxycarbonylalanate, propargyl N-t-butoxycarbonylphenylalanate, propargyl N-t-butoxycarbonyl barate, propargyl N-carbobenzoxyalanate, propargyl N -carbobenzoxyphenylalanate, propargyl N-carbobenzoxybarate, propargyl N-4-nitrophenylalanate, propargyl N-4-nitrophenylphenylalanate, or propargyl N-4-nitrophenylvalanate diacetylene, which is produced by self-coupling of nerds. (11) Coupling a compound represented by the formula R_1-C≡CH with a compound represented by the formula R_2-C≡CH [wherein R_1 and R_2 have the meanings defined in any one of claims 1 to 10] and
The compound of formula (I) obtained as desired can be converted to another formula (I).
2. A method for producing the compound according to claim 1, which comprises converting the compound into the compound of claim 1. (12) A method for producing polydiacetylene, which comprises polymerizing the compound according to any one of claims 1 to 10 in a solid state.