JPH0244826B2 - - Google Patents

Description

[Detailed description of the invention]

(Technical Field) The present invention relates to a novel diethynylbenzene derivative compound useful as a resist material, an organic semiconductor, an electronic material such as a conductive material, and the like. (Industrial Application Field) Diethynylbenzene compounds, in which two ethynyl groups are directly bonded to the benzene ring, generally have γ
It is highly sensitive to energy irradiation such as beams, electron beams, , X-ray resists, patterning materials such as photoresists, or dry heat materials. In addition, the polymer obtained by the energy irradiation becomes a conjugated polymer in which the C≡C triple bond opens to form a conjugated double bond.
It can also be used as an electronic material such as a conductive material. In addition, a hydrophobic structural part such as a long chain structure consisting of an appropriate number of methylene groups in the molecule, an amino group,
Amphiphilic compounds that have both hydrophilic structural moieties such as hydroxyl groups and carboxyl groups form a monomolecular film on the water surface. This monomolecular film is manufactured using the Langmuir Blosget method (hereinafter referred to as the "LB method").The film produced by this method is also called the "LB film".
That's what it means. ), it is possible to accumulate on a suitable substrate to form a molecular accumulation film with high blendability. In particular, the diethynylbenzene derivative compound of the present invention has an amphiphilic structure that has both a hydrophobic structural part consisting of 9 to 21 methylene groups and a hydrophilic structural part such as a carboxyl group in the molecule. molecules, which are accumulated on a suitable substrate using the LB method,
A highly oriented monomolecular film or a molecular cumulative film can be formed. The LB film using the diethynylbenzene derivative compound of the present invention thus obtained can be applied to pattern forming materials such as resists, electronic materials such as organic semiconductors and conductive materials, and optoelectronic materials such as nonlinear optical materials. and is very useful industrially. (Prior art and problems) Until now, diethynylbenzene or the general formula

[Formula] Compounds represented by (n=1, 2, 4, 5, 6, 10) and general formula

Compounds represented by the formula (R is a methyl group, a cyclohexyl group, or a phenyl group) are already known. [W.
L.01sen et al., Journal of Bacteriology, 137(3),
1443-6 (1979); US4536515, etc.). Diethynylbenzene compounds are resistant to gamma rays, electron beams,
It is sensitive to energy irradiation such as ultraviolet rays, visible light, and infrared rays (heat), but its small molecular weight makes it difficult to produce high-quality thin films, and it is difficult to handle under reduced pressure due to sublimation. It was hot. Although the LB method can be applied to the production of thin films of compounds having a diethynylbenzene structure, there are no known diethynylbenzene compounds that have amphiphilic properties, which are necessary for the production of LB films. (Means for Solving the Problem) In view of these problems, the present inventors have developed a diethynylbenzene compound that can be made into a thin film, is non-sublimable, and is suitable for the LB technology. As a result of intensive studies to obtain a diethynylbenzene compound, which is a medium compound, the diethynylbenzene derivative compound of the present invention was obtained. That is, the present invention provides a novel diethynyl compound represented by the general formula below, which has a diethynylbenzene structure and a methylene chain in the molecule, a carboxyl group at one molecular end, and a hydrogen or alkylsilyl group at the other molecular end. This invention relates to benzene derivative compounds. [R in the formula is hydrogen or -SiX ₁ X ₂ X ₃ , X ₁ , X ₂ ,
Each of X ₃ is independently hydrogen or an alkyl group having 1 to 7 carbon atoms (excluding cases where X ₁ , X ₂ , and X ₃ are all hydrogen), and n is an integer of 9 to 21.] The diethynylbenzene derivative compound of the present invention is
Due to its molecular structure characteristics, in the IR absorption spectrum, the C-H stretching vibration of the benzene ring, the C-H stretching vibration of the methylene group, and the C≡C stretching vibration of the ethynyl group are 3000 to 3080 cm ^-1 and 2850 to 2960 cm ^- , respectively. ¹ ,
Observed from 2010 to 2260 cm ^-1 . In addition, the absorption peculiar to the benzene ring is around 1600 cm ^-1 and around 1500 cm ^-1 , and the C-H out-of-plane bending vibration of the benzene ring is between 690 and 860 cm ^-1
, the C=O stretching vibration of the carboxyl group is 1700 cm ^-1
Observed nearby. In addition, in the ¹ H-NMR spectrum, the protons of the benzene ring are 6.9 to 7.8 ppm, and the protons of the methylene group adjacent to C≡C are 2.2 to 2.5 ppm.
In addition, protons of methylene groups adjacent to carboxyl groups are observed at 2.25 to 2.5 ppm, and protons of other methylene groups are observed at 0.6 to 1.9 ppm. IR absorption due to the structure of substituent R, ¹ H−
NMR signals are also observed in each spectrum. In the general formula of the diethynylbenzene derivative compound of the present invention, the substituent R is hydrogen or -SiX ₁ X ₂ X ₃
However, examples of -SiX ₁ X ₂ X ₃ include trimethylsilyl, triethylsilyl, methyldiethylsilyl, tributylsilyl, triheptylsilyl, diethylsilyl, and the like. However, a diethynylbenzene derivative compound in which R is hydrogen can be obtained by a desilylation reaction of a derivative in which R=-SiX ₁ X ₂ X ₃ . The diethynylbenzene derivative of the present invention is an amphipathic compound that is solid at 15° C. and is soluble in acetone, methyl ethyl ketone, ethanol, methanol, tetrahydrofuran, diethyl ether, ethyl acetate, and the like. Furthermore, it is soluble in volatile organic solvents that are not soluble in water, such as chloroform, hexane, benzene, and heptane. Next, an example of the method for synthesizing the diethynylbenzene derivative of the present invention will be explained. First, a scheme of the synthesis reaction is shown below. First, using diethynylbenzene (1) as one of the starting materials, two ethynyl groups of diethynylbenzene are metal halogenated by the Grignard method,
Compound (2) is obtained. This compound ( _{2 )} is converted into chloroalkylsilane X ₁ X ₂ X ₃ SiCl ( _{X 1 ,} X ₂ and X ₃ are not all hydrogen at the same time) to form bisalkylsilylated ethynylbenzene (3) ~ Synthesize. On the other hand, alkenyl alcohol (4) ~ CH ₂ = CH−
(CH ₂ ) _o -OH (where n is an integer between 9 and 21)
is used as another starting material and reacted with tosyl chloride to form alkenyl tosylate (5) ~ CH ₂ =CH
-(CH ₂ ) _o -OTs (where n is an integer of 9 or more and 21 or more, and Ts is a tosyl group) is synthesized. The above bisalkylsilylated ethynylbenzene (3) and alkenyl tosylate (5) are desilylated using methyllithium or the like to form an organometallic compound (6). By reacting with rate (5)~, [R' in _the formula is -SiX _{1 X 2 X 3} , and _{X 1 ,} are all hydrogen), and n is an integer between 9 and 21.]
It is possible to synthesize diethynylbenzene derivatives (7) represented by: Further, the derivative (7') ~ in which R' is hydrogen is a derivative (7) ~ in which R is a silyl group -SiX ₁ X ₂ X ₃ , R ₄ NF,
It can be obtained by desilylating KF, RLi, etc. (R", R represents an alkyl group having 1 to 5 carbon atoms or a phenyl group) in the presence of a desilylating agent. Desilylating agent When using KF as a compound, it is preferable to use it together with a crown compound.Next, the above diethynylbenzene derivatives (7) to
Alternatively, the diethynylbenzene derivative compound (8) or (8') of the present invention can be obtained by oxidatively decomposing the vinyl group portion of (7') by ozone oxidation or the like to convert it into a carboxyl group. Can be done. Although an example of the method for producing the diethynylbenzene derivative compound of the present invention has been described above, the production method is not limited thereto. (Effect of the invention) The diethynylbenzene derivative compound of the present invention is
It is possible to form a thin film and is non-sublimable. Therefore, the diethynylbenzene derivative compound of the present invention can be used as a pattern forming material, by forming it into a thin film.
It can be used as a heat-sensitive material, and by making it into a polymer, it can be applied as an electronic material such as an organic semiconductor or a conductive material. Furthermore, the diethynylbenzene derivative compound of the present invention is an amphiphilic compound, and by preparing an LB film, it can be used as a pattern forming material, an electronic material such as a conductive material, or an optoelectronic material such as a nonlinear optical material. It can be applied. The present invention will be explained in more detail with reference to Examples below. Example 1 0.2 mol of p-diethynylbenzene was dissolved in 350 ml of sufficiently dehydrated tetrahydrofuran,
0.4 mol of ethylmagnesium bromide was added at 25° C. and reacted for 1 hour at 25° C. Next, this reaction solution was cooled again to -78°C, 0.4 mol of trimethylsilyl chloride was added, and the mixture was reacted at 25°C for 2 hours to obtain bis-(trimethylsilylethynyl)-benzene. Additionally, 0.04 mol of ω-heptadecenyl alcohol was dissolved in 30 ml of pyridine, and while the reaction vessel was immersed in an ice bath, 0.045 mol of toluenesulfonyl chloride (tosyl chloride) was added and reacted at 15°C for 24 hours to form heptadecenyl toxin. Got the rate. Next, bis-(trimethylsilyl)-benzene 0.01
mol was dissolved in 60 ml of sufficiently dehydrated tetrahydrofuran, 0.01 mol of methyllithium was added at -78°C, and the mixture was reacted at 25°C for 2 hours. The reaction solution was cooled again to -78°C, and hexamethylphosphoramide 35
ml and 0.01 mol of heptadecenyl tosylate were added and reacted at 25°C for 1 hour. To this reaction solution were added 250 ml of a saturated aqueous solution of sodium hydrogen carbonate and 180 ml of diethyl ether, and the mixture was thoroughly shaken to extract the product into the ether phase. The ether phase was washed with a saturated aqueous solution of sodium chloride and then dehydrated with magnesium sulfate. This ether solution was concentrated to give white yellow crystals. Purification by GPC yielded 1-(18-nonadecen-1-ynyl)-4-(trimethylsilylethynyl)-benzene. 40 mmol of white crystals were obtained. Next, the above 1-(18-nonadecen-1-ynyl)
-4-(trimethylsilylethylyl)-benzene was dissolved in 300 ml of ethyl acetate, cooled to -10°C, and an equimolar amount of ozone O ₃ was blown in. The refrigerant was removed.
After evaporating the solvent by blowing argon gas,
The residue was dissolved in 60 ml of acetone and the reaction vessel was immersed in an ice bath. Jones reagent was added to this solution until the brown color was maintained, and the mixture was stirred and reacted at 25° C. for 15 minutes. Add 350ml of ice water to the reaction solution,
Organic matter was extracted with diethyl ether. This ether phase was shaken with an aqueous sodium hydroxide solution and the aqueous phase was separated. After making the aqueous phase acidic by adding an aqueous hydrochloric acid solution, the target product was extracted with diethyl ether. Concentrate the ether solution to give 18-(4
-trimethylsilylethynylphenyl)-17-octadecinoic acid 34 mmol of white crystals were obtained. IR spectrum, ¹ H-NMR of this crystal
We measured its spectrum and investigated its structure.
First, when we measured the IR spectrum using the KBr tablet method, we found that the C-H stretching vibration of the benzene ring was 3030
cm ^-1 , the C-H stretching vibration of the methylene group is 2850,
At 2930cm ^-1 , the C-H stretching vibration of the methyl group is at 2960cm
^-1 , the C≡C stretching vibration of -C≡C- becomes 2150 cm ^-1 ,
The C=O stretching vibration of the carboxyl group is 1700 cm ^-1 ,
Skeletal vibration and C-H out-of-plane bending vibration of the benzene ring were observed at 1500 cm ^-1 and 840 cm ^-1 , respectively. Also,
1400 cm ^-1 , 1250 cm ^-1 derived from the methyl group of Si-CH ₃ ,
Absorption at 855 cm ^-1 derived from Si-C stretching vibration was observed. Next, when the ¹ H-NMR spectrum of the compound was measured in a deuterated chloroform solution, the protons of the benzene ring were 7.44 ppm, the protons of the methylene group adjacent to -C≡C-, and the protons of the methylene group adjacent to the carboxyl group. is almost the same at 2.4ppm,
Other methylene group protons are 0.6 to 1.9 ppm
In addition, protons of the trimethylsilyl group were observed at 1.04 ppm with a signal integrated intensity ratio of 4:4:26:9, respectively. The compound is an amphiphilic molecule, and a stable monolayer was formed by dropping a chloroform solution onto the water surface. This monomolecular layer was deposited on a SiO ₂ -coated silicon wafer by the Langmuir blodget method to produce a 59-layer cumulative film. This LB film was covered with a photoresist mask, exposed for 1 minute with a 100W low-pressure mercury lamp, and then developed with ethanol for 1 minute. As a result, only the unexposed areas were dissolved in ethanol, and a negative pattern was formed. . Example 2 1-(18-nonadecene- obtained by the method of Example 1)
1-ynyl)-4-(trimethylsilylethynyl)
- A solution of (C ₄ H ₉ ) ₄ NF in tetrahydrofuran was added to a solution of benzene in tetrahydrofuran so that (C ₄ H ₉ ) ₄ NF was 25 equivalents of the trimethylsilyl group, and the mixture was stirred and mixed at 25°C for 20 hours. A desilylation reaction was performed. Next, a small amount of water was added to this reaction solution, and after thorough shaking, the ether layer was separated. Repeat this operation to combine the ether layers and concentrate to obtain 1-ethynyl-4-(18-nonadecen-1-ynyl)-benzene. 30 mmol of white crystals were obtained. Next, the above 1-ethynyl-4-(18-nonadecen-1-ynyl)-benzene was dissolved in 300 ml of ethyl acetate, and after cooling to -10°C, an equimolar amount of ozone was blown into the solution. Remove the refrigerant, evaporate the solvent by blowing argon gas, and remove the residue with 60ml of acetone.
The reaction vessel was immersed in an ice bath. John's reagent was added to this solution until the brown color was maintained, and the mixture was stirred and reacted at 25° C. for 15 minutes. 350 to the reaction solution
ml of ice water was added, organic matter was extracted with diethyl ether, the ether phase was shaken with an aqueous sodium hydroxide solution, and the aqueous phase was separated. After making the aqueous phase acidic by adding an aqueous hydrochloric acid solution, the target product was extracted with diethyl ether. Concentrate the ether solution to obtain 18-(4-ethynyl phenyl)-17-octadecinoic acid. 26 mmol of white crystals were obtained. Figure 1 shows the ¹ H-NMR spectrum measured with a deuterated chloroform solution. As can be seen from this spectrum, the proton of the benzene ring is at 7.44 ppm, the proton of the ethylene group at the end of the molecule is at 3.1 ppm, and -C≡C in the molecule.
The protons of the methylene group adjacent to - and the methylene group adjacent to carboxyl group are almost the same 2.4ppm
In addition, the protons of other methylene groups are 0.6~
1.9 ppm, respectively, with a signal integrated intensity ratio of 4:1:4:26. Moreover, the IR spectrum measured by the KBr tablet method is shown in FIG. As can be seen from this spectrum, C- of the terminal ethynyl group -C≡C-H
The H stretching vibration is at 3300 cm ^-1 , the C-H stretching vibration of the benzene ring is at 3030 cm ^-1 , the C-H stretching vibration of the methylene group is at 2850 cm ^-1 and 2950 cm ^-1 , and the C-H stretching vibration of the carboxyl group is at 3030 cm -1 .
= O stretching vibration is 1700 cm ^-1 , benzene ring skeleton vibration and C-H out-of-plane bending vibration are each 1500 cm ^-1 ,
It was observed at 840cm ^-1 . The compound is an amphipathic molecule, and a stable monomolecular film could be formed by spreading a chloroform solution on the water surface. This monomolecular film was deposited on a SiO ₂ -coated silicon wafer by the Langmuir blodget method to produce a 59-layer cumulative film. Cover this LB film with a photoresist mask,
After exposure for 1 minute with a 100W low-pressure mercury lamp, the film was developed with ethanol for 1 minute. As a result, only the unexposed areas were dissolved in ethanol, and a negative pattern could be formed. Example 3 A similar reaction was carried out in Example 1 using ω-undecylenyl alcohol instead of ω-heptadecenyl alcohol, and first 1-(12-tridecen-1-ynyl)-4-trimethylsilylethynyl ) - benzene Obtained 46 mmol. This compound was used in Example 1 as 1-(18-nonadecen-1-ynyl)-4-
Similar ozone oxidation was performed using (trimethylsilylethynyl)-benzene to obtain the desired product.
12-(4-trimethylsilylethynylphenyl)-
11-Dodecinoic acid Obtained 40 mmol. From the IR spectrum measured by the KBr tablet method,
The C-H stretching vibration of the benzene ring is at 3030 cm ^-1 , the C-H stretching vibration of the methylene group is at 2850 and 2930 cm ^-1 , the C-H stretching vibration of the methyl group is at 2960 cm ^-1 , -C≡C
The C≡C stretching vibration of - is 2150 cm ^-1 , the C=O stretching vibration of the carboxyl group is 1700 cm ^-1 , and the skeletal vibration and C-H out-of-plane bending vibration of the benzene ring are each 1500 cm -1.
cm ^-1 , observed at 840 cm ^-1 . In addition, absorptions at 1400 cm ^-1 and 1250 cm ^-1 derived from the methyl group of Si-CH ₃ and at 855 cm ^-1 derived from Si-C stretching vibration were observed. ¹ H−
From the NMR spectrum, the protons of the benzene ring are
The protons of the methylene group adjacent to -C≡C- and the protons of the methylene group adjacent to the carboxyl group are approximately the same at 7.44ppm, the protons of other methylene groups are 0.6 to 1.9ppm, and the protons of the trimethylsilyl group are approximately the same. is 1.04ppm each 4:
It was observed with a signal integrated intensity ratio of 4:14:9. The compound is an amphiphilic molecule, and a stable monolayer was formed by dropping a chloroform solution onto the water surface. This monolayer was deposited on a SiO ₂ coated silicon wafer using the LB method.
A cumulative film of 59 layers was fabricated. Cover this LB film with a photoresist mask,
After exposure with a 100W low-pressure mercury lamp for 1 minute, the film was developed with ethanol for 1 minute. As a result, only the unexposed areas were dissolved in ethanol, and a negative pattern could be formed. Example 4 In Example 2, 1-(18-nonadecene-1
-ynyl)-4-(trimethylsilylethynyl)-
1-(12-tridecene-1-
A similar reaction was carried out using 1-ethynyl)-4-trimethylsilylethynyl)-benzene, and 1-ethynyl-
4-(12-tridecen-1-ynyl)-benzene Obtained 34 mmol. This compound was used in Example 2 as 1-ethynyl-4-(18-nonadecene-1-
Similar ozone oxidation was carried out using instead of (enyl)-benzene, and the target product, 12-(4-ethynyl phenyl)-11-dodecinoic acid, was obtained. Obtained 30 mmol. This diethynylbenzene derivative carboxylic acid
The IR spectrum measured by coating on the KBr plate was
As shown in the figure. As can be seen from this spectrum, the C-H stretching vibrations of the benzene ring and methylene group are at 3030 cm ^-1 and 2850 to 2920 cm ^-1 , respectively, the C-H stretching vibration of the ethynyl group at the end of the molecule, and the -C≡C- C≡C
The stretching vibrations are 3300 cm ^-1 and 2150 cm ^-1 , respectively, the C=O stretching vibration of the carboxyl group is 1700 cm ^-1 , and the skeletal vibration and C-H out-of-plane bending vibration of the benzene ring are 1500 cm ^-1 and 840 cm ^-1, respectively. was observed. In addition, broad absorption of O-H stretching vibration of carboxylic acid
It was observed in the region of 2500 to 3500 cm ^-1 . Figure 4 shows the ¹ H-NMR spectrum measured with a deuterated chloroform solution. As can be seen from this spectrum, the protons of the benzene ring are at 7.43 ppm,
The proton of the ethynyl group is 3.1 ppm, and the proton of the methylene group adjacent to C≡C and the proton of the methylene group adjacent to the carboxyl group are the same 2.4 ppm.
In addition, the protons of other methylene groups are 0.8~
The signals were observed at a signal integrated intensity ratio of 4:1:4:14 at 1.8 ppm, respectively. Using the thus obtained diethynylbenzene derivative carboxylic acid, a 59-layer cumulative film was fabricated on a SiO ₂ -coated silicon wafer by the LB method. Cover this LB film with a photoresist mask,
After exposure for 1 minute with a 100W low-pressure mercury lamp, the film was developed with ethanol for 1 minute. As a result, only the unexposed areas were dissolved in ethanol, and a negative pattern could be formed. Example 5 The same reaction as in Example 1 was carried out using chlorotriethylsilane instead of trimethylsilyl chloride to obtain bis-(triethylsilylethynyl)-benzene. A similar reaction was carried out in Example 1 using this compound in place of bis-(trimethylsilylethynyl)-benzene, and 1-
White crystals of (18-nonadecen-1-ynyl)-4-(triethylsilylethynyl)-benzene were obtained.
A similar reaction was carried out in Example 1 using this compound in place of 1-(18-nonadecen-1-ynyl)-4-(trimethylsilylethynyl)-benzene, resulting in 18-(4-triethylsilylethynylphenyl). 32 mmol of white crystals of -17-octadecinoic acid was obtained. From the IR spectrum, the C-H stretching vibration of the benzene ring is at 3030 cm ^-1 , the C-H stretching vibration of the methylene group is at 2850 and 2930 cm ^-1 , the C-H stretching vibration of the methyl group is at 2960 cm ^-1 , and -C The C≡C stretching vibration of ≡C-
At 2150 cm ^-1 , the C≡O stretching vibration of the carboxyl group
At 1700 cm ^-1 , skeletal vibration of the benzene ring and C-H out-of-plane bending vibration were observed at 1500 cm ^-1 and 840 cm ^-1 , respectively. In addition, the methylene group derived from Si-CH ₂ CH ₃
1408cm ^-1 , 1234cm ^-1 , 855 derived from Si-C stretching vibration
Absorption at cm ^-1 was observed. Also, from the ¹ H-NMR spectrum, the proton of the benzene ring was 7.44 ppm.
The protons of the methylene group adjacent to -C≡C- and the protons of the methylene group adjacent to the carboxyl group are approximately the same at 2.4 ppm, and the other protons are
The protons of the methyl group and methylene group of the triethylsilyl group are 0.9 ppm and 0.6 to 1.9 ppm, respectively.
The integrated signal intensity ratio was 0.6 ppm and 4:4:26:9:6. The compound is an amphipathic molecule, and a stable monomolecular film could be formed by spreading a chloroform solution on the water surface. This monolayer
A 59-layer cumulative film was fabricated on a SiO ₂ -coated silicon wafer using the LB method. Cover this LB film with a photoresist mask,
After exposure for 1 minute with a 100W low-pressure mercury lamp, the film was developed with ethanol for 1 minute. As a result, only the unexposed areas were dissolved in ethanol, and a negative pattern could be formed. Example 6 The same reaction as in Example 1 was carried out using chlorotriheptylsilane instead of trimethylsilyl chloride to obtain bis-(triheptylsilylethynyl)-benzene. This compound was used in Example 1 as bis-(trimethylsilylethynyl)
- Carry out a similar reaction using instead of benzene,
White crystals of 1-(18-nonadecen-1-ynyl)-4-(triheptylsilylethynyl)-benzene were obtained. In Example 1, this compound was used as 1-
A similar reaction was carried out using (18-nonadecen-1-ynyl)-4-(trimethylsilylethynyl)-benzene instead of 18-(4-triheptylsilylethynylphenyl)-17-octadecinoitsquaside. 28 mmol of white crystals were obtained. The compound is an amphiphilic compound, and a stable monomolecular film could be formed by spreading a chloroform solution on the water surface. This monomolecular film was accumulated on a SiO ₂ -coated silicon wafer by the LB method to produce a 39-layer cumulative film. Cover this LB film with a photoresist mask,
After exposure for 1 minute with a 100W low-pressure mercury lamp, the film was developed with ethanol for 1 minute. As a result, only the unexposed areas were dissolved in ethanol, and a negative pattern could be formed. Example 7 First, ω-tricosenoic acid CH ₂ =CH
( _CH2 ) ₂₀ -COOH is cyclized with lithium aluminum hydride to produce ω-tricosenyl alcohol.
_CH2 =CH-( _CH2 ) ₂₁ -OH was obtained. In Example 1, this ω-tricosenyl alcohol was
A similar reaction was carried out using heptadecenyl alcohol instead of 1-(24-bentacocene-1).
-ynyl)-4-trimethylsilylethynyl)-benzene Obtained 40 mmol. This compound was used in Example 2 as 1-(18-nonadecen-1-ynyl)-4-
(trimethylsilylethynyl)-benzene, 1-ethynyl-4-(24-pentacocen-1-ynyl)-benzene Obtained 30 mmol. This compound was used in Example 2 instead of 1-ethynyl-4-(18-nonadecen-1-ynyl)benzene, and 24-(4-ethynyl phenyl)
−23-tetrachosinoitsuquaside 22 mmol of white crystals were obtained. The compound is an amphiphilic compound, and a stable monomolecular film could be formed by spreading a chloroform solution on the water surface. This monomolecular film was accumulated on a SiO ₂ -coated silicon wafer by the LB method to produce a 59-layer cumulative film. Cover this LB film with a photoresist mask,
After exposure for 1 minute with a 100W low-pressure mercury lamp, the film was developed with ethanol for 1 minute. As a result, only the unexposed areas were dissolved in ethanol, and a negative pattern could be formed.

[Brief explanation of drawings]

Figure 1 shows 18− measured in deuterated chloroform solution.
¹ H-NMR spectrum of (4-ethynyl phenyl)-17-octadecinoic acid, Figure 2 is
IR spectrum of 18-(4-ethynylphenyl)-17-octadecinoic acid measured by the KBr tablet method. Figure 3 shows the IR spectrum measured by coating it on a KBr plate.
IR spectrum of 12-(4-ethynyl phenyl)-11-dodecinoic acid, Figure 4 shows 12-(4-ethynyl phenyl) measured in deuterated chloroform solution.
¹ H-NMR spectrum of -11-dodecinoic acid.

Claims (1)

[Claims] 1. General formula [R in the formula is hydrogen or -SiX ₁ X ₂ X ₃ and X ₁ , X ₂ ,
Each of X ₃ is independently hydrogen or an alkyl group having 1 to 7 carbon atoms (excluding cases where X ₁ , X ₂ , and X ₃ are all hydrogen), and n is an integer of 9 to 21.] A diethynylbenzene derivative compound represented by