JP2010275299A - Aromatic compound and production method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aromatic compound sufficiently small in the molecular size compared with common polymer materials and having material properties expectably usable as a resist material. <P>SOLUTION: There is provided a new aromatic compound having a double resorcinarene ring structure by reacting a resorcinol-based compound with a specific aldehyde. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an aromatic compound and a method for producing the same. More specifically, the present invention relates to an aromatic compound having a material size that is sufficiently small compared to a general polymer material and has material properties that can be expected to be used as a resist material, and a method for producing the same.

  The calixarene compound is generally a cyclic oligomer obtained by condensation of a phenol compound such as phenol and resorcinol with an aldehyde compound. In recent years, calixarene compounds have attracted attention as third inclusion compounds following crown ethers and cyclodextrins in the field of host-guest chemistry.

  A calixarene compound usually has many hydroxyl groups in one molecule, is excellent in thermal stability, has a high glass transition temperature and a high melting point, and has a film forming property depending on the structure. Has attracted attention as a functional material. For example, application to an electron beam negative photoresist using p-methylcalix [6] arene hexaacetate (see, for example, Non-Patent Document 1), calix [4] resorcinarene, crosslinking agent, photoacid generator Application to an alkali developing type negative photoresist based thereon (for example, see Non-Patent Document 2) has been reported.

  In addition, for the purpose of applying calixarene compounds to high-performance photocuring materials, it is intended to introduce radically polymerizable functional groups and cationically polymerizable functional groups, and to protect high-resolution resist materials. Synthesis of calixarene derivatives by introduction of a group and evaluation of the photoreaction characteristics have been reported (for example, see Non-Patent Documents 3 and 4). Furthermore, the synthesis of p-alkylcalix [n] arene derivatives having various cationically polymerizable functional groups and studies on their photocationic polymerization have been reported (for example, see Non-Patent Document 5).

  Among calixarene compounds, calixresorcinolarene compounds, which are condensates of resorcinol compounds and aldehyde compounds, have chemically-modifiable hydroxyl groups, so they have been applied to resist materials. (For example, refer to Patent Document 1).

International Publication No. 2005/075398

Y. Ochiai, S .; Manako, H .; Yamamoto, T .; Teshima, J .; Fujita, E .; Nomura: J. et al. Photopolymer. Sci. Tech. , 13, 413 (2000) T.A. Nakayama, M .; Nomura, K .; Haga, M .; Ueda: Bull. Chem. Soc. Jpn. 71, 2979 (1998) T.A. Nishikubo, A .; Kameyama, and H.K. Kudo, K .; Tsutsui: J. Polym. Sci. Part A. Polym. Chem. 39, 1293 (2002) T.A. Nishikubo, A .; Kameyama, and H.K. Kudo: Polym. J. et al. , 35, 213 (2003) K. Tsutsui, S .; Kishimoto, A. et al. Kameyama, T .; Nishikubo: Polym. Prep. Jpn. , 37, 1805 (1999)

  However, the calix resorcinol arene compound, which is a condensate of the resorcinol compound and the aldehyde compound disclosed in Patent Document 1, is compared with, for example, a general polymer material having a number average molecular weight exceeding 10,000. Although the molecular size is small, it is a monocyclic compound, the mechanical properties as a material are not sufficient, and in particular, the performance as a resist material may not be sufficient.

  The present invention has been made in view of such problems of the prior art, and the problem is that the molecular size is sufficiently small compared to general polymer materials, An object is to provide an aromatic compound having material properties that can be expected to be used.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a novel aromatic compound having a double resorcinarene ring structure can be obtained by reacting a resorcinol compound with a specific aldehyde, and the present invention It came to be completed.

  That is, according to the present invention, the following aromatic compounds and methods for producing the same are provided.

  [1] An aromatic compound represented by the following general formula (1).

In the general formula (1), a plurality of X's are independently of each other a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, and 2 to 2 carbon atoms. A substituted or unsubstituted alkynyl group having 10 or 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group; Y represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, or 7 to 7 carbon atoms. A substituted or unsubstituted aralkyl group having 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, wherein a plurality of R ^{1 s} are independent of each other; In addition, a hydrogen atom, a group having a polymerizable functional group, a group having an alkali-soluble group, a group having an acid-dissociable group, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a trivalent group having 3 to 12 carbon atoms. An alkylsilyl group, or a methylene group formed by combining two R ^{1 s} , or a substituted or unsubstituted alkylene group having 2 to 8 carbon atoms, wherein a plurality of m's are each independently 0 Or a plurality of n's independently represent 0 or 1;

  [2] An aromatic compound obtained by reacting the compound (A) represented by the following general formula (2) with the compound (B) represented by the following general formula (3).

  In the general formula (2), X is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted group having 2 to 10 carbon atoms. An alkynyl group, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, and m represents 0 or 1 .

  In the general formula (3), Y represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted group having 2 to 10 carbon atoms. An alkynyl group, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, and n represents 0 or 1 .

  [3] A method for producing an aromatic compound, comprising reacting a compound (A) represented by the following general formula (2) with a compound (B) represented by the following general formula (3).

  In the general formula (2), X is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted group having 2 to 10 carbon atoms. An alkynyl group, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, and m represents 0 or 1 .

  In the general formula (3), Y represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted group having 2 to 10 carbon atoms. An alkynyl group, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, and n represents 0 or 1 .

  The aromatic compound of the present invention has a sufficiently small molecular size as compared with a general polymer material and has a double resorcinarene structure, so that it can be expected to have excellent mechanical properties and can be used as a resist material. It has the effect that it can be expected.

  In addition, the aromatic compound of the present invention has a sufficiently small molecular size as compared with general polymer materials, and can be expected to have excellent mechanical properties and can be used as a resist material. There is an effect that the functionalization is possible.

  Furthermore, according to the method for producing an aromatic compound of the present invention, the molecular size is sufficiently small compared to a general polymer material, and it can be expected to be used as a resist material, and can be functionalized by introducing a functional group. This produces an effect that a simple aromatic compound can be produced.

3 is a chart showing ¹ H-NMR measurement results of a compound represented by formula (9) obtained in Example 6. FIG. 6 is a chart showing ¹³ C-NMR measurement results of the compound represented by formula (9) obtained in Example 6. FIG. 4 is a chart showing a conversion rate with respect to a heating time measured in Reference Experiment 1. 6 is a chart showing a change with time of an IR spectrum with respect to a heating time measured in Reference Experiment 1. 6 is a chart showing a conversion rate with respect to an irradiation time measured in Reference Experiment 2.

  Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments. It is understood that the scope of the present invention includes modifications, improvements, and the like as appropriate to the following embodiments based on ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. Should.

I. Aromatic compounds:
One embodiment of the aromatic compound of the present invention is a compound represented by the general formula (1) (hereinafter also referred to as “aromatic compound (I)”), which is a molecule compared with a general polymer material. Since the size is sufficiently small and the structure has a double resorcinarene structure, excellent mechanical properties can be expected and use as a resist material can be expected.

In the general formula (1), a plurality of X's are independently of each other a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, and 2 to 10 carbon atoms. A substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, Y is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, or 7 to 10 carbon atoms. A substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, and a plurality of R ^{1 s} independently of each other, A hydrogen atom, a group having a polymerizable functional group, a group having an alkali-soluble group, a group having an acid-dissociable group, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms A methylene group formed by combining two R ¹ groups, or a substituted or unsubstituted alkylene group having 2 to 8 carbon atoms, and a plurality of m's are each independently 0 or 1 And a plurality of n's independently represents 0 or 1.

In general formula (1), at least one group represented by R ¹ is preferably a group having a polymerizable functional group. When at least one of the groups represented by R ¹ is a group having a polymerizable functional group, the aromatic compound (I) can be used for the curable composition. In addition, the solubility in a solvent and the film formability are also improved.

  Examples of the polymerizable functional group include a group having a polymerizable unsaturated bond and a group having a cyclic ether structure. More specifically, a vinyl group, a vinylidene group, an acryloyl group, a methacryloyl group, a substituted or unsubstituted glycidyl group, a substituted or unsubstituted oxetanyl group, a substituted or unsubstituted spiro orthoester group, and the like can be given.

When at least one of the groups represented by R ¹ is a group having a polymerizable functional group, the aromatic compound (I) can be used for the curable composition. However, from the viewpoint of increasing the speed of curing, the group represented by R ¹ is preferably a group having more polymerizable functional groups. That is, one of two R ¹ existing on one aromatic ring is preferably a group having a polymerizable functional group, and more preferably two of them are groups having a polymerizable functional group.

In the general formula (1), at least one group represented by R ¹ is preferably a group having an alkali-soluble group. When at least one of the groups represented by R ¹ is a group having an alkali-soluble group, the aromatic compound (I) can be suitably used for a resist composition. For example, after reacting an alkali-soluble group with a cross-linking agent such as a polyfunctional vinyl ether compound to cross-link, and then irradiating a specific part with light in the presence of a photoacid generator to hydrolyze and make it alkali-soluble A specific uneven pattern can be formed by dissolving and removing a specific portion with an alkaline aqueous solution. In addition, since the group represented by R ¹ is a group having an alkali-soluble group, the film formability is also improved.

  Examples of the alkali-soluble group include a carboxyl group, an amino group, a sulfonamide group, a sulfonic acid group, and a phosphoric acid group.

Since at least one of the groups represented by R ¹ is a group having an alkali-soluble group, the aromatic compound (I) can be used in a resist composition, but the solubility in an aqueous alkali solution is further increased. From the viewpoint, the group represented as R ¹ is preferably a group having more alkali-soluble groups. That is, one of two R ¹ existing on one aromatic ring is preferably a group having an alkali-soluble group, more preferably two of them are groups having an alkali-soluble group.

Furthermore, in the general formula (1), the group represented by R ¹ has both a group having a polymerizable functional group and a group having an alkali-soluble group, which can be suitably used for a composition for a photoresist. Therefore, it is particularly preferable. For example, after forming a film using a composition for a photoresist containing the aromatic compound (I), the specific part is cured by irradiating the specific part with light, and the other part is removed with an alkaline aqueous solution. A specific uneven pattern can be formed by dissolving and removing.

From the viewpoint that more polymerizable functional groups and alkali-soluble groups can be introduced, the group represented by R ¹ in the general formula (1) is a group having both a polymerizable functional group and an alkali-soluble group. It is also preferable.

In general formula (1), at least one group represented by R ¹ is preferably a substituted alkyl group having 1 to 8 carbon atoms in the alkyl chain. For example, by introducing a functional group as described above at the tip of an alkyl chain as a spacer, the degree of freedom of the functional group is improved and the reactivity is improved. Alternatively, a derivative having a substituted alkyl group substituted with a substituent capable of adding or substituting a functional group as described above can also be suitably used as an intermediate for synthesizing a derivative that can be used in a resist composition or the like. it can. Furthermore, a derivative having a substituted alkyl group in which the functional group or substituent as described above is protected by a protecting group can also be suitably used as an intermediate or the like.

Furthermore, in the general formula (1), at least one group represented by R ¹ is preferably a group having an acid dissociable group. When at least one of the groups represented by R ¹ is a group having an acid dissociable group, the aromatic compound (I) can be suitably used for a resist composition. For example, by irradiating a specific portion with light in the presence of a photoacid generator, an acid-dissociable group is eliminated by the action of an acid generated from the photoacid generator to generate an alkali-soluble site. The solubility of the exposed portion in the alkaline developer is increased, and the exposed portion is dissolved and removed by the aqueous alkali solution, whereby a specific uneven pattern can be formed.

  Examples of the acid dissociable group include a substituted methyl group, 1-substituted ethyl group, 1-substituted n-propyl group, 1-branched alkyl group, silyl group, germyl group, alkoxycarbonyl group, and cyclic acid dissociable group. Etc. More specifically, benzyl group, t-butoxycarbonylmethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-cyclohexyloxyethyl group, 1-ethoxy-n-propyl group, t-butyl group, 1 , 1-dimethylpropyl group, trimethylsilyl group, t-butoxycarbonyl group, adamantyl group, tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group, 2-methyl-2-adamantyloxycarbonylmethyl Group, an ethoxycarbonylmethyl group and the like are preferable.

II. Aromatic compounds:
Another embodiment of the aromatic compound of the present invention is represented by the compound (A) represented by the general formula (2) (hereinafter also referred to as “compound (A)”) and the general formula (3). Compound (B) (hereinafter also referred to as “compound (B)”) (hereinafter also referred to as “aromatic compound (II)”), In comparison, the molecular size is sufficiently small, and excellent mechanical properties can be expected, and it can be expected to be used as a resist material, and can be functionalized by introducing functional groups.

  The compound (A) is an aromatic diol compound represented by the general formula (2).

  In general formula (2), X is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms. A group, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, and m represents 0 or 1.

  Compound (A) is substituted or unsubstituted dihydroxybenzene. Specific examples of the compound (A) include 1,3-dihydroxybenzene (resorcinol), 2-methylresorcinol, 2-butylresorcinol and the like. Among these, resorcinol and 2-methylresorcinol are preferable. In addition, these compounds (A) can be used individually by 1 type or in combination of 2 or more types.

  The compound (B) is an aldehyde compound represented by the general formula (3).

  In general formula (3), Y represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, and a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms. A group, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, and n represents 0 or 1.

  Specific examples of the compound (B) include 2,4-dihydroxybenzaldehyde. In addition, it is preferable to use a compound (B) individually by 1 type.

  As an aromatic compound (II) obtained by the condensation reaction of such a compound (A) and a compound (B), the structure is represented by following General formula (4) or following General formula (5), for example. There is something.

  In the general formula (4), a plurality of X's are independently of each other a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, and 2 to 10 carbon atoms. A substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, Y is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, or 7 to 10 carbon atoms. A substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, and a plurality of m's are each independently 0 Represents a 1, the plurality of n, independently of one another, 0 or 1.

  In general formula (5), a plurality of X's are independently of each other a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, or 2 to 10 carbon atoms. A substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, Y is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, or 7 to 10 carbon atoms. A substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, and a plurality of m's are each independently 0 Represents a 1, the plurality of n, independently of one another, 0 or 1.

For the aromatic compound (II) having such a structure, under basic conditions, general formula (6): R ¹ Z (in general formula (6), R ¹ is a group having a polymerizable functional group, A group having an alkali-soluble group, a group having an acid-dissociable group, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms, Z represents a halogen atom .) Can be functionalized by introducing a functional group, and can be suitably used as a resist material.

III. A method for producing an aromatic compound.
The manufacturing method of the aromatic compound of this invention is a method including making a compound (A) and a compound (B) react. The reaction between the compound (A) and the compound (B) is a condensation reaction, but the conditions for the condensation reaction are not particularly limited and can be performed under conventionally known conditions. Specific examples include a method of dehydrating condensation in an appropriate reaction solvent at 60 to 120 ° C. for 6 to 72 hours in the presence of an appropriate catalyst such as an acid catalyst.

  Specific examples of the catalyst used in the dehydration condensation reaction include hydrochloric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, perfluorobutanesulfonic acid, pentafluorobenzenesulfonic acid and the like. Among these, hydrochloric acid and trifluoroacetic acid are preferable because the desired aromatic compound can be produced with higher yield.

  Preferred examples of the reaction solvent used in the dehydration condensation reaction include pure water; dimethylformamide; halogen-containing solvents such as dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene; methanol, ethanol, isopropyl alcohol, butanol, etc. Examples thereof include alcohol solvents.

  The ratio of the compound (A) and the compound (B) used in the condensation reaction is not particularly limited, but from the viewpoint of improving the yield, the compound (A) is 1 to 8 mol with respect to 1 mol of the compound (B). It is preferably 2-6 mol, more preferably 3-5 mol. If the ratio is out of the above range, the yield of the target aromatic compound may decrease.

  The substrate concentration in the reaction solution in the condensation reaction (the total concentration of the compound (A) and the compound (B)) is not particularly limited, but is preferably 2 mol / L or more from the viewpoint of yield improvement, It is more preferably 4 mol / L or more, and particularly preferably 4 to 10 mol / L. If the substrate concentration is less than 2 mol / L, the yield of the target aromatic compound may be reduced.

  After the condensation reaction, the product can be obtained as a condensate (precipitate). The obtained product is preferably purified by washing with water, an organic solvent, or a mixed solvent of water and an organic solvent. Specific examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl i-butyl ketone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, and 2,6-dimethylcyclohexanone; methanol, ethanol, n-propyl alcohol, alcohols such as i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol, 1,4-hexanedimethylol; ethers such as diethyl ether, tetrahydrofuran and dioxane And the like; esters such as ethyl acetate, n-butyl acetate and i-amyl acetate; aromatic hydrocarbons such as toluene and xylene; phenol, acetonylacetone and dimethylformamide. Among these, methanol, ethanol, and diethyl ether are preferable. Moreover, it is preferable to purify by washing with an organic solvent containing water and an ether solvent. In addition, these organic solvents can be used individually by 1 type or in combination of 2 or more types. The remaining raw materials and by-products can also be removed by dissolving the obtained product in an organic solvent and washing the dissolved organic solvent with water.

  The aromatic compound (I) can be produced by reacting the product obtained as described above with the compound represented by the general formula (6) under basic conditions.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In addition, the measuring method of various physical-property values and the evaluation method of various characteristics are shown below.

[Gel filtration chromatography (GPC)]: The analysis was performed under the following conditions.
System: Model number “HLC-8220” manufactured by Tosoh Corporation
Detector: Model number “HLC-8200”, built-in RI / UV-8200 (280 nm)
Column oven temperature: 40 ° C
Column: manufactured by Showa Denko KK, trade name “Shodex Asahipak GF-510 HQ” + trade name “GF-310 HQ” × 2
Eluent: dimethylformamide solution containing 20 mM LiBr and 20 mM H ₃ PO ₄ .

[ESI-MASS measurement]: The analysis was performed under the following conditions.
System: JEOL Ltd., Accu-TOF
Ionization mode: negative mode Sample concentration: 500 ppb
Orifice 1 voltage sweep: -60V
Ring lens voltage: -34V
Solvent: methanol

[IR (cm ⁻¹ )]: Measured using a model number “NICOLET 380 FT-IR” manufactured by Thermo ELECTRON.

[ ¹ H-NMR and ¹³ C-NMR]: model number “JNM-ECA-500” (500 MHz ( ¹ H), 150 MHz ( ¹³ C)) manufactured by JEOL Ltd., model number “JNM-ECA- manufactured by JEOL Ltd. 600 "was measured using ^(600MHz (1 H)).

Example 1
To a 100 mL two-necked eggplant flask containing a rotor, 1.20 g (10.9 mmol) of resorcinol, 1.51 g (10.9 mmol) of 2,4-dihydroxybenzaldehyde, and 30 mL of distilled water are added and heated to add resorcinol and 2 , 4-Dihydroxybenzaldehyde was dissolved. After adding 5 mL of hydrochloric acid as a catalyst, the mixture was stirred at 80 ° C. for 5.5 hours. After completion of the reaction, the mixture was allowed to cool to room temperature and washed with methanol. After separating into a solution layer and a solid layer using a centrifuge, the solution layer was decanted and washed again with methanol. Centrifugation and washing were repeated three times, and the resulting solid was collected by filtration and dried under reduced pressure to obtain a reaction product (yield 0.69 g). When the obtained reaction product was measured by gel filtration chromatography, Mn was 1550 and Mw / Mn was 1.037. Further, when ESI-MASS measurement was performed, peaks were observed at 919.45, 1149.57, and 1269.58. From this result, it is expected that the reaction product is a mixture of compounds represented by the following formulas (7) and (8).

Actual value (m / z): 1269.58 ([M−H ⁺ ] ⁻ )
Calculated value (m / z): 1269.31 ([M−H ⁺ ] ⁻ )

Actual value (m / z): 1149.57 ([M−H ⁺ ] ⁻ )
Calculated value (m / z): 1149.29 ([M−H ⁺ ] ⁻ )

(Example 2)
To a 25 mL eggplant flask containing a rotor, 0.36 g (3.26 mmol) of resorcinol, 0.45 g (3.26 mmol) of 2,4-dihydroxybenzaldehyde, 9 mL of distilled water, and 1.5 mL of hydrochloric acid as a catalyst were added. Then, it stirred at 60 degreeC for 5.5 hours. After completion of the reaction, the mixture was allowed to cool to room temperature, and the precipitated solid was collected by filtration. After washing with water and cold methanol, the reaction product was obtained by drying under reduced pressure (yield 0.18 g). When the obtained reaction product was measured by gel filtration chromatography, the ratio of the compound represented by formula (7) was 76%.

(Examples 3-5 and Comparative Example 1)
A reaction product was obtained in the same manner as in Example 2 except that the reaction was performed under the temperature conditions shown in Table 1. The obtained reaction product was measured by gel filtration chromatography, and the ratio of the compound represented by the formula (7) was measured. The measurement results are also shown in Table 1. In Example 5, dimethylformamide was used instead of distilled water.

  As can be seen from Table 1, the proportion of the compound represented by the formula (7) increased as the reaction temperature increased. In Comparative Example 1, 2,4-dihydroxybenzaldehyde was not completely dissolved in the solvent, and the reaction did not proceed. Moreover, in Example 5, the insoluble part was confirmed in dimethylformamide.

(Example 6)
To a 100 mL two-necked flask containing a rotor, 3.81 g of the reaction product obtained in Example 1 and 24.9 g of imidazole were added, and argon was sealed. As a solvent, 60 mL of dehydrated tetrahydrofuran was added and stirred, suspended at 80 ° C., and then 18.3 mL of trimethylsilyl chloride was added and heated to reflux for 48 hours. After completion of the reaction, 60 mL of n-hexane was added, and a pale yellow liquid was separated by column chromatography. After concentrating the liquid, recrystallization was performed twice using acetone and n-hexane to obtain colorless and transparent columnar crystals. The analysis results of this crystal are shown below, and charts showing the measurement results of ¹ H-NMR and ¹³ C-NMR are shown in FIGS. 1 and 2.

^{IR (film, cm -1):} 2959,2902 (ν> CH), 1602,1572,1493 (ν C = C aromatic), 1252 (ν Si-C), 1190 (ν Si-O)

¹ H (500 MHz, CDCl ₃ ) δ (ppm): −0.17 to 0.08 (m, 196H, TMS-H), 5.67 to 5.85, 6.00 to 6.61 (m, 26H) , Aromatic-H), 5.90-5.94 (m, 6H,> CH)

  Melting point: 208.4 ° C. (by DSC)

Decomposition temperature ^_(T d i): 387.7 ℃
5 mass% decomposition temperature ( _Td ^{5 mass%} ): 444.5 ° C
10% by mass decomposition temperature (T _d ^{10% by mass} ): 460.7 ° C.

  From the above analysis results, the obtained crystal is expected to be a compound represented by the following formula (9).

(Example 7)
In a 200 mL two-necked eggplant flask containing a rotor, 0.355 g (1.1 mmol, 5 mol% with respect to the hydroxyl group) of tetrabutylammonium bromide (hereinafter also referred to as “TBAB”) as a dissolution accelerator and pyridine as a solvent 10 mL was added. To this, 1.27 g of the reaction product obtained in Example 4 was added and suspended. Thereto, 10.1 mL of di-tert-butyl dicarbonate (44 mmol, 2 equivalents relative to the hydroxyl group) was slowly added dropwise and stirred at room temperature for 48 hours.

  After completion of the reaction, the reaction mixture was diluted with chloroform, washed 3 times with 1N aqueous hydrochloric acid solution and twice with water, and the organic layer was dried over anhydrous magnesium sulfate. The desiccant was filtered off, concentrated, and purified by precipitation using a water-methanol mixed solvent. The obtained solid was collected by filtration and dried under reduced pressure to obtain a yellow powdery solid (yield 2.83 g, yield 82%). The analysis results of this solid are shown below.

IR (film, cm ⁻¹ ): 2981, 2934 (ν _{C-H aromatic} ), 1760 (ν _C═O ), 1594 (ν _{C = C aromatic} ), 1387 (ν _t-butyl ), 1249, 1143 (ν _{C-O-C ether} )

_{^{1 H (600MHz, CDCl 3,}} TMS) δ (ppm): 1.10~1.61 (m, 218H, t-butyl H), 5.53~7.13 (m, 32H, aromatic-H and methyn -H)

  From the above analysis results, the obtained solid is expected to be a main product of a compound represented by the following formula (10).

(Reference Experiment 1)
0.104 g (0.03 mmol) of the solid obtained in Example 7 was weighed, 0.014 g of triphenylsulfonium trifluoromethanesulfonate (5 mol% based on hydroxyl group) was added as a photoacid generator, and a small amount of dehydrated tetrahydrofuran was added. And applied to KBr. Light irradiation was performed for 30 minutes using a 250 W ultra-high pressure mercury lamp as a light source, and then heated at 110 ° C. for 1 hour. Using a Fourier transform infrared spectrophotometer (trade name “NICOKET 380FT / IR”, manufactured by Thermo ELECTRON), the time course of the infrared spectrum was measured. The sample after the completion of the heating reaction was soluble in a 2.38% by mass tetramethylhydroxyammonium aqueous solution.

The conversion rate of the photodeprotection reaction was calculated from the decrease in the absorption peak of the t-butyl group at 1387 cm ^{−1 with} the aromatic absorption peak at 1611 cm ⁻¹ as a reference. A chart showing the conversion with respect to the heating time is shown in FIG. Further, FIG. 4 shows a chart showing the change with time of the IR spectrum with respect to the heating time. Since the presence of a hydroxyl group can be confirmed from the chart of heating time 0 minutes in FIG. 4, it is considered that deprotection proceeds only by light irradiation.

(Reference Experiment 2)
Using a real-time infrared spectroscope (trade name “Real Time IR FTS3000 type”, manufactured by Nippon Bio-Rad Laboratories, Inc.), the temporal change of deprotection only by light irradiation was measured. A chart showing the conversion rate with respect to the irradiation time is shown in FIG.

  As can be seen from FIG. 5, the obtained individuals proceeded with the deprotection reaction only by light irradiation. In addition, even if light irradiation was performed for 1 hour, the conversion rate was 20% and it did not reach the steady state.

  From the results of Reference Experiments 1 and 2, the solid obtained in Example 7 undergoes a deprotection reaction upon exposure and becomes soluble in an aqueous alkali solution, so that it can be expected to be used as a resist material.

(Example 8)
In a 50 mL eggplant flask containing a rotor, 0.32 g of the reaction product obtained in Example 4, 90 mg of TBAB (0.275 mmol, 5 mol% with respect to the hydroxyl group), 1.14 g of potassium carbonate (8.25 mmol, hydroxyl group) 1.5 equivalents) and 10 mL of N-methyl-2-pyrrolidinone (hereinafter also referred to as “NMP”) was added as a solvent. After stirring at 60 ° C. for 3 hours, 0.79 g of 2-methyl-2-adamantyl bromoacetate (2.75 mmol, 0.5 equivalent to the hydroxyl group) dissolved in 5 mL of NMP was added, and the mixture was stirred at 60 ° C. for 24 hours. did.

  After completion of the reaction, the reaction mixture was added dropwise to 1N aqueous hydrochloric acid, and the precipitate was collected by filtration. This solid was dissolved in ethyl acetate and dried over magnesium sulfate. After the desiccant is filtered off, the solvent is distilled off under reduced pressure, isolated by column chromatography (developing solvent: THF / n-hexane = 3/1), and further precipitated by using n-hexane to obtain a solid. (Yield 0.60 g, Yield 78%, Introduction rate 40%). The analysis results of this solid are shown below. The introduction rate of the 2-methyl-2-adamantylcarbonyloxymethyl group was calculated from the proton of the aromatic ring, the methine proton, and the methylene proton of the 2-methyl-2-adamantylcarbonyloxymethyl group.

IR (film, cm ⁻¹ ): 3440 (ν _O—H ), 2913, 2862 (ν _{> CH 2} ), 1729 (ν _{C = O ester} ), 1612 (ν _{C = C aromatic} ), 1213, 1103 (ν _COOC ) _ester )

_{^{1 H (600MHz, CDCl 3,}} TMS) δ (ppm): 1.14~2.54 (m, 180H, H b-k), 3.82~4.96 (m, 18H, H a), 5 .05 to 7.13 (m, 32H, aromatic-H and methyn-H)

H ^ak represents a proton corresponding to the following position ^ak of the introduced 2-methyl-2-adamantylcarbonyloxymethyl group.

  From the above analysis results, it is expected that the compound obtained by the following formula (11) is the main product in the obtained crystal.

Example 9
In a 50 mL three-necked eggplant flask containing a rotor, 0.63 g of the reaction product obtained in Example 4, 0.36 g of TBAB (1.1 mmol, 10 mol% with respect to the hydroxyl group) as an interlayer transfer catalyst, 5 mL of dimethylformamide, And 0.5 mL of water was added to dissolve completely. Thereafter, 5.38 g (16.5 mmol, 1.5 equivalents relative to the hydroxyl group) of cesium carbonate was added, and the mixture was stirred at 50 ° C. for 2 hours. Thereafter, 2.76 g of ethyl bromoacetate (16.5 mmol, 1.5 equivalents relative to the hydroxyl group) was added dropwise, and the mixture was stirred at 50 ° C. for 5 hours.

  After completion of the reaction, the reaction mixture was diluted with chloroform, washed once with brine and twice with water, and the organic layer was dried over anhydrous magnesium sulfate. The desiccant was filtered off, concentrated, isolated by silica gel chromatography (developing solvent: ethyl acetate), and further precipitated with n-hexane. The solvent was removed by decantation, and a brown viscous liquid was obtained by drying under reduced pressure (yield 0.915 g, yield 58%, introduction rate 111%). The analysis results of this solid are shown below. In addition, a yield and the introduction rate of an ethyl ester group are the values which assumed that all the reaction products obtained in Example 1 were a compound represented by Formula (7).

IR (film, cm ⁻¹ ): 2983, 2938 (ν _{> CH 2} ), 1758, 1736 (ν _{C = O ester} ), 1611, 1518 (ν _{C = C aromatic} ), 1206, 1183 (ν _{COOC ester} )

¹ H (600 MHz, DMSO-d ₆ , TMS) δ (ppm): 1.13 to 1.27 (m, 75 H, H ^c ), 3.79 to 4.77 (m, 99 H, H ^a and H ^b ) 5.56 to 6.51 (m, 32H, aromatic-H and methyn-H)

H ^a-c represents a proton corresponding to the following position a-c of the introduced ethyl ester group.

  From the above analysis results, it is expected that the compound obtained by the following formula (12) is the main product in the obtained liquid.

  The aromatic compound of the present invention has a sufficiently small molecular size as compared with a general polymer material, and can be expected to have excellent mechanical properties because it has a double resorcinarene structure. Can be used as a resist material.

Claims (3)

An aromatic compound represented by the following general formula (1).

(In the general formula (1), a plurality of X's are independently of each other a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, and 2 carbon atoms. A substituted or unsubstituted alkynyl group having 10 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group; Plural Ys are substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 10 carbon atoms, substituted or unsubstituted alkynyl groups having 2 to 10 carbon atoms, and 7 carbon atoms. 10 substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenoxy group having 1 to 10 carbon atoms, more of R ¹ are mutually Germany Standingly, a hydrogen atom, a group having a polymerizable functional group, a group having an alkali-soluble group, a group having an acid dissociable group, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or 3 to 12 carbon atoms or showing a trialkylsilyl group, or two methylene groups which R ¹ is formed by bonding, or a substituted or unsubstituted alkylene group having 2 to 8 carbon atoms, and a plurality of m, independently of one another, 0 or 1 is represented, and a plurality of n represents 0 or 1.) An aromatic compound obtained by reacting a compound (A) represented by the following general formula (2) with a compound (B) represented by the following general formula (3).

(In the general formula (2), X is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted group having 2 to 10 carbon atoms. An alkynyl group, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, and m represents 0 or 1 Show.)

(In the general formula (3), Y represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, and a substituted or unsubstituted group having 2 to 10 carbon atoms. An alkynyl group, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, and n represents 0 or 1 Show.) The manufacturing method of an aromatic compound including making the compound (A) represented by the following general formula (2) react with the compound (B) represented by the following general formula (3).

(In the general formula (2), X is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted group having 2 to 10 carbon atoms. An alkynyl group, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, and m represents 0 or 1 Show.)

(In the general formula (3), Y represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, and a substituted or unsubstituted group having 2 to 10 carbon atoms. An alkynyl group, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, and n represents 0 or 1 Show.)

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