KR100749928B1 - Surface modified ito glass and producing method thereof - Google Patents

Abstract

The present invention relates to a surface-modified ITO glass and a method for manufacturing the same. More specifically, the surface-modified ITO glass by introducing an organic group at room temperature by reacting an silane compound having an allyl or allyl derivative in the ITO glass under an organic solvent. And a method for producing the same.

The present invention can effectively introduce organic groups into ITO glass even at room temperature, and is very effective for introducing compounds having heat-sensitive functional groups such as natural compounds and proteins. In addition, it is possible to introduce a variety of organic groups, and can be separated by a silica gel column to purify the organo-silane compound combined with large organic molecules can be efficiently attached to ITO glass is a very useful invention in the chemical industry.

Silane compounds with allyl or allyl derivatives, acids, Lewis acids, room temperature, ITO glass

Description

Surface-modified ITO glass and its manufacturing method {SURFACE MODIFIED ITO GLASS AND PRODUCING METHOD THEREOF}

 1 is a photograph showing a contact angle test result of ITO glass treated with a piranha solution.

FIG. 2 is a photograph showing the results of conducting a contact angle experiment after reacting dodecyldimethylmethallylsilane with ITO glass using HCl as a catalyst in an ethanol solvent.

3 is a photograph showing the results of experiments in which dodecyldimethylmethallylsilane was reacted with ITO glass using Sc (OTf) ₃ as a catalyst in an acetonitrile solvent and then subjected to contact angle experiments.

FIG. 4 is a photograph showing the results of conducting a contact angle experiment after reacting dodecylmethyldimethallylsilane with ITO glass using HCl as a catalyst in an ethanol solvent.

FIG. 5 is a photograph showing the results of experiments in which dodecylmethyldimethalylsilane was reacted with ITO glass using Sc (OTf) ₃ as a catalyst in an acetonitrile solvent and then subjected to contact angle experiments.

6 is a photograph showing the results of conducting a contact angle experiment after reacting dodecyltrimethallylsilane with ITO glass using HCl as a catalyst in an ethanol solvent.

FIG. 7 is a photograph showing the results of a contact angle experiment after reacting dodecyltrimethallylsilane with ITO glass using Sc (OTf) ₃ as a catalyst in an acetonitrile solvent.

8 is a graph showing the results of cyclic voltammetry experiments after ferrocin-trimethallyl-silane was reacted with ITO glass using HCl as a catalyst in ethanol solvent.

The present invention relates to a surface-modified ITO glass and a method for manufacturing the same. More specifically, the surface-modified ITO glass by introducing an organic group at room temperature by reacting an silane compound having an allyl or allyl derivative in the ITO glass under an organic solvent. And to provide a method for producing the same.

Attaching the organic group to the surface of the ITO glass by covalent bonding is the most reliable method of modifying the surface of the ITO glass. This covalent bond is an In-O-Si and / or Sn-O-Si bond in which In and / or Sn atoms present on the surface of the ITO glass and a silicon atom of the organosilicon compound form an In-OH on the surface of the ITO glass. And or a Sn-OH group reacts with an organosilicon compound having a leaving group such as a halide, alkoxy, or an amino group on a silicon atom to form the covalent bond. However, since the organosilicon compound having a high leaving group as described above is very sensitive to hydrolysis, it could not be used in the presence of water. In particular, the organosilicon compound had a limitation in that a purification method through a silica gel column could not be used to remove impurities after synthesis. Recently, in order to solve these limitations, a method of using an allylsilane organic compound that is relatively stable to moisture has been developed. However, in order to proceed with this reaction, a high temperature reflux method has to be used. The compound had problems that were difficult to apply. The metaallyl organosilane compound used in the present invention can be used stably under water and hydrolysis conditions, and can be separated and purified using a silica gel column. However, when a catalyst is used, it is activated and reacts with ITO glass even at room temperature, which has the advantage that it can be conveniently used even in the presence of heat sensitive organic compounds or functional groups. In particular, it is not only applicable to chiral separation column fillers that can introduce chiral organic compounds into ITO glass and can separate chiral compounds, but also to fix catalyst ligands in this way for recovery of catalysts. It is very effective for surface modification of ITO glass.

SUMMARY OF THE INVENTION The present invention has been made to overcome the above-mentioned problems. An object of the present invention is to dissolve a silane compound having an allyl or allyl derivative in an ITO glass in an organic solvent, react with an acid catalyst, and introduce an organic group at room temperature to modify the surface of the ITO glass. And to provide a method for producing the same.

In order to achieve the above technical problem, the surface-modified ITO glass according to an aspect of the present invention, by reacting a silane compound having an allyl or allyl derivative represented by the following formula (1) to the ITO glass in an acid and an organic solvent Modify the surface of the ITO glass.

[Formula 1]

Provided that R ₁ to R ₅ are H or a linear or branched C ₁ to C ₃₀ alkyl group and R ₆ is a linear or branched C ₁ to C ₁₈ alkyl group, a linear or branched C ₁ to C ₃₀ aliphatic group of the cyclic compound of an unsaturated _{hydrocarbon, C 1 ~ C 30, C} 1 ~ C 30 Linear or branched C ₁ to C ₁₈ alkyl groups or linear containing any one or more functional groups selected from the group consisting of aromatic cyclic compounds, halogens, azides, amines, ketones, ethers, amides, esters, triazoles and isocyanates or branched and branched aliphatic unsaturated hydrocarbon of C ₁ ~ C _18, n is an integer from 1-3.

The reaction is preferably made at 0 to 60 ℃, more preferably at 10 to 30 ℃.

The acid is any one or more selected from the group consisting of HCl, H ₂ SO ₄ , HNO _{3 ,} Sc (OTf) ₃ , In (OTf) ₃ , Zn (OTf) ₃ , Yb (OTf) ₃ and Eu (OTf) ₃ . It is advantageous to use Sc, and more preferably Sc (OTf) ₃ .

The organic solvent may be preferably any one or more selected from the group consisting of alcohol, toluene, benzene, dimethylformamide (DMF) and acetonitrile.

The alkyl group of R ₆ may preferably be a propyl group, and more particularly, may be used a propyl group including a functional group.

A general organic group may be preferably introduced into R ₆ , and more preferably, the organic group may be any one or more selected from the group consisting of amino acids, proteins, chiral compounds, and natural compounds. Preferably, it may be introduced into R ₆ of the silane compound before or after the reaction between the ITO glass and the silane compound having an allyl or allyl derivative represented by Chemical Formula 1 above.

As the silane compound having an allyl or allyl derivative represented by Formula 1, a metaallyl silane compound may be preferably used.

In the method for modifying the surface of the ITO glass according to another feature of the present invention, 1) purifying the silane compound having an allyl or allyl derivative represented by the following formula (1), and 2) the silane purified on the ITO glass Mixing the compound, acid and organic solvent.

[Formula 1]

Provided that R ₁ to R ₅ are H or a linear or branched C ₁ to C ₃₀ alkyl group and R ₆ is a linear or branched C ₁ to C ₁₈ alkyl group, a linear or branched C ₁ to C ₃₀ aliphatic group of the cyclic compound of an unsaturated _{hydrocarbon, C 1 ~ C 30, C} 1 ~ C 30 Linear or branched C ₁ to C ₁₈ alkyl groups or linear containing any one or more functional groups selected from the group consisting of aromatic cyclic compounds, halogens, azides, amines, ketones, ethers, amides, esters, triazoles and isocyanates or branched and branched aliphatic unsaturated hydrocarbon of C ₁ ~ C _18, n is an integer from 1-3.

The purification step of step 1) is preferably carried out in a column chromatography, the step 2) is preferably carried out at 10 to 30 ℃.

The acid is preferably selected from the group consisting of HCl, H ₂ SO ₄ , HNO _{3 ,} Sc (OTf) ₃ , In (OTf) ₃ , Zn (OTf) ₃ , Yb (OTf) ₃ and Eu (OTf) ₃ . Use one or more of them.

It is also possible to further include a step of stirring for preferably 5 minutes to 5 hours after the step 2).

Preferably, before step 1) or after step 2), the method may further include introducing an organic group to R ₆ .

The organic group may preferably include any one or more selected from the group consisting of amino acids, proteins, chiral compounds and natural compounds.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a surface-modified ITO glass characterized in that the surface of the ITO glass is modified by reacting an silane compound having an allyl or allyl derivative represented by the following formula (1) to an ITO glass in an organic solvent.

[Formula 1]

Provided that R ₁ to R ₅ are H or a linear or branched C ₁ to C ₃₀ alkyl group and R ₆ is a linear or branched C ₁ to C ₁₈ alkyl group, a linear or branched C ₁ to C ₃₀ aliphatic group of the cyclic compound of an unsaturated _{hydrocarbon, C 1 ~ C 30, C} 1 ~ C 30 Linear or branched C ₁ to C ₁₈ alkyl groups comprising any one or more functional groups selected from the group consisting of aromatic cyclic compounds, halogens, azides, amines, ketones, ethers, amides, esters, triazoles and isocyanates, or Linear or branched C ₁ to C ₁₈ aliphatic unsaturated hydrocarbons, n is an integer from 1 to 3.

In the case of the ITO glass used in the present invention, conventional ones generally used in the electronics industry or sensors can be used.

The silane compound having an allyl or allyl derivative of the present invention may be applied to the case where allyl or allyl derivatives are substituted with one to three silicon atoms in the silicon atom as shown in Formula 1 above, but preferably, the efficiency of the methallyl silane compound This is the best.

The functional group of the silane compound having the allyl or allyl derivative (R ₆₎ can be introduced into a group different organic through a series of chemical reactions (for example, S _N 1, 2 reaction, the click chemistry, star right dinggeo ligation, etc.) Any functional group is applicable, but preferably, linear or branched C ₁ to C ₁₈ alkyl group, linear or branched C ₁ to C ₃₀ aliphatic unsaturated hydrocarbon, C ₁ to C ₃₀ cyclic compound , C ₁ ~ C ₃₀ Linear or branched C ₁ to C ₁₈ alkyl groups or linear containing any one or more functional groups selected from the group consisting of aromatic cyclic compounds, halogens, azides, amines, ketones, ethers, amides, esters, triazoles and isocyanates Or branched C ₁ to C ₁₈ aliphatic unsaturated hydrocarbons are mainly used, more preferably the alkyl group is a propyl group, and more preferably, the propyl group contains a functional group, which is highly efficient considering the reactivity and manufacturing cost. . Meanwhile, the aliphatic unsaturated hydrocarbons include alkenes and alkynes.

After all, the present invention is to introduce a variety of organic groups to the ITO glass by substituting a variety of organic groups in the above-described substitutable functional group, to modify the surface of the ITO glass by introducing a variety of desired organic groups to the ITO glass through an appropriate organic reaction. In particular, since the present invention can be carried out at room temperature, it is also useful for introducing high temperature compounds, such as natural compounds, proteins, amino acids, and chiral compounds that are difficult to separate and purify. Furthermore, R ₆ is The organic group may be introduced through an organic reaction by appropriately selecting the organic group to be introduced. In this case, the organic group may be introduced through one or several organic reactions.

Meanwhile, the organic group introduced in the present invention may first introduce the organic group into a silane compound having an allyl or allyl derivative, and then react with the ITO glass, or conversely, after reacting the silane compound having an allyl or allyl derivative with an ITO glass, It can also be introduced. In other words, first, a desired organic group is introduced into R ₆ of the allyl or allyl derivative having an allyl derivative of the present invention and subjected to purification means such as column chromatography, followed by reaction with ITO glass, or ITO glass and the allyl or allyl derivative. After the reaction with the silane compound having the desired organic group may be introduced into R ₆ .

The present invention, unlike the synthetic method of proceeding the reaction by refluxing at a high temperature with a conventional toluene solvent as a solvent can be combined with various organic groups on the surface of the ITO glass even if the reaction at room temperature using an acid catalyst. The acid that can be used as a catalyst in the present invention is not particularly limited, but preferably, Lewis acid is used. Specifically, + trivalent cations such as Sc (OTf) ₃ , In (OTf) ₃ , Zn (OTf) ₃ , Yb (OTf) ₃ , Eu (OTf) ₃ , protons (H ⁺ ) from HCl, and the like are used. More preferably, the reaction activity of Sc (OTf) ₃ is the best. The mechanism of this reaction is that the hydroxyl group of ITO glass or alcohol increases acidity by Lewis acid, and the metaallyl group of silane compound having allyl or allyl derivative is removed in the form of isobutene. It is expected.

The reaction temperature of the present invention is not particularly limited and the reaction yield is high even at a high temperature, but preferably the reaction may proceed actively at 0 to 60 ° C., more preferably at 10 to 30 ° C. without the reflux or heating process. have. As a result, the present invention uses a highly active acid, especially Lewis acid, as a catalyst to improve the reaction yield even at room temperature, and is very effective for introducing temperature-sensitive organic groups into ITO glass, thus simplifying the reaction process and reducing the production cost. It is advantageous.

The organic solvent of the present invention can be used both polar and nonpolar solvents, but preferably at least one selected from the group consisting of alcohol, toluene, benzene, dimethylformamide (DMF) and acetonitrile, more preferably For example, ethanol is used for protic acid and acetonitrile is good for Lewis acid.

After all, the present invention, unlike conventional methods using alkoxysilanes or chlorosilanes, since the metaallylsilane or allylsilane used in the present invention does not react with ITO glass at room temperature, it can be purified by column chromatography. Therefore, even if it is possible to make a metaallylsilane combined with an organic compound having a large molecular weight so that fractional distillation is impossible, it is possible to purify by column chromatography. Since they are activated and reacted with an acid catalyst even at room temperature, when an organic catalyst containing various organic groups can be introduced into the ITO glass when the acid catalyst is desired to be introduced into the ITO glass.

In the method for modifying the surface of the ITO glass according to another feature of the present invention, 1) purifying the silane compound having an allyl or allyl derivative represented by the following formula (1), and 2) the silane purified on the ITO glass Mixing the compound, acid and organic solvent.

[Formula 1]

Provided that R ₁ to R ₅ are H or a linear or branched C ₁ to C ₃₀ alkyl group and R ₆ is a linear or branched C ₁ to C 18 alkyl group, a linear or branched C ₁ to C ₃₀ aliphatic unsaturated hydrocarbon , C ₁ ~ C ₃₀ cyclic compounds, C ₁ ~ C ₃₀ Linear or branched C ₁ to C ₁₈ alkyl groups or linear containing any one or more functional groups selected from the group consisting of aromatic cyclic compounds, halogens, azides, amines, ketones, ethers, amides, esters, triazoles and isocyanates or branched and branched aliphatic unsaturated hydrocarbon of C ₁ ~ C _18, n is an integer from 1-3.

The purification step of step 1) may use an appropriate reaction to obtain a silane compound having the desired allyl or allyl derivative, and the silane compound subjected to the reaction may use a conventional purification method, but preferably Purification by chromatography.

In the mixing step of step 2), the purified silane compound, acid and organic solvent are appropriately mixed with ITO glass. In this case the acid is preferably from the group consisting of HCl, H ₂ SO ₄ , HNO _{3 ,} Sc (OTf) ₃ , In (OTf) ₃ , Zn (OTf) ₃ , Yb (OTf) ₃ and Eu (OTf) ₃ . Any one or more selected may be used, and a separate heating or reflux reaction may be performed. Preferably, the reaction may be performed at 10 to 30 ° C. without performing the heating and reflux reaction.

After step 2), preferably, the method may further include stirring the mixture for 5 minutes to 5 hours according to the type of the silane compound and the organic group introduced therein.

Preferably, before step 1) or after step 2), the method may further include introducing an organic group to R ₆ . The organic group may preferably include any one or more selected from the group consisting of amino acids, proteins, chiral compounds and natural compounds.

Hereinafter, the present invention will be described in detail by way of examples. The following examples are merely to illustrate the invention, but the scope of the present invention is not limited to the following examples.

<Examples 1-3: Synthesis of dodecyldimethylmethallyl-silane derivative>

<Example 1>

After drying the reaction vessel in Scheme 1 and filled with nitrogen and H ₂ PtCl ₆ (308 mg, 0.63 mmol) was added to the reaction vessel and 30 ml of THF was added. 1-dodecine (4.3 g, 25.36 mmol) was added and chlorodimethyl-silane (2.0 g, 21.14 mmol) was added slowly, and the temperature was raised to 70 ° C. at room temperature and stirred for 2 hours. After the reaction was completed, 60 ml of 1.0 M methallyl magnesium chloride was added, followed by stirring for 2 hours. After the reaction, the organic layer was extracted using NH ₄ Cl aqueous solution and ether, and washed with saturated NaCl. Water was removed using anhydrous MgSO ₄ , and then passed through celite to filter MgSO ₄ , removing solvent, and fractional distillation under reduced pressure to remove 1-dodecine remaining without reaction. The remaining mixture was purified by column chromatography (n-Hex: EA = 10: 1, Rf = 0.80) to give 2.0 g (33% yield) of pure dodecyldimethylmethallyl-silane (14).

14 : ¹ H NMR (250 MHz, CDCl ₃ ) (ppm) 4.56-4.46 (d, J = 27.7 Hz, 2H), 1.97 (q, 3H), 1.27 (s, 25H), 0.52 (m, 2H); ¹³ C NMR (62.9 MHz, CDCl ₃ ) (ppm) 143.3, 108.2, 33.9, 32.2, 30.0, 29.6, 27.5, 25.5, 24.1, 23.0, 15.7, 14.4, -1.8; IR spectrum (neat) 3414, 3072, 2918, 2852, 1739, 1635, 1455, 1382, 1170, 1062, 873, 792; MS m / z (% relative intensity) 282 (M ⁺ , 0.2), 267 (1), 227 (54), 211 (0.7), 199 (0.7), 185 (0.5), 171 (1), 157 (2 ), 141 (7), 127 (14), 113 (20), 99 (28), 87 (20), 73 (25), 59 (100), 43 (10); Anal. Calcd for C ₁₈ H ₃₈ Si: C, 76.51; H, 13.55; found: C, 77.04; H, 13.32

<Example 2>

2.0 g (17.4 mmol) of dichloromethylsilane was used as in Scheme 2, and the remainder was reacted in the same manner as 14 in Scheme 1 of Example 1 to 2.6 g (51% yield) of pure dodecylmethyldimethalyl- Silane (15) was obtained.

15 : ¹ H NMR (250 MHz, CDCl ₃ ) (ppm) 4.60-4.49 (d, J = 27.3 Hz, 4H), 1.72 (s, 6H), 1.58 (s, 4H), 1.26 (s, 20H), 0.91 (t, J _ab = 11.9 Hz, J _bc = 6.2 2H), 0.04 (s, 3H); ¹³ C NMR (62.9 MHz, CDCl ₃ ) (ppm) 143.8, 108.9, 34.0, 32.2, 31.9, 29.9, 29.6, 25.9, 25.6, 24.0, 23.0, 14.4, -4.2; IR spectrum (neat) 3084, 2971, 2930, 2863, 1639, 1465, 1378, 1281, 1260, 1163, 979, 876, 845; MS m / z (% relative intensity) 322 (M ⁺ , 0.4), 307 (0.4), 267 (24), 251 (0.5), 239 (0.3), 225 (26), 211 (2), 197 (0.5 ), 182 (0.4), 169 (0.4), 154 (12.3), 139 (1), 127 (3), 113 (7), 99 (100), 85 (6), 71 (10), 59 (11 ), 43 (6); Anal. Calcd for C ₂₁ H ₄₂ Si: C, 78.17; H, 13. 12; found: C, 78.11; H, 13.32

<Example 3>

Dodecyltrichloro-silane (3.0 g, 9.87 mmol) was dissolved in THF 20 ml as in Scheme 3, 100 ml of 1.0 M metaallyl magnesium chloride was added, and the mixture was stirred at room temperature for 2 hours. After the reaction, the organic layer was extracted using NH ₄ Cl aqueous solution and ether, and washed with saturated NaCl. Water was removed using anhydrous MgSO ₄ , passed through celite to filter MgSO ₄ , solvent removed, and purified by column chromatography (n-Hex: EA = 10: 1, Rf = 0.80) to 5.3g (88% yield). Pure dodecyltrimethallyl-silane (16) Got it.

16 : ¹ H NMR (250 MHz, CDCl ₃ ) (ppm) 4.64-4.54 (d, J = 23.0 Hz, 6H), 1.74 (s, 9H), 1.26 (s, 24H), 0.86 (t, J = 6.4Hz , 3H), 0.60 (t, J = 7.8 Hz, 2H); ¹³ C NMR (62.9 MHz, CDCl ₃ ) (ppm) 143.3, 109.7, 34.1, 32.2, 30.1, 25.9, 24.3, 23.9, 23.0, 14.4, 13.5 IR spectrum (neat) 3414, 3072, 2918, 2852, 1739, 1635 , 1455, 1382, 1170, 1062, 873, 792; Anal. Calcd for C ₂₄ H ₄₆ Si: C, 79.47; H, 12.78; found: C, 79.19; H, 12.95

<Examples 4 to 6>

<Example 4>

In order to covalently bond various metaallyl-silane derivatives synthesized above to ITO glass to indium tin oxide (ITO) glass, which is mainly used in electronic sensors or semiconductors, it is necessary to go through the activation step of making the surface of ITO with -OH group. Same as ITO glass was soaked in pirahna solution made by slowly adding H ₂ SO ₄ and H ₂ O ₂ in a ratio of 3: 1 for about 30 minutes, and then washed with ethanol and distilled water to clean the surface of ITO glass with hydroxyl group (-OH). Make it. When the pretreatment is performed, the surface of the glass becomes hydrophilic due to the hydroxyl (hydroxyl) of the surface. As shown in FIG. 1, droplets are dropped on the surface to measure the contact angle between the glass surface and the droplet. 58.1 °. The dodecyldimethylmethallyl-silane derivative was reacted on the surface of the thus prepared ITO glass as in Scheme 4 below.

As shown in Scheme 4, 423 mg (1.5 mmol) of dodecyldimethylmethallylsilane (14 in Scheme 1) was added to 2 mol% HCl (4 mg) in 2 ml ethanol, followed by reaction with ITO glass for 2 hours, and the same amount of metaallylsilane. Was reacted with 2 mol% Sc (OTf) ₃ (15 mg) in 2 ml acetonitrile solvent and then the two contact angles were compared. As a result, when 2 mol% HCl was used as the acid catalyst, the contact angle was 78.6 ° as shown in FIG. 2, but when Sc (OTf) ₃ was used, the contact angle was 81.5 ° as shown in FIG. 3. In both cases, the surface of the ITO glass showed hydrophobicity due to the dodecyl group attached, but it was found that it was more effective to react with Sc (OTf) ₃ than with HCl as the acid catalyst.

Example 5

As in Scheme 5, the experiment was carried out in the same manner as in Example 82, except that dodecylmethyldimethallyl-silane (15 of Scheme 2) (483 mg, 1.5 mmol) was used instead of dodecyldimethylmethallyl-silane. Was performed to compare contact angles. As a result, when using 2 mol% HCl as an acid catalyst as shown in FIG. 4, it was 79.7 °, but when using 2 mol% Sc (OTf) ₃ as shown in FIG. 5, the contact angle was 84.9 °. This suggests that Sc (OTf) ₃ is more active than HCl.

<Example 6>

Except for using dodecyltrimethallyl-silane (16 in Scheme 3) (544mg, 1.5mmol) in place of dodecyldimethylmethallyl-silane, the experiment was carried out in the same manner as in Example 4 to compare the contact angle. As a result, in the case of using 2 mol% HCl in FIG. 6, 76.6 ° was shown. However, when 2 mol% Sc (OTf) ₃ was used as shown in FIG. 7, the contact angle was 77.3 °, indicating that Sc (OTf) ₃ was hydrochloric acid. It was confirmed that the more active.

<Example 7>

17 Synthesis of Scheme 7

Pyridine (0.08 mL, 2.53 mmol) was added to omega-undecynyl alcohol (10 g, 58.7 mmol), SOCl ₂ (4.7 mL) was slowly added at 25 ° C. for 5 minutes, and then refluxed at 65 ° C. for 5 hours. . This was extracted with methylene chloride and water and then distilled to give 11 g (98% yield) of pure omega-undecynylchloride (17).

17 : ¹ H NMR (250 MHz, CDCl ₃ ) (ppm) 5.87-5.73 (m, 1H), 5.04-4.91 (t, 2H), 3.56-3.51 (t, J = 6.78, 2H), 2.08-2.00 (q , J _{ab =} 6.7 Hz, J _bc = 7.1, J _cd = 6.9 2H), 1.82-1.71 (q, J _ab = 6.7 Hz, J _bc = 6.8, J _cd = 7.8, J _de = 6.8, 2H), 1.29 (s, 12H)

18 Synthesis of Scheme 7

The trichlorosilane (5.35 mL, 53 mmol) was added and the temperature was raised to 90 ° C. at room temperature, and then a mixture of t -butyl perbenzoate and omega-undecynyl chloride (16 g, 26.5 mmol) was slowly added. It was refluxed for 12 hours after the addition. The reaction mixture was then distilled to yield 1.5 g (90% yield) of pure 11-chloroundecynyl-trichloro-silane (18).

<Synthesis of 19 of Scheme 7>

The 11-chloroundecyl-trichloro-silane (18) (9.5 g, 104.9 mmol) was reacted with metaallyl-magnesium chloride at 0 ° C., and then the temperature was raised to room temperature, followed by further stirring for 2 hours. The organic layer was extracted with saturated NH ₄ Cl aqueous solution and ether, separated by column chromatography (n-Hex: EA = 20: 1, Rf = 0.74) to give 4.3 g (92% yield) of pure 11-chloroundecynyl. -Trimethallyl-silane (19) was obtained.

19 : ¹ H NMR (250 MHz, CDCl ₃ ) (ppm) 4.64-4.58 (d, J = 17.5 6H), 3.56-3.50 (t, J = 13.5, 2H), 1.74 (s, 9H), 1.67 (s, 6H), 1.27 (s, 18H), 0.66-0.60 (m, 2H)

20 Synthesis of Scheme 7

11-Chloroundecyl-trimethallyl-silane (19). Dimethylformamide (DMF) was added to (1000 mg, 2.61 mmol) and sodium azide (340 mg, 5.22 mmol), filled with nitrogen gas, and refluxed for 2 hours. After the reaction, dimethylformamide (DMF) was removed using distilled water and ether, and the organic layer was extracted. The organic layer was removed with anhydrous MgSO ₄ , filtered through Celite, the solvent was removed, and purified by column chromatography (n-Hex: EA = 10: 1, Rf = 0.6) to give 905 mg (89% yield) of pure water. 11-azidoundecynyl-trimethallyl-silane (20) was obtained.

20 : ¹ H NMR (250 MHz, CDCl ₃ ) (ppm) 4.64-4.58 (d, J = 17.5 6H), 3.28-3.23 (t, J = 6.9, 2H), 1.74 (s, 9H), 1.57 (s, 6H), 1.27 (s, 18H), 0.66-0.60 (m, 2H)

21 Synthesis of Scheme 7

The mixed solution of THF and water in 1-azidoundecynyl-trimethallylsilane (20) (900 mg, 2.31 mmol) and ethylene ferrocene (ethynyl ferrocene) (533.6 mg, 2.54 mmol) (THF: H ₂ O = 1: 1) 2mL of CuSO ₄ ㅇ 5H ₂ O (29mg, 0.116mmol) and Na ascorbate (45.8mg, 0.231mmol) were added and stirred at room temperature for 12 hours. After the reaction, the organic layer was extracted using distilled water and ether, and then separated by column chromatography (n-Hex: EA = 1: 1, Rf = 0.5) to obtain 1360 mg (98% yield) of pure ferrosine derivative (21).

21: HR-MS: m / z cacld for C ₁₅ H ₂₉ NSi [M + H] ⁺ = 599.3359 found: 599.3365

<Example 8>

In order to apply the ferrosine derivative (21 in Scheme 7) synthesized in Example 7 to ITO (Indium Tin Oxide) glass, piranha was first made by slowly adding H ₂ SO ₄ and H ₂ O ₂ in a ratio of 3: 1. The ITO glass was soaked in pirahna solution for about 30 minutes and washed with ethanol and distilled water to activate the surface of ITO glass with hydroxyl (-OH). Ferrocene derivatives in ITO glass pretreated with piranha solution (21 in Scheme 7) (500mg, 0.834mmol) was added to HCl (9mg, 50mol%) with 2ml of ethanol as an acid catalyst as shown in Scheme 8, and shaken for 2 hours. The results of the experiment by cyclic voltammetry are shown in FIG. 8. .

      As shown in FIG. 8, the oxidative-reduction reaction was confirmed from the cyclic switching ammeter test results. Through this, the characteristics of the ferrocin-immobilized ITO glass were confirmed.

The present invention uses an acid as a catalyst in a method of introducing an organic group to an ITO glass using a silane compound having an allyl or metaallyl derivative, thereby increasing the activity of the reaction and effectively introducing the organic group even at room temperature. Therefore, it is very effective for introducing heat-sensitive organic groups such as natural compounds and proteins. In addition, since allyl or methallyl derivatives are stable compounds at room temperature, they have the advantage of easy separation and purification using a silica gel column.

Although the present invention has been described in detail only with respect to the embodiments described, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical spirit of the present invention, and such modifications and variations belong to the appended claims. .

Claims (18)

delete delete delete delete delete delete delete delete delete delete delete In the method of modifying the surface of the ITO glass, 1) purifying a silane compound having an allyl or allyl derivative represented by Formula 1 below; And 2) mixing the purified silane compound, acid and organic solvent in the ITO glass at 0 ~ 60 ℃; surface modification method of the ITO glass comprising a. [Formula 1]

Provided that R ₁ to R ₅ are H or a linear or branched C ₁ to C ₃₀ alkyl group and R ₆ is a linear or branched C ₁ to C ₁₈ alkyl group, a linear or branched C ₁ to C ₃₀ aliphatic group of the cyclic compound of an unsaturated _{hydrocarbon, C 1 ~ C 30, C} 1 ~ C 30 Linear or branched C ₁ to C ₁₈ alkyl groups or linear containing any one or more functional groups selected from the group consisting of aromatic cyclic compounds, halogens, azides, amines, ketones, ethers, amides, esters, triazoles and isocyanates or branched and branched aliphatic unsaturated hydrocarbon of C ₁ ~ C _18, n is an integer from 1-3. The method of claim 12, The purification step of step 1) is the surface modification method of the ITO glass, characterized in that made in the column chromatography. The method of claim 12, The step 2) is the surface modification method of the ITO glass, characterized in that at 10 to 30 ℃. The method of claim 12, The acid is any one or more selected from the group consisting of HCl, H ₂ SO ₄ , HNO _{3 ,} Sc (OTf) ₃ , In (OTf) ₃ , Zn (OTf) ₃ , Yb (OTf) ₃ and Eu (OTf) ₃ . Surface modification method of the ITO glass, characterized in that. The method of claim 12, Method for surface modification of the ITO glass, characterized in that further comprising the step of stirring for 5 minutes to 5 hours after the step 2). The method of claim 12, The surface modification method of the ITO glass, characterized in that further comprising the step of introducing an organic group to the R ₆ before or after step 1). The method of claim 17, The organic group surface modification method of the ITO glass, characterized in that any one or more selected from the group consisting of amino acids, proteins, chiral compounds and natural compounds.

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