JP2856926B2 - Organosilicon compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel silicon compound.

[0002]

2. Description of the Related Art Heretofore, photochromic compounds which exhibit a color change upon irradiation with light have been attempted to be applied as photosensitive materials. Among many organic photochromic compounds, spiropyran compounds, particularly nitro-substituted benzospiropyran compounds, are well known, and many derivatives have been synthesized. However, the spiropyran compound has a problem in terms of light durability such that photochromism is lost by long-time ultraviolet irradiation or alternate irradiation of ultraviolet and visible light.

On the other hand, spirooxazine compounds having better durability than spiropyran compounds have been actively studied for practical use. For example, studies have been conducted to improve the light durability by dispersing spirooxazine in a polymer or copolymerizing spirooxazine having a polymerizable group with a polymerizable monomer. Products using spirooxazine, such as photochromic ink and photochromic fiber, are also on the market.

Heretofore, no organosilicon compound containing spirooxazine and capable of easily bonding to a reactive hydroxyl group or amino group by a dealkoxylation reaction has been known at all. There is also no known photochromic material produced by using.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an organosilicon compound which has photochromic activity and can be easily bonded to a reactive hydroxyl group or amino group by a dealkoxylation reaction.

[0006]

Means for Solving the Problems The present inventors have been conducting synthesis and application studies of various functional organosilicon compounds for many years. As a result, a novel and useful organosilicon compound was synthesized, its structure and use were confirmed, and the present invention was completed.

That is, the present invention provides a compound represented by the general formula (I)

Embedded image (Wherein R ¹ and R ² are lower alkyl groups, R ³ is an alkylene group having 2 to 8 carbon atoms, R ⁴ and R ⁵
Is a hydrogen atom, a halogen atom, a methyl group, a methoxy group, X is an NHCOO group or an NHCO group, and m is 3,
4 or 11, and n is an integer of 1 to 3. ) Is provided.

In the above general formula (I), lower alkyl groups represented by R ¹ and R ² are generally alkyl groups having 1 to 3 carbon atoms such as methyl group, ethyl group and propyl group because of their availability and easy handling. Is preferably used. In addition, the general formula (I)
R ^{3 in the above} is an alkylene group having 2 to 8 carbon atoms. Specific examples of the alkylene group include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group,
Examples thereof include a linear or branched alkylene group such as a heptylene group and an octylene group. In the general formula (I), R ⁴
And the halogen atom represented by R ⁵ are a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In general, the organosilicon compound of the present invention can be confirmed to be a compound represented by the above general formula by the following means (a) to (d). (A) The structure specific to the organosilicon compound of the present invention can be known by measuring the infrared absorption spectrum (IR). For example, absorption based on an NH bond around 3300 to 3400 cm, absorption based on a CH bond around 3000 to 2900 cm, and around 1720 cm (in the case of carbamate)
Alternatively, absorption based on a CＯO group is observed around 1640 cm (in the case of an amide), and absorption based on a Si—O bond is observed around 1100 to 1060 cm.

(B) ¹ H-nuclear magnetic resonance spectrum ( ¹ H-
NMR), it is possible to know the number and bonding mode of hydrogen atoms in the organosilicon compound of the present invention. ¹ H-NMR of the compound represented by the general formula (I)
As a representative example of (δ; ppm, based on tetramethylsilane, in a CDCl ₃ solvent), the analysis results of the following compounds are as follows.

[0011]

Embedded image δ (ppm) = 8.55 (d.1H, J = 7.6 Hz, k) 7.8-6.6 (m.10H, j) 5.1-4.6 (br.1H, f) 4 .25 (t.2H, J = 5.9 Hz, g) 3.80 (q.6H, J = 7.0 Hz, b) 3.46 (t.2H, J = 6.4 Hz, e) 3.07 (T.2H, J = 5.9 Hz, h) 2.0-1.4 (m.2H, d) 1.32 (s.6H, i) 1.21 (t.9H, J = 7.0 Hz) , A) 0.57 (t.2H, J = 6.7 Hz, c)

(C) The mass spectrum (MS) is measured and the composition formula of each observed peak (in the general formula, the mass number represented by m / e obtained by dividing the molecular weight of the ion by the charge number e) is calculated. Thereby, the molecular weight and the binding mode of the sample subjected to the measurement can be estimated. That is, the molecular weight and binding mode of the sample subjected to the measurement can be estimated. That is,
When the sample subjected to the measurement is represented by the general formula (I),
Since a molecular ion peak (M ⁺ ) or M ⁺ +1 is generally observed, the molecular weight of the compound used for the measurement can be determined. Further, with respect to the compound of the present invention represented by the above general formula (I), M ⁺ -CH ₃ , M ⁺ -OR ¹ , M ^+
+ -(R ₃ ) naphthooxazine, M ⁺ -(R ¹ O)
A characteristic peak corresponding to _n (R ² ) _3-n Si (CH ₂ ) _m X is observed, and the binding mode of the molecule can be known.

(D) Carbon, hydrogen, nitrogen,
The weight percent of oxygen can be calculated by determining each weight percent of silicon (or halogen, if containing halogen), and further subtracting the sum of the recognized weight percents of each element from 100.
Therefore, the composition formula of the sample subjected to the measurement can be determined.

The properties of the organosilicon compound represented by the above general formula slightly vary depending on R ¹ , R ² , R ₃ , R ⁴ , R ⁵ , X, m, n and the degree of purification. It is a blue to pale green viscous liquid or a white to pale yellow solid. The compound is soluble in common organic solvents such as benzene, alcohol and ether. Furthermore, the organosilicon compound of the present invention exhibits excellent photochromic activity, as is apparent from the examples described later.

The method for producing the organosilicon compound of the present invention is not particularly limited. Any method may be used. A typical production method generally preferably used will be described. When X in the general formula (I) is a carbamate compound in which NH is a NHCOO group, the following general formula:

Embedded image (However, the definitions of R ¹ , R ² , m and n are the same as those described above), and the following general formula:

[0016]

Embedded image (However, the definition of R ₃ , R ^4, and R ⁵ is as described above.) The desired organosilicon compound of the present invention can be obtained by reacting with a spironaphthoxazine compound represented by the formula:

Although the molar ratio of the above reaction is not particularly limited, it is usually preferable to carry out the reaction in equimolar amounts. It is preferable to use a reaction solvent for the above reaction, and examples thereof include benzene, toluene, ethanol, and chloroform. Reaction temperature is 0 to 150 ° C, especially 20 to 100 ° C
Is preferred. Although the reaction time varies depending on the reaction temperature, it can be generally selected from several minutes to several days.

The means for adding a catalyst to promote the above reaction is often suitably used. Examples of the catalyst in the reaction include organic tin compounds such as dibutyltin maleate, tributyltin acetate, dibutyltin laurate, N-methylmorpholine, triethylamine, and the like.
Tertiary amine compounds such as pyridine are useful. The addition amount is preferably 0.001 to 10% by weight, particularly preferably 0.1 to 5% by weight based on the isocyanate alkylsilane compound.

The following manufacturing method is also preferably used.
That is, the following general formula

Embedded image (However, the definitions of R ¹ , R ² , m and n are as described above), and an aminoalkylsilane compound represented by the following general formula:

[0020]

Embedded image (However, the definition of R ₃ , R ^4, and R ⁵ is as described above.) The desired organosilicon compound of the present invention can be obtained by reacting with a spironaphthoxazine compound represented by the formula:

The molar ratio of the above reaction is not particularly limited, but it is usually preferable to carry out the reaction in equimolar amounts. It is preferable to use a reaction solvent for the above reaction, and examples thereof include benzene, toluene, ether, and chloroform. The reaction temperature is preferably from 0 to 150C, particularly preferably from 0 to 100C. Although the reaction time varies depending on the reaction temperature, it can be generally selected from several minutes to several days.

In the above reaction, since hydrogen chloride is by-produced, it is usually preferable to use a hydrogen chloride scavenger. The capturing agent is not particularly limited, and a known agent can be used. Examples of the scavenger generally preferably used include triethylamine, pyridine, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and the like.

In the general formula (I), X is NH
In the case of an amide compound having a CO group, the following production method is suitably used. That is, the following general formula

Embedded image (However, the definitions of R ¹ , R ² , m and n are as described above), and an aminoalkylsilane compound represented by the following general formula:

[0024]

Embedded image (However, the definitions of R ³ , R ⁴ and R ⁵ are as described above,
Y is a chlorine atom, a hydroxyl group or a lower alkoxy group. ), The desired organosilicon compound of the present invention can be obtained.

The molar ratio of the above reaction is not particularly limited, but it is usually preferable to carry out the reaction in an equimolar amount. It is preferable to use a reaction solvent for the above reaction, and examples thereof include benzene, toluene, ether, and chloroform. The reaction temperature is preferably from 0 to 150C, particularly preferably from 0 to 100C. Although the reaction time varies depending on the reaction temperature, it can be generally selected from several minutes to several days.

In the above reaction, when the substituent Y of the spironaphthoxazine compound is a carboxylic acid chloride in which the substituent Y is a chlorine atom, hydrogen chloride is by-produced. Therefore, it is usually preferable to use a hydrogen chloride scavenger. The capturing agent is not particularly limited, and a known agent can be used. Examples of the scavenger generally preferably used include triethylamine, pyridine, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and the like.

When the substituent Y of the spironaphthoxazine compound in the above reaction is a hydroxyl group, the reaction is a dehydration condensation reaction, and it is usually preferable to use a dehydrating agent. The dehydrating agent is not particularly limited, and a known dehydrating agent can be used. Examples of the dehydration method generally preferably used include a method using a carbodiimide represented by dicyclohexylcarbodiimide, a method using azeotropic distillation, a method using a dehydrating agent such as molecular sieves, anhydrous sodium sulfate and anhydrous magnesium sulfate, and the like. Can be

Further, in the above reaction, when the substituent Y of the spironaphthooxazine compound is an alkoxy group, the above reaction is an aminolysis reaction of an ester, and it is usually desirable to use an ester activator. The activator is not particularly limited, and a known activator can be used. Activators generally preferably used include sodium methoxide, pyridine, dimethylaminopyridine, 1,8-
Diazabicyclo [5.4.0] undec-7-ene, triethylamine, 1,4-diazabicyclo [2.2.
2] octane and the like.

Since the organosilicon compound of the present invention contains an alkoxysilyl group which is liable to be condensed by hydrolysis in the molecule, it can be hydrolyzed alone or together with another organic or inorganic silicon compound to obtain a polycycloxane derivative or The silyl group-containing silicon compound can be obtained. The hydrolysis reaction proceeds at room temperature in water or a mixture of water and an organic solvent such as alcohol, benzene and the like. The rate of the hydrolysis reaction can be accelerated by heating or by adding a small amount of acid or base to the reaction system.

Further, the organosilicon compound can be easily attached to the surface by reacting with a substance having a hydroxyl group or an amino group capable of reacting with the compound, and various photochromic materials can be produced. .

As the substance having a reactive hydroxyl group or amino group to be reacted with the organosilicon compound represented by the general formula (I), inorganic or organic substances having various shapes such as film, powder, fibrous, lump, etc. Is mentioned. Specific examples of the substance include silica, alumina, zirconia,
Inorganic oxides such as tin oxide, silica-alumina and silica-titania; and inorganic substances such as silica gel, glass and quartz; and organic substances such as paper, cellulose, chitosan, polysaccharides, polyvinyl alcohol and polyallylamine.

The method of reacting the organosilicon compound represented by the general formula (I) with a substance having a reactive hydroxyl group or an amino group may be any method. For example, a commonly used method such as a solution method, a dipping method, a spray method, and a spin coating method may be used.

In general, in the condensation reaction, an organic silicon compound and a substance having a reactive hydroxyl group or amino group are heated and dried in the presence or absence of a general organic solvent such as alcohol, benzene, toluene, chloroform, and tetrahydrofuran. It can be done by doing. At that time, the heating temperature and the heating time are determined by the properties of the substance used. The reaction rate of the reaction is increased by adding an acid or a base to the system.

The organosilicon compound represented by the above general formula can also be prepared by removing the corresponding alkoxy group in an aqueous alcohol solution in the presence or absence of an acid such as hydrochloric acid, acetic acid or phosphoric acid. The same reaction can be performed.

[0035]

The organosilicon compound provided by the present invention has a photochromic activity and is therefore a useful raw material as a photochromic material. The photochromic material obtained by using the organosilicon compound of the present invention as a raw material is a useful material that can be used for fibers, toys, sunglasses, recording materials, display materials, paints, light variable materials, and the like.

[0036]

EXAMPLES The present invention will be described in more detail with reference to the following examples and application examples, but the present invention is not limited to these examples and application examples. Example 1 16 g of 2,3,3-trimethylindolenine and 12.5 g of ethylene bromohydrin were stirred at 80 ° C for about 5 hours until the system was solidified. The resulting solid was poured into an aqueous sodium carbonate solution at room temperature, and the aqueous layer was extracted with ether. After the organic layer was washed with water and dried over magnesium sulfate, the solvent was distilled off to obtain a crude product. This was distilled under reduced pressure (113 ° C /
Purification at 3 mmHg) yielded 17 g (85%) of trimethylindolinoxoxazolidine. Next, 14 g of 1-nitro-2-naphthol was added to 100 ml of ethanol, and dissolved by heating and stirring. To this solution, 16.4 g of trimethylindolinoxoxazolidine and 9 g of triethylamine were added, and the mixture was refluxed for 5 hours. Thereafter, ethanol was distilled off under reduced pressure to obtain a dark red to black crude product. Column chromatography (SiO ₂ , 500 80 mmφ, eluate phH)
With 1- (2-hydroxyethyl) -3,3-dimethylspiro [indoline-2,3'-naphtho (2,1-b)]
The fraction containing [1,4] oxazine) was separated. When this fraction was concentrated, a solid precipitated. The solid was taken out and recrystallized from ethanol repeatedly to give 1- (2-hydroxyethyl) -3,3-dimethylspiro [indoline-2,3'-naphtho (2,1-b).
(1,4) oxazine] was obtained as pale yellow crystals. 1 g of this compound and 0.69 g of 3-isocyanatopropyltriethoxysilane were dissolved in 50 ml of hot toluene, and a small amount of dibutyltin maleate was added as a catalyst and refluxed. During reflux, the solution developed a deep blue color. After confirming the end of the reaction by IR based on the absorption of isocyanate, toluene was distilled off under reduced pressure. Column chromatography (SiO ₂ , 150
× 30 mmφ, phH → Ether) to obtain 1.45 g of a blue viscous liquid compound. ¹ H-N for this compound
The following results were obtained by conducting MR, IR and CHN analyses.

[0037]¹ H-NMR (CDCl_Three, TMS) spectrum δ (ppm) = 8.55 (d.1H, -CH = N-) 7.8-6.6 (m.10H, Ph) 5.1-4.6 (br.1H,- NHCOO-) 4.25 (t.2H, -NHCOOCH)_Two−) 3.80 (q.6H, —SiOCH)_Two-) 3.46 (t.2H, -CH_TwoNHCOO-) 3.07 (t.2H, -NCH_Two−) 1.7-1.0 (m.2H, -CH_Two−) 1.44 (s.6H, -CH_Three1.21 (t. 9H, -SiOCH)_TwoCH_Three) 0.57 (t.2H, -CH_TwoSi-) specific IR (neat) spectrum ν (cm^-1) = 3348 (N−H), 1722 (C =
O), 1082 (Si-O) Elemental analysis C: 65.25, H: 6.92, N: 6.99 Calculated C: 65.43, H: 7.15, N: 6.94 (C₃₃H₄₃N_ThreeO ₆ Si₁From the above results, the product obtained is

[0038]

Embedded image It was confirmed to be a compound having a structure represented by

EXAMPLE 2 As in Example 1, 16 g of 2,3,3-trimethylindolenine and 12.5 g of 3-bromo-1-propanol
Was stirred at 80 ° C. for about 10 hours until the system solidified. The resulting solid is treated with an aqueous sodium carbonate solution, and the organic layer is purified by distillation to obtain 1- (3-hydroxypropyl) -3,3.
-Dimethyl-2-methyleneindoline was obtained. This was reacted with 1-nitrone-2-naphthol in ethanol,
By column chromatography and recrystallization, 1- (3-hydroxypropyl) -3,3-dimethylspiro [idrin-2,
3'-naphtho (2,1-b) (1,4) oxazine] was obtained. 1 g of this was reacted with 0.7 g of 3-isocyanatopropyltriethoxysilane in toluene to obtain 1.40 g of a blue-green viscous liquid compound by column chromatography. The compound was subjected to various analyzes in the same manner as in Example 1, and the following results were obtained.

[0040]¹H-NMR spectrum δ (ppm) = 8.60 (d.1H, -CH = N-) 7.9-6.5 (m.10H, Ph) 5.0-4.6 (br.1H,- NHCOO-) 4.28 (t.2H, -NHCOOCH)_Two−) 3.78 (q.6H, —SiOCH)_Two-) 3.50 (t.2H, -CH_TwoNHCOO-) 3.08 (t.2H, -NCH_Two−) 1.7-1.0 (m.4H, -CH_Two−) 1.43 (s.6H, -CH_Three1.22 (t. 9H, -SiOCH)_TwoCH_Three) 0.57 (t.2H, -CH_TwoSi-) specific IR (neat) spectrum ν (cm^-1) = 3348 (N−H), 1722 (C =
O), 1082 (Si-O) Elemental analysis: C: 65.93, H: 7.10, N: 6.55 Calculated: C: 65.88, H: 7.32, N: 6.78 (C₃₄H₄₅N_ThreeO ₆ Si₁From the above results, the product obtained is

[0041]

Embedded image It was confirmed to be a compound having a structure represented by

Example 3 1- (2-hydroxyethyl)-synthesized in Example 1
A solution of 1 g of 3,3-dimethylspiro [indoline-2,3'-naphtho (2,1-b) (1,4) oxazine] and 0.3 g of triethylamine in methylene chloride was cooled under ice-cooling with 0.5 g of diphosgene in methylene chloride. It was dropped into the solution. After completion of the dropwise addition, stirring was continued for about 1 hour under ice cooling, and then a methylene chloride solution of 0.55 g of 3-aminopropylmethyldiethoxysilane and 0.3 g of triethylamine was added dropwise. After completion of the dropwise addition, the temperature was gradually returned to room temperature while stirring was continued, and stirring was continued for about one hour. The methylene chloride was distilled off, and the mixture was extracted with a water-ether system. The organic layer was taken and the solvent was distilled off. The residue was purified by column chromatography to obtain 1.36 g of a blue-green viscous liquid compound. The compound was subjected to various analyzes in the same manner as in Example 1, and the following results were obtained.

[0043]¹H-NMR spectrum δ (ppm) = 8.55 (d.1H, -CH = N-) 7.8-6.5 (m.10H, Ph) 5.5-5.0 (br.1H,- NHCOO-) 4.30 (t.2H, -COOCH)_Two−) 3.78 (q.4H, —SiOCH)_Two−) 3.43 (t. 2H, —CH_TwoNHCOO-) 3.10 (t.2H, -NCH_Two−) 1.7-1.0 (m.2H, -CH_Two−) 1.41 (s.6H, -CH_Three1.18 (t.6H, -SiOCH)_TwoCH_Three) 0.57 (t.2H, -CH_TwoSi-) 0.11 (s.3H, -SiCH)_Three) Specific IR (neat) spectrum ν (cm^-1) = 3348 (N−H), 1722 (C =
O), 1082 (Si-O) Elemental analysis: C: 66.81, H: 6.87, N: 7.53 Calculated: C: 66.75, H: 7.18, N: 7.30 (C₃₂H₄₁N_ThreeO _Five Si₁From the above results, the product obtained is

[0044]

Embedded image It was confirmed to be a compound having a structure represented by

Example 4 As in Example 1, 16 g of 2,3,3-trimethylindolenine and 20 g of 3-iodopropionic acid were heated at 80 ° C. for 1.5 hours. This was poured into ethanol, and 22 g of triethylamine was added and heated and dissolved. This solution was added to an ethanol solution of 1-nitroso-2-naphthol and refluxed for 3 hours. Thereafter, ethanol was distilled off under reduced pressure to obtain a crude product, which was then subjected to column chromatography (SiO ₂ , 50
0 80 mm, Ether) and subsequently recrystallization (E
Purification by tOH or CHCl ₃ ) gave 1- (2-carboxyethyl) -3,3-dimethylspiro [indoline-2,3′-naphtho (2,1-b) (1,4) oxazine]. Next, 1.0 g of this compound and 0.57 g of 3-aminopropyltriethoxysilane were added to methylene chloride 3
The solution was dissolved in 0 ml, and 0.55 g of dicyclohexylcarbodiimide (hereinafter, DCC) was added thereto, followed by stirring. The completion of the reaction was confirmed by IR based on the absorption of carbodiimide, and methylene chloride was distilled off. Column chromatography (SiO ₂ , 150 × 30
mmφ, PhH → Ether) to obtain 1.25 g of a blue-green viscous liquid compound. The compound was subjected to various analyzes in the same manner as in Example 1, and the following results were obtained.

[0046]¹H-NMR spectrum δ (ppm) = 8.55 (d.1H, -CH = N-) 7.8-6.5 (m.10H, Ph) 5.8-5.2 (br.1H,- NHCO-) 3.77 (q.6H, -SiOCH)_Two−) 3.38 (t. 2H, —CH_TwoNHCO-) 3.05 (t.2H, -NCH_Two−) 2.50 (t. 2H, —COCH_Two−) 1.7-1.0 (m.2H, -CH_Two−) 1.31 (s.6H, -CH_Three1.18 (t. 9H, -SiOCH)_TwoCH_Three) 0.54 (t.2H, -CH_TwoSi-) specific IR (neat) spectrum ν (cm^-1) = 3296 (N−H), 1644 (C =
O), 1080 (Si-O) Elemental analysis C: 67.04, H: 7.44, N: 7.11 Calculated C: 67.20, H: 7.35, N: 7.12 (C₃₃H₄₃N_ThreeO _Five Si₁From the above results, the product obtained is

[0047]

Embedded image It was confirmed to be a compound having a structure represented by

Example 5 1- (2-carboxyethyl)-synthesized in Example 4
3,3-Dimethylspiro [indoline-2,3'-naphtho (2,1-b) (1,4) oxazine] and 3-aminopropylmethyldiethoxysilane in methylene chloride
The compound was similarly condensed with CC to obtain a compound having the following structure. Various analytical data obtained for structure confirmation are shown below.

[0049]¹H-NMR spectrum δ (ppm) = 8.53 (d.1H, -CH = N-) 7.9-6.7 (m.10H, Ph) 5.0-4.3 (br.1H,- NHCO-) 3.85 (q.4H, -SiOCH)_Two−) 3.38 (t. 2H, —CH_TwoNHCO-) 3.11 (t.2H, -NCH)_Two−) 2.45 (t. 2H, —COCH_Two−) 1.7-1.0 (m.2H, -CH_Two-) 1.28 (s.6H, -CH_Three) 1.15 (t.6H, -SiOH)_TwoCH_Three) 0.52 (t. 2H, -CH_TwoSi-) 0.10 (s.3H, -SiCH_Three) Specific IR (neat) spectrum ν (cm^-1) = 3300 (N−H), 1643 (C =
O), 1082 (Si-O) Elemental analysis C: 69.00, H: 7.56, N: 7.49 Calculated C: 68.66, H: 7.38, N: 7.51 (C₃₂H₄₁N_ThreeO _Four Si₁)

[0050]

Embedded image

Example 6 1- (2-carboxyethyl)-synthesized in Example 4
3,3-Dimethylspiro [indoline-2,3'-naphtho (2,1-b) (1,4) oxazine] and 3-aminoundecyltrimethoxysilane in methylene chloride in DC
Condensation was carried out in the same manner as in C to obtain a compound having the following structure. Various analytical data obtained for structure confirmation are shown below.

[0052]¹H-NMR spectrum δ (ppm) = 8.55 (d.1H, —CH ＝ N—) 7.8-6.7 (m.10H, Ph) 5.0-4.2 (br.1H, − NHCO-) 3.70 (s.9H, -SiOCH)_Three−) 3.42 (t.2H, -CH_TwoNHCO-) 3.07 (t.2H, -NCH_Two−) 2.45 (t. 2H, —COCH_Two−) 2.1-0.9 (m.24H, -CH_Two−, CH_Three) 0.60 (t.2H, -CH_TwoSi-) specific IR (neat) spectrum ν (cm^-1) = 3300 (N−H), 1645 (C =
O), 1082 (Si-O) Elemental analysis C: 69.23, H: 7.96, N: 6.49 Calculated C: 69.16, H: 8.10, N: 6.37 (C₃₃H₄₃N_ThreeO ₆ Si₁)

[0053]

Embedded image

Example 7 1- (3-Ethoxycarbonylpropyl) -2-methylene-3,3-dimethylindoline was obtained from 2,3,3-trimethylindolenine and ethyl 4-bromobutanoate. From 2-naphthol to 1- (3
-Ethoxycarbonylpropyl) -3,3-dimethylspiro [indoline-2,3'-naphtho (2,1-b)
(1,4) oxazine] was synthesized. This is put in 3-aminopropylpropyldimethoxysilane and methylene chloride,
Aminolysis of the ester using dimethylaminopyridine as a catalyst gave a compound having the following structure. Various analytical data obtained for structure confirmation are shown below.

[0055]¹H-NMR spectrum δ (ppm) = 8.53 (d.1H, -CH = N-) 7.9-6.7 (m.10H, Ph) 5.5-4.9 (br.1H, -NHCO −) 3.76 (s.6H, —SiOCH)_Three) 3.43 (t. 2H, -CH)_TwoNHCO-) 3.10 (t.2H, -NCH_Two−) 2.48 (t. 2H, —COCH_Two−) 1.8-0.9 (m.15H, -CH_Two−, CH_Three) 0.7-0.2 (m.4H, -CH_TwoSi-) specific IR (neat) spectrum ν (cm^-1) = 3285 (N−H), 1645 (C =
O), 1080 (Si-O) Elemental analysis C: 68.84, H: 7.86, N: 7.17 Calculated C: 69.08, H: 7.55, N: 7.32 (C₃₃H₄₃N_ThreeO _Four Si₁)

[0056]

Embedded image

Example 8 1- (5-Carboxypentyl) -2-methylene-3,3-dimethylindolenine was synthesized from 2,3,3-trimethylindolenine and 6-chlorohexanoic acid. From nitroso-6-methoxy-2-naphthol to 1-
(5-carboxypentyl) -3,3-dimethyl-8 '
-Methoxyspiro [indoline-2,3'-naphtho (2,1-b) (1,4) oxazine] was synthesized and 3-aminopropyltriethoxysilane was condensed with DCC to obtain a compound having the following structure. . Various analytical data obtained for structure confirmation are shown below.

[0058]¹H-NMR spectrum δ (ppm) = 8.55 (d.1H, -CH = N-) 8.2-6.8 (m.9H, Ph) 5.9-5.1 (br.1H,- NHCO-) 3.99 (s.3H, CH_ThreeO-) 3.81 (q.6H, -SiOCH)_Two−) 3.45 (t. 2H, —CH_TwoNHCO-) 3.07 (t.2H, -NCH_Two−) 2.44 (t. 2H, —COCH_Two−) 1.8-0.9 (m.23H, -CH_Two-, -CH_Three) 0.61 (t.2H, -CH_TwoSi-) specific IR (neat) spectrum ν (cm^-1) = 3250 (N−H), 1644 (C =
O), 1082 (Si-O) Elemental analysis: C: 64.44, H: 8.12, N: 6.94 Calculated: C: 64.57, H: 8.37, N: 6.85 (C₃₃H₅₁N_ThreeO ₆ Si₁)

[0059]

Embedded image

Example 9 2,3,3-Trimethyl-6-bromoindolenine and 3
1- (3-hydroxypropyl) -2-methylene-3,3-dimethyl-6-bromoindoline was synthesized from -bromo-1-propanol, and 1- (3-hydroxypropyl) was synthesized from 1-nitroso-2-naphthol. Propyl) -3,3
-Dimethyl-6-bromospiro [indoline-2,3 '
-Naphtho (2,1-b) (1,4) oxazine]. This was reacted with 3-isocyanatopropyltrimethoxysilane in the presence of dibutyltin maleate to obtain a compound having the following structure. Various analytical data obtained for structure confirmation are shown below.

¹ H-NMR spectrum δ (ppm) = 8.55 (d.1H, —CH ＝ N—) 7.8-6.5 (m.9H, Ph) 5.3-4.9 (br .1H, -NHCOO-) 4.32 (t.2H, -COOCH 2 -) 3.76 (s.9H, -SiOCH 3) 3.43 (t.2H, -CH 2 NHCOO-) 3.13 ( _{t.2H, -NCH 2 -) 1.7-1.0 (} m.4H, -CH 2 -) 1.38 (s.6H, -CH 3) 0.56 (t.2H, -CH 2 Si −) Specific IR (neat) spectrum ν (cm ⁻¹ ) = 3340 (N−H), 1722 (C =
O), 1080 (Si-O) Elemental analysis C: 56.78, H: 6.02, N: 6.40, Br: 11.9 1 Calculated C: 56.70, H: 5.83, N: 6.40, Br: 12.1 7 (C 31 H 38 N 3 O 6 Si 1 Br 1)

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Example 10 1- (4-Hydroxybutyl) -2-methylene-3,3-dimethyl-5-methoxy from 2,3,3-trimethyl-5-methoxyindolenine and 4-chloro-1-butanol Indoline was synthesized, and 1- (4-hydroxybutyl) -3,3-dimethyl-5-methoxy-9'-fluorospiro [indoline-2,3 'was synthesized from 1-nitroso-7-fluoro-2-naphthol. -Naphtho (2,1-
b) (1,4) oxazine] was synthesized. This compound was reacted with 4-isocyanatobutyldimethylethoxysilane previously synthesized from 4-aminobutyldimethylethoxysilane and diphosgene in the presence of dibutyltin maleate to obtain a compound having the following structure. Various analytical data obtained for structure confirmation are shown below.

¹ H-NMR spectrum δ (ppm) = 8.53 (d.1H, —CH ＝ N—) 8.7-6.7 (m.8H, Ph) 5.6-5.3 (br .1H, -NHCOO-) 4.03 (t.2H, -NHCOOCH 2 -) 3.80 (q.2H, -SiOCH 2 -) 3.35 (t.2H, -CH 2 NHCOO-) 3.10 _{(t.2H, -NCH 2 -) 1.8-1.0} (m.14H, -CH 2 -, CH 3) 0.53 (s.2H, -CH 2 Si-) 0.07 (s. 6H, —SiCH ₃ ) specific IR (neat) spectrum ν (cm ⁻¹ ) = 3340 (N−H), 1722 (C =
O), 1082 (Si-O) Elemental analysis value C: 65.33, H: 7.70, N: 6.51, F:-Calculated value C: 65.46, H: 7.43, N: 6 _{.74, F: 3.05 (C 34} H 46 N 3 O 5 Si 1 F 1)

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Example 11 1- (7-Carboxyheptyl) -2 from 2,3,3,6-tetramethylindolenine and 8-chlorooctanoic acid
-Methylene-3,3,6-trimethylindoline was synthesized and 1- (7
-Carboxyheptyl) -3,3,6-trimethylspiro [indoline-2,3'-naphtho (2,1-b)
(1,4) oxazine] was obtained. This was condensed with 4-aminobutyltriethoxysilane using DCC to obtain a compound having the following structure. Various analytical data obtained for structure confirmation are shown below. ¹ H-NMR spectrum

Δ (ppm) = 8.55 (d.1H, —CH ＝ N—) 7.8-6.6 (m.9H, Ph) 5.5-4.9 (br.1H, —NHCO) −) 3.77 (q.6H, —SiOCH)_Two−) 3.45 (t. 2H, —CH_TwoNHCO-) 3.05 (t.2H, -NCH_Two−) 2.37 (t. 2H, —COCH_Two-) 1.9-0.9 (m.31H, -CH_Two-, -CH_Three) 0.55 (t. 2H, -CH_TwoSi-) specific IR (neat) spectrum ν (cm^-1) = 3300 (N−H), 1644 (C =
O), 1082 (Si-O) Elemental analysis: C: 69.52, H: 8.86, N: 5.87 Calculated: C: 69.53, H: 8.75, N: 6.08 (C₄₀H₆₀N_ThreeO _Five Si₁)

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Example 12 1- (5-Carboxypentyl) -2 from 2,3,3,5-tetramethylindolenine and 6-chlorohexanoic acid
-Methylene-3,3,5-trimethylindoline was synthesized and 1- (5) was synthesized from 1-nitroso-2-naphthol.
-Carboxypentyl) -3,3,5-trimethylspiro [indoline-2,3'-naphtho (2,1-b)
(1,4) oxazine] was obtained. This was condensed with 4-aminobutyldimethylmethoxysilane using DCC to obtain a compound having the following structure. Various analytical data obtained for structure confirmation are shown below.

[0070]¹H-NMR spectrum δ (ppm) = 8.50 (d.1H, —CH ＝ N—) 7.8-6.5 (m.9H, Ph) 5.2-4.8 (br.1H, − NHCO-) 3.89 (s.3H, -SiOCH)_Three) 3.44 (t. 2H, -CH)_TwoNHCO-) 3.10 (t.2H, -NCH_Two−) 2.24 (t. 2H, —COCH_Two-) 1.9-0.9 (m. 19H, -CH_Two-, -CH_Three) 0.55 (t. 2H, -CH_TwoSi-) specific IR (neat) spectrum ν (cm^-1) = 3300 (N−H), 1644 (C =
O), 1082 (Si-O) Elemental analysis: C: 71.83, H: 8.00, N: 7.15 Calculated: C: 71.75, H: 8.09, N: 7.17 (C₃₅H₄₇N_ThreeO _Three Si₁)

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Example 13 2,3,3-Trimethylindolenine and 2-methyl-3
-From chloropropionic acid to 1- (2-carboxy-2-
Methylethyl) -2-methylene-3,3-dimethylindoline was synthesized and combined with 1-nitroso-6-chloro-2.
1- (2-carboxy-2-methylethyl) -3,3-dimethyl-8'-chlorospiro [indoline-2,3'-naphtho (2,1-b) (1,4) oxazine] from naphthol Obtained. This was condensed with 3-aminopropylmethyldiethoxysilane using CDD to obtain a compound having the following structure. Various analytical data obtained for structure confirmation are shown below.

¹ H-NMR spectrum δ (ppm) = 8.53 (d.1H, —CH ＝ N—) 8.2-6.8 (m.9H, Ph) 5.8-5.5 (br) .1H, -NHCO-) 3.82 (q.4H, -SiOCH 2 -) 3.46 (t.2H, -CH 2 NHCO-) 3.06 (t.2H, -NCH 2 -) 2.4 -2.1 (m.1H, -COCH-) 1.9-0.9 ( m.17H, -CH 2 -, - CH 3) 0.51 (t.2H, -CH 2 Si-) 0. 09 (s, 3H, SiCH ₃ ) specific IR (neat) spectrum ν (cm ⁻¹ ) = 3240 (N−H), 1640 (C =
O), 1082 (Si-O) Elemental analysis: C: 69.21, H: 7.97, N: 6.29 Cl: 5.55 Calculated: C: 69.16, H: 8.10, N: _{6.37, Cl: 5.83 (C 33} H 42 N 3 O 4 Si 1 Cl 1)

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Example 14 1- (3-Ethoxycarbonylpropyl) -2-methylene-3,3-dimethylindoline was synthesized from 2,3,3-trimethylindolenine and ethyl 4-bromobutanoate. From nitroso-7-methoxy-2-naphthol to 1- (3-ethoxycarbonylpropyl)-
3,3-Dimethyl-9'-methoxyspiro [indoline-2,3'-naphtho (2,1-b) (1,4) oxazine] was obtained. This was subjected to aminolysis with 3-aminopropylmethyldipropoxysilane in the presence of dimethylaminopyridine to obtain a compound having the following structure. Various analytical data obtained for structure confirmation are shown below.

[0076]¹ H-NMR (CDCl_Three, TMS) spectrum δ (ppm) = 8.53 (d.1H, -CH = N-) 7.9-6.5 (m.9H, Ph) 5.0-4.7 (br.1H,- NHCO-) 3.78 (q.4H, -SiOCH)_Two−) 3.42 (t.2H, -CH_TwoNHCO-) 3.12 (t.2H, -NCH_Two−) 2.23 (t. 2H, —COCH_Two−) 1.8-1.0 (m.20H, -CH_Two-, -CH_Three) 0.55 (t. 2H, -CH_TwoSi-) 0.08 (s, 3H, SiCH_Three) Specific IR (neat) spectrum ν (cm^-1) = 3300 (N−H), 1644 (C =
O), 1082 (Si-O) Elemental analysis value C: 68.33, H: 7.72, N: 6.41 Calculated value C: 68.43, H: 7.82, N: 6.65 (C₃₆H₄₉N_ThreeO _Five Si₁)

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Example 15 Synthesis of 1- (2-hydroxyethyl) -2-methylene-3,3-dimethyl-5-chloroindoline from 2,3,3-trimethyl-5-chloroindolenine and ethylene bromohydrin And 1-nitroso-6-methyl-
By reacting 2-naphthol, 1- (2-hydroxyethyl) -3,3-dimethyl-5-chloro-8'-methylspiro [indoline-2,3'-naphtho (2,1-b)
(1,4) oxazine] was obtained. This and 11 in advance
-Aminoundecyltrimethoxysilane and 11-isocyanatoundecyltrimethoxysilane synthesized from diphosgene were reacted in the presence of dibutyltin malate to obtain a compound having the following structure. Various analytical data obtained for structure confirmation are shown below.

¹ H-NMR spectrum δ (ppm) = 8.55 (d.1H, —CH ＝ N—) 8.2-6.7 (m.8H, Ph) 5.5-4.8 (br .1H, -NHCOO-) 4.31 (t.2H, -NHCOOCH 2 -) 3.89 (s.9H, -SiOCH 3) 3.43 (t.2H, -CH 2 NHCOO-) 3.13 ( _{t.2H, -NCH 2 -) 1.7-1.0 (} m.24H, -CH 2 -, - CH 3) 0.55 (t.2H, -CH 2 Si-) specific IR (neat) spectrum ν (cm ⁻¹ ) = 3348 (N−H), 1722 (C =
O), 1082 (Si-O) Elemental analysis C: 64.61, H: 7.38, N: 5.74, Cl: 5.13 Calculated C: 64.66, H: 7.51, N : 5.80, Cl: 4.8 9 ( C 39 H 54 N 3 O 6 Si 1 Cl 1)

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Application Example 1 The organosilicon compound obtained in Example 1 was dissolved in ethanol and irradiated with ultraviolet rays. As a result, a deep blue color was formed immediately, and the color was quickly erased when the irradiation was stopped.

Application Example 2 10 mg of the organosilicon compound obtained in Example 1 was dissolved in dioxane together with 100 mg of polymethyl methacrylate, and developed on a glass plate to form a cast film. The cast film immediately developed a dark blue color upon irradiation with sunlight or ultraviolet light, and was quickly decolorized upon irradiation with visible light or standing in a dark place.

Application Example 3 A dealkoxylation reaction was carried out by heating 0.5 g of the organosilicon compound obtained in Example 1 together with 1 g of silica gel (Leosileal manufactured by Tokuyama Soda) in dioxane. This reaction proceeded more rapidly in the presence of acid or alkali. The obtained silica gel is thoroughly washed with acetone,
Dried. When the silica gel was irradiated with sunlight or ultraviolet rays, the silica gel immediately developed a dark blue color, and was quickly erased by irradiation with visible light or left in a dark place.

Application Example 4 20 mg of the silica gel obtained in Application Example 3 was dispersed in a dioxane solution of 100 mg of polymethyl methacrylate, and developed on a glass plate to form a cast film. The cast film immediately developed a dark blue color upon irradiation with sunlight or ultraviolet light, and was quickly decolorized upon irradiation with visible light or standing in a dark place.

Application Example 5 0.5 g of the organosilicon compound obtained in Example 1 was applied to a cotton cloth of 5 cm square and heat-treated at 100 ° C. for 1 hour.
The cloth was washed with acetone. The washed cloth immediately developed a dark blue color upon irradiation with sunlight or ultraviolet rays, and was quickly erased upon irradiation with visible light or standing in a dark place.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-164537 (JP, A) JP-A-63-301288 (JP, A) JP-A-4-99781 (JP, A) Special table 501145 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07F 7/18 C09K 9/02 CA (STN) REGISTRY (STN) WPIDS (STN)

Claims (1)

(57) [Claims] 1. A compound of the general formula (I) (Wherein R ¹ and R ² are lower alkyl groups, R ³ is an alkylene group having 2 to 8 carbon atoms, R ⁴ and R ⁵
Is a hydrogen atom, a halogen atom, a methyl group, a methoxy group, X is an NHCOO group or an NHCO group, and m is 3,
4 or 11, and n is an integer of 1 to 3. An organosilicon compound represented by the formula: