JP3055234B2 - Spiropyridopyrane compound and guanine indicator using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel spiropyridopyran compound and a guanine indicator using the same. More specifically, the present invention relates to a novel spiropyridopyran-based compound that selectively recognizes a guanine derivative and forms a color, and a guanine indicator using the same.

[0002]

2. Description of the Related Art Hitherto, compounds which selectively recognize a guanine derivative and form a color have been already known, and these are used as guanine indicators.

[0003]

In various industrial fields, it has always been desired to develop a novel compound as a functional compound, which has never existed before.

[0004] The present invention is a compound which can be used as a guanine indicator, which can selectively recognize a guanine derivative to form a color,
An object of the present invention is to provide a novel spiropyridopyran compound having a chemical structure different from that of a conventionally known compound.

[0005]

The spiropyridopyrane compound of claim 1 is represented by the following general formula [I].

[0006]

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(Wherein R ¹ and R ² represent an alkyl group;
R ³ represents an alkyl group which may have a substituent;
⁴ represents a hydrogen atom, an alkyl group, or an acyl group;
Represents ＣＨCH— or ＮN—, Y represents an oxygen atom or a sulfur atom, and ring A represents an optionally substituted hydrocarbon-based aromatic ring. ) The guanine indicator of claim 2 uses the spiropyridopyran-based compound of claim 1.

Hereinafter, the present invention will be described in detail.

In the above general formula [I], the alkyl group represented by R ¹ and R ² is an alkyl group having 1 to 7 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a heptyl group. And preferably a methyl group, an ethyl group or a propyl group.

The optionally substituted alkyl group represented by R ³ includes an alkyl group having 1 to 12 carbon atoms, and an alkyl group having 1 to 1 carbon atoms substituted by an alkoxy group having 1 to 10 carbon atoms.
An alkoxyalkyl group such as an alkyl group of 2;
An acyloxyalkyl group such as an alkyl group having 1 to 12 carbon atoms substituted with an acyloxy group such as an alkylcarbonyloxy group or a benzoyloxy group having 10 to 10 carbon atoms;
1 to 12 carbon atoms substituted with an alkoxycarbonyl group
And the like, an alkoxycarbonylalkyl group such as an alkyl group, an alkoxyalkoxyalkyl group, an aralkyl group represented by the following formula and the like.

[0011]

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(In the formula, m represents an integer of 1 to 3, R ⁵ represents an alkyl group or an alkoxy group having 1 to 10 carbon atoms.) As R ⁴ , in addition to a hydrogen atom, 1 to 10 carbon atoms. An alkyl group, an alkylcarbonyl group having 1 to 10 carbon atoms,
An acyl group such as a benzoyl group is exemplified.

Examples of the hydrocarbon aromatic ring for ring A include a benzene ring and a naphthalene ring, preferably a benzene ring. Examples of the substituent of the aromatic ring of Ring A include a hydrogen atom; a halogen atom such as a chlorine atom, a bromine atom and an iodine atom; a nitro group; an alkyl group such as an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms. An alkoxycarbonyl group such as an alkoxycarbonyl group having 1 to 6 carbon atoms; an alkoxysulfonyl group such as a methoxysulfonyl group and an ethoxysulfonyl group; an alkylsulfonyl group such as a methylsulfonyl group and an ethylsulfonyl group.

The spiropyridopyrane compound of the present invention represented by the above general formula [I] develops a color with a guanine derivative, which is selected from guanine by hydrogen bonding as shown in the following general formula [II]. This is the result of the recognition.

[0015]

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(R ¹ , R ² , R in the general formula [II]
³ , R ⁴ , X, Y and ring A have the same meaning as in the general formula [I], and G has the same meaning as in the following general formula [III]. Note that the guanine derivative only needs to contain a guanine group, and is not particularly limited. Examples thereof include a guanine derivative represented by the following general formula [III].

[0017]

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(In the formula, G represents a hydrogen atom or a group represented by the following formula.)

[0019]

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(Wherein R ⁶ is a hydrogen atom or —OSiMe
₂ Bu (t). Note that Me is a methyl group and Bu is a butyl group. The spiropyridopyran-based compound of the present invention represented by the general formula [I] can be produced, for example, as follows. That is, it can be synthesized by reacting a compound represented by the following general formula [IV] with a compound represented by the following general formula [V].

[0021]

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[0022] (wherein, R ^1, R ^2, R ³ and ring A are the same meanings as definitive in the general formula [I], X ^- 1 represented by ^- the .X showing a monovalent anion Examples of the valent anion include a halogen ion such as a chloride ion, a bromide ion, and an iodide ion, a perchlorate ion, and a tetrafluoroborate ion.

[0023]

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(In the formula, X, Y and R ⁴ have the same meanings as in the above formula [I].) This reaction is usually carried out by halogenated hydrocarbons such as methylene chloride and chloroform, or methanol, ethanol and the like. The reaction temperature is -20 in the presence of an alcoholic solvent such as
Carried out at １００100 ° C.

Specific examples of the spiropyridopyran-based compound of the present invention thus obtained are shown in Tables 1 and 2 below.

[0026]

[Table 1]

[0027]

[Table 2]

The spiropyridopyran compound of the present invention may be dissolved in a solvent together with a binder to form an ink composition, or may be applied to a suitable substrate and dried, for example, depending on the intended use. Alternatively, it can be used by dissolving or dispersing in a resin and then forming a film.

The solvent used in the ink composition using the compound of the present invention is not particularly limited as long as it dissolves the compound of the present invention.

The resin for dissolving or dispersing the compound of the present invention includes polyester resin, polystyrene resin, polyvinyl butyral resin, polyvinylidene chloride, polyvinyl chloride, polymethyl methacrylate, polyvinyl acetate, and the like.
Examples include cellulose acetate, epoxy resin, and phenol resin. Various known methods can be adopted as a film forming method.

When the compound of the present invention is used by dissolving or dispersing it in a resin, an antioxidant, a singlet oxygen quencher or the like may be added for the purpose of improving stability and light resistance.

The spiropyridopyrane compound of the present invention comprises
The guanine derivative can be effectively used as a guanine indicator because it selectively recognizes and develops a color, but it can also be used effectively as a guanine indicator. It can also be used as

[0033]

EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.

Example 1 Table 1, No. Production of Spiropyridopyran Compounds of 1: (1) Synthesis of 6-acetylamino-3-cyano-2-acetyloxypyridine

[0035]

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6-amino-3-cyano-2-hydroxypyridine (P. Pojanagaroon, Ph. D. Thesis. Universi
of North Carolina, 1969) was suspended in acetic anhydride (Ac ₂ O) (30 ml),
Allowed to react for hours. After completion of the reaction, acetic anhydride was removed under reduced pressure, and the residue was purified by silica gel column chromatography (developing solution; CH ₂ Cl ₂ : AcOEt (ethyl acetate) = 20: 1). Yield 70%.

Analysis results IR (KBr): 3250, 2230, 1790, 16
^{80,1520cm -1 1 H-NMR (270MHz} , CDCl 3): δ 2.
24 (s, 3H), 2.41 (s, 3H), 8.01
(D, J = 8.6 Hz, 1H), 8.27 (d, J =
8.6 Hz, 1 H) ¹³ C-NMR (67.5 MHz, CDCl ₃ ): δ 2
1.26, 25.26, 98.10, 111.86, 1
14.47, 145.46, 153.45, 158.2
4,168.04, 169.17 MS (m / z): 219 (M ⁺ , 6%), 177 (M ⁺
_{-COCH 3 + H, 37%)} , 135 (M + -2COC
_{H 3 + 2H, 100%)} (2) 6- acetylamino -3-cyano-2-hydroxypyridine

[0038]

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6-acetylamino-3 obtained in (1)
-Cyano-2-acetyloxypyridine 10 mmol in MeOH: CH ₂ Cl ₂ : AcOH: H ₂ O (20: 2
0: 1: 1 (ml)) and stirred at room temperature for 25 hours. The desired product was obtained by filtering the resulting precipitate. 94% yield.

Analysis result IR (KBr): 3430, 3100, 2210, 15
^{90,1560cm -1 1 H-NMR (270MHz} , DMSO-d 6): δ
2.15 (s, 3H), 6.89 (d, J = 8.2H
z, 1H), 7.84 (d, J = 8.2 Hz, 1H),
11.01 (s, 1H), 12.15 (s, 1H) ¹³ C-NMR (67.5 MHz, DMSO-d ⁶ ): δ
24.40, 91.17, 96.38, 118.5
0, 147.43, 151.89, 166.53, 17
0.41 MS (m / z): 177 (M ⁺ , 20%), 135 (M
_{^{+ -COCH 3 + H, 100%}} ) (3) 6- Synthesis of acetyl-amino-3-formyl-2-hydroxypyridine [Va]

[0041]

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6-acetylamino-3 obtained in (2)
-Cyano-2-hydroxypyridine (5.0 mmol)
And Raney Ni (W-6,1.0g), sodium monohydrate phosphinic acid _{(1.7g) H 2 O: AcOH} : pyridine (6.3:: 6.3 12.5 (ml )) The suspension was stirred in an autoclave under a hydrogen pressure of 12 atm at room temperature for 24 hours. After completion of the reaction, the reaction mixture was filtered,
After the filtrate was treated under reduced pressure to remove the solvent, the residue was purified by silica gel column chromatography (developing solution;
CH ₂ Cl ₂ : EtOH = 20: 1). 73% yield.

Analysis results IR (KBr): 3400, 3150, 2950, 16
^{90,1570cm -1 1 H-NMR (270MHz} , DMSO-d 6): δ
2.17 (s, 3H), 6.69 (d, J = 8.2H)
z, 1H), 7.94 (d, J = 8.2 Hz, 1H),
9.96 (s, 1H) ¹³ C-NMR (67.5 MHz, DMSO-d ⁶ ): δ
24.48, 96.14, 116.33, 143.6
0,151.95,162.61,172.03,18
7.67 MS (m / z): 180 (M ⁺ , 25%), 138 (M
_{^{+ -COCH 3 + H, 92%}} ) (4) Synthesis of Spiro pyrido pyran-based compounds [Ia]

[0044]

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6-acetylamino-3 obtained in (3)
-Formyl-2-hydroxypyridine [Va] (in the above general formula [V], X = CH, Y = O, R ⁴ = COC
H ₃₎ 1.0 mmol and 1,2,3,3-tetramethyl-indolenium iodide [IVa] (Formula [I
V], ring A is a benzene ring, R ¹ ＝ R ² ＲR ³ ＣC
H ₃ , X ⁻ = I ⁻ ) 1.1 mmol and CH ₂ Cl ₂
(7 ml) for 12 hours at room temperature. After completion of the reaction, a 1.0% aqueous potassium carbonate solution (50 ml) was added, and the mixture was extracted several times with methylene chloride. After the solvent was removed from the extract using a rotary evaporator, the residue was purified by silica gel column chromatography (developing solution; hexane: AcOEt: Et ₃ N = 10: 10: 1). Yield 5
7%.

The analytical results ^{IR (KBr): 3400,3210,1730,1710cm -1 1} H-NMR (CDCl 3, 270MHz): δ 1.
18 (s, 3H), 1.32 (s, 3H), 2.10
(S, 3H), 2.75 (s, 3H), 5.69 (d,
J = 10.4 Hz, 1H), 6.51 (d, J = 7.5)
Hz, 1H), 6.80 (t−d, J = 7.5, 1.2)
Hz, 1H), 6.82 (d, J = 10.4 Hz, 1
H), 7.04 (t−d, J = 7.5, 1.2 Hz, 1)
H), 7.12 (t-d, J = 7.5, 1.2 Hz, 1
H), 7.40 (d, J = 7.9 Hz, 1H), 7.7
0 (d, J = 7.9 Hz, 1H), 7.77 (br.
s, 1H) ¹³ C-NMR (CDCl ₃ , 67.5 MHz): δ 2
0.40, 25.07, 26.44, 29.35, 5
2.33, 106.65, 107.64, 108.2
9, 110.49, 119.51, 120.01, 12
1.95,128.06,128.40,136.7
1,137.64,148.29,149.85,15
9.83, 168.83 MS (m / z): 335 (M ⁺ , 63%) Example 2 Coloring of spiropyridopyran-based compound [Ia] obtained in Example 1 with a guanine derivative: Example 1 To the obtained spiropyridopyran-based compound [Ia] 2.99 × 10 ⁻⁵ mol of a methylene chloride solution, the following nucleoside derivatives [IIIG], [IIIC], [IIIA], [IIIT] were added 10 times in molar ratio. ]
, [IIIU] were added and the UV-visible spectrum was measured. The result is shown in FIG. As a result, only when the nucleoside derivative [IIIG] having a guanine group was added, a strong red color was formed. This is the result of the spiropyridopyran-based compound [Ia] selectively recognizing the guanine group of the nucleoside derivative [IIIG] and opening the ring as in the general formula [II].

[0047]

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[IIIG]: B = guanine, R = OSiMe
₂ Bu (t) [IIIC]: B = cytosine, R = OSiMe ₂ Bu (t) [IIIA]: B = adenine, R = OSiMe ₂ Bu (t) [IIIT]: B = thymine, R = H [IIIU] ]: B = uracil, R = OSiMe ₂ Bu (t) Example 3 Inhibition of color development in Example 2 by cytosine derivative: spiropyridopyran-based compound [Ia] and guanine derivative [IIIG] prepared in Example 2 Then, the nucleoside derivatives [IIIU], [IIIT], [IIIA], and [IIIC] were added at a molar ratio three times that of the guanine derivative, and then the ultraviolet-visible absorption spectrum was measured. The results are shown in FIG.

As shown in FIG. 2, the nucleoside derivative
Only when [IIIC] was added, the color development (red) was inhibited. This is because the guanine and cytosine groups are strong
This is because the bond between the spiropyridopyran-based compound [Ia] and the guanine derivative [IIIG] was cleaved due to n-Crick type complementary interaction, and the spiropyridopyran-based compound [Ia] of the present invention This indicates that the guanine derivative [IIIG] had an interaction due to molecular recognition.

[0050]

As described in detail above, the spiropyridopyrane compound of the present invention is a novel substance and selectively recognizes a guanine derivative to form a color. Therefore, the spiropyridopyrane compound is industrially used as a guanine indicator or the like. Extremely useful.

[Brief description of the drawings]

FIG. 1 is an ultraviolet-visible spectrum diagram showing the results of Example 2.

FIG. 2 is an ultraviolet-visible spectrum diagram showing the results of Example 3.

Claims (2)

(57) [Claims] 1. A spiropyridopyran compound represented by the following general formula [I]. Embedded image (Wherein, R ¹ and R ² represent an alkyl group, R ³ represents an alkyl group which may have a substituent, R ⁴ represents a hydrogen atom or an alkyl group or an acyl group, and ＝ X- represents = CH- or = N-, Y represents an oxygen atom or a sulfur atom,
Ring A represents a hydrocarbon-based aromatic ring which may be substituted. ) 2. A guanine indicator using the spiropyridopyrane compound according to claim 1.