JP3127603B2 - Novel dibenzopentalene derivative and method for producing 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 dibenzopentalene derivative which can be expected to be used as a functional reagent or utilizing its electrochemical properties, and a method for producing the same.

[0002]

2. Description of the Related Art Cheno [3,4-C] thiophene must involve the expansion of the valency of sulfur for stabilization of resonance. Substituents such as an aryl group and an alkylthio group such as cheno [3,4-C] thiophene, tetraisopropylthiothieno [3,4-C] thiophene and tetra-t-butylthiothieno [3,4-C] thiophene Only those that have are known. In addition, seleno [3,4-
[C] Selenophene has been tried in various syntheses, but there is no isolated example in a stable form.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel dibenzopentalene which can be expected to be applied utilizing electrochemical characteristics and a method for producing the same.

[0004]

That is, the present invention provides the following formula (I): (Wherein, X and Y represent a sulfur atom or a selenium atom).

Further, the present invention provides the following formula (II): (Wherein, X and Y represent the above-mentioned meanings, and R represents a phenyl group or a methyl group.). A compound represented by the formula: The following formula (I) characterized by: (Wherein, X and Y have the same meanings as described above). The present invention also provides the following formula (IV): A photolysis reaction of a thiosulfonate represented by the following formula (Ia): Is a method for producing a novel dibenzopentalene.

The compound represented by the formula (I) of the present invention is
It can be produced by the method shown in the following reaction formula. (I) When X and Y represent a sulfur atom

(II) When X represents a sulfur atom or a selenium atom and Y represents a selenium atom

In the above reaction formula, the photolysis reaction (hν) can be carried out by a known method of irradiating ultraviolet rays using, for example, a high-pressure mercury lamp. In the thermal decomposition reaction (Δ), the raw material may be placed in a heat-resistant container such as Pyrex and heated by direct heat.

[0009]

Next, the present invention will be further described with reference to examples, but the present invention is not limited to these examples. In the examples, symbols in the above reaction formulas were used as symbols representing compounds. Example 1: Photolysis reaction of reaction formula (I) (1) 1,9-bis (methylthio) dibenzothiophene (II
a) was irradiated with a 400-watt high-pressure mercury lamp for 10 hours to perform a photolysis reaction. Dibenzo [bc, fg] [1,4] dithiopentalene (Ia), which is a dibenzopentalene derivative of the present invention, was obtained in a yield of 11%. At the same time, cheno [2,3,4,5-lmn] [9,10] dithiophenanthrene (IIIa) was produced in a yield of 16%. Physical properties and constants of the compound were as follows. Melting point 165 ° C
(Sublimation); ¹ H-NMR (500 MHz, CDCl ₃ )
δ7.73 (d, J = 7.7 Hz, 4H, Ar-H),
7.60 (t, J = 7.7 Hz, 2H, Ar-H);
¹³ C-NMR (125 MHz, CDCl ₃ ) δ14
1.6, 135.7, 128.3, 116.2; MS
(M / z) 214 (M ⁺ ); UV (CH ₃ CN) λ
_max nm (ε) 243 (32000), 270 (43
00), 329 (1900); calculated values for elemental analysis (C ₁₂
H ₆ as _{S 2): C, 67.25;} H, 2.82, Found: C, 67.34; H, 2.90

Example 2: Thermal decomposition reaction of reaction formula (I) (1) 1,9-bis (methylthio) dibenzothiophene (II
a) was placed in a long Pyrex tube and gently heated with a burner flame. The reaction mixture was purified by column chromatography, separated into two products by preparative HPLC, and dibenzo [bc, fg] [1,4] dithiopentalene (Ia), a dibenzopentalene derivative of the present invention.
I got At the same time Cheno [2,3,4,5-lmn]
[9,10] Dithiophenanthrene (IIIa) was by-produced in large quantities. The physical properties and constants of the above compound were measured, and it was confirmed that the compound was the same as the compound obtained in Example 1.

Example 3: Thermal decomposition reaction of reaction formula (II) (when X = Se) 1,9-bis (phenylseleno) dibenzoselenophene (IIb, X = Se) was used in the same manner as in Example 2 above. To the dibenzopentalene derivative dibenzo [bc, fg] [1,4] diselenopentalene (I
b, X = Se) as colorless needles in 24% yield. At the same time, seleno [2,3,4,5-lmn] [9,1
0] Diselenophenanthrene (IIIb, X = Se) was obtained in 28% yield. Physical properties and constants of the compound were as follows. Melting point 201 ° C. (sublimation); ¹ H-NMR (2
70 MHz, CDCl ₃ ) δ 7.77 (d, J = 7.8
Hz, 4H, Ar-H), 7.43 (t, J = 7.8H)
z, 2H, Ar-H); ¹³ C-NMR (68 MHz,
CDCl ₃₎ δ145.9,134.5,127.3,
121.5; ⁷⁷ Se-NMR (51 MHz, CDCl
₃ ) δ 600.5; MS (m / z) 310 (M ⁺ ); Elemental analysis calculated value (as C ₁₂ H ₆ Se ₂ ): C, 46.
78; H, 1.96; Found: C, 46.60; H,
1.72

Example 4: Pyrolysis reaction of the reaction formula (II) (when X = S) 1,9-bis (phenylthio) dibenzoselenophene (IIb, X = S) was prepared in Example 3 in benzene. To give dibenzo [bc, fg] [1,4] selenothiopentalene (Ib, X = S), which is a dibenzopentalene derivative of the present invention, in a yield of 5%. Physical properties and constants of the compound were as follows. 201 ° C
(Sublimation), ¹ H-NMR (270 MHz, CDCl ₃ )
δ 7.75 (dd, J ₁ = 7.6 Hz, J ₂ = 1.1H
z, 4H, Ar-H), 7.51 (t, J = 7.6H)
z, 2H, ArH); ¹³ C-NMR (68 MHz, C
DCl ₃₎ δ143.7,135.6,134.2,1
27.7; ⁷⁷ Se-NMR (51 MHz, CDC
_{l 3) δ622.6; MS (m} / z) 262 (M +);
Analysis Calculated _{(as C 12 H 6 SSe): C} , 5
5.18; H, 2.32, found: C, 54.89;
H, 2.37

Example 5: Photodecomposition reaction of the reaction formula (II) 1,9-bis (phenylseleno) dibenzoselenophene (IIb, X = Se) is photodecomposed in benzene in the same manner as in Example 1 above. As a result, dibenzo [bc, fg] [1,4] diselenopentalene (Ib, X = Se), which is a dibenzopentalene derivative of the present invention, was obtained with a yield of 18%. Example 6: Photodegradation reaction of reaction formula (I) (2) Dichloromethane of cheno [2,3,4,5-lmn] [9,10] dithiophenanthrene (IIIa) and m-chloroperbenzoic acid Thiosulfonate (IV) produced by oxidation reaction in benzene is irradiated with a high-pressure mercury lamp in benzene for a photodecomposition reaction for 72 hours to obtain dibenzo [bc, f
g] [1,4] dithiopentalene (Ia) was obtained in a yield of 61%. Unreacted raw material thiosulfonate (IV) 33%
Was recovered.

Next, the physical and chemical properties of the pentalene (Ia) of the present invention obtained in the above Examples were measured.
The UV spectrum of pentalene (Ia) lacked a visible band near 530 nm observed in tetraphenylcheno [3,4-C] thiophene corresponding to a biradical structure. This suggests that pentalene (Ia) has neither a biradical structure nor a charged structure. Detailed structural analysis of the compound (Ia) of the present invention was performed by using X-
It was performed by line crystal structure analysis. The results are shown in FIG.
Shown in

[0015]

[Table-1]

From the above results, pentalene (Ia) was converted to S ₁
-S _{1, C 5} -C 5 axis has three _{C 2} axes 2 minutes,
1 is perpendicular to the plane of the pentalene ring belonging to the point group of the D _2h, clearly it shows that it is a completely flat molecules. The CS bond of the thiophene ring was 1.791 ° and 1.792 °. This is due to the 1.705 ° and 1.70 of tetraphenylcheno [3,4-C] thiophene.
It was much longer than the normal CS bond length of 7 ° and thiophene (1.714 °) and dibenzothiophene (1.740 °). As is apparent from Table 1, the benzene ring of the compound (Ia) of the present invention was considerably distorted from the normal hexagonal structure. C ₃ -C ₃ bond length, 1.386
Å, which is shorter than the bond length of chenothiophene. This means that the two benzene rings are stabilized by a bond, and the chenophiophene ring containing two sulfur atoms is less involved in the necessary π-bond in the thiophene ring itself. Is shown.

In order to consider the theoretically most stable structure of the compound (Ia) of the present invention, MNDO calculation was carried out with the most energetically stable structure. The calculated bond length is
It was compared with the value obtained by X-ray crystal structure analysis. The results are shown in the following table.
It is shown in FIG.

[0018]

[Table-2]

The results in Table 2 above show that the structure of the compound (Ia) of the present invention, determined by X-ray crystal structure analysis, is
This suggests that the structure is substantially different from the structure obtained by the MNDO calculation. Since the electrochemical properties of compounds Ia and Ib are exciting, compounds Ia and Ib and compound I
The oxidation potentials of Ia and IIb were measured in acetonitrile at 20 ° C. with a platinum electrode and a reference electrode Ag / 0.01 MAgNO ₃ using cyclic voltammetry.
The oxidation potentials of these compounds were as follows. Compound Ia (Ep = 1.16 V, irreversible); Compound IIa (E
_1/2 = 0.91 V, reversible); dibenzothiophene (E
Compound Ib (Ep = 1.0, p = 1.31 V, irreversible)
3V, irreversible); compound IIIb (E _1/2 = 0.64)
V, reversible); dibenzoselenophene (Ep = 1.02)
V, irreversible). The cyclic voltammogram of compound Ia after 20 sweeps at 200 mV / s shows almost the same behavior as that of polythiophene in electrolysis.
The results are shown in FIG. The electrode was covered with a yellow resin of unknown structure. On the other hand, in the case of selenium homolog Ib, this phenomenon was not observed even after repeated sweeping.

[0020]

As described above, the compound of the present invention is a novel compound, and can be expected to be applied utilizing its electrochemical properties and is useful as a functional reagent.

[0021]

[Brief description of the drawings]

FIG. 1 is a diagram showing the X-ray crystal structure analysis of the compound of the present invention.

FIG. 2 is a cyclic voltammogram of the compound of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C07D 495/06 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. The following formula (I): (In the formula, X and Y each independently represent a sulfur atom or a selenium atom.) 2. The following formula (II): (Wherein, X and Y each independently represent a sulfur atom or a selenium atom, and R represents a phenyl group or a methyl group.) A compound represented by the formula: The following equation (I): (Wherein X and Y represent the above-mentioned meanings). 3. In the above formulas (II) and (I), X
The method for producing a novel dibenzopentalene derivative according to claim 2, wherein and Y have the same meaning. 3. The following formula (II): Wherein X and Y each represent a sulfur atom or a selenium atom, and R represents a phenyl group or a methyl group. The compound represented by the following formula (I): (Wherein X and Y represent the above-mentioned meanings). 4. The following formula (IV): A photolysis reaction of a thiosulfonate represented by the following formula (Ia): A method for producing a novel dibenzopentalene represented by the formula: