JPH01238546A - Naphthacene derivative - Google Patents

Abstract

NEW MATERIAL:The naphthacene derivative of formula VII (X is H or halogen). EXAMPLE:1,2,3-Tri-t-butyl-5,11-dibromonaphthacene. USE:An optical recording medium, optical memory material, etc. It exhibits photochromism in long-wavelength region, has excellent thermal stability of isomers and is useful as a photochromic compound. PREPARATION:A compound of formula VII wherein both Xs are Br can be produced by (1) reacting a compound of formula I with a compound of formula VIII and isoamyl nitrite, (2) converting the resultant compound of formula II into the compound of formula IV without separating from the system, (3) reacting the compound of formula IV with a compound of formula III and n-butyllithium at room temperature, (4) heating the obtained compound of formula V at 120-170 deg.C to obtain a compound of formula VI and (5) reacting the product with N-bromosuccinmide and azoisobutyro-nitrile at 40-80 deg.C. Another compound of formula VII wherein both Xs are H is produced by reacting the compound of formula VI with O2 at 70-90 deg.C.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to tacene derivatives.

[Conventional technology]

Conventionally, various compounds having photochromic properties that develop or discolor when irradiated with light are known, and photochromic light-sensitive materials using such compounds have been proposed.

Examples of such compounds include spirooxazine compounds; for example, in Japanese Patent Publication No. 22292,
A photochromic light-sensitive material containing a spironaphthoxazine compound as shown in the following formula has been proposed.

(In the formula, Ha represents a hydrogen atom, a halogen atom, a cyan group, an alkyl group or an alkoxy group with carbon number/~.) Also, spiropyran-based compounds (for example, Sho Kutag and Otsu 3/ Publication No. 41Fl Showa Tata 13≦Recognition? Publication No. 41, U.S. Patent No. 11
34t2t<t<See the specification of No. F, etc. ) are known, and it has also been found that other types of compounds, such as compounds of the following formula, also exhibit photochromic properties.

The photochromic compound as described above is used in an optical recording medium in which a thin film of such a compound dissolved or dispersed in a polymer compound is formed on a substrate as a recording layer.

[Problem to be solved by the invention]

However, optical recording media using conventional photochromic compounds have some problems, such as insufficient color density, insufficient storage stability, and insufficient durability for repeated use. It has been desired to improve this.

The present invention aims to provide a novel naphthacene derivative, which is a photochromic compound capable of solving the above conventional problems.

[Failure to solve the problem]

As a result of intensive research to achieve the above object, the present inventor discovered for the first time that a specific naphthacene compound can exhibit particularly excellent effects as a photochromic compound for optical recording media, and has thus arrived at the present invention. . That is, the present invention provides -maximum (1) (wherein, X represents a hydrogen atom or a halogen atom.)
The gist is the naphthacene derivative shown in

The naphthacene derivative represented by the general formula (1) of the present invention exhibits photochromicity by a reversible reaction as shown in the following formula (where X is the same as defined above).

The naphthacene derivative of the present invention is produced according to the following method.

(3) (4) <5)r That is, compound (1) and 2-aminoque,! - Dibromobenzoic acid and isoamyl nitrite (iAm-〇NO)
Compound (2) is obtained by heating and reacting at 06 to 100°C.

Compound (2) is then heated to 700-/jO<0>C to obtain compound (4). However, in this reaction, compound (2) may not be separated, and the reaction solution may be used as it is in the reaction to obtain compound (4).

Next, compound (4), compound (3), and n-butyllithium (n-BuLi) are reacted at room temperature to obtain a reaction solution containing compound (5). This reaction solution was heated at 7.2.0° to 770°.
Compound (6) is obtained by heating to ℃.

Compound (6) is oxidized at 70° to 20°C by blowing with 02 to obtain compound (8).

On the other hand, compound (6) was heated at 90° to 0°C, N-bromosuccinimide (NBS) and azoisobutyronitrile (A
Compound (7) is obtained by reacting with N).

The above compound (1) is Chem, Ber,...
/ / 4t (/9.4!'/), and the above compound (3) can be obtained by (!ana, J.

(!hem,, 2, 7 tata (/tough 2) can be manufactured respectively.

Further, the naphthacene derivative of the present invention is represented by the above-mentioned general formula (1), in which X represents a hydrogen atom or a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom, and in particular, as a halogen atom, is preferably a bromine atom.

〔Effect of the invention〕

The naphthacene derivative of the present invention has 7 otochromic properties in the long wavelength region and is also excellent in thermal stability of isomers, so it is useful as a photochromic compound used in optical recording media or optical storage materials.

〔Example〕

The present invention will be described in detail below with reference to Examples, but the present invention is not limited to the Examples unless the gist thereof is exceeded.

2. /] Synthesis of Heptar λ-Nine (2) In a jO, 120 flask equipped with a condenser and a rotor, under a nitrogen atmosphere, J, 3. g-) IJ-t-butylcyclopentan-/-one (1) 0.44! ? (-2,67mmob)
Dry dioxane 10 times to solute aromatic acid/, θf (3,3
9 mmol) was added and heated to 0°C. Stir until foaming stops, then return to room temperature. ! Aqueous potassium dihydroxide solution was added to the reaction mixture and extracted three times from n-pentane. The n-pentane layer was dried over magnesium sulfate, the solvent was distilled off, and then separated and purified using silica gel column chromatography (developing solvent: n-hexane: methylene chloride = 3:/) to give a white-yellow color of compound (2). Semi-solid 0, &
4tf (0.97.7, mol) was obtained.

Yield 36.3% (based on compound (1)) Compound (2)
Physical property values n, m, r, (CD013) δP: 7. J'7(S
/H) 7. jJ(S/H) 7.3! (S/f()
4t, 44 (S/H) /JQ (broad H)
/, # (S9H) /, 2 (89H) (b) /
, 2.3-tri-t-butyl-za,7-dibromonaphthalene (4) synthesis compound (2) 0. 'I 4tf (θ, ?7mmol
) was heated at 720° C. for 2 hours under an argon atmosphere. The reaction mixture was dissolved in n-hexane and separated by silica gel column chromatography (developing solvent: n-hexane).
Purify compound (4) to 0.33 f
(θ, 7 j fimol) was obtained.

Yield 2! % (relative to compound (2)) Physical property values of compound (4) n0m, r, (CDCl2) δp: ♂, g, g (S/H
) 7,2g (S/H) 7 Takayu (S/H) /, Otsu J
(S9H) /, gu4t (S9H) /J! (S 9H
) Calculated value (c22H30Br2) ¥6.2.07
/jexact mass Actual value M+'lj2.
07223(c) /, 2.3-tri-t-butyl-7,10-ethano-t, 7,10. //-Dihydronaphthacene (5) Compound (4) θ, g J” f (
0,7,2 mmol) and compound (3) 0.2 r
? (2,/mmol) and dry toluene 10rt
tl, and while stirring, add n-BuLi-n-hexane solution/, Oml (/, 6N) to dry toluene! A solution diluted to 1 ml was added dropwise over 2 hours. After stirring again for 7 hours, the reaction was complete. (TTJQ check) After adding water/resistance to decompose n-BuLi, it was dried over sodium sulfate, the ν-passed toluene was distilled off under reduced pressure, and the formation was confirmed by NMRK. Since compound (5) is unstable under 02,
It was used in the next reaction without purification.

(d) J-, /2-dihydro-7, Otardley t
-Synthesis of Butylnaphthacene (6) The reaction mixture of the pre-reaction containing compound (5) was mixed with /! under an argon atmosphere. After heating at θ°C for 7 hours, removal of ethylene was completed. The contents of the flask were dissolved in n-hexane and purified by silica gel column chromatography (developing solvent: n-hexane). Compound (6) was added to 0.
3/iiF (0.79 mmol) was obtained.

yield,? ,<,3% (relative to compound (4) used in (c)) Physical property values of compound (6) n, rn, r, (C!DC'13) δppm: r,
/2 (fEi /H) 7. jJ(S/H) 7.3
j (S/H) 7.3 evening - entry #: (m @H) 41.
06-g, 03(mQH)/,, <7(89H)/, GJ-(S9H)/, 36(S 9H) calculated value (030
H38) 39F, 2ri7! Guexact maEI
8 Actual measurement value M+, 39F, 297', t41(f
) /, 2,3-tri-t-butylnaphthacene (8)
Equipped with rotor cooling pipe and calcium chloride pipe! 0.1.2
0.7 of compound (6) in an eggplant-shaped flask (0,
Add a solution of 3F mmc+1) dissolved in dry t-butyl alcohol, and add 0.2% of potassium t-butoxide.
/ ? After adding (/, 9 mm01), the mixture was refluxed while blowing in 02. The reaction was completed in 7 hours. After returning to room temperature, the solvent was distilled off, and the residue was dissolved in n-hexane and purified by silica gel column chromatography (developing solvent: n-hexane). Omg (0./3 mmol) of red-orange semi-solid material was obtained. It was purified by sublimation method to obtain 30 mg (0,θ♂771 mol).

Crude yield: 3 pieces (for compound (6)) Physical property values of compound (8) m, p, r4tT:.

n 0m, r, (CDC!13) δyp: ,?
, 77(S/H)♂, J-Q(S/H)? , ¥6(
S/H),! ', 2 evenings (S/H)♂, 0/~7, p
O(m2H) 7. gO(S/H) input 0-7. ．．
2J” (m jH) Steam♂0 (S 9H) Steam G9 (E
39H) /, 3za (S 9H) U, V (OH3ON
) λll1laX (εmax) 2ri, r
nm (/17!00) Geta, 2nm (/900) Calculated value (C3oH3s) 39 Otsu, 2F7r, l
? exact ma8Q actual value M+ 396.2
F29 yen (g) /, recognition, 3-tree t-butyl-j
, //-dibromonaphthacene (7) Compound (6) θ, / 02 f (
0,2& ,, mOl), N-pomo:ff succinimide 0.093 S' (0,j 2 mmol)
, α, α′ Azobisisobutyronitrile 0.023 ?
(0,/11θfimol) and hydrogen carbonate (IJ) were added in an excess amount, and the mixture was heated to 70° C. with stirring. The solution turned red with heating. After heating for 30 minutes, return to room temperature,
After distilling off the solvent, the compound (
7) was obtained at 7/rrq (θ,/4tmmol).

By recrystallization from diethyl ether, 3/3 mg (
0,0! fimo'l) was obtained. red crystal.

Crude yield j'1% (relative to compound (6)) Compound (7)
Physical property value m, p 23F-24tθ℃ n0m, r, (CDCl2) δPF: 9J7
(S/H) 9.02 (S/H) ♂, Gu Otsu (m/H
)/, 0J-(m/H)7. J-9(S/H)7j￥(
m/H) 7. pg (m /H) U, V, λmax
(gmax) 30♂nm (j4t2F gua♂
nm (3070) mass, rr1//LII:
tl+'(M+) 419'7(M"-t7) 417
F(M+-/3/,) r7(t-Bu+)(h)
/, 2.3 tri-t-butylnaphthacene (8) was quantitatively produced by NMR.

n, m, r, (CDC!13) δp ♂, #(S /H
) r, (M(S/H) Otsu90~7J3(m 2H”
) Iriotwa (S /H) 7, g2 (S /H) 7.39
~7. jJ'(m, 2H)/,! :X~ to 4t, 2(b
road 9H) 7.2g(S/rH) (i) /, , 2.3-tri-t-butyl-! , //
- Photoreactive compound (7) of dipronaphthacene (7) 3o vq (o, o 771 mol
) in chloroform 10. It was degassed by dissolving it in l and blowing in N2. It was irradiated with light transmitted through a high-pressure mercury lamp L-filter for 2 hours. It was separated by silica gel thin layer chromatography (developing solvent: n-hexane) and recrystallized from acetonitrile to obtain a yellow-orange solid represented by the following structural formula (9).

Physical property values of Br compound (9) m, p, /9ta~/tao℃ n, m, r, (CDCl2) f, 4@(S /H)
e! ', ¥, 2 (m /H) /? , 30 (F3 /
! ()7, ri/(m/H)ottJ(m/H)otto￥even(
m /H) / J3 (broad 9H) /, 27
(S//H) Compound (7) was dissolved in chloroform and degassed, and the absorbance change was recorded over time when irradiated with light of 0 to 50 nm for a period of time, and the results are shown in Figure 2. Ta.

That is, the absorption of guar <nm compound (7) disappears by the photoisomerization reaction shown below.

Br
BrAlso, by irradiating this with light of 3≦θ to 1100 nm, the absorption of the compound (7) is restored.

[Brief explanation of the drawing]

Figure - / shows the absorbance of compound (7) recorded over time when it was irradiated with K light in Examples. In the figure, the vertical axis represents absorbance, and the horizontal axis represents wavelength (nm). Applicant Mitsubishi Chemical Industries, Ltd. Agent Patent Attorney Hase - (and 7 others)

Claims (1)

[Claims] (1) Naphthacene derivatives represented by the following general formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, X is a hydrogen atom or a halogen atom.)