JPH02202864A - 2,3-dicyano-6-naphthylmethanol derivative and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R is 1-20C straight-chain, branched or cyclic alkyl or aryl which may have substituent group; n is 0 or 1). EXAMPLE:6-Amyloxymethyl-2,3-dicyanonaphthalene. USE:A fluorescent substance or raw material for optical information recording media or electrophotographic sensitive materials. PREPARATION:For example, 4,5-dibromo-alpha,alpha,alpha',alpha'-tetraboromo-o-xylene expressed by formula II is reacted with methyl acrylate in the presence of sodium iodide to provide a compound expressed by formula III, which is then reduced to afford 2,3-dibromo-6-naphthylmethanol expressed by formula IV. The resultant compound expressed by formula IV is subsequently reacted with a compound expressed by the formula RCl to provide a compound expressed by formula V, which is then reacted with cuprous cyanide to afford the compound expressed by formula I. The compound expressed by formula II is obtained by reacting o-xylene with bromine and then reacting the resultant compound with N-bromosuccinimide while irradiation the reaction mixture with while light.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a 2,3-dicyano-6-naphthylmethanol derivative and a method for producing the same, and relates to a 2,3-dicyano-6-naphthylmethanol derivative and a method for producing the same. Regarding raw material compounds.

[Conventional technology]

Dicyanonaphthalene derivatives are known in which an alkyl group or an alkoxy group is directly bonded to a 2,3-dicyanonaphthalene ring [JP-A No. 60-23451,
JP-A No. 61-215663, and Journal Obsei Khim (Zh, Obs, Khim,) 42
Vol., pp. 696-699 (1972)].

[Problem to be solved by the invention]

The dicyanonaphthalene derivatives have insufficient solubility in organic solvents because the alkyl group or alkoxy group is directly bonded to the 2,3-dicyanonaphthalene ring. Therefore, this has been a bottleneck in developing its application.

The object of the present invention is to provide 2,3 molecule having good solubility in organic solvents.
An object of the present invention is to provide a -dicyano-6-naphthylmethanol derivative and a method for producing the same.

[Means to solve the problem]

The gist of the present invention for achieving the above object is as described below.

(1) General formula (1) (wherein R is a straight chain monobranched or cyclic alkyl group having 1 to 2 carbon atoms or an aryl group which may have a substituent, and n is 0 or 1) 2,3-dicyano-6-naphthylmethanol derivative.

(2) O-xylene and bromine are reacted to form 4,5-dibromo-〇-xylene, which is then reacted with N-bromosuccinimide under irradiation with white light to form the following formula (IV):
4,5-dibromo-α represented by

2,3-dibromo-6- After halogenating with methyl naphthoate or hydrogen halide, an alcohol represented by the following formula % (in the formula, R represents the same meaning as above and M represents a hydrogen atom or an alkali metal atom) or 2,3-dibromo-6- represented by the following formula (Vl) by reacting with a metal alcoholade and reducing the compound (V) of the following formula (Vl).
naphthylmethanol, a 2,3-dibromo-6-naphthylmethanol derivative represented by the formula (wherein R represents the same meaning as above), and the compound (X) is reacted with cupric cyanide. General formula (I) where the compound (Vl) is a halide Rcn (■) represented by the following formula (■) (wherein R
represents a straight chain, branched or cyclic alkyl group having 1 to 20 carbon atoms or an aryl group which may have a substituent), or is represented by (wherein R represents the same meaning as above) Method for producing 2,3-dicyano-6-naphthylmethanol derivative.

(3) In the preceding item (2), the compound (IV) represented by the following formula (IV) is reacted with methyl acrylate in the presence of sodium iodide to form the following formula (V) (wherein R is as defined above). A method for producing a 2,3-dicyano-6-naphthylmethanol derivative represented by (having the same meaning).

(4) In the previous section (2), 2 expressed by the following formula (IV)
, methyl 3-dibromo-6-naphthoate is hydrolyzed to form 2,3-dibromo-6-naphthoic acid represented by the following formula (■), and the compound (■) is reduced to form the following formula (VI). 4 shown,
5-dibromo-α, α, α', α'tetrabromo〇-
Xylene is reacted with acrylic acid to form 2,3-dibromo-6-naphthoic acid represented by the following formula (■), and the compound (■) is reduced to form 2, represented by the following formula (VI).
2,3-dibromo-6 represented by general formula (I), characterized in that it is 3-dibromo-6-naphthylmethanol
- general formula characterized in that it is naphthylmethanol (
1) (wherein R represents the same meaning as above) 2
, a method for producing a 3-dicyano-6-naphthylmethanol derivative.

(5) O-xylene and bromine are reacted to form 4,5-dibromo-〇-xylene, which is then reacted with N-bromosuccinimide under white light irradiation to form the following formula (IV
) 4,5-dibromo-α, α, α′, α′-
Tetrabromo-〇-xylene is used, and the compound (V) is reduced to give 2,3 represented by the following formula (W).
-dibromo-6-naphthylmethanol, and the compound (
V[) is an acid halide RCOX represented by the following formula (X[)
(X [) (wherein, R is a linear 9-branched or cyclic alkyl group having 1 to 20 carbon atoms or an aryl group that may have a substituent, X is Cff, B
r, l) to form a 2,3-dibromo-6-naphthylmethanol derivative represented by the following formula (X[l), and the compound (IV) was reacted with methyl acrylate in the presence of sodium iodide. 2, 3 shown by the following formula (V) by reacting
- Methyl dibromo-6-naphthoate (wherein R represents the same meaning as above), characterized in that the compound (X[l) is reacted with cupric cyanide - the following formula (I) The compound (■) is reduced to produce 2,3-dicyano-6 represented by the following formula (Vl) (wherein R represents the same meaning as above)
-Production method of naphthylmethanol derivative.

(6) In the preceding item (5), the 2,3-dibromo- A method for producing a 2,3-dicyano-6-naphthylmethanol derivative represented by the general formula (1) (in the formula, R represents the same meaning as above), characterized in that the derivative is 6-naphthylmethanol.

(7) In the previous section (7), 2 expressed by the following formula (IV)
, methyl 3-dibromo-6-naphthoate is hydrolyzed to produce 2,3 dibromo-6-naphthoic acid represented by the following formula (■), and 4,5-dibromo-α, α, α′! α'tetrabromo-0-xylene is reacted with acrylic acid to form 2,3-dibromo-6-naph-1-dioic acid represented by the following formula (■), and the compound (■) is reduced to form the following formula (Vl ) 2,
A method for producing a 2,3-dicyano-6-naphthylmethanol derivative represented by the general formula (1) (wherein R represents the same meaning as above), characterized in that the derivative is 3-dibromo-6-naphthylmethanol.

The synthesis process of the 2°3-dicyano-6-naphthylmethanol derivative represented by the above formula (1) carried out by the present inventors is summarized as follows.

Countryゝ＼---/' The manufacturing method of compound (m) is 2-2 to 0-xylene.
．． 5 equivalents of bromine in the presence of 0.01 to 0.1 equivalents of iron and iodine in a halogenated solvent such as carbon tetrachloride,
The reaction is carried out in a solvent such as chloroform or methylene chloride.

The reaction temperature is preferably 0 to 50°C, and the reaction is usually completed in 5 to 10 hours. In addition, the method for producing compound (IV) involves adding 4 to 4.5 equivalents of N-bromosuccinimide (NBS) to compound (m) in the presence of 0.01 to 0.05 equivalents of benzoyl peroxide (BPO). , react in carbon tetrachloride while irradiating with white light (hv). The reaction temperature is preferably 50 to 80°C, and the reaction is usually completed in 7 to 12 hours.

The method for producing compound (V) is as follows: 1.
5 to 4.0 equivalents of methyl acrylate to 2.0 to 7.0
A highly polar solvent such as N,N-dimethylformamide in the presence of an equivalent amount of sodium iodide.

The reaction is carried out in a solvent such as dimethyl sulfoxide.

The reaction temperature is preferably 50 to 100°C, usually 3 to 1
The reaction is completed at 0 hours.

The method for producing compound (VI) is based on compound (V).
25-1.0 equivalents of lithium aluminum hydride in an aprotic solvent such as diethyl ether, tetrahydrofuran at a temperature of 0 to 30°C.

React for 10 minutes to 5 hours.

Another method for producing compound (Vl) is to hydrolyze compound (V) with sulfuric acid or the like, or to react compound (mV) and acrylic acid under the same conditions as those for producing compound (V). (2)) After that, a reduction reaction is carried out.

The reduction reaction of compound (■) is carried out by reacting 1.0 to 2.0 equivalents of borane in an aprotic solvent such as diethyl ether or tetrahydrofuran. The reaction temperature is 0~
The temperature is preferably 100°C, and the reaction is usually completed in 2 to 10 hours.

The method for producing compound (X) is to halogenate the hydroxyl group of compound (VI) with hydrogen halide, and then react with alcohol, metal alcoholade, phenol or metal salt of phenol, or as another method, compound (VI) is reacted with hydrogen halide. Reacts directly with halides.

The halogenation of the hydroxyl group of compound (VI) is carried out by mixing 1 to 5 times the mole of hydrohalic acid in the presence of 0.1 to 2.0 times the mole of concentrated sulfuric acid in an aprotic solvent such as n-hexane, tetrahydrofuran, The reaction is carried out in a solvent such as diethyl ether, benzene, or toluene. Reaction temperature is 20-100℃
is suitable, and the reaction is usually completed in 1 to 5 hours.

The obtained halomethylated product is reacted with 1 to 2 times the mole of metal alcoholade or metal salt of phenol, or
Compound (X) can be easily obtained by reacting with alcohol or phenol in the presence of 1 to 2 times the mole of amine. The reaction is carried out in an aprotic solvent such as benzene, toluene, xylene. The reaction temperature varies depending on the solvent used, but is preferably 10 to 150°C, and is usually completed in 1 to 5 hours.

The method for producing compound (X) by reacting compound (VI) with an alkyl halide or aryl halide includes
) to 1 to 2.5 equivalents of halide.
The reaction is carried out in the presence of 5 equivalents of amine in an aprotic solvent such as benzene, toluene, xylene, etc. The reaction temperature varies depending on the solvent used, but is between 50 and
A temperature of 150°C is suitable, and the reaction is usually completed in 1 to 5 hours.

The method for producing compound (Bi) involves the addition of 2 to 3
Equivalent amounts of cupric cyanide are reacted in a highly polar solvent such as N,N-dimethylformamide, dimethyl sulfoxide, and the like. The reaction temperature is preferably 100 to 200°C, and is usually completed in 1 to 5 hours.

The method for producing compound (Xll) involves adding 1 to 1.5 equivalents of acid halide to compound (VI) in an aprotic solvent such as n-hexane, benzene, or toluene.

The reaction is carried out in a solvent such as xylene. The reaction temperature varies depending on the solvent, but is preferably 50 to 150°C, and usually 1 to 5°C.
The reaction is completed in time.

The method for producing compound (■") involves adding 2 to 3 equivalents of cupric cyanide to compound (X [l)] in a highly polar solvent such as N,
The reaction is carried out in a solvent such as N-dimethylformamide or dimethyl sulfoxide. The reaction temperature is preferably 100 to 200°C, and is usually completed in 1 to 5 hours.

[Effect]

The reason why the 2,3-dicyano-6-naphthylmethanol derivative represented by the formula (1) of the present invention has good solubility in a solvent is considered to be because it has a -CHxO- group.

〔Example〕

Example 1 [Synthesis of 4,5-dibromo-0-xylene] In a 2Q four-loaf flask equipped with a stirrer, a thermometer, two dropping funnels, and a cooling tube, methylene chloride 80 g and iron powder 1 1.6 g (0
．． 21 mol), 5.3 g (0.021 mol) of iodine, and 1338 g (8.37 mol) of bromine at 0 to 10°C.
It dripped in time.

After the dropwise addition was completed, the mixture was aged at 20 to 40°C to complete the reaction. After the reaction, wash with 5% sodium bisulfite aqueous solution, then wash with water,
After drying and concentrating under reduced pressure, 335.1 g of 4 was recrystallized from 2000 mR of methanol.

5-dibromo-〇-xylene was obtained (yield 31%).

Melting point: 87.5-88.0°C Mass spectrum: 264 (M+) Figure 1 shows the mass spectrum, Figure 2 shows the NMR spectrum,
Figure 3 shows the infrared absorption spectrum.

[Synthesis of 4,5-dibromo-α,α,α′,α′-tetrabromo-〇-xylene] 2 units equipped with a stirrer, a thermometer, 2 dropping funnels, and a cooling tube.
Q: In the fourth flask, 150 g (0.57 mol) of 4,5-dibromo-xylene, 425 g (2.39 mol) of N-bromosuccinimide, and 2.8 g of benzoyl peroxide.
g (0.0 1 2 mol) and carbon tetrachloride 2000
mR was charged, heated to 70 to 80°C, and reacted for 10 hours while irradiating with 150 W incandescent light. After cooling, the by-produced succinimide was filtered off, concentrated under reduced pressure, and the residue was recrystallized from 660 mn of cyclohexane to give 293
g of 4,5-dipromo α, α, α', α'-tetrabromo 〇-xylene was obtained (yield 87%).

Melting point = 131-133℃ Mass spectrum: 579 (M+) IHNMR spectrum (200 MHz).

CD Cna), δ (ppm) 6.9 (s, 2H, CHB rx)
7.9 (s, 2H, benzene ring) Figure 4 shows the mass spectrum, Figure 5 shows the NMR spectrum,
Figure 6 shows the infrared absorption spectrum.

[Synthesis of methyl 2,3-dibromo-6-naphthoate] 1Ω equipped with a stirrer, a thermometer, 2 dropping funnels, and a cooling tube.
In the fourth flask, add N,N-dimethylformamide (D
MF) 300mQ, methyl acrylate 37.6 g (
0,44 mol), sodium iodide 95.3 g (0,
64 mol), 4,5-dibromo-α, α, α′
, α'-tetrabromo0-xylene 126.5g (0
, 21 mol) dissolved in 200 mQ of DMF was added dropwise at 70 to 80°C over 2 hours. After completion of the dropwise addition, the mixture was aged at the same temperature to complete the reaction. After cooling, the crystals were poured into a 5% aqueous sodium bisulfite solution and separated by filtration, washed with water, dried, and recrystallized from 270 mm of acetone to give 53.7 g of 2
゜Methyl 3-dibromo-6-naphthoate was obtained (yield: 7
4%).

Melting point = 134-135℃ Mass spectrum: 344 (M+) Technical HNMR spectrum (200, MHz.

CDCΩ8), δ (ppm) 3.95 (s, 3H, CHaCOO-)7
．． 6-8.4 (m, 5H, naphthalene ring) Figure 7 shows the mass spectrum, Figure 8 shows the NMR spectrum,
Figure 9 shows the infrared absorption spectrum.

[Synthesis of 2,3-dibromo-6-naphthoic acid] Method A 2 equipped with a stirrer, a thermometer, 9 dropping funnels, and a cooling tube.
a In a fourth flask, add 177 g (0.51 mol) of methyl 2,3-dibromo-6-naphthoate and 560 m of acetic acid.
180 m Q of water and 177 g of concentrated sulfuric acid were charged, and the mixture was reacted for 7 hours under reflux while heating to 106 to 111°C. After the reaction, 930 mΩ of water was added to crystallize, and the crystals were filtered off, washed with water, dried, and washed with 1000 m of tetrahydrofuran.
(Recrystallized from 1, 156 g of 2,3-dibromo-6
-Naphthoic acid was obtained (yield 92%).

Melting point: 284℃ Mass spectrum: 330 (M+) IHNMR spectrum (200 MHz).

CDCf1+dG-DMSO) δ (ppm) 7.8~R,6 (m, 6H, naphthalene ring + C00H) Figure 10 shows the mass spectrum, Figure 11 shows the NMR spectrum, and Figure 12 shows the infrared absorption spectrum.

■Method B 3 equipped with a stirrer, 2 thermometers, a dropping funnel, and a cooling tube.
In a 00mQ four-loop flask, 160mn of N,N-dimethylformamide (DMF) and 14.4g of acrylic acid (
0,20 mol), sodium iodide 45.0 g (0,
30 mol), 4,5-dipromo α, α, α′
, α'-tetrabromo〇-xylene 29.0g (0,
A solution of 05 mol) dissolved in 60 m m of DMF was
The mixture was added dropwise at ~80°C for 2 hours. After completion of the dropwise addition, the mixture was aged at the same temperature to complete the reaction. After cooling, the crystals were poured into a 5% aqueous sodium bisulfite solution and the crystals were separated by filtration, washed with water, dried, and recrystallized from tetrahydrofuran LoomΩ to obtain 11.7 g of 2,3-dibromo-6-naphthoic acid (yield 71%
).

Melting point = 284℃ Mass spectrum: 330 (M+) IHNMR spectrum (200MHz.

CDCf1+dG-DMSO) δ (ppm) 7, 8-8.6 (m, 6H, naphthalene ring + -COOH) [Synthesis of 2,3-dibromo-6-naphthylmethanol] ■Method A Stirrer, thermometer, dropping funnel and one equipped with cooling pipes.
00mM in a four-loop flask, add 10% tetrahydrofuran
m Q, 0.14 g of lithium aluminum hydride (
A solution of 2.0 g (5.8 mmol) of methyl 2,3-dibromo-6-naphthoate dissolved in 10 mQ of tetrahydrofuran was heated at 0 to 10°C for 3.5 mmol.
It was dropped in 0 minutes. After the dropwise addition was completed, the mixture was aged at the same temperature for 1 hour to complete the reaction. After cooling, add 10% hydrochloric acid to decompose, wash with water,
After drying, the residue was purified by silica gel chromatography to obtain 0.55 g of 2,3 dibromo-6-naphthylmethanol (yield 30%).

Melting point: 140-14.1℃ Mass spectrum: 316 (M+) IHNMR spectrum (200 MHz).

CDCΩ8) δ (ppm) 1.8 (s, L H, -CH20
H) 4.8 (s, 2H, -CH20H) 7, 2-8, 2 (m, 5 H, naphthalene ring) Figure 13 shows the mass spectrum, Figure 14 shows the NMR spectrum, and Figure 15 shows the infrared absorption spectrum. shows.

■Method B 3 equipped with a stirrer, 2 thermometers, a dropping funnel, and a cooling tube.
Ω A fourth flask was charged with 156 g (0.47 mol) of 2,3-dibromo-6-naphthoic acid and 1900 mΩ of tetrahydrofuran, and after replacing the entire system with Ar gas, the IM borane-tetrahydrofuran was heated at 0 to 10°C. 600 mu (0.6 mol) of the solution was added dropwise over 1.5 hours. After the dropwise addition was completed, the mixture was aged at 30 to 40°C for 2.5 hours to complete the reaction.

After cooling, add 150 m of water dropwise to hydrolyze, and then wash with water.

After drying, concentrate under reduced pressure and dissolve the residue in isopropyl alcohol 6
Recrystallization from 00 mQ gave 144 g of 2,3-dibromo-6-naphthylmethanol (yield 95%).

Melting point = 140-141℃ Mass spectrum: 316 (M+) "HNMR spectrum (200MHz).

CD CQ s) δ (ppm) 1.8-(s, IH, -CHzOH) 4.
8 (s, 2H, -CH20H) 7.2-8.2 (m, 5H, naphthalene ring) [Synthesis of 6-bromomethyl-2,3-dibromonaphthalene] 300 mA equipped with a stirrer, thermometer, and cooling tube A three-necked flask was charged with 8.0 g (25 mmol) of 2,3-dibromo-6-naphthylmethanol, 16 g of 47% hydrobromic acid, 30 mA of benzene, and 4 g of concentrated sulfuric acid.
The reaction was carried out under reflux for 2 hours.

After cooling, the benzene layer was washed with water and dried, and the residue obtained after concentration under reduced pressure was recrystallized from 40 mQ of acetone to obtain 8.
5 g of 6-promomethyl-2,3 dibromonaphthalene was obtained (yield: 90%).

Melting point: 105-106℃ Mass spectrum: 378 (M+) Technical HNMR spectrum (200MHz.

CDCf1a) δ (ppm) 4.6 (s, 2H, -CHzB
r) 7.4 to 8.2 (m, 5H, naphthalene ring) Figure 16 shows the mass spectrum, Figure 17 shows the NMR spectrum, and Figure 18 shows the infrared absorption spectrum.

[Synthesis of 6-tert-butoxymethyl-2,3-dibromonaphthalene] 40 mR of toluene, 2.6 g (23.3 mmol) of tert-butoxypotassium were added to a 100 mμ three-necked flask equipped with a stirrer, a thermometer, and a condenser. Prepare
6-promomethyl-2,3-dibromonaphthalene 6.0
g (15.5 mmol) in 20 mQ of tetrahydrofuran
was added dropwise at 20 to 30°C over 30 minutes. After the dropwise addition was completed, the mixture was aged at the same temperature for 3 hours to complete the reaction. After the reaction, the reaction was washed with water, dried and concentrated under reduced pressure, and the residue was purified by silica gel chromatography to obtain n-hexane/benzene=8
5.0 g of 6-tert from the part eluted at /2
-Butoxymethyl-2,3-dibromonaphthalene was obtained (yield 86%).

Melting point: 58-59°C Mass spectrum: 372 (M+) "HNMR spectrum (200MHz).

CDCQa) δ(PPm) 1.3 (s, 9H, -C(
Figure 19 shows the mass spectrum, Figure 20 shows the NMR spectrum, and Figure 21 shows the infrared absorption. Spectrum 1 is shown.

(Synthesis of 6-tert-butoxymethyl-2,3-dicyanonaatalene) 6-tert-butoxymethyl-2
, 3-dibromonaphthalene 2.1 g (5.6 mmol)
, cupric cyanide 1.6 g (17 mmol) and N, N
- Prepare 25mQ of dimethylformamide, 150~1
The reaction was carried out at 55°C for 2 hours.

After cooling, the reaction solution was poured into 75 mQ of 15% aqueous ammonia to precipitate crystals. The crystallized crystals were mixed with benzene 100 mQ
After extraction, the residue obtained by concentration under reduced pressure was purified by silica gel column chromatography, and the 6-tert
-Butoxymethyl-2゜3-dicyanonaphthalene 0.9
5g was obtained (yield 63%).

Melting point = 130-131°C Mass spectrum: 264 (M+) "HNMR spectrum (200MHz).

CDCΩ3) δ (ppm) 1.3 (s, 9H, -C (pHs Agency) 4.
65 (s, 2H, -CH2O-) 7.7-8.3 (m, 5H, naphthalene ring) IR spectrum (νCN) 2200 mark-1 Figure 22 shows the mass spectrum, and Figure 23 shows the NMR spectrum. , 24th
The figure shows the infrared absorption spectrum.

Example 2 [Synthesis of 6-amyloxymethyl-2,3-dibromonaphthalene] 140- To a 100 mQ three-necked flask equipped with a stirrer, a thermometer, and a condenser, 300 mQ of toluene and sodium amyloxide were added. 44.3 g (400 mmol) was charged, and 119.8 g (310 mmol) of 6-bromomethyl-2,3-dibromonaphthalene was added to 300 m of toluene.
A solution dissolved in Q was added dropwise at 108 to 110°C over 1 hour. After the dropwise addition was completed, the mixture was aged at the same temperature for 3 hours to complete the reaction. Wash with water after reaction.

It was dried and concentrated under reduced pressure, and the residue was purified by silica gel chromatography to obtain 120.2 g of 6-amyloxymethyl-2,3-dibromonaphthalene from the portion eluted with n-hexane/benzene = 8/2 ( yield 100%)
.

Mass spectrum: 386 (M+) "HNMR spectrum (200MHz.

CDC11g) δ (ppm) o, s-3,6 (m, 11H.

n -C5Hxx○-) 4.6 (s, 2.H, -CH20) 7.4-8.1 (m, 5H, naphthalene ring) Figure 25 shows the mass spectrum, Figure 26 shows the NMR spectrum, and Figure 27 The figure shows the infrared absorption spectrum.

[Synthesis of 6-amyloxymethyl-2,3-dicyanonaphthalene] 120 g (310 mmol) of 6-amyloxymethyl-2゜3-dibromonaphthalene was placed in a 3Q three-necked flask equipped with a stirrer, a thermometer, and a condenser. ), 86 g (930 mmol) of cupric cyanide and 1.30 g of N,N-dimethylformamide, and heated at 150 to 155°C for 3 hours.
Time reacted. After cooling, the reaction solution was mixed with 15% ammonia water3.
30 to precipitate crystals. The crystallized crystals were extracted with 1.5Q of benzene, concentrated under reduced pressure, the resulting residue was purified by silica gel column chromatography, and the portion eluted with benzene/ethyl acetate = 9515 was
-amyloxymethyl-2,3-dicyanonaphthalene 55
．． 3 g (yield 64%).

Melting point = 76-78℃ Mass spectrum: 278 (M+) Technical HNMR spectrum (200 MHz.

CDCQa) δ (ppm) 0.8-3.6 (m, 11H.

n-C6H Engineering 1-〇-) 4, 7 (s, 2H, -CH2-○-) 7.7
-8.3 (m, 5H, naphthalene ring) IR spectrum (v CN) 2210an-'28th
The figure shows the mass spectrum, FIG. 29 shows the NMR spectrum, and FIG. 30 shows the infrared absorption spectrum.

Example 3 [Synthesis of 6-capryloyloxymethyl-2,3-dibromonaphthalene] 5 equipped with a stirrer, thermometer, dropping funnel and cooling tube
2,3-dibromo-6-
79.0 g (0.24.4 mol) of naphthylmethanol and 300 mΩ of toluene were charged, and 4.4.5 g (0.27 mol) of n-caprylic acid chloride was added dropwise at 105 to 110° C. over 1 hour.

After the dropwise addition was completed, the mixture was aged at 110 to 115°C to complete the reaction. After cooling, wash with 6% sodium bicarbonate aqueous solution, then wash with water.
Dry, concentrate under reduced pressure, and add 600 mQ of acetone to the resulting residue.
103 g of 6-capryloyloxymethyl-2,3-dibromonaphthalene was obtained (yield 91%).
.

Melting point = 43-44℃ Mass spectrum: 442 (M+) "HNMR spectrum (200MHz).

CDCQa) δ(P pm) 0.7~2-5 (m + 15
H+n-C7H111COO-) 5.2 (s, 2H, -CHzOCO) 7.4-8.1 (m, 5H, naphthalene ring) Figure 31 shows the mass spectrum, Figure 32 shows the NMR spectrum, and Figure 33 shows the infrared spectrum. The absorption spectrum is shown.

[Synthesis of 6-capryloyloxymethyl-2,3-disymanonaphthalene] 2 equipped with a stirrer, thermometer, dropping funnel and cooling tube
94.0 g of 6-capryloyloxymethyl-2,3-dibromonaphthalene (0,211
mol), cupric cyanide, and 800 mΩ of N,N-dimethylformamide were charged and reacted at 150 to 155°C for 2 hours. After cooling, add 2000ml of 15% ammonia water to the reaction solution.
The mixture was poured into fl and crystals were crystallized. The crystallized crystals were extracted with 2000 mQ of tetrahydrofuran, concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography, and the portion eluted with benzene/ethyl acetate = 98/2 was extracted with 6-capryloyloxymethyl- 2,3
-51 g of dicyanonaphthalene was obtained (yield 72%).

Melting point = 87-88°C Mass spectrum: 334 (M+) IHNMR spectrum (200 MHz).

CDCua) δ (ppm) 0.7-2.5 (m, 15H, nC7H1
5COO-) 5.3 (s, 2H, -CHzOCO-) 7.7-8.4
(m, 5H, naphthalene ring) IR spectrum (νCN) 2210G-1 Figure 34 shows the mass spectrum, Figure 35 shows the NMR spectrum, and Figure 36 shows the infrared absorption spectrum.

Example 4 [Synthesis of 6-caproylokdimethyl-2,3-dibromonaphthalene] 5 equipped with a stirrer, a thermometer, two dropping funnels, and a cooling tube.
00 m (l) was charged with 87.0 g (0.27 mol) of 2,3-dibromo-6-naphthylmethanol and 260 mΩ of toluene, and 47.3 g (0.35 mol) of n-caproyl chloride. ) from 105 to 11
The mixture was added dropwise at 0° C. over 30 minutes. 110-115℃ after completion of dropping
The reaction was completed by aging.

After cooling, wash with 6% aqueous sodium hydrogen carbonate solution, wash with water, dry, and concentrate under reduced pressure. The resulting residue was dissolved in 500 m of acetone.
Recrystallization from A gave 111 g of 6-caproylokidimethyl-2,3-dibromonaphthalene (yield 99%).

Melting point: 44-45℃ Mass spectrum: 414 (M+) "HNMR spectrum (200MHz).

CDCRa) δ (ppm) 0.8-2.5 (m, 11H.

n -C5Hif CO0-) 5.2 (s, 2H, -CHzOCO-) 7.4-8.1
(m, 5H, naphthalene ring) Figure 37 shows the mass spectrum, Figure 38 shows the NMR spectrum, and Figure 39 shows the infrared absorption spectrum.

[Synthesis of 6-caproylokodimethyl-2,3-dicyanonaphthalene] 3 equipped with a stirrer, a thermometer, 9 dropping funnels, and a cooling tube.
6-caproyloxydimethyl-2 in a four-bottle flask, Q.
,3-dibromonaphthalene 111g (0.27mol/L
/), 73.0 g (0.80 mol) of Schiff'/cupric oxide and N,N-dimethylformamide IQ were charged and reacted at 150 to 155°C for 3 hours. After cooling, the reaction solution was diluted with 15% ammonia. The crystals were poured into 2500 mQ of water and crystallized. The crystals were extracted with 1500 mQ of benzene, concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography. Benzene/ethyl acetate = 98/2
56.4 g of 6-caproylokidimethyl-2,3-dicyanonaphthalene was obtained from the eluted portion (yield: 68%).

Melting point = 114-115℃ Mass spectrum: 306 (M+) "HNMR spectrum (200MHz.

CD CQs) δ (ppm) 0.8-2.5 (m, 11H.

n -Cs H11COO-) 5.3 (s, 2H, CHzOCO) 7.7-8.4 (m, 5H, natutalene ring) IR spectrum (v CN) 2200an-' 40th
Figure 41 shows the mass spectrum, Figure 41 shows the NMR spectrum, and Figure 42 shows the infrared absorption spectrum.

Example 5 6-tert-butoxymethyl-2,3-dicyanonaphthalene, 6-amyloxymethyl-2,3-dicyanonaphthalene, 6-capryloyloxymethyl-2,3-dicyanonaphthalene, 6-caproylokidimethylene Lou 2,3-
When the solubility of dicyanonaphthalene in ethanol, benzene, toluene, cyclohexane, methyl ethyl ketone, and chloroform was investigated, it showed good solubility in all of them.

In addition, since the fluorescence spectra are subject to solvent effects, each is made into an ethanol solution (10-'moΩ/Q).
The fluorescence spectrum was measured (Hitachi MPF-4 type fluorescence spectrum measurement device, light source: Canon lamp). The measurement results are shown in Table 1.

Table 1 [Effects of the Invention] The compounds of the present invention have the effect of having sufficient solubility in general-purpose organic solvents, and therefore are excellent in application development as raw material compounds. It is also useful as a new fluorescent substance.

[Brief explanation of the drawing]

1, 4, 7, 10, and 13. Fig. 16, Fig. 19, Fig. 22, Fig. 25, Fig. 28,
Fig. 31, Fig. 34, Fig. 37 and Fig. 40 are mass spectra of compounds synthesized in Examples of the present invention, Fig. 2, Fig. 5, Fig. 8, Fig. 11, Fig. 14, Figures 17, 20, and 23. Figures 26, 29, 32, 35, 38, and 41 show the NM of the compounds synthesized in the examples of the present invention.
R spectrum diagrams, Figures 3 and 6. 9, 12, 15, 18, 21, 24, 27, 30, and 33. FIG. 36, FIG. 39, and FIG. 42 are infrared absorption spectra of compounds synthesized in Examples of the present invention. ■ Shima Hiroko; Ma, sad day Pe fake ≧, old man miss Σ procedure amendment book illusion

Claims (1)

[Claims] 1. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R is a straight chain, branched or cyclic alkyl group having 1 to 20 carbon atoms or a substituent a 2,3-dicyano-6-naphthylmethanol derivative represented by an aryl group (which may have an aryl group, n represents 0 or 1). 2, o-xylene is reacted with bromine to produce 4,5-dibromo-o-xylene, which is then reacted with N-bromosuccinimide under irradiation with white light to produce 4,5- Dibromo-α, α, α′, α′-tetrabromo-o-xylene, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (IV) The compound (IV) is reacted with methyl acrylate in the presence of sodium iodide. The compound (V) is reduced to form methyl 2,3-dibromo-6-naphthoate represented by the following formula (V), which has mathematical formulas, chemical formulas, tables, etc. 2,3 indicated by
-dibromo-6-naphthylmethanol, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VI) The compound (VI) is a halide RCl (VIII) represented by the following formula (VIII) (wherein, R is the number of carbon atoms 1 to 20 linear, branched or cyclic alkyl groups or aryl groups which may have substituents) or halogenated with hydrogen halide, the following formula (IX) ROM (IX) (In the formula, R represents the same meaning as above and M represents a hydrogen atom or an alkali metal atom) It reacts with the alcohol or metal alcoholade represented by the following formula (X) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (X) (wherein R represents the same meaning as above) 2,3
-Dibromo-6-naphthylmethanol derivative, general formula (I) characterized by reacting the compound (X) with cuprous cyanide▲There are mathematical formulas, chemical formulas, tables, etc.▼
(I) 2,3 represented by (in the formula, R represents the same meaning as above)
-Production method of dicyano-6-naphthylmethanol derivative. 3. In claim 2, the compound (IV) represented by the following formula (IV) ▲Mathematical formula, chemical formula, table, etc.▼(IV) is reacted with methyl acrylate in the presence of sodium iodide. The following formula (V) ▲Mathematical formulas, chemical formulas, tables, etc. are available▼(V) Hydrolyzing methyl 2,3-dibromo-6-naphthoate shown by the following formula (VII) -6-naphthoic acid, ▲There are mathematical formulas, chemical formulas, tables, etc.▼(VII) The compound (VII) is reduced to the following formula (VI) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(VI) 2,3-dibromo-6-naphthylmethanol, represented by the general formula (I)▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (in the formula, R represents the same meaning as above) 2,3
-Production method of dicyano-6-naphthylmethanol derivative. 4. In claim 2, 4,5-dibromo-α,α,α′,α′-tetrabromo-o- represented by the following formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) By reacting xylene with acrylic acid,
2,3-dibromo-6-naphthoic acid shown by the following formula (VII), ▲There are mathematical formulas, chemical formulas, tables, etc.▼(VII) The compound (VII) is reduced to the following formula (VI) ▲Mathematical formula, There are chemical formulas, tables, etc. ▼ General formula (I) characterized by 2,3-dibromo-6-naphthylmethanol represented by (VI) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (Formula (R represents the same meaning as above) 2,3
-Production method of dicyano-6-naphthylmethanol derivative. 5, o-xylene and bromine are reacted to produce 4,5-dibromo-o-xylene, which is then reacted with N-bromosuccinimide under irradiation with white light to produce 4,5- Dibromo-α, α, α′, α′-tetrabromo-o-xylene, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (IV) The compound (IV) is reacted with methyl acrylate in the presence of sodium iodide. The compound (V) is reduced to form methyl 2,3-dibromo-6-naphthoate represented by the following formula (V), which has mathematical formulas, chemical formulas, tables, etc. 2,3 indicated by
-dibromo-6-naphthylmethanol, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VI) The compound (VI) is an acid halide RCOX (X I) represented by the following formula (X I) (wherein R is A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or an aryl group which may have a substituent (X represents Cl, Br, I) to form the following formula (XI
The 2,3-dibromo-6-naphthylmethanol derivative represented by I) has ▲mathematical formulas, chemical formulas, tables, etc.▼(
XII) The compound (XII) (wherein R represents the same meaning as above)
General formula (I) characterized by the reaction of cuprous cyanide with 3
-Production method of dicyano-6-naphthylmethanol derivative. 6. In claim 5, the compound (IV) represented by the following formula (IV) ▲Mathematical formula, chemical formula, table, etc.▼(IV) is reacted with methyl acrylate in the presence of sodium iodide. The resulting formula (V) ▲Mathematical formulas, chemical formulas, tables, etc. are available▼(V) Hydrolyzing methyl 2,3-dibromo-6-naphthoate shown by the following formula (VII) -dibromo-6-naphthoic acid, ▲There are mathematical formulas, chemical formulas, tables, etc.▼(VII) The compound (VII) is reduced to the following formula (VI) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(VI) General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) (In the formula, R represents the same meaning as above) 2,3 indicated by
-Production method of dicyano-6-naphthylmethanol derivative. 7. In claim 5, 4,5-dibromo-α,α,α′,α′-tetrabromo-o- represented by the following formula (IV) ▲Mathematical formula, chemical formula, table, etc.▼(IV) By reacting xylene with acrylic acid,
2,3-dibromo-6-naphthoic acid shown by the following formula (VII), ▲There are mathematical formulas, chemical formulas, tables, etc.▼(VII) The compound (VII) is reduced to the following formula (VI) ▲Mathematical formula, There are chemical formulas, tables, etc. ▼ (VI) General formula (I) characterized by the following 2,3-dibromo-6-naphthylmethanol ▲ Numerical formulas, chemical formulas,
There are tables, etc. ▼ (I) (in the formula, R represents the same meaning as above) 2,3
-Production method of dicyano-6-naphthylmethanol derivative.