JP3131061B2 - Spiro (anthrone-phthalide) derivative, method for producing the same, and recording material containing the derivative - 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 spiro (anthrone-phthalide) derivative, a method for producing the same, and a recording material containing the derivative and a color-developing substance for developing the derivative.

[0002]

2. Description of the Related Art Conventionally, recording materials utilizing a color reaction between a colorless or pale-colored coloring agent and an inorganic or organic color developing substance are already well known as pressure-sensitive recording materials, heat-sensitive recording materials and the like. .

For example, pressure-sensitive recording materials are disclosed in
As disclosed in Japanese Patent No. 201444, slips,
It is used in fields such as computer printers. Further, as disclosed in Japanese Patent Publication No. 45-14039, heat-sensitive recording materials are used in a wide range of fields such as measurement recorders, facsimile machines, printers, and automatic ticket vending machines.

Recently, for example, near-infrared reading for optically and mechanically reading a bar code or a character of a POS label has been actively performed in conjunction with rapid development of semiconductor lasers and the like. Therefore,
A coloring material having absorption in the near infrared region has been strongly demanded.

Compounds having absorption in the near infrared region at the time of color development include, for example, JP-A-51-21035, JP-A-51-21037, and JP-A-51-21038.
No., JP-A-57-167979, JP-A-58-157
779, JP-A-60-8364, JP-A-60-27
No. 589, phthalide compounds described in JP-A-59-148695 and JP-B-57-57064.
Thiofluorane compounds disclosed in JP-B-58-51967 and JP-A-59-199757.
And fluorene compounds disclosed in JP-A-60-225871 and the like.

However, phthalide compounds and fluorene compounds have absorption maximum wavelengths on the relatively long wavelength side (800 nm or more) and are inferior in stability of a color image, and thiofluorane compounds have a wavelength of 700 nm.
Although it has an absorption maximum before and after, it has the disadvantage that the absorption is broad and the extinction coefficient is low.

[0007]

The present invention has light absorption in the near-infrared region, has excellent color image fastness, and is applicable to an optical character reading device and a bar code system using a semiconductor laser. It is to provide a simple recording material.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, synthesized compounds which have not been known so far, and these compounds are in a color-developed state in the near infrared region. The present invention has been found to have useful properties showing strong absorption in the region and has completed the present invention. That is, the present invention
General formula (I)

[0009]

Embedded image Wherein X is

[0010]

Embedded image (However, R ² represents an alkyl group having 1 to 4 carbon atoms); Y represents an amino group having an alkyl group having 1 to 8 carbon atoms or a phenyl group; May be. Z represents a hydrogen atom, a halogen atom, or a phenoxy group. R ¹ represents a halogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 4. And a method for producing the spiro (anthrone-phthalide) derivative, and a recording material using the derivative.

When a recording material was prepared using the compound of the present invention, this recording material was found to have very specific and useful properties different from conventional near-infrared absorbing color formers. . When light is applied to a color-developed image, the conventional near-infrared-absorbing color former is easily faded due to low robustness, and the light-absorbing ability in the near-infrared region has almost always disappeared. However, in the case of the recording material of the present invention, when light is applied to the coloring portion, the maximum absorption position in the near-infrared portion moves by a short wavelength of about 200 nm,
In addition, not only the extinction coefficient was increased, but also a light-fast colored image was obtained (see FIG. 6). This short wavelength shift effect of the absorption position by light irradiation can be expected to be greatly utilized in the erasing and writing of recording at a specific wavelength.

The compound represented by the general formula (I) can be produced by the following method. That is, the general formula (I
I)

[0013]

Embedded image [Wherein, X, Y, and Z represent X, Y,
Represents the same meaning as Z. And a compound represented by the general formula (III)

[0014]

Embedded image Wherein, R ^1, n represents the same meaning as R ^1, n in the formula (I). And a phthalic anhydride derivative of the formula (1) in the presence of a Lewis acid catalyst.

The reaction is carried out in a solvent or without a solvent.
The benzophenone derivative (II) and the acid anhydride (III) are mixed in a molar ratio of 1: 0.5 to 1: 2, preferably equimolar,
At 20 to 120 ° C., preferably 50 to 80 ° C., for 1 to 16 hours, preferably
６6 hours, then concentrated sulfuric acid was added, and
Stir at 0 ° C. for 1-10 hours. The obtained reaction mixture is discharged into 10 to 20 times the volume of ice water, made weakly alkaline with a basic compound, and then extracted with an appropriate extraction solvent.
After distilling off the extraction solvent, the compound represented by the general formula (I) can be obtained by purification by a generally known purification method, for example, column chromatography, recrystallization method or the like.

Preferred examples of the reaction solvent include methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, tetrachloroethylene, chlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene and the like.

As the acid catalyst, a Lewis acid catalyst such as aluminum chloride, zinc chloride, and iron chloride is used.

As the base for neutralizing sulfuric acid, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate and the like are preferably used.

The extraction solvent is ether, chloroform,
Butyl acetate, methyl isobutyl ketone, benzene, toluene and xylene are preferably used.

The compound represented by the general formula (II) as a raw material can be prepared by a method described in J. Org. Chem., 23 350 (1958), that is, nitrating a benzophenone derivative with a mixed acid, and then tin / HCl. It can be obtained by a reduction method and the like. Further, the compound represented by the general formula (III)
Commercial products are readily available.

Specific examples of the compound represented by the general formula (I) of the present invention include 3,6-bis (dimethylamino)
Spiro [anthrone-9,3'-phthalide], 3,6-
Bis (diethylamino) spiro [anthrone-9,3 '
-Phthalide], 3,6-bis (di-n-propylamino) spiro [anthrone-9,3′-phthalide], 3,
6-bis (diisopropylamino) spiro [anthrone-9,3′-phthalide], 3,6-bis (di-n-butylamino) spiro [anthrone-9,3′-phthalide], 3,6-bis ( Diisobutylamino) spiro [anthrone-9,3'-phthalide], 3,6-bis (di-
n-pentylamino) spiro [anthrone-9,3'-
Phthalide], 3,6-bis (diisopentylamino) spiro [anthrone-9,3'-phthalide], 3,6-bis (pyrrolidino) spiro [anthrone-9,3'-phthalide], 3,6- Bis (piperidino) spiro [anthrone-9,3'-phthalide], 3,6-bis (N-methyl-N-isopropylamino) spiro [anthrone-9,
3′-phthalide], 3,6-bis (N-ethyl-N-isopropylamino) spiro [anthrone-9,3′-phthalide], 3,6-bis (N-methyl-N-phenylamino) spiro [ Anthrone-9,3'-phthalide],
3,6-bis (N-ethyl-N-phenylamino) spiro [anthrone-9,3′-phthalide],

3,6-bis (dimethylamino) spiro [anthrone-9,3 ′-(4 ′, 5 ′, 6 ′, 7′-
Tetrachlorophthalide)], 3,6-bis (diethylamino) spiro [anthrone-9,3 '-(4', 5 ',
6 ', 7'-tetrachlorophthalide)], 3,6-bis (di-n-propylamino) spiro [anthrone-9,
3 ′-(4 ′, 5 ′, 6 ′, 7′-tetrachlorophthalide)], 3,6-bis (diisopropylamino) spiro [anthrone-9,3 ′-(4 ′, 5 ′, 6 ′) , 7'-
Tetrachlorophthalide)], 3,6-bis (di-n-butylamino) spiro [anthrone-9,3 '-(4',
5 ', 6', 7'-tetrachlorophthalide)], 3,6
-Bis (diisobutylamino) spiro [anthrone-
9,3 ′-(4 ′, 5 ′, 6 ′, 7′-tetrachlorophthalide)], 3,6-bis (di-n-pentylamino)
Spiro [anthrone-9,3 '-(4', 5 ', 6',
7'-tetrachlorophthalide)], 3,6-bis (diisoamylamino) spiro [anthrone-9,3'-
(4 ', 5', 6 ', 7'-tetrachlorophthalide)], 3,6-bis (pyrrolidino) spiro [anthrone-9,3'-(4 ', 5', 6 ', 7'- Tetrachlorophthalide)], 3,6-bis (piperidino) spiro [anthrone-9,3 '-(4', 5 ', 6', 7'-
Tetrachlorophthalide)], 3,6-bis (N-methyl-N-isopropylamino) spiro [anthrone-9,
3 '-(4', 5 ', 6', 7'-tetrachlorophthalide)], 3,6-bis (N-ethyl-N-isopropylamino) spiro [anthrone-9,3 '-(4' ,
5 ', 6', 7'-tetrachlorophthalide)], 3,6
-Bis (N-methyl-N-phenylamino) spiro [anthrone-9,3 '-(4', 5 ', 6', 7'-tetrachlorophthalide)], 3,6-bis (N-ethyl -N
-Phenylamino) spiro [anthrone-9,3'-
(4 ′, 5 ′, 6 ′, 7′-tetrachlorophthalide)],

2,7-dichloro-3,6-bis (dimethylamino) spiro [anthrone-9,3′-phthalide], 2,7-dichloro-3,6-bis (diethylamino) spiro [anthrone-9, 3′-phthalide], 2,
7-dichloro-3,6-bis (di-n-propylamino) spiro [anthrone-9,3′-phthalide], 2,
7-dichloro-3,6-bis (diisopropylamino)
Spiro [anthrone-9,3'-phthalide], 2,7-
Dichloro-3,6-bis (di-n-butylamino) spiro [anthrone-9,3'-phthalide], 2,7-dichloro-3,6-bis (diisobutylamino) spiro [anthrone-9,3 ' -Phthalide], 2,7-dichloro-
3,6-bis (di-n-butylamino) spiro [anthrone-9,3′-phthalide], 2,7-dichloro-3,
6-bis (diisobutylamino) spiro [anthrone-
9,3'-phthalide], 2,7-dichloro-3,6-bis (di-n-pentylamino) spiro [anthrone-
9,3′-phthalide], 2,7-dichloro-3,6-bis (diisopentylamino) spiro [anthrone-9,
3'-phthalide], 2,7-dichloro-3,6-bis (pyrrolidino) spiro [anthrone-9,3'-phthalide], 2,7-dichloro-3,6-bis (piperidino)
Spiro [anthrone-9,3'-phthalide], 2,7-
Dichloro-3,6-bis (N-methyl-N-isopropylamino) spiro [anthrone-9,3'-phthalide], 2,7-dichloro-3,6-bis (N-ethyl-
N-isopropylamino) spiro [anthrone-9,
3'-phthalide], 2,7-dichloro-3,6-bis (N-methyl-N-phenylamino) spiro [anthrone-9,3'-phthalide], 2,7-dichloro-3,6
-Bis (N-ethyl-N-phenylamino) spiro [anthrone-9,3'-phthalide],

2,7-diphenoxy-3,6-bis (dimethylamino) spiro [anthrone-9,3′-phthalide], 2,7-diphenoxy-3,6-bis (diethylamino) spiro [anthrone-9, 3'-phthalide], 2,7-diphenoxy-3,6-bis (di-n-
Propylamino) spiro [anthrone-9,3'-phthalide], 2,7-diphenoxy-3,6-bis (diisopropylamino) spiro [anthrone-9,3'-phthalide], 2,7-diphenoxy-3, 6-bis (di-n
-Butylamino) spiro [anthrone-9,3'-phthalide], 2,7-diphenoxy-3,6-bis (diisobutylamino) spiro [anthrone-9,3'-phthalide], 2,7-diphenoxy-3 , 6-bis (di-n-
Pentylamino) spiro [anthrone-9,3'-phthalide], 2,7-diphenoxy-3,6-bis (diisopentylamino) spiro [anthrone-9,3'-phthalide], 2,7-diphenoxy- 3,6-bis (pyrrolidino) spiro [anthrone-9,3'-phthalide],
2,7-diphenoxy-3,6-bis (piperidino) spiro [anthrone-9,3'-phthalide], 2,7-diphenoxy-3,6-bis (N-methyl-N-isopropylamino) spiro [anthrone -9,3'-phthalide], 2,7-diphenoxy-3,6-bis (N-ethyl-N-isopropylamino) spiro [anthrone-
9,3′-phthalide], 2,7-diphenoxy-3,6
-Bis (N-methyl-N-phenylamino) spiro [anthrone-9,3'-phthalide], 2,7-diphenoxy-3,6-bis (N-ethyl-N-phenylamino)
Spiro [anthrone-9,3'-phthalide],

3,6-bis (dimethylamino) spiro [thioanthrone-9,3′-phthalide], 3,6-bis (diethylamino) spiro [thioanthrone-9,
3′-phthalide], 3,6-bis (di-n-propylamino) spiro [thioanthrone-9,3′-phthalide], 3,6-bis (diisopropylamino) spiro [thioanthrone-9,3 ′ -Phthalide], 3,6-bis (di-n-butylamino) spiro [thioanthrone-
9,3′-phthalide], 3,6-bis (diisobutylamino) spiro [thioanthrone-9,3′-phthalide], 3,6-bis (di-n-pentylamino) spiro [thioanthrone-9, 3'-phthalide], 3,6-bis (diisopentylamino) spiro [thioanthrone-
9,3'-phthalide], 3,6-bis (pyrrolidino) spiro [thioanthrone-9,3'-phthalide], 3,6
-Bis (piperidino) spiro [thioanthrone-9,
3'-phthalide], 3,6-bis (N-methyl-N-isopropylamino) spiro [thioanthrone-9,3 '
-Phthalide], 3,6-bis (N-ethyl-N-isopropylamino) spiro [thioanthrone-9,3'-phthalide], 3,6-bis (N-methyl-N-phenylamino) spiro [thio Anthrone-9,3'-phthalide], 3,6-bis (N-ethyl-N-phenylamino) spiro [thioanthrone-9,3'-phthalide],

3,6-bis (dimethylamino) spiro [thioanthrone-9,3 ′-(4 ′, 5 ′, 6 ′,
7'-tetrachlorophthalide)], 3,6-bis (diethylamino) spiro [thioanthrone-9,3'-
(4 ', 5', 6 ', 7'-tetrachlorophthalide)], 3,6-bis (di-n-propylamino) spiro [thioanthrone-9,3'-(4 ', 5', 6 ',
7'-tetrachlorophthalide)], 3,6-bis (diisopropylamino) spiro [thioanthrone-9,3 '
-(4 ', 5', 6 ', 7'-tetrachlorophthalide)], 3,6-bis (di-n-butylamino) spiro [thioanthrone-9,3'-(4 ', 5' , 6 ',
7'-tetrachlorophthalide)], 3,6-bis (diisobutylamino) spiro [thioanthrone-9,3'-
(4 ', 5', 6 ', 7'-tetrachlorophthalide)], 3,6-bis (di-n-pentylamino) spiro [thioanthrone-9,3'-(4 ', 5', 6 ',
7'-tetrachlorophthalide)], 3,6-bis (diisoamylamino) spiro [thioanthrone-9,3'-
(4 ', 5', 6 ', 7'-tetrachlorophthalide)], 3,6-bis (pyrrolidino) spiro [thioanthrone-9,3'-(4 ', 5', 6 ', 7' -Tetrachlorophthalide)], 3,6-bis (piperidino) spiro [thioanthrone-9,3 '-(4', 5 ', 6',
7'-tetrachlorophthalide)], 3,6-bis (N-
Methyl-N-isopropylamino) spiro [thioanthrone-9,3 '-(4', 5 ', 6', 7'-tetrachlorophthalide)], 3,6-bis (N-ethyl-N-isopropyl) Amino) spiro [thioanthrone-9,3 '
-(4 ', 5', 6 ', 7'-tetrachlorophthalide)], 3,6-bis (N-methyl-N-phenylamino) spiro [thioanthrone-9,3'-(4 ',
5 ', 6', 7'-tetrachlorophthalide)], 3,6
-Bis (N-ethyl-N-phenylamino) spiro [thioanthrone-9,3 '-(4', 5 ', 6', 7'-
Tetrachlorophthalide)),

2,7-dichloro-3,6-bis (dimethylamino) spiro [thioanthrone-9,3′-phthalide], 2,7-dichloro-3,6-bis (diethylamino) spiro [thioanthrone- 9,3'-phthalide], 2,7-dichloro-3,6-bis (di-n-propylamino) spiro [thioanthrone-9,3'-phthalide], 2,7-dichloro-3,6- Bis (diisopropylamino) spiro [thioanthrone-9,3'-phthalide], 2,7-dichloro-3,6-bis (di-n-butylamino) spiro [thioanthrone-9,3'-phthalide], 2,7-dichloro-3,6-bis (diisobutylamino) spiro [thioanthrone-9,3'-phthalide], 2,7-dichloro-3,6-bis (di-n-butylamino) spiro [thioanthro 9,3'-phthalide], 2,7-dichloro-3,6-bis (diisobutylamino) spiro [thioanthrone-9,3'-phthalide], 2,7-dichloro-3,6-bis ( Di-n-pentylamino) spiro [thioanthrone-9,3'-phthalide], 2,7-dichloro-3,6-bis (diisopentylamino) spiro [thioanthrone-9,3'-phthalide], 2,7-dichloro-3,6-bis (pyrrolidino) spiro [thioanthrone-9,3'-phthalide],
2,7-dichloro-3,6-bis (piperidino) spiro [thioanthrone-9,3'-phthalide], 2,7-dichloro-3,6-bis (N-methyl-N-isopropylamino) spiro [ Thioanthrone-9,3'-phthalide], 2,7-dichloro-3,6-bis (N-ethyl-
N-isopropylamino) spiro [thioanthrone-
9,3′-phthalide], 2,7-dichloro-3,6-bis (N-methyl-N-phenylamino) spiro [thioanthrone-9,3′-phthalide], 2,7-dichloro-
3,6-bis (N-ethyl-N-phenylamino) spiro [thioanthrone-9,3′-phthalide],

2,7-diphenoxy-3,6-bis (dimethylamino) spiro [thioanthrone-9,3 ′
-Phthalide], 2,7-diphenoxy-3,6-bis (diethylamino) spiro [thioanthrone-9,3 '
-Phthalide], 2,7-diphenoxy-3,6-bis (di-n-propylamino) spiro [thioanthrone-
9,3′-phthalide], 2,7-diphenoxy-3,6
-Bis (diisopropylamino) spiro [thioanthrone-9,3'-phthalide], 2,7-diphenoxy-
3,6-bis (di-n-butylamino) spiro [thioanthrone-9,3'-phthalide], 2,7-diphenoxy-3,6-bis (diisobutylamino) spiro [thioanthrone-9,3 ' -Phthalide], 2,7-diphenoxy-3,6-bis (di-n-pentylamino) spiro [thioanthrone-9,3'-phthalide], 2,7-diphenoxy-3,6-bis (diiso Pentylamino) spiro [thioanthrone-9,3'-phthalide], 2,7
-Diphenoxy-3,6-bis (pyrrolidino) spiro [thioanthrone-9,3'-phthalide], 2,7-diphenoxy-3,6-bis (piperidino) spiro [thioanthrone-9,3'-phthalide] , 2,7-diphenoxy-3,6-bis (N-methyl-N-isopropylamino) spiro [thioanthrone-9,3'-phthalide], 2,7-diphenoxy-3,6-bis (N-ethyl -N-isopropylamino) spiro [thioanthrone-9,3'-phthalide], 2,7-diphenoxy-3,
6-bis (N-methyl-N-phenylamino) spiro [thioanthrone-9,3'-phthalide], 2,7-diphenoxy-3,6-bis (N-ethyl-N-phenylamino) spiro [thio Anthrone-9,3'-phthalide],

3,6-bis (dimethylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3′-phthalide], 3,6-bis (diethylamino) spiro [10-hydroxy-9,10 -Dihydroanthracene-9,3'-phthalide], 3,6-bis (di-n-propylamino) spiro [10-hydroxy-
9,10-dihydroanthracene-9,3′-phthalide], 3,6-bis (diisopropylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3′-phthalide], 3,6-bis (Di-n-butylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3′-phthalide], 3,6-bis (diisobutylamino) spiro [10-hydroxy-
9,10-dihydroanthracene-9,3'-phthalide], 3,6-bis (di-n-pentylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3'-phthalide], 3 , 6-Bis (diisopentylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3'-phthalide], 3,6-bis (pyrrolidino) spiro [10-hydroxy-9,10
-Dihydroanthracene-9,3'-phthalide], 3,
6-bis (piperidino) spiro [10-hydroxy-
9,10-dihydroanthracene-9,3'-phthalide], 3,6-bis (N-methyl-N-isopropylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3'-phthalide] , 3,6-bis (N-ethyl-N-isopropylamino) spiro [10
-Hydroxy-9,10-dihydroanthracene-9,
3'-phthalide], 3,6-bis (N-methyl-N-phenylamino) spiro [10-hydroxy-9,10-
Dihydroanthracene-9,3'-phthalide], 3,6
-Bis (N-ethyl-N-phenylamino) spiro [1
0-hydroxy-9,10-dihydroanthracene-
9,3′-phthalide],

3,6-bis (dimethylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3 ′-(4 ′, 5 ′, 6 ′, 7′-tetrachlorophthalide)], 3,6-bis (diethylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3 ′-(4 ′, 5 ′, 6 ′, 7′-tetrachlorophthalide)], 3,6- Bis (di-n-propylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3 ′-(4 ′, 5 ′, 6 ′, 7′-tetrachlorophthalide)], 3,6 -Bis (diisopropylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3 '-(4', 5 ', 6',
7'-tetrachlorophthalide)], 3,6-bis (di-
n-butylamino) spiro [10-hydroxy-9,1
0-dihydroanthracene-9,3 '-(4', 5 ',
6 ', 7'-tetrachlorophthalide)], 3,6-bis (diisobutylamino) spiro [10-hydroxy-
9,10-dihydroanthracene-9,3 ′-(4 ′,
5 ', 6', 7'-tetrachlorophthalide)], 3,6
-Bis (di-n-pentylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3'-
(4 ′, 5 ′, 6 ′, 7′-tetrachlorophthalide)], 3,6-bis (diisoamylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3 ′-(4 ', 5', 6 ', 7'-tetrachlorophthalide)], 3,6-bis (pyrrolidino) spiro [1
0-hydroxy-9,10-dihydroanthracene-
9,3 ′-(4 ′, 5 ′, 6 ′, 7′-tetrachlorophthalide)], 3,6-bis (piperidino) spiro [10
-Hydroxy-9,10-dihydroanthracene-9,
3 '-(4', 5 ', 6', 7'-tetrachlorophthalide)], 3,6-bis (N-methyl-N-isopropylamino) spiro [10-hydroxy-9,10-dihydroanthracene -9,3 '-(4', 5 ', 6', 7 '
-Tetrachlorophthalide)], 3,6-bis (N-ethyl-N-isopropylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3'-
(4 ', 5', 6 ', 7'-tetrachlorophthalide)], 3,6-bis (N-methyl-N-phenylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9, 3 ′-(4 ′, 5 ′, 6 ′, 7′-tetrachlorophthalide)], 3,6-bis (N-ethyl-
N-phenylamino) spiro [10-hydroxy-9,
10-dihydroanthracene-9,3 '-(4',
5 ', 6', 7'-tetrachlorophthalide)),

2,7-dichloro-3,6-bis (dimethylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3′-phthalide], 2,7-
Dichloro-3,6-bis (diethylamino) spiro [1
0-hydroxy-9,10-dihydroanthracene-
9,3′-phthalide], 2,7-dichloro-3,6-bis (di-n-propylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3′-phthalide], 2, 7-dichloro-3,6-bis (diisopropylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3′-phthalide], 2,7-
Dichloro-3,6-bis (di-n-butylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3′-phthalide], 2,7-dichloro-3,6
-Bis (diisobutylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3'-phthalide], 2,7-dichloro-3,6-bis (di-n-butylamino) spiro [10- Hydroxy-9,10-dihydroanthracene-9,3′-phthalide], 2,7-
Dichloro-3,6-bis (diisobutylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3′-phthalide], 2,7-dichloro-3,6-
Bis (di-n-pentylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3′-phthalide], 2,7-dichloro-3,6-bis (diisopentylamino) spiro [10 -Hydroxy-9,10-
Dihydroanthracene-9,3'-phthalide], 2,7
-Dichloro-3,6-bis (pyrrolidino) spiro [10
-Hydroxy-9,10-dihydroanthracene-9,
3'-phthalide], 2,7-dichloro-3,6-bis (piperidino) spiro [10-hydroxy-9,10-
Dihydroanthracene-9,3'-phthalide], 2,7
-Dichloro-3,6-bis (N-methyl-N-isopropylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3'-phthalide], 2,7-
Dichloro-3,6-bis (N-ethyl-N-isopropylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3′-phthalide], 2,7-dichloro-3,6-bis ( N-methyl-N-phenylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3'-phthalide], 2,7-dichloro-3,6-bis (N-ethyl-N-phenylamino ) Spiro [10-hydroxy-9,10-dihydroanthracene-9,3'-phthalide],

2,7-diphenoxy-3,6-bis (dimethylamino) spiro [10-hydroxy-9,1
0-dihydroanthracene-9,3'-phthalide],
2,7-diphenoxy-3,6-bis (diethylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3′-phthalide], 2,7-diphenoxy-3,6-bis (di-n -Propylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3'-phthalide], 2,7-diphenoxy-3,
6-bis (diisopropylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3′-
Phthalide], 2,7-diphenoxy-3,6-bis (di-n-butylamino) spiro [10-hydroxy-9,
10-dihydroanthracene-9,3'-phthalide],
2,7-diphenoxy-3,6-bis (diisobutylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3′-phthalide], 2,7-diphenoxy-3,6-bis (di- n-pentylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3′-phthalide], 2,7-diphenoxy-
3,6-bis (diisopentylamino) spiro [10-
Hydroxy-9,10-dihydroanthracene-9,
3'-phthalide], 2,7-diphenoxy-3,6-bis (pyrrolidino) spiro [10-hydroxy-9,10
-Dihydroanthracene-9,3'-phthalide], 2,
7-diphenoxy-3,6-bis (piperidino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3′-phthalide], 2,7-diphenoxy-3,
6-bis (N-methyl-N-isopropylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3′-phthalide], 2,7-diphenoxy-
3,6-bis (N-ethyl-N-isopropylamino)
Spiro [10-hydroxy-9,10-dihydroanthracene-9,3′-phthalide], 2,7-diphenoxy-3,6-bis (N-methyl-N-phenylamino) spiro [10-hydroxy-9, 10-dihydroanthracene-9,3'-phthalide], 2,7-diphenoxy-
3,6-bis (N-ethyl-N-phenylamino) spiro [10-hydroxy-9,10-dihydroanthracene-9,3′-phthalide],

3,6-bis (dimethylamino) spiro [10-methoxy-9,10-dihydroanthracene-
9,3′-phthalide], 3,6-bis (diethylamino) spiro [10-methoxy-9,10-dihydroanthracene-9,3′-phthalide], 3,6-bis (di-
n-propylamino) spiro [10-methoxy-9,1
0-dihydroanthracene-9,3'-phthalide],
3,6-bis (diisopropylamino) spiro [10-
Methoxy-9,10-dihydroanthracene-9,3 ′
-Phthalide], 3,6-bis (di-n-butylamino)
Spiro [10-methoxy-9,10-dihydroanthracene-9,3'-phthalide], 3,6-bis (diisobutylamino) spiro [10-methoxy-9,10-dihydroanthracene-9,3'-phthalide] 3,6-bis (di-n-pentylamino) spiro [10-methoxy-9,10-dihydroanthracene-9,3'-phthalide], 3,6-bis (diisopentylamino) spiro [10- Methoxy-9,10-dihydroanthracene-
9,3′-phthalide], 3,6-bis (pyrrolidino) spiro [10-methoxy-9,10-dihydroanthracene-9,3′-phthalide], 3,6-bis (piperidino) spiro [10-methoxy] -9,10-dihydroanthracene-9,3'-phthalide], 3,6-bis (N-
Methyl-N-isopropylamino) spiro [10-methoxy-9,10-dihydroanthracene-9,3′-phthalide], 3,6-bis (N-ethyl-N-isopropylamino) spiro [10-methoxy-9] , 10-Dihydroanthracene-9,3'-phthalide], 3,6-bis (N-methyl-N-phenylamino) spiro [10-methoxy-9,10-dihydroanthracene-9,3'-
Phthalide], 3,6-bis (N-ethyl-N-phenylamino) spiro [10-methoxy-9,10-dihydroanthracene-9,3′-phthalide],

3,6-bis (dimethylamino) spiro [10-methoxy-9,10-dihydroanthracene-
9,3 '-(4', 5 ', 6', 7'-tetrachlorophthalide)], 3,6-bis (diethylamino) spiro [10-methoxy-9,10-dihydroanthracene-
9,3 ′-(4 ′, 5 ′, 6 ′, 7′-tetrachlorophthalide)], 3,6-bis (di-n-propylamino)
Spiro [10-methoxy-9,10-dihydroanthracene-9,3 '-(4', 5 ', 6', 7'-tetrachlorophthalide)], 3,6-bis (diisopropylamino) spiro [10 -Methoxy-9,10-dihydroanthracene-9,3 '-(4', 5 ', 6', 7'-tetrachlorophthalide)], 3,6-bis (di-n-butylamino) spiro [ 10-methoxy-9,10-dihydroanthracene-9,3 ′-(4 ′, 5 ′, 6 ′, 7′-
Tetrachlorophthalide)], 3,6-bis (diisobutylamino) spiro [10-methoxy-9,10-dihydroanthracene-9,3 ′-(4 ′, 5 ′, 6 ′, 7 ′)
-Tetrachlorophthalide)], 3,6-bis (di-n-
Pentylamino) spiro [10-methoxy-9,10-
Dihydroanthracene-9,3 '-(4', 5 ',
6 ', 7'-tetrachlorophthalide)], 3,6-bis (diisoamylamino) spiro [10-methoxy-9,
10-dihydroanthracene-9,3 '-(4',
5 ', 6', 7'-tetrachlorophthalide)], 3,6
-Bis (pyrrolidino) spiro [10-methoxy-9,1
0-dihydroanthracene-9,3 '-(4', 5 ',
6 ', 7'-tetrachlorophthalide)], 3,6-bis (piperidino) spiro [10-methoxy-9,10-dihydroanthracene-9,3'-(4 ', 5', 6 ',
7'-tetrachlorophthalide)], 3,6-bis (N-
Methyl-N-isopropylamino) spiro [10-methoxy-9,10-dihydroanthracene-9,3′-
(4 ′, 5 ′, 6 ′, 7′-tetrachlorophthalide)], 3,6-bis (N-ethyl-N-isopropylamino) spiro [10-methoxy-9,10-dihydroanthracene-9, 3 '-(4', 5 ', 6', 7'-
Tetrachlorophthalide)], 3,6-bis (N-methyl-N-phenylamino) spiro [10-methoxy-9,
10-dihydroanthracene-9,3 '-(4',
5 ', 6', 7'-tetrachlorophthalide)], 3,6
-Bis (N-ethyl-N-phenylamino) spiro [1
0-methoxy-9,10-dihydroanthracene-9,
3 ′-(4 ′, 5 ′, 6 ′, 7′-tetrachlorophthalide)],

2,7-dichloro-3,6-bis (dimethylamino) spiro [10-methoxy-9,10-dihydroanthracene-9,3′-phthalide], 2,7-dichloro-3,6-bis (Diethylamino) spiro [10
-Methoxy-9,10-dihydroanthracene-9,
3'-phthalide], 2,7-dichloro-3,6-bis (di-n-propylamino) spiro [10-methoxy-
9,10-dihydroanthracene-9,3′-phthalide], 2,7-dichloro-3,6-bis (diisopropylamino) spiro [10-methoxy-9,10-dihydroanthracene-9,3′-phthalide] , 2,7-Dichloro-3,6-bis (di-n-butylamino) spiro [10-methoxy-9,10-dihydroanthracene-
9,3'-phthalide], 2,7-dichloro-3,6-bis (diisobutylamino) spiro [10-methoxy-
9,10-dihydroanthracene-9,3'-phthalide], 2,7-dichloro-3,6-bis (di-n-butylamino) spiro [10-methoxy-9,10-dihydroanthracene-9,3 '-Phthalide], 2,7-dichloro-3,6-bis (diisobutylamino) spiro [1
0-methoxy-9,10-dihydroanthracene-9,
3'-phthalide], 2,7-dichloro-3,6-bis (di-n-pentylamino) spiro [10-methoxy-
9,10-dihydroanthracene-9,3'-phthalide], 2,7-dichloro-3,6-bis (diisopentylamino) spiro [10-methoxy-9,10-dihydroanthracene-9,3'- Phthalide], 2,7-dichloro-3,6-bis (pyrrolidino) spiro [10-methoxy-9,10-dihydroanthracene-9,3′-phthalide], 2,7-dichloro-3,6-bis ( Piperidino) spiro [10-methoxy-9,10-dihydroanthracene-9,3′-phthalide], 2,7-dichloro-
3,6-bis (N-methyl-N-isopropylamino)
Spiro [10-methoxy-9,10-dihydroanthracene-9,3'-phthalide], 2,7-dichloro-3,
6-bis (N-ethyl-N-isopropylamino) spiro [10-methoxy-9,10-dihydroanthracene-9,3′-phthalide], 2,7-dichloro-3,6-
Bis (N-methyl-N-phenylamino) spiro [10
-Methoxy-9,10-dihydroanthracene-9,
3'-phthalide], 2,7-dichloro-3,6-bis (N-ethyl-N-phenylamino) spiro [10-methoxy-9,10-dihydroanthracene-9,3'-
Phthalide),

2,7-diphenoxy-3,6-bis (dimethylamino) spiro [10-methoxy-9,10
-Dihydroanthracene-9,3'-phthalide], 2,
7-diphenoxy-3,6-bis (diethylamino) spiro [10-methoxy-9,10-dihydroanthracene-9,3′-phthalide], 2,7-diphenoxy-
3,6-bis (di-n-propylamino) spiro [10
-Methoxy-9,10-dihydroanthracene-9,
3'-phthalide], 2,7-diphenoxy-3,6-bis (diisopropylamino) spiro [10-methoxy-
9,10-dihydroanthracene-9,3′-phthalide], 2,7-diphenoxy-3,6-bis (di-n-
Butylamino) spiro [10-methoxy-9,10-dihydroanthracene-9,3′-phthalide], 2,7-
Diphenoxy-3,6-bis (diisobutylamino) spiro [10-methoxy-9,10-dihydroanthracene-9,3′-phthalide], 2,7-diphenoxy-
3,6-bis (di-n-pentylamino) spiro [10
-Methoxy-9,10-dihydroanthracene-9,
3'-phthalide], 2,7-diphenoxy-3,6-bis (diisopentylamino) spiro [10-methoxy-
9,10-dihydroanthracene-9,3′-phthalide], 2,7-diphenoxy-3,6-bis (pyrrolidino) spiro [10-methoxy-9,10-dihydroanthracene-9,3′-phthalide], 2,7-diphenoxy-3,6-bis (piperidino) spiro [10-methoxy-9,10-dihydroanthracene-9,3′-phthalide], 2,7-diphenoxy-3,6-bis (N-methyl -N-isopropylamino) spiro [10-methoxy-9,10-dihydroanthracene-9,3'-phthalide], 2,7-diphenoxy-3,6-bis (N-ethyl-N-isopropylamino) spiro [ 10-methoxy-9,10-dihydroanthracene-9,3'-phthalide], 2,7-diphenoxy-3,6-bis (N-methyl-N-phenylamino Spiro [10-methoxy -
9,10-dihydroanthracene-9,3′-phthalide], 2,7-diphenoxy-3,6-bis (N-ethyl-N-phenylamino) spiro [10-methoxy-
9,10-dihydroanthracene-9,3′-phthalide], and the like.

When a recording material is prepared using the compound of the present invention, these can be used alone or in combination of two or more, including commonly used coloring agents.

In order to apply the compound of the present invention as a pressure-sensitive recording material, for example, a known method disclosed in Japanese Patent Publication No. 42-20144 can be used. Generally,
A color former solution obtained by dissolving the compound of the present invention (color former) in an encapsulating solvent is encapsulated with a polymer compound as a film agent, and then applied to the back surface of a support such as woodfree paper, synthetic paper, plastic film, or the like. Create the top paper. On the other hand, a developer is applied to the surface of another support to prepare a lower sheet. The upper sheet and the lower sheet are overlapped so that the coated surfaces face each other. If you add pen pressure or pressure such as pressing pressure to this,
The capsule in the pressurized portion is broken, and the color former in the capsule reacts with the color developer to form a recorded image on the surface of the lower sheet. In addition, a plurality of copy records can be obtained by inserting several sheets of middle paper having a developer coated on the front surface and a capsule on the back surface between the upper and lower sheets.

Examples of the developer used in the pressure-sensitive recording material include acid clay, a zinc salt of a salicylic acid derivative, a zinc salt of a p-octylphenol resin, and a p-phenylphenol resin. In particular, salicylic acid derivative zinc salt, and
A zinc salt of p-octylphenol resin is preferably used.

In order to apply the compound of the present invention to a heat-sensitive recording material, for example, a known method disclosed in JP-B No. 45-14039 or the like can be used. In general, the compound of the present invention (color former), a developer and, if necessary, a sensitizer together with an aqueous solution of a water-soluble polymer such as polyvinyl alcohol are used together with an attritor, a sand mill or the like to reduce the particle size of the drug. Disperse to below micron. The sensitizer may be dispersed simultaneously with one or both of the color former and the developer, or in some cases, a eutectic with the color former or the developer may be prepared and dispersed in advance. You may. These dispersions are mixed, and if necessary, pigments, binders, waxes, metal soaps, antioxidants, ultraviolet absorbers and the like are added to form a heat-sensitive coating liquid. The obtained heat-sensitive coating liquid is
After applying to a support such as high-quality paper, synthetic paper, plastic film, etc., and imparting smoothness by calendaring,
A heat-sensitive recording material is obtained. In addition, the heat-sensitive coating liquid may be applied to a support having an undercoat layer of a plastic pigment or a heat insulating agent such as silica, if necessary, in order to improve color development. Further, if necessary, an overcoat layer of a water-soluble polymer or the like may be provided on the heat-sensitive recording layer in order to impart water resistance and chemical resistance.

Various phenolic compounds can be used as the developer used in the heat-sensitive recording material. Specific examples include 2,2-bis (p-hydroxyphenyl) propane and 2,2-bis (p-hydroxyphenyl) -4-
Methylpentane, 1,1-bis (p-hydroxyphenyl) cyclohexane, bis (p-hydroxyphenyl)
Sulfone, bisphenol S monoisopropyl ether, 3,3′-diallylbisphenol S, 1,5-bis (p-hydroxyphenylmercapto) -3-oxapentane, benzyl p-hydroxybenzoate, tetrabromobisphenol A, tetrabromobisphenol S
And the like. In particular, 2,2-bis (p-hydroxyphenyl) propane is preferably used.

The ratio of the compound (color former) of the present invention to the color developer is 100 parts by weight of the color developer and 20 parts by weight of the color developer.
0 to 500 parts by weight.

Examples of the sensitizer include p-benzylbiphenyl, m-terphenyl, 2-benzyloxynaphthalene, dibenzyl oxalate, di-p-methylbenzyl oxalate, 1,2-diphenoxyethane, 1,2- Di-m-
Toluoxyethane, 1,2-di-p-toluoxyethane, 1,4-diphenoxybutane, benzyl p-benzyloxybenzoate, phenyl 2-naphthoate, phenyl 1-hydroxy-2-naphthoate, terephthalic acid Dibenzyl and the like. Particularly, p-benzylbiphenyl, m-terphenyl, 2-benzyloxynaphthalene, di-p-methylbenzyl oxalate, 1,2-di-m
-Toluoxyethane is preferably used.

As the pigment, organic and inorganic pigments can be used. Preferred specific examples include calcium carbonate, barium sulfate, titanium oxide, aluminum hydroxide,
Examples thereof include amorphous silica, urea formalin resin powder, and polyethylene resin powder.

As the binder, a water-soluble polymer and a water-insoluble polymer can be used. Preferred specific examples include water-soluble polymers such as methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, starches, styrene-maleic anhydride copolymer hydrolyzate, ethylene-maleic anhydride copolymer hydrolyzate, and isobutylene-anhydrous. A maleic acid copolymer hydrolyzate, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, polyacrylamide, and the like, and water-insoluble polymers include styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, and vinyl acetate emulsion.

Preferred specific examples of the wax include paraffin wax, carboxy-modified paraffin wax, polyethylene wax and the like.

As the metal soap, a higher fatty acid metal salt is used. Preferred specific examples include zinc stearate, calcium stearate, aluminum stearate and the like.

As an antioxidant, hindered phenols are used.

As the ultraviolet absorber, a benzophenone-based or benzotriazole-based ultraviolet absorber is used.

[0050]

EXAMPLES Examples are shown below, but the present invention is not limited to these examples.

Example 1 3,6-bis (diethylamino) spiro [anthrone-
Synthesis of 9,3′-phthalide] Phthalic anhydride in 80 ml of ethylene dichloride.
4 g was dissolved, and 33.4 g of aluminum chloride was added thereto at 20 ° C. or lower over 30 minutes. After the addition, the mixture was stirred for 30 minutes, and at 20 to 25 ° C., 16.2 g of 3,3′-bis (diethylamino) benzophenone was dissolved in 20 ml of ethylene dichloride, and added dropwise over 1 hour. 20-2
After stirring at 5 ° C for 24 hours, the mixture was stirred at 50 to 55 ° C for 5 hours. After cooling to room temperature and stirring at 130-140 ° C. for 10 hours, ethylene dichloride was evaporated off during this time. The content was cooled to room temperature, discharged into 200 ml of ice water, made weakly alkaline with a 50% aqueous sodium hydroxide solution, and extracted with 200 ml of toluene. The toluene extract was purified by silica gel column chromatography to obtain 14.1 g (yield 62%) of a yellow powder. The melting point, elemental analysis value, mass analysis value, and characteristic absorption of the infrared absorption spectrum were as follows. FIG. 1 shows the infrared absorption spectrum of this compound, and FIG.
FIG. 3 shows the mass spectrum.

Melting point: 201 to 203 ° C.
MS (m / e): 454 (M ⁺ ) IR: ν _CO = 1760 cm ⁻¹ , 1665 cm ⁻¹

Example 2 Synthesis of 3,6-bis (di-n-butylamino) spiro [anthrone-9,3′-phthalide] Phthalic anhydride 2 in 200 ml of ethylene dichloride
9.6 g were suspended therein, and aluminum chloride 53.4 was added thereto.
g was added over 1 hour while maintaining the internal temperature at 25 ° C. or lower. After the addition, the mixture was stirred at room temperature for 24 hours, and a solution prepared by dissolving 87.2 g of 3,3′-bis (di-n-butylamino) benzophenone in 50 ml of ethylene dichloride was added.
It was added dropwise at ５５55 ° C. for 3 hours. In addition, 50-55
After stirring was continued at 10 ° C. for 10 hours, the mixture was stirred at 125 to 130 ° C. for 5 hours. After cooling, 350 ml of 96% sulfuric acid was added, and 1
Stirred at 30-135 ° C for 10 hours. The reaction mixture was discharged into 1000 ml of ice water, made alkaline with a 20% aqueous sodium hydroxide solution, and extracted with toluene. By silica gel column chromatography purification, 73.6 g (yield 65%) of a yellow powder was obtained. The elemental analysis value, the mass analysis value, and the characteristic absorption of the infrared absorption spectrum of this compound were as follows.

[0054] MS (m / e): 566 (M ⁺ ) IR: ν _CO = 1755 cm ⁻¹ , 1665 cm ⁻¹

Example 3 3,6-bis (piperidino) spiro [anthrone-9,
Synthesis of 3'-phthalide] 2.96 g of phthalic anhydride was added to 50 m of ethylene dichloride.
of aluminum chloride at room temperature.
g was added to give a pale yellow solution. Add 3,3 'to this solution
3.48 g of -bis (piperidino) benzophenone was added, and the mixture was stirred at 60 ° C for 45 minutes and at 70 ° C for 105 minutes.
After cooling, 60 ml of 96% sulfuric acid was added, and the mixture was stirred at 100 ° C for 30 minutes and at 150 ° C for 45 minutes. The internal temperature was lowered to around room temperature, and the solution was discharged into 300 ml of ice water. Caustic soda 48
g was added and extracted with 250 ml of toluene, and 1.82 g (yield 38%) of a yellow powder was obtained by column chromatography separation. The melting point, elemental analysis value, mass analysis value, and characteristic absorption of infrared absorption spectrum of this compound were as follows.

Melting point: 158 to 160 ° C. MS (m / e): 478 (M ⁺ ) IR: ν _CO = 1764 cm ^-1 , 1656 cm ^-1

Example 4 3,6-bis (pyrrolidino) spiro [anthrone-9,
Synthesis of 3′-phthalide] 1.48 g of phthalic anhydride was refluxed in 10 ml of ethanol for 1 hour, and then ethanol was distilled off. 3 ml of thionyl chloride was added thereto, and the mixture was stirred at 55 to 60 ° C for 20 minutes. 10
The temperature was raised to 0 ° C. to remove excess thionyl chloride. 3,3′-bis (pyrrolidino) benzophenone 3.2 in the residue
g and 50 ml of ethylene dichloride were added to obtain a yellow solution. 1.34 g of aluminum chloride was added to this solution,
After refluxing for 3 hours with stirring, the mixture was cooled to 40 ° C. 30 ml of 96% sulfuric acid was added, and the mixture was stirred at 40 ° C. for 20 minutes.
Stirred at ８０80 ° C. for 1 hour. The mixture was discharged into 250 ml of ice water, added with 24 g of caustic soda to make it weakly acidic, and extracted with 250 ml of toluene. This toluene extract was subjected to silica gel column chromatography separation, and 3.56 g of a yellow powder was obtained.
(72% yield). The melting point, elemental analysis value, mass analysis value, and characteristic absorption of infrared absorption spectrum of this compound were as follows.

Melting point: 269-271 ° C. MS (m / e): 450 (M ⁺ ) IR: ν _CO = 1760 cm ⁻¹ , 1662 cm ⁻¹

Example 5 3,6-bis (diethylamino) spiro [anthrone-
Synthesis of 9,3 ′-(4 ′, 5 ′, 6 ′, 7′-tetrachlorophthalide)] 3,3′-bis (diethylamino) benzophenone
24 g was dissolved in 50 ml of ethylene dichloride,
At ５０50 ° C., 4.0 g of aluminum chloride was added. To this, 5.72 g of tetrachlorophthalic anhydride was added, and 50
Stirred at ~ 55 ° C for 4 hours. 96% after cooling to 25 ° C
60 ml of sulfuric acid was added, and the mixture was stirred at 135 ° C. for 5 hours. The mixture was discharged into 300 ml of ice water, 50 g of caustic soda was added little by little, extracted with 250 ml of toluene, and 4.32 g (yield 73%) of yellow powder was obtained by silica gel column chromatography. The melting point, elemental analysis value, mass analysis value, and characteristic absorption of infrared absorption spectrum of this compound were as follows.

Melting point: 250-253 ° C. MS (m / e): 590 (M ⁺ ) IR: ν _CO = 177
5cm ^-1 , 1665cm ^-1

Example 6 3,6-bis (pyrrolidino) spiro [anthrone-9,
Synthesis of 3 ′-(4 ′, 5 ′, 6 ′, 7′-tetrachlorophthalide)] 5.92 g of tetrachlorophthalic anhydride was added to 5 m of ethanol.
After stirring for 1 hour under reflux with 1 l, ethanol was distilled off. 3 ml of thionyl chloride was added to the residue, and the mixture was stirred at 55 to 60 ° C for 20 minutes. The excess thionyl chloride is distilled off to give 3,3′-
20 ml of an ethylene dichloride solution containing 1.60 g of bis (pyrrolidino) benzophenone was added. 1.34 g of aluminum chloride was added to this solution,
For 1.5 hours and at 100 to 105 ° C for 1 hour. The reaction mixture was discharged into 250 ml of ice water, 24 g of sodium hydroxide was added, and the precipitate was extracted with 250 ml of toluene. This toluene extract was subjected to silica gel column chromatography to obtain 0.31 g (yield 11%) of ocher powder. The melting point, elemental analysis value, mass analysis value, and characteristic absorption of infrared absorption spectrum of this compound were as follows.

Melting point: 277-280 ° C. MS (m / e): 586 (M ⁺ ) IR: ν _{C = O} = 1775 cm ⁻¹ , 1655 cm ⁻¹

Example 7 3,6-bis (pyrrolidino) spiro [thioanthrone-
Synthesis of 9,3'-phthalide] 1.48 g of phthalic anhydride was added to 30 m of ethylene dichloride.
While stirring in 1 l, 2.67 g of aluminum chloride were added. To this, 1.68 g of 3,3′-bis (pyrrolidino) thiobenzophenone was added, and the mixture was added at 20 to 25 ° C. for 3 hours.
Stirred at 40-45 ° C for 6 hours. After distilling off ethylene dichloride, the mixture was cooled, and 40 ml of 98% sulfuric acid was added.
Stirred at 80 ° C. for 1 hour. 200 g of ice on the reaction mixture
The mixture was drained, made alkaline with 100 ml of a 40% aqueous sodium hydroxide solution, and extracted with 300 ml of toluene. The obtained toluene extract was subjected to silica gel column chromatography to obtain 2.35 g (yield: 50%) of green powder. The melting point, elemental analysis value, mass analysis value, and characteristic absorption of infrared absorption spectrum of this compound were as follows.

Melting point: 141 to 143 ° C. MS (m / e): 466 (M ⁺ ) IR: ν _{C = O} = 177
0cm ^-1

Example 8 Synthesis of 3,6-bis (diethylamino) spiro [thioanthrone-9,3′-phthalide] 1.48 g of phthalic anhydride was added to 30 m of ethylene dichloride.
2.67 g of aluminum chloride are added while stirring in
Stirring was continued at 20-25 ° C. for 30 minutes. This is 3,3 '
3.40 g of -bis (diethylamino) benzophenone was added, and the mixture was stirred at 45 to 50 ° C for 4 hours. 98% after cooling
40 ml of sulfuric acid was added and reacted at 75-80 ° C. for 1 hour. The reaction mixture was discharged into 200 g of ice, made alkaline with 100 ml of a 40% aqueous sodium hydroxide solution, and the precipitate was extracted with 300 ml of toluene. The obtained toluene extract was subjected to silica gel column chromatography to obtain 1.93 g (yield: 41%) of a blackish green powder. Melting point of this compound,
The elemental analysis value, the mass analysis value, and the characteristic absorption of the infrared absorption spectrum were as follows.

Melting point: 94-96 ° C. MS (m / e): 470 (M ⁺ ) IR: ν _{C = O} = 1770 cm ⁻¹

Example 9 3,6-bis (diethylamino) spiro [anthrone-
Synthesis of 9,3 ′-(5-methyl) phthalide] 3.24 g of 4-methylphthalic anhydride was dissolved in 40 ml of ethylene dichloride, and aluminum chloride was added thereto.
0 g was added and stirred at 20-25 ° C. for 30 minutes. To this, 6.48 g of 3,3′-bis (diethylamino) benzophenone was diluted and added with 10 ml of ethylene dichloride, and the mixture was stirred at 50 to 55 ° C. for 8 hours. After cooling, 98
% Sulfuric acid was added, and the mixture was stirred at 95 to 100 ° C for 1 hour. The reaction mixture was discharged into 300 g of ice, made alkaline with 100 g of a 50% aqueous sodium hydroxide solution, and the precipitate was extracted with 300 ml of toluene. The toluene extract was dried over magnesium sulfate, and then subjected to silica gel column chromatography to obtain 0.52 g (yield 5.6%) of a yellow powder. The melting point, elemental analysis value, mass analysis value, and characteristic absorption of infrared absorption spectrum of this compound were as follows.

Melting point: 143 to 145 ° C. MS (m / e): 468 (M ⁺ ) IR: ν _{C = O} = 1762 cm ⁻¹ , 1662 cm ⁻¹

Example 10 3,6-bis (N-ethyl-N-isopropylamino)
Synthesis of Spiro [anthrone-9,3'-phthalide] 14. Phthalic anhydride in 100 ml of ethylene dichloride.
8 g, and at 20 ° C. or lower, aluminum chloride 2
6.7 g was added and the mixture was stirred for 1 hour. Add 3 to this mixture
32.3 g of 3′-bis (ethylisopropylamino) benzophenone was dissolved in 35 ml of ethylene dichloride and added dropwise, followed by stirring at 50 ° C. for 6 hours. The reaction mixture was discharged onto 400 g of ice, and the ethylene dichloride layer was separated and washed with hot water. To this ethylene dichloride solution was added 200 ml of toluene, and the mixture was extracted with 1 liter of a 5% aqueous sodium hydroxide solution. The pH of the alkaline layer was adjusted to pH 3 with dilute hydrochloric acid, and the deposited precipitate was collected by filtration and dried to obtain 23.8 g (yield: 52%) of keto acid as a yellow powder. 9.65 g of this keto acid was dissolved in 20 ml of 98% sulfuric acid, stirred at 110 ° C. for 5 hours, and discharged into 100 ml of ice water. 50% aqueous sodium hydroxide solution 64
g and made alkaline, and extracted with 200 ml of toluene. The toluene extract was concentrated, and 50 ml of methanol was added to precipitate a precipitate. The precipitate was collected by filtration and dried to obtain 21.3 g (yield: 48%) of a yellow powder. Melting point of this compound,
The elemental analysis value, mass analysis value, and characteristic absorption of the infrared absorption spectrum were as follows.

Melting point: 183-185 ° C. MS (m / e): 482 (M ⁺ ) IR: ν _{C = O} = 1760 cm ⁻¹

Example 11 Synthesis of 2,7-dichloro-3,6-bis (pyrrolidino) spiro [anthrone-9,3′-phthalide] 1.48 g of phthalic anhydride was added to 30 m of ethylene dichloride.
and 1.34 g of aluminum chloride was added and dissolved therein. 4,4'-Dichloro-3,3 '
1.40 g of -bis (pyrrolidino) benzophenone was added, and the mixture was stirred at 45 to 50 ° C for 6 hours. Ethylene dichloride was distilled off, and after cooling, 30 ml of 98% sulfuric acid was added.
Stirred at ~ 90 ° C for 1.5 hours. The reaction mixture is added to ice 2
The mixture was discharged into 00 g, made alkaline with 60 g of a 50% aqueous sodium hydroxide solution, and the precipitate was extracted with 200 ml of toluene. After drying the toluene extract with magnesium sulfate, silica gel column chromatography was performed, and 0.6 g of a yellow powder was obtained.
(12% yield). The melting point, elemental analysis value, mass analysis value and characteristic absorption of infrared absorption spectrum of this compound were as follows.

Melting point: 243-245 ° C. MS (m / e): 518 (M ⁺ ), 520, 522 IR: ν _{C = O} = 1775 cm ⁻¹ , 1665 cm ⁻¹

Example 12 3,6-Bis (di-n-butylamino) spiro [10-
Hydroxy-9,10-dihydroanthracene-9,
Synthesis of 3′-phthalide] 2.36 g of 3,6-bis (di-n-butylamino) spiro [anthrone-9,3′-phthalide] was dissolved in 8 ml of acetic acid, and 0.5 g of copper acetate and 5 g of zinc were added. Added and refluxed with stirring. To this, 7 ml of 35% hydrochloric acid was added dropwise over 6 hours. The separated yellow viscous substance was extracted with 100 ml of toluene. After washing the toluene layer with hot water, toluene was distilled off. To this residue, 40 ml of methanol was added, and the mixture was stirred overnight, and the resulting precipitate was collected by filtration and dried to obtain 1.36 g (yield 57%) of white powder. The melting point, elemental analysis value, mass analysis value, and characteristic absorption of infrared absorption spectrum of this compound were as follows.

Melting point: 202-204 ° C. MS (m / e): 474 (M ⁺ ) IR: ν _{C = O} = 1710 cm ⁻¹ , ν _OH = 3420 cm ⁻¹

Example 13 3,6-Bis (di-n-butylamino) spiro [10-
Ethoxy-9,10-dihydroanthracene-9,3 '
-Phthalide] 3,6-bis (di-n-butylamino) spiro [10-
Hydroxy-9,10-dihydroanthracene-9,
3′-phthalide] 2 g, 50 g of a 50% aqueous sodium hydroxide solution, 40 ml of toluene and 0.5 g of benzyltriethylammonium chloride were added thereto, followed by stirring at 40 to 50 ° C. To this, 3.08 g of diethyl sulfate was added dropwise over a period of 30 minutes. After dropping, the mixture was stirred at the same temperature for 1 hour,
1 and extracted with 100 ml of toluene. The toluene solution was separated, washed with hot water, and then subjected to silica gel column chromatography to obtain 1.98 g (yield: 95%) of a pale yellow resinous substance which developed a pale yellow brown color on silica gel. The elemental analysis value, the mass analysis value, and the characteristic absorption of the infrared absorption spectrum of this compound were as follows.

[0076] MS (m / e): 502 (M ⁺ ) IR: ν _{C = O} = 1710 cm ⁻¹

Table 1 shows the absorption maximum in 95% acetic acid and the molar extinction coefficient of the compound of the present invention obtained in Examples 1, 2, 6, 9 and 10 above.

[0078]

[Table 1]

Example 14 Production of Pressure-Sensitive Recording Material 3 g of 3,6-bis (diethylamino) spiro [anthrone-9,3′-phthalide] synthesized in Example 1 was added to KM.
47 g of C-113 (trade name, solvent manufactured by Kureha Chemical Industry Co., Ltd.)
Was dissolved under heating to prepare a color former solution.

On the other hand, 100 g of water was added to a system modifier (trade name:
5 g of EMA-31, manufactured by Monsanto Co., Ltd., and adjusted to pH 4 with an aqueous solution of caustic soda. in addition,
The mixture was emulsified with a homogenizer until the oil droplet diameter became 4 microns. Then, the mixture was heated to 60 ° C. with stirring, and stirred at the same temperature for 1 hour. After cooling to room temperature, p with 25% ammonia water
H was adjusted to 7.5 to prepare a capsule dispersion of a color former.

[0081] 10 g of the capsule dispersion liquid of the coloring agent thus prepared, 2 g of flour starch, and latex 1
g, mixed well, and applied to a high-quality paper at a solid content of 5 g /
It was applied and dried so as to obtain an upper paper of m ² .

FIG. 4 shows a reflection spectrum of a lower image sheet obtained by applying a zinc salt of a copolymer resin of salicylic acid and styrene to the upper sheet produced as described above, and a color image formed by roll-coloring with the coated surfaces facing each other.

Example 15 Production of Thermal Recording Material 5 g of 3,6-bis (diethylamino) spiro [anthrone-9,3′-phthalide] synthesized in Example 1 was added to 2.
In 45 g of a 5% aqueous solution of polyvinyl alcohol (PVA-117, manufactured by Kuraray Co., Ltd.), an average particle size of 1 was measured using a sand mill.
It was pulverized to a micron size to obtain a color former dispersion.

On the other hand, 10 g of bisphenol A as a developer
And 10 g of sensitizer p-benzylbiphenyl.
The mixture was pulverized with a sand mill in 80 g of a 5% aqueous polyvinyl alcohol solution so that the average particle size became 3 μm, to obtain a developer dispersion.

After mixing the above two dispersions, 30 g of a 50% dispersion of calcium carbonate and paraffin wax 3
15 g of a 0% dispersion was added and mixed well to obtain a heat-sensitive coating liquid.

The heat-sensitive coating liquid thus prepared was applied on a high-quality paper so that the solid content was 4.5 g / m ² . After drying, by calendering treatment, the Bekk smoothness of the heat-sensitive recording layer surface is adjusted to be 400 to 500 seconds,
A heat-sensitive recording material was produced.

The heat-sensitive recording material thus obtained was brought into contact with a heated metal block for 5 seconds to develop color on the entire surface. FIG. 5 shows the reflection spectrum of this color image. FIG. 6 shows the change over time in the reflection spectrum when the color image was irradiated with a fluorescent lamp (20,000 lux).

Comparative Example 1 Production of Thermosensitive Recording Material In Example 14, 3,6-bis (diethylamino)
Instead of spiro [anthrone-9,3'-phthalide], 3,6-bis (dimethylamino) spiro [fluorene-
9,3 '-(6'-dimethylamino) phthalide] was used, and a heat-sensitive recording material was produced in the same manner as in Example 14.

The heat-sensitive recording material thus obtained was brought into contact with the heated metal block for 5 seconds to develop color on the entire surface. FIG. 7 shows the change over time in the reflection spectrum when the color image is irradiated with a fluorescent lamp (20,000 lux).

[0090]

According to the recording material prepared using the spiro (anthrone-phthalide) derivative of the present invention, the absorption maximum near 900 nm disappears by irradiation with a fluorescent lamp, and a new one near 700 nm as shown in FIG. Since it has the specificity that the absorption maximum occurs, new development can be expected in the erasing and reproduction of recording. Further, this new absorption is extremely strong against irradiation with a fluorescent lamp as compared with the change over time of the spectrum of the compound of Comparative Example 1 (FIG. 7), so that it is very useful as a coloring agent for pressure-sensitive recording materials and heat-sensitive recording materials. Useful.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of 3,6-bis (diethylamino) spiro [anthrone-9,3′-phthalide] synthesized in Example 1.

FIG. 2 is a proton NMR spectrum of 3,6-bis (diethylamino) spiro [anthrone-9,3′-phthalide] synthesized in Example 1.

FIG. 3 is a mass spectrum of 3,6-bis (diethylamino) spiro [anthrone-9,3′-phthalide] synthesized in Example 1.

FIG. 4 is a reflection spectrum of a color-formed image of a pressure-sensitive recording paper roll manufactured in Example 14.

FIG. 5 is a reflection spectrum of a full-color image of the thermal recording paper manufactured in Example 15.

FIG. 6 is a time-dependent change in the reflection spectrum when a full-color image of the thermal recording paper manufactured in Example 15 is irradiated with a fluorescent lamp (20,000 lux).

FIG. 7 is a time-dependent change of a reflection spectrum when a full-color image of the thermal recording paper manufactured in Comparative Example 1 is irradiated with a fluorescent lamp (20,000 lux).

Continuation of the front page (72) Inventor Mansuke Matsumoto 1-43, Minami, Yuge-cho, Yao-shi, Osaka Yamamoto Kasei Co., Ltd. (58) Field surveyed (Int. Cl. ⁷ , DB name) C07D 307/94 C09B 11 / 16 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A compound of the general formula (I) [Wherein X is (However, R ² represents an alkyl group having 1 to 4 carbon atoms); Y represents an amino group having an alkyl group having 1 to 8 carbon atoms or a phenyl group; May be. Z represents a hydrogen atom, a halogen atom, or a phenoxy group. R ¹ represents a halogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 4. ] A spiro (anthrone-phthalide) derivative represented by the formula: 2. A compound of the general formula (II) [Wherein, X, Y, and Z represent the same meanings as X, Y, and Z in the formula (I) of claim 1. And a compound represented by the general formula (III): Wherein, R ¹ R ^1, n in Formula of claim 1 (I), n
Represents the same meaning as The method for producing a spiro (anthrone-phthalide) derivative according to claim 1, wherein the phthalic anhydride derivative represented by the formula (1) is reacted under a Lewis acid catalyst. 3. A recording material comprising the spiro (anthrone-phthalide) derivative according to claim 1, and a color developing substance that causes the derivative to develop color.