JPS5952672B2 - New lactone compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel lactone compound represented by the following general formula (1).

[In the formula, R1 is a hydrogen atom, a lower alkyl group, a benzyl group (
It can have a halogen atom or a lower alkyl group as a substituent.

), and R2 is a lower alkyl group, a cyclohexyl group, a benzyl group (which can have a halogen atom or a lower alkyl group as a substituent), or a phenyl group (which can have a halogen atom or a lower alkyl group as a substituent). .
), or R1 and R2 are combined to form -(CH2)
4- -(CH2)5- -(CH2)20-(CH,
)-, R3 and R4 represent a hydrogen atom, a lower alkyl group, an aralkyl group, an amyl group, or a phenyl group (provided that at least one of R3 and R4 is a hydrogen atom), R5 represents a hydrogen atom, a lower Alkyl group, benzyl group (
It can have a halogen atom or a lower alkyl group as a substituent. ). Xl and X2 each independently represent a hydrogen atom, a lower alkyl group, or a halogen atom;
3 represents a hydrogen atom or a halogen atom. ] This new lactone compound is a compound useful as a coloring dye for heat-sensitive recording materials. In other words, the lactone compound of the present invention reacts with an acidic substance when heated to form an ether bond, converting into the corresponding fluoran derivative, and developing color.The mechanism of color development is different from that of conventional fluoran-type dyes, so it cannot be heated under pressure. It does not have the disadvantage that it easily develops color due to the presence of organic solvents such as alcohol.

In addition, the lactone compound of the present invention has 2.6
A diaminofluorane derivative is produced, and the dye produced by introducing a phenyl group having a trifluoromethyl group at the meta-position of the amino group at the 2-position is characterized by a black color with strong light resistance.

To synthesize the compound of the above general formula (1), first, as shown below, m-aminophenol derivative (11) and butanolic anhydride (111) are condensed to form a 4-amino-2-hydroxy-2''-monocarboxylic compound. Synthesize benzophenone (IV).

(Rl, R2 have the above-mentioned meanings) Next, this 4-amino-2-hydroxy-2''-carboxybenzophenone (1) and diphenylamine derivative (
V) (X1, X2, X3, R4, R5 have the above-mentioned meanings) and -1
The reaction is allowed to take place at a temperature of about 0°C to 100°C for several hours to several tens of hours.

The reaction was then poured into ice water and the pH was adjusted with NaOH.
After neutralization to 8 and filtration, the resulting crude product is recrystallized from an organic solvent. Synthesis examples of these compounds are shown below.

Synthesis Example 1 3-(4″-diethylamino-2″-hydroxyphenyl)-3-{5″-(3″-monotrifluoromethylphenyl)-amino-2″-methoxyphenyl}phthalide 4
31.3 g of -diethynoleaamino-2-hydroxy-2''-carboxybenzophenone and 26.7 g of 4-methoxy-3''-trifluoromethyldiphenylamine are stirred in 100 ml of concentrated sulfuric acid at 10 DEG C. for 48 hours.

Then drain into 1000ml of water and adjust the pH to 8 with NaOH.
It will be neutralized until it passes.

The obtained crude product was recrystallized from toluene and ethanol to obtain 28 g of 3-(4″-diethylamino-2″-hydroxyphenyl)-3{5″-(3″-monotrifluoromethylphenyl)amino- 2″-Methoxyphenyl}phthalide was obtained. Melting point: 194-195°C Yield: 50% This product was determined by IR and elemental analysis to be 3-(4″-diethylamino-2″-hydroxyphenyl)-3{5″-(3)″
The product was confirmed to be monotrifluoromethylphenyl)-amino-2''-methoxyphenyl}phthalide.

The coloring hue of the compound obtained in this synthesis example and bisphenol is black.

The 4-methoxy-3''-trifluoromethyldiphenylamine used here can be obtained as follows.

m-acetylaminobenzotrifluoride 20.3g
．． P-promuanisole 22.5g, hydrium carbonate 15
g, 1 g of copper powder, and 0.04 g of iodine on an oil bath at 190~2
Stir at 00°C for 48 hours.

Next, 20 g of n-butyl alcohol and 17 g of 48% caustic soda were added and stirred at 100 to 110° C. for 3 hours.
After steam distilling the reaction product, cool it and filter out the precipitate. Then, vacuum distillation was performed to obtain 21.6 g of 4-methoxy-3''-trifluoromethyldiphenylamine. Yield: 81% white crystals.
・P56~58℃ BPl56~162℃/2mmHg
. Synthesis example 23-(4″-diethylamino-2″-hydroxyfuenyl)-3-{5″-N-methyl-N-(
3″-trifluoromethylphenyl)amino-2″-methoxyphenyl}phthalide 4-diethynoleaamino-2-
Hydroxy-2″-carboxybenzophenone 31.3
g and 28.1 g of 4-methoxy 3″-trifluoromethyl-N-methyldiphenylamine in 100 ml of concentrated sulfuric acid.
Stir for 48 hours at 10°C.

Then drain into 1000 ml of water and remove P with NaOH.
It is neutralized until H8. The obtained crude product was recrystallized from toluene/ethanol to obtain 34.5 g of 3-(4″-diethylamino-2″-hydroxyphenyl)-3-{5
"-N-methyl-N(3"-monotrifluoromethylphenyl)amino2"-methoxyphenyl}phthalide was obtained. Melting point: 198-198.5°C Yield: 60% This product was determined by IR elemental analysis to be 3-(4″-diethylamino-
2″-hydroxyphenyl)-3{5″-N-methyl-
N-(3″″-trifluoromethylphenyl)amino-
It was confirmed that it was 2''-methoxyphenyl}phthalide.The color hue of the compound obtained in this synthesis example and bisphenol was black.

The 4-methoxy-3''-trifluoromethyl-N-methyldiphenylamine used here can be obtained as follows.

70 ~ 26.7 g of 4-methoxy 3''-trifluoromethyldiphenylamine, 63 g of dimethyl sulfate, and 10 g of water.
Stir at 80°C for 4 hours.

After washing the reaction product with diluted NaOH, the oily substance is separated and vacuum distilled. 22.5 g of 4-methoxy-3''-trifluoromethyl-N-methyldiphenylamine are obtained.

Yield 80%, white crystal m-P47-49℃, BPl43
~145°C/3mmHg0 Other specific examples of the compounds of the present invention synthesized by the same method as above include the following.

Claims (1)

[Claims] 1 (1) General formula ▲ Numerical formulas, chemical formulas, tables, etc. ), and R_2 represents a lower alkyl group, a cyclohexyl group, a benzyl group (which can have a halogen atom or a lower alkyl group as a substituent), or a phenyl group (which can have a halogen atom or a lower alkyl group as a substituent). ), or R_1 and R_2 can be combined to form -(C
H_2)_4-, -(CH_2)_5-, -(CH_2
)_2-O-(CH_2)-, R_3, R_4
represents a hydrogen atom, a lower alkyl group, an aralkyl group, an amyl group, a phenyl group (however, at least one of R_3 and R_4 is a hydrogen atom) R_5 represents a hydrogen atom, a lower alkyl group, a benzyl group (a halogen atom, can have a lower alkyl group as a substituent). X_1 and X_2 each independently represent a hydrogen atom, a lower alkyl group, or a halogen atom, and X_3 is a hydrogen atom,
Represents a halogen atom. ] A novel lactone compound. The lactone compound according to claim 1, which is a compound represented by formula (2) ▲ where there are mathematical formulas, chemical formulas, tables, etc. ▼. The lactone compound according to claim 1, which is a compound represented by formula (3) ▲There are mathematical formulas, chemical formulas, tables, etc.▼.