JPS5865755A - 3-(substituted amino)-9-(2"-phenylanilino)-benzo(d)fluoran - Google Patents

Abstract

NEW MATERIAL:The fluoran is represented by formulaI(where R<1> and R<2> are each H, alkyl, cycloalkyl, allyl, phenyl, substd. phenyl or aralkyl, or combined together to form a heterocycle.; R<3> is H, halogen or nitro; n is 0-4). USE:Colorant for pressure- or heat-sensitive recording paper. PREPARATION:The compd. is prepared by interaction of o-benzoyl-benzoic acid of formula II and 1-naphthol of formula III at 0-100 deg.C for 1-48hr in an acid binding agent such as conc. sulfuric acid, phosphoric acid or polyphosphoric acid. The reaction product is usually poured into ice water and recovered as crystals. When necessary, the product is purified by column chromatography, recrystallization, sublimation, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel J-substituted amino-ter(co'-7-elanilino)-benzo((1) fluorans).

The following general formula (1) of the present invention (wherein R1 and R3 represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a phenyl group, a substituted phenyl group, an aralkyl group, or Rs.

and V may form a homoheterocycle. 2 represents a hydrogen atom or a lower alkyl group, X represents a hydrogen atom, a halogen atom, or a nitro group, and n represents an integer from O to Z. ) The 3-substituted amino-ter<,21-phenylanilino)benzo(1) fluorans are novel compounds and are extremely valuable as chromogens for paper, for example pressure-sensitive and thermal paper. .

The substituents represented by R1 and R in the general formula [I] include a hydrogen atom, a methyl group, an ethyl group, a tetravir group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group.

Alkyl groups such as decyl group, cyclohexyl group.

Schifftetraalkyl groups such as cycloheptyl groups, allyl groups such as propenyl groups and butenyl groups, phenyl groups, tolyl groups, p
~ethylphenyl &, p-butylphenyl group * p −
/ Substituted phenyl groups such as lorphenyl group, p-bromphenyl group, p-nitrophenyl group, aralkyl groups such as benzyl group, phenethyl group, etc.0 Also, with R1 and R'', the same heterocycle is formed. Specific examples include piperidino residue and 1 morpholino residue.

Examples include pyrrolidinyl residues.

The substituents represented by X include hydrogen atom, chlorine atom,
Indicates a bromine atom, a nitro group, and n is θ.
Indicates an integer from ~Hiro.

The substituent represented by R3 includes a hydrogen atom, a methyl group,
Examples include lower alkyl groups such as ethyl group, propyl group, butyl group, pentyl group, and hexyl group. “Compounds of the present invention, for example, those of the general formula (II) (wherein R',
R'', X and n have the same meanings as in the general formula (r)k.) and the O-benzoylbenzoic acids represented by the following general formula (II) (wherein R is the general formula having the same meaning as in [I]) in an acid binder such as concentrated sulfuric acid, phosphoric acid or polyphosphor 1 at a temperature of 0°C to 100°C for /~4IIr hours. Manufactured by.

The reaction product is usually easily obtained as a crystal by discharging it into ice water, but if desired, a pure product can be obtained by adding refinements such as column chromatography, photography, recrystallization, sublimation, etc.

One of the raw materials, 0-benzoylbenzoic acids represented by the general formula [■], is produced by heating and condensing m-aminophenols represented by the omniscient reaction formula below and phthalic anhydrides.

The other raw material, l-Na7tols represented by the general formula [-], is represented by the following general formula (IV) (where xl is a hydroxyl group, an aino group, or a hydrochloride thereof,
Represents sulfate. ) and 0-phenylanilines represented by the following general formula (V) without a solvent or in a solvent inert to the reaction at a temperature of from iso°C to 0°C. EXAMPLES The present invention will be explained in more detail with reference to Examples below.

Example 1 μm dihydroxina 7 tarenko jII and 0-phenylaniline 711 were reacted at a temperature of -00°C for 7 hours, and after cooling to 60°C, JjS hydrochloric acid to- and water 300- were added, and the mixture was reacted again. The mixture was heated to 90°C and suspended for 1 hour.

After completion, the obtained crystals were filtered at room temperature, and the obtained crystals were again heated and washed with 3j-hydrochloric acid SO- and 300% water, filtered, and dried to give p-(J'- Phenylae IJ/)=/-naphtholdaj# (melting point tr3-irs1::) was obtained.

Arakajime 0-(Cohydroxy-diethylaminobenzoyl)-benzoic acid≠,≠I and the u-(r '−
Phenylanilino)-/-naphthol, 2g and θ℃
Condensation was carried out in def.% concentrated sulfuric acid jVl at a temperature of -io<0>C for a cog time.

After the reaction was completed, the mixture was poured into 200ml of ice water, stirred for 7 hours, filtered, and washed with 200ml of a 1.2*NaOH aqueous solution.

Then extracted with chloroform jOO- and 1.2-NaOH
After washing with YK solution 100- and drying using sodium sulfate, chloroform was distilled off under reduced pressure, and to the residue, beef san was added to N- for crystallization. After filtration and drying, 3-diethylaminoter(λ'-phenylanilino)-ben/-((1) fluoran tl represented by the following structural formula) was obtained.

Next, this compound was purified by column chromatography to obtain a pure product 4III having a melting point of 0.degree. C./-2/0.degree.

Elemental analysis value mass spectrum CaoHs*N*Os -j r lr parent ion beak sty visible region absorption spectrum (glacial acetic acid solution) maximum absorption wavelength u
A/jnrn, A/jnrnThe toluene solution of this compound was colorless, and it quickly developed color on silica gel, giving it a greenish-black color. O-(,2-hydroxyedadiptyladenobenzoyl)-benzoic acid shown by the following structural formula manufactured by Yosho 3.71 and Example/Description 4
(-(j-7enylanilino)su7toroo/,ko,!
9 and. Condensation was carried out in 97's @ 301i sulfuric acid at a temperature of -10[deg.]C for a cog time.

After completion of the reaction, post-treatment was carried out according to Example/1 to obtain J-dibutylamino-ter<Jl-phenylanilino)-benz[d]fluoran 211 shown by the following structural formula.

Next, this compound was recrystallized using toluene to obtain a pure product with a melting point of 1°C.

Elemental analysis visible absorption spectrum (glacial acetic acid solution) maximum absorption wavelength
u6/nm, 6/AnrnThe toluene solution of the present compound is colorless, quickly develops color on silica gel, and is tasteless black fi-0. The compounds shown in Table C were obtained.

Claims (1)

[Claims] (1) General formula CI) (wherein at and R3 are hydrogen atoms, alkyl groups, cycloalkyl groups, allyl groups, phenyl groups. Substituted phenyl groups, aralkyl groups, or R' pg
It is good that they form a homoheterocycle. R3 represents a hydrogen atom or a lower alkyl group, and! represents a hydrogen atom, a halogen atom, 2) an o group, and n represents an integer of 0-+. -(-1-7
enylanilino)-benzo[d]fluoranes.