JP4158060B2 - Method for producing salt of aminium compound - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a salt by changing a compound containing a nitrogen atom to aminium, and more specifically, reacting a dialkylaminophenylphenylenediamine with an inorganic acid salt to produce the oxidation product of the aminium. The present invention relates to a method for producing an aminium salt, characterized in that when the inorganic acid residue salt is produced, the reaction is allowed to proceed using an iron complex salt.
[0002]
[Prior art]
N, N, N ′, N′-tetrakis- (p-dibutylaminophenyl) -p-phenylenediamineaminium perchlorate, which is one of the compounds produced in the present invention, strongly absorbs wavelengths in the infrared region. As a compound that can be used for a long time, it has been widely used as an auxiliary in the production of recording media in recent years. The method based on oxidation and the method based on chemical oxidation can be broadly classified. The electrical method is also disclosed in Japanese Patent Application Laid-Open No. 61-246391, which requires a so-called electrolysis field device, while the chemical method. Uses acid silver salts of various acids to form acid residue salts of compounds amidated (Japanese Examined Patent Publication No. 43-25335) and methods using ferric salts (Japanese Patent Laid-Open No. 2-311447). There is.
[0003]
However, in the chemical method here, since it is unavoidable that a trace amount of the metal of the salt used in the reaction product is mixed, in order to require a salt of a high purity aminium compound, In order to use those produced by these methods, it is necessary to repeat purification and to remove the metal contained in a trace amount. Japanese Patent Laid-Open No. 5-98243 has a detailed description about a small amount of iron.
[0004]
[Problems to be solved by the invention]
The present invention provides a compound of formula (1) by a chemical method:
(In the formula, R represents H or a lower alkyl group.)
Aminium compound salt of formula (2)
[Chemical 2]
(Wherein R represents H or a lower alkyl group, and A represents an anion residue of an inorganic acid salt)
The manufacturing method of the compound shown by is provided.
[0005]
[Means for Solving the Problems]
The present inventor repeats trial and error, and when the compound of the formula (2) is produced from the compound of the formula (1) by a chemical method, the reaction may be that the salt used is dissolved in the organic solvent used in the reaction. The product was found to be a cause of metal contamination even though it was a trace amount, and the problem was solved by using a compound insoluble in the organic solvent used in the reaction, and the present invention was completed. It is a thing. That is, the present invention makes it possible to produce a compound of formula (2) in which no ferrous metal is mixed into the reaction product by using a ferric complex salt as an iron compound capable of producing aminium.
[0006]
Here, ferric complex salts as iron compounds that can be used, that is, iron complex salts containing ferric ions include 1,3-propylenediaminetetraacetic acid iron complex, ethylenediaminetetraacetic acid iron complex, diethylenetriaminepentaacetic acid. An iron complex, an ethylenediamine disuccinate iron complex, a 1,2-propylenediaminetetraacetate iron complex and the like can be mentioned. These complexes are usually used as salt bodies of alkaline compounds such as sodium, potassium, ammonium and amine, although there is no particular problem even if they are used as they are. It seems that the present invention is advantageously practiced by dissolving these ferric complexes in the amount of water necessary to dissolve them and subjecting them to the reaction.
[0007]
Examples of R in the compound represented by the formula (1) include a hydrogen atom and lower alkyl groups such as methyl, ethyl, propyl, butyl and pentyl. The compounds represented by the formula (1) having these groups as R are lower alcohol solvents such as methanol, ethanol and propanol, ester organic solvents such as acetic acid ethyl ester, acetic acid methyl ester and acetic acid butyl ester, heptane and octane. Petroleum solvents such as nonane, dimethylformamide, dimethylacetamide, acetonitrile, acetone, methyl ethyl ketone, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, etc. are used alone or mixed and dissolved in this to be subjected to the reaction.
[0008]
Next, A, which is a salt of an aminium compound in the formula (2), is an anion residue of an acid salt used in the reaction, sodium perchlorate, potassium perchlorate, potassium hexafluorophosphate, Sodium hexafluorophosphate, ammonium hexafluorophosphate, ammonium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, sodium p-toluenesulfonate, potassium benzene sulfonate, sodium methanesulfonate, ethanesulfonic acid Anion residues such as potassium, sodium trifluoroacetate and sodium benzoate.
[0009]
Thus, when the compound represented by the formula (1), the acid or a salt thereof, and the ferric complex salt are appropriately reacted in a solvent, a salt of the aminium compound represented by the formula (2) is obtained.
Hereinafter, examples will be described in order to specifically explain the present invention.
【Example】
[0010]
Example 1
Synthesis of N, N, N ′, N′-tetrakis (p-dibutylphenyl) -p-phenylenediamineaminium monoperchlorate:
1.38 g of N, N, N ′, N′-tetrakis (p-dibutylphenyl) -p-phenylenediamine is dissolved in ethyl acetate, 6 ml of acetonitrile, 0.22 g of sodium perchlorate and 1,3-diaminopropanetetraacetic acid A solution prepared by dissolving 1.13 g of the ammonium salt of the ferric complex salt in 6 ml of water was added. Stir at 30 ° C. for 6 hours. The reaction mixture was washed with water, concentrated under reduced pressure, n-heptane was added, and the precipitated crystals were collected by filtration and dried to give the title compound as a green powder.
Yield 1.19 g Yield 77.8% mp 162 ° C
Maximum absorption wavelength 950 nm Molar extinction coefficient 2.1 × 10 ⁴
[0011]
Example 2
Synthesis of N, N, N ′, N′-tetrakis (p-dibutylphenyl) -p-phenylenediamineaminium monoperchlorate:
Example 1 except that 1.78 g of the ferric complex ammonium salt of diethylenetriaminepentaacetic acid was used instead of 1.13 g of the ferric complex ammonium salt of 1,3-diaminopropanetetraacetic acid in Example 1. In the same manner, the title compound was obtained.
Yield 1.24 g Yield 81% Melting point and other characteristic values were the same as the compound obtained in Example 1.
[0012]
Example 3
Synthesis of N, N, N ′, N′-tetrakis (p-dibutylphenyl) -p-phenylenediamineaminium monotetrafluoroborate:
4.15 g of N, N, N ′, N′-tetrakis (p-dibutylphenyl) -p-phenylenediamine was dissolved in 45 ml of ethyl acetate, 18 ml of acetonitrile and 0.59 g of sodium fluoroborate were added, and 1,3-diaminopropane was added. Ammonium salt of ferric tetraacetate (3.39 g) was dissolved in 18 ml of water and added. Stir at 30 ° C. for 6 hours. The reaction mixture was washed with water, concentrated under reduced pressure, n-heptane was added, and the precipitated crystals were collected by filtration and dried to give the title compound as a green powder.
Yield 2.74 g Yield 60.4% mp 156 ° C
Maximum absorption wavelength 950 nm Molar extinction coefficient 2.4 × 10 ⁴
[0012]
Example 4
Synthesis of N, N, N ′, N′-tetrakis (p-dibutylphenyl) -p-phenylenediamineaminium monohexafluorophosphate:
The title compound was obtained in the same manner as in Example 3, except that 0.88 g of ammonium hexafluorophosphate was used instead of 0.59 g of sodium fluoroborate in Example 3.
Yield 4.12 g Yield 85.8% mp 140-150 ° C
Maximum absorption wavelength 950 nm Molar extinction coefficient 2.5 × 10 ⁴
[0013]
Reference example 1
1.38 g of N, N, N ′, N′-tetrakis (p-dibutylphenyl) -p-phenylenediamine is dissolved in ethyl acetate, 6 ml of acetonitrile, 0.22 g of sodium perchlorate and 1,3-diaminopropanetetraacetic acid 1.13 g of the ammonium salt of the ferric complex was added. Stir at 30 ° C. for 6 hours. The reaction mixture was washed with water, concentrated under reduced pressure, n-heptane was added, and the precipitated crystals were collected by filtration and dried to obtain a very small amount of a compound that was a green powder, but unreacted raw materials were recovered.

Claims (4)

Formula (1)

(Wherein R represents a compound represented by H or a lower alkyl group, and reacting with an acid or a salt thereof to form a salt of an aminium compound, a ferric complex salt is used.)

(Wherein R represents H or a lower alkyl group, and A represents an anion residue)
For producing a salt of an aminium compound represented by formula (1) The method according to claim 1, wherein a salt of an aminium compound is produced using a compound wherein R is an n-butyl group. The method according to claim 1 or 2, wherein the ferric complex salt is 1,3-propylenediaminetetraacetic acid iron ammonium salt. 4. The method according to claim 1, wherein the ferric complex salt is used as an aqueous solution.