JPS6169991A - Manufacture of ammonium salt of n,n,n',n'-tetrakis-(p-dialkylamino)-p-phenylenediamine - Google Patents

Abstract

PURPOSE:To manufacture the ammonium salt of N,N,N',N'-tetrakis(p- dialkylamino)-p-phenylenediamine by electrolytically oxidizing a specified amine in the presence of the ammonium salt of an inorg. acid in a polar org. solvent in an electrolytic cell provided with a diaphragm. CONSTITUTION:An amine represented by formula I is electrolytically oxidized in the presence of the ammonium salt of an inorg. acid in a polar org. solvent in an electrolytic cell provided with a diaphragm to manufacture the ammonium salt of N,N,N',N'-tetrakis(p-dialkylamino)-p-phenylenediamine repesented by formula II. In the formulae I, II, each of R1-R8 is alkyl; A is the anionic residue of the ammonium salt of an inorg. acid; when A is a univalent anion, n=1; when A is a bivalent anion, n=2; and when A is a tervalent anion, n=3.

Description

DETAILED DESCRIPTION OF THE INVENTION Monotetrakis(p-dialkylaminopheni#)-1)
-7 Relating to a method for producing noaminium salts of 22 diamines.

"Prior art" Aminium salts of N, N, N, N-tetrakis(p-alkylaminophenyl)-p-7 22-diamine have strong absorption in the infrared region, so they can be used to make use of this property, for example, to block sunlight. Applications include windows, light selection filters, optical memory disks, and sunscreens in the manufacture of eyeglasses, etc.

Conventionally, the method for producing the aminium salt was disclosed in the Japanese Patent Publication No. 4
3-25335, that is, N , N , N ,
N-tetrakis(p-dialkylaminophenyl)-p
- A method is known in which phenylenediamines are dissolved in an organic solvent such as DMF or acetone and oxidized with a silver salt such as silver perchlorate or silver hexafluoroantimonate to form an aminium salt.

Furthermore, in Japanese Patent Publication No. 5810/1986, an anolyte consisting of diamine, acetone, and sodium hexafluoroantimonate and a catholyte consisting of acetone and sodium hexafluoroantimonate were electrolytically oxidized in an electrolytic cell with a diaphragm. A method for producing quinone bisimmonium hexafluoroantimonate is described.

"Problems to be Solved by the Invention" Each of the above-mentioned conventional techniques has problems to be solved.

Oxidation by the chemical method described in Japanese Patent Publication No. 43-25335 requires the use of expensive inorganic acid silver salts, and N
It is not possible to use metal salts of group 1 of the periodic table such as a, K, and Li, metal salts of group 2 of the periodic table such as Mg, Ca, and Zn, or inexpensive salts such as ammonium salts. Furthermore, the silver salt used turns into metallic silver, which is difficult to remove from the production system. In other words, some of the silver salt used becomes glue-like silver, which is difficult to completely separate from the target product, and such metallic silver may be mixed into the product and deteriorate the quality as an infrared absorber. What we bring about is the 1970s
It is clear from the description of -129532.

Furthermore, among the methods described in Japanese Patent Publication No. 46-5810, the method using chemical oxidation requires the use of a silver salt, as in the case of Japanese Patent Publication No. 43-25335, and it is troublesome to remove the generated metallic silver from the product. . Furthermore, in the electrolytic oxidation method described in the same publication, the metal salt used adheres to the cathode in the form of metal, causing a significant decrease in current value and making it difficult to continue electrolysis.

"Means for Solving the Problems" The present invention was achieved as a result of intensive research on the method for producing aminium salt of lakis(p-dialkylamino)-p-phinyl diamine I-). . That is, the present invention involves electrolytically oxidizing a compound represented by the formula (in formula (1), R1 to R8 represent an alkyl group) in a polar organic solvent in the presence of an ammonium salt of an inorganic acid using an electrolytic cell having a diaphragm. and the formula (Formula (2), the middle represents the anion residue of the inorganic acid ammonium salt, n represents 1 when A is a monovalent anion, 2 when A is a divalent anion, 3 when A is a trivalent anion, and R1 to 8 have the same meanings as above.) Aminium salts represented by the following are produced.

In the present invention, specific examples of the amines represented by the formula (1) include the following.

Also, as an ammonium salt of an inorganic acid, (NH4)2SO4
, NH4NO3, NH4F, NH4C1, NH4Br
, NH4BF4゜NH4Sb'P6. NH4SCN
, NH4Cl0. , NH4As F,, NH45
bCI,.

BF4, NI-(4SCN, NH4ClO
4 gives more favorable results.

Further, as the polar organic solvent, DMF is most preferable, but alcohols such as methanol, ethanol, butanol, propatool, and impropatool, acetone, MIB
In addition to ketones such as K and MEK, methyl selonurp, ethyl cellosolve, DMSO, dimethylacetamide, N
-Methylpyrrolidone, pyridine, or a mixture of these solvents can be used.

Additionally, these solvents may contain a small amount of water. Note that polar solvents that have the necessary solubility for the aromatic amines represented by the other formulas (1) and (2), their aminium salts, and ammonium salts of inorganic acids and are stable under electrolytic conditions may be used. I can do this.

The electrolytic cell used is one in which the anode and cathode are separated by a diaphragm, and the diaphragm material is smelt glass, asbestos, unglazed plate, or sulfur ion (trade name, ion exchange resin membrane, DuE). 'ont), Selemion (trade name, ion exchange resin membrane, Asahi Glass), etc. are used.

The electrode materials used for the anode include carbon, platinum, platinum plated (for example, titanium plated with platinum), gold, DSB (trade name: ruthenium oxide based electrode, Bermerex Electrode Co., Ltd. M), etc. The cathode may be made of platinum, platinum plated (for example, titanium plated with platinum), silver, lead, copper, iron, nickel, or 5US-
Alloy materials such as 2'7 can be used.

Electrolytic oxidation is 5 mA/crn% 500 rr+A/c
mA/z, preferably at a current density of 10 mA/z
~100 mA/cm2 is good.

Although the electrolysis temperature varies depending on the organic solvent used, it is generally preferable to carry out the electrolysis at a temperature of 40°C to 100°C.

The amount of electricity required for electrolytic oxidation is the theoretical amount (IP/mo
1) is fine, but the reaction can be checked by thin layer chromatography or the like and adjusted as necessary.

During an electrolytic reaction, an appropriate flow of liquid is required to make the electrolytic system uniform. Furthermore, since ammonia gas and hydrogen gas are generated, it is necessary to discharge these gases outside the electrolytic system as necessary to ensure safety. After the electrolytic reaction is complete, the anolyte is extracted, a small amount of water is added, and the target product is extracted as crystals. The crystals can be made sufficiently pure to be used as an infrared absorber without any special purification steps.

"Example" The invention will be explained in more detail by way of examples.

Example 1 Separation into anode chamber and cathode chamber by glass filter - Separation
Add 79.2P of ethylene diamide (n-7" thylaminophenyl)-p-7, KDMF53rn6 to the cathode chamber, and 4.24P of ammonium perchlorate. Next, attach 3 m platinum plates to the anode and cathode chambers. A device for extraction was attached to the bipolar chamber, and electrolytic oxidation was carried out at a temperature of 30 to 50°C, a voltage of 35 to 40 V between one terminal, and a current value of 90 mA (DC) with stirring for 2 hours and 50 minutes.Next, the reaction solution was removed from the anode chamber. The entire amount was taken out into a beaker, and then about 8 ml of water was added dropwise while stirring at room temperature to precipitate crystals. After further stirring for 1 hour, filtration, washing with water, and drying yielded 9.91 g of green crystals represented by the following formula. Yield 97.2%mp
Absorbance at 400-2000 nm was measured in acetone at 152-7°C. λ410 nm, λ95 Q nm, λ145
It showed the maximum absorption value at 0 nm.

The elemental analysis values were in good agreement with the first theory.

Example 2゜DMF'48m/! in the anode chamber of the same electrolytic cell as Example 1!
, ruphenyl)-p-phenyl diamine 3.71 cathode chamber 1c DMF 52 rnl, NH48F42.1
Add 2 f% to each. 40℃, terminal voltage 35~
Electrolytic oxidation was performed at 40 V and a current value of 75 mA (DC) for 1 hour and 26 minutes.

Thereafter, the product was post-treated in the same manner as in Example 1 to obtain green crystals represented by the linear formula at a yield of 3.74 fl-1 and 92.3%.

Very thick absorption wavelength (acetone) at m2154~6°C 4Q Q nm~2000 nm λ41 Q nm, λ950 nm.

λ1450 nm Examples 3 to 10° An aminium salt represented by the following formula was obtained in the same manner as in Example 1.

"Effect of the invention" Improved efficiency without metal adhesion to the cathode < N, N, NN'
Electrolytic oxidation of -tetrakis(p-dialkylamino)-p-7 22-diamine to its aminium salt has become possible. In addition, a target product of good purity without contamination with metals produced by reduction of metal salts can be obtained.

Claims (1)

[Claims] (1) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) (In formula (1), R_1_ to_8 represent alkyl groups) A compound represented by the formula Formulas characterized by electrolytic oxidation in the presence of ammonium salts of acids ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) (In formula (2), A is the anion residue of the inorganic acid ammonium salt, and n is When A is a monovalent anion, it represents 1, when it is a divalent anion, it represents 2, and when it is a trivalent anion, it represents 3, and R_1_~
_8 represents the same meaning as above. ) A method for producing aminium salt represented by