JPH0841193A - Production of polycarbonate - Google Patents

Abstract

PURPOSE:To produce a less colored polycarbonate at an improved reaction rate by using a tetrazole derivative as the catalyst in the production of the polymer by the transesterification of a dihydroxy compound with a carbonic diester. CONSTITUTION:This reduction process is one for producing a polycarbonate by the transesterification of a dihydroxy compound such as bisphenol A with a carbonic diester such as diphenyl carbonate, which process comprises using a tetrazole derivative or a combination thereof with another nitrogenous organic compound as the catalyst. An example of the tetrazole derivative is a compound represented by the formula ]wherein R<1> and R<2> are each a single bond, 1-20 C alkylene, 2-20 C alkylidene or the like; A is Nr<1>2, Nr<2>3<+>X<-> (wherein r<1> and r<2> are each 1-8 C alkyl or the like; and X is OH, halogen or the like), pyridyl, aza-bicycloalkyl or the like; B is H, OY, CO2Y (wherein Y is H or an ion of an alkyl compound of NPB) or the like or a metallic ion]. Examples of the nitrogenous organic compounds used include a pyridine and an ammonium hydroxide. When this catalyst is used, the reaction rate can be improved and a product having a low content of a residual catalyst and good properties can be obtained.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing polycarbonate. Specifically, while improving the reaction speed,
The present invention relates to a method for efficiently producing a polycarbonate having an excellent color tone, with less residual catalyst and without impairing hydrolysis resistance.

[0002]

2. Description of the Related Art Polycarbonate is an engineering plastic excellent in transparency, heat resistance or impact resistance, and is currently used in the electric and electronic fields, automobile fields, optical parts fields and other industrial fields. Widely used in the field. Generally, as a method for producing a polycarbonate (hereinafter sometimes referred to as PC), a method of directly reacting an aromatic dihydroxy compound such as bisphenol A and phosgene (interfacial polycondensation method),
Alternatively, a method (melt polymerization method) is known in which an aromatic dihydroxy compound such as bisphenol A and a carbonic acid diester such as diphenyl carbonate are subjected to transesterification reaction in a molten state. In this PC production method, the interfacial polycondensation method requires the use of toxic phosgene, the production equipment is corroded by chlorine-containing compounds such as hydrogen chloride and sodium chloride, and water mixed in the resin. There are various problems such as difficulty in separating impurities that adversely affect the physical properties of polymers such as sodium oxide, and improvement in the production method thereof has been desired. From this point of view, the development of the melt polymerization method without using the above methylene chloride or phosgene gas has been actively conducted.

On the other hand, the transesterification method (melt polymerization method) is
Compared with the interfacial polycondensation method, although it has an advantage that PC can be manufactured at low cost, it is usually 280 to 310.
Since the reaction is carried out at a high temperature of ℃ for a long time, there is a great drawback that the problem of coloring the resin cannot be avoided. In addition, since a basic catalyst is often used, there is a problem that the resulting PC has poor hydrolysis resistance. In such a melt polymerization method, various improved techniques have been proposed in order to reduce this coloring. For example, Japanese Patent Publication Sho 61-39
972, JP-A-63-223036 and the like disclose a method of using a specific catalyst. In addition, JP-A-61-151236 and JP-A-62-1
Japanese Patent No. 58719 discloses a method of adding an antioxidant in the latter stage of the reaction. And, JP-A-61-62
JP-A-522-522 discloses a process-improving technique such as using a twin-screw vent type kneading extruder in the latter stage of the reaction, and JP-A-2-153925 and the like using a horizontal stirring polymerization tank. Further, in order to improve the hydrolysis resistance of the obtained PC, it has been conventionally known to neutralize with an acid such as dimethylsulfate, and recently, neutralization with an acid such as p-toluenesulfonic acid. There is known a technique for neutralizing excess acid with an epoxy (Japanese Patent Laid-Open No. 4-175368). However, the problem of quality has not been completely solved yet, and the actual situation is that a satisfactory PC has not been obtained yet.

[0004]

Means for Solving the Problems Accordingly, the present inventors have:
In view of the above situation, the drawbacks of the conventional method are solved, and in the transesterification method, the reaction rate is improved, the residual catalyst is small, and the PC having an excellent color tone is efficiently produced without impairing the hydrolysis resistance. We have earnestly conducted research to develop a manufacturing method of a PC that can achieve this. As a result, it was found that the above problem can be solved by using a specific tetrazole derivative or a combination of the tetrazole derivative and a nitrogen-containing organic compound (excluding the tetrazole derivative) in producing PC by transesterification. It was
The present invention has been completed based on such findings.

That is, according to the present invention, (1) a polycarbonate is produced from (A) a dihydroxy compound and (B) a carbonic acid diester by a transesterification method.
A method for producing a polycarbonate characterized by using a (C) tetrazole derivative as a catalyst, and (2) using a (C) tetrazole derivative and a (D) nitrogen-containing organic compound (excluding the tetrazole derivative) as a catalyst. A method for producing the above polycarbonate is provided.

In the present invention, there are various dihydroxy compounds used as the component (A). Examples thereof include aromatic dihydroxy compounds and aliphatic dihydroxy compounds, and at least one compound selected from these. The aromatic dihydroxy compound used as one of the components (A) has the general formula (4)

[0007]

Embedded image

[In the formula, R is a halogen atom (for example, chlorine, bromine, fluorine, iodine) or a carbon number of 1 to 8 respectively.
Is an alkyl group (eg, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, etc.)
They may be the same or different,
m is an integer of 0-4. Z is a single bond, an alkylene group having 1 to 8 carbon atoms or an alkylidene group having 2 to 8 carbon atoms (eg, methylene group, ethylene group, propylene group, butylene group, penterylene group, hexylene group, ethylidene group, isopropylidene group). Ridene group, etc., 5 to 15 carbon atoms
Cycloalkylene group or cycloalkylidene group having 5 to 15 carbon atoms (for example, cyclopentylene group, cyclohexylene group, cyclopentylidene group, cyclohexylidene group, etc.), or -S-, -SO-, -SO ₂ -, -O
-, -CO- bond or general formula (5) or (5 ')

[0009]

[Chemical 6]

The bond represented by ] The aromatic dihydroxy compound represented by these is mentioned. Examples of such an aromatic dihydroxy compound include bis (4-hydroxyphenyl) methane; bis (3-methyl-4-hydroxyphenyl) methane; bis (3-chloro-4-hydroxyphenyl) methane; bis (3 , 5-dibromo-4
-Hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 1,1-bis (2-t-butyl-4-hydroxy-3-methylphenyl) ethane;
1,1-bis (2-t-butyl-4-hydroxy-3-
Methylphenyl) ethane; 1-phenyl-1,1-bis (3-fluoro-4-hydroxy-3-methylphenyl) ethane; 2,2-bis (4-hydroxyphenyl)
Propane (commonly called bisphenol A: BPA); 2,2-
Bis (3-methyl-4-hydroxyphenyl) propane; 2,2-bis (2-methyl-4-hydroxyphenyl) propane; 2,2-bis (3,5-dimethyl-4-)
Hydroxyphenyl) propane; 1,1-bis (2-t
-Butyl-4-hydroxy-5-methylphenyl) propane; 2,2-bis (3-chloro-4-hydroxyphenyl) propane; 2,2-bis (3-fluoro-4-hydroxyphenyl) propane; 2, 2-bis (3-bromo-4-hydroxyphenyl) propane; 2,2-bis (3,5-difluoro-4-hydroxyphenyl) propane; 2,2-bis (3,5-dichloro-4-hydroxyphenyl) ) Propane; 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane; 2,2-bis (4-hydroxyphenyl) butane; 2,2-bis (4
-Hydroxyphenyl) octane; 2,2-bis (4-
Hydroxyphenyl) phenylmethane; 2,2-bis (4-hydroxy-1-methylphenyl) propane;
1,1-bis (4-hydroxy-t-butylphenyl)
Propane: 2,2-bis (4-hydroxy-3-bromophenyl) propane; 2,2-bis (4-hydroxy-)
3,5-dimethylphenyl) propane; 2,2-bis (4-hydroxy-3-chlorophenyl) propane;
2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane; 2,2-bis (4-hydroxy-3,2
5-dibromophenyl) propane; 2,2-bis (3-
Bromo-4-hydroxy-5-chlorophenyl) propane; 2,2-bis (3-phenyl-4-hydroxyphenyl) propane; 2,2-bis (4-hydroxyphenyl) butane; 2,2-bis (3- Methyl-4-hydroxyphenyl) butane; 1,1-bis (2-butyl-4-)
Hydroxy-5-methylphenyl) butane; 1,1-bis (2-t-butyl-4-hydroxy-5-methylphenyl) butane; 1,1-bis (2-t-butyl-4-hydroxy-5- Methylphenyl) isobutane; 1,1-
Bis (2-t-amyl-4-hydroxy-5-methylphenyl) butane; 2,2-bis (3,5-dichloro-4)
-Hydroxyphenyl) butane; 2,2-bis (3,5)
-Dibromo-4-hydroxyphenyl) butane; 4,4
-Bis (4-hydroxyphenyl) heptane; 1,1-
Bis (2-t-butyl-4-hydroxy-5-methylphenyl) heptane; 2,2-bis (4-hydroxyphenyl) octane; 1,1- (4-hydroxyphenyl)
Bis (hydroxyaryl) alkanes such as ethane;
1,1-bis (4-hydroxyphenyl) cyclopentane; 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane; 1,1-bis ( 3-cyclohexyl-4-hydroxyphenyl) cyclohexane;
1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane; bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) -3,5,5-trimethylcyclohexane; bis ( 4-hydroxyphenyl) ether; bis (hydroxyaryl) ethers such as bis (4, -hydroxy-3-methylphenyl) ether; bis (4-hydroxyphenyl) sulfide; bis (3-methyl-4-hydroxyphenyl) Bis (hydroxyaryl) sulfides such as sulfides; bis (4-hydroxyphenyl) sulfoxide; bis (3-methyl-4-hydroxyphenyl) sulfoxide; bis (hydroxy) such as bis (3-phenyl-4-hydroxyphenyl) sulfoxide Aryl) sulfoki Bis (4-hydroxyphenyl) sulfone; Bis (3-methyl-4-hydroxyphenyl) sulfone; Bis (3-phenyl-4-hydroxyphenyl) sulfone and other bis (hydroxyaryl) sulfones, 4,4 ′ -Dihydroxybiphenyl;
4,4'-dihydroxy-2,2'-dimethylbiphenyl;4,4'-dihydroxy-3,3'-dimethylbiphenyl;4,4'-dihydroxy-3,3'-dicyclohexylbiphenyl;3,3'- Difluoro-4,4 '
And dihydroxybiphenyls such as dihydroxybiphenyl.

Examples of aromatic dihydroxy compounds other than the above general formula (4) include dihydroxybenzenes, halogen- and alkyl-substituted dihydroxybenzenes.
For example, resorcin, 3-methylresorcin, 3-ethylresorcin, 3-propylresorcin, 3-butylresorcin, 3-t-butylresorcin, 3-phenylresorcin, 3-cumylresorcin; 2,3,4,6- Tetrafluororesorcin; 2,3,4,6-tetrabromoresorcin; catechol, hydroquinone, 3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3-butylhydroquinone, 3
-T-butylhydroquinone, 3-phenylhydroquinone, 3-cumylhydroquinone; 2,5-dichlorohydroquinone; 2,3,5,6-tetramethylhydroquinone; 2,3,4,6-tetra-t-butylhydroquinone 2,3,5,6-tetrafluorohydroquinone; 2,3,5,6-tetrabromohydroquinone and the like.

There are various kinds of aliphatic dihydroxy compounds used as one of the components (A). For example, butane-1,4-diol; 2,2-dimethylpropane-1,3-diol; hexane-1,6-
Diethylene glycol; Triethylene glycol; Tetraethylene glycol; Octaethylene glycol; Dipropylene glycol; N, N-Methyldiethanolamine; Cyclohexane-1,3-diol;
Cyclohexane-1,4-diol; 1,4-dimethylolcyclohexane; p-xylylene glycol; 2,
Ethoxylated or propoxylated products of 2-bis- (4-hydroxycyclohexyl) -propane and dihydric alcohols or phenols, such as bis-oxyethyl-bisphenol A; bis-oxyethyl-tetrachlorobisphenol A or bis-oxyethyl-tetrachloro. Hydroquinone etc. are mentioned. In the preferred production method of the present invention, the above-mentioned compounds are appropriately selected and used as the dihydroxy compound as the component (A). Among these, bisphenol A which is an aromatic dihydroxy compound is preferably used.

On the other hand, in the present invention, various kinds of carbonic acid diesters are used as the component (B). For example, it is at least one compound selected from a diaryl carbonate compound, a dialkyl carbonate compound or an alkylaryl carbonate compound. The diaryl carbonate compound used as one of the components (B) has the general formula (6)

[0014]

[Chemical 7]

[In the formula, Ar ² represents an aryl group. ] The compound or general formula (7) represented by

[0016]

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[In the formula, Ar ¹ represents a residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound, and Ar ² is the same as above. ] It is a compound represented by these. The dialkyl carbonate compound has the general formula (8)

[0018]

[Chemical 9]

(Wherein R ⁵ represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms) or the general formula (9).

[0020]

[Chemical 10]

[In the formula, R ⁵ and Ar ¹ are the same as defined above. ] It is a compound represented by these. The alkyl aryl carbonate compound has the general formula (10)

[0022]

[Chemical 11]

[In the formula, R ⁵ and Ar ² are the same as defined above. ] Or a compound represented by the general formula (11)

[0024]

[Chemical 12]

[In the formula, R ⁵ , Ar ¹ and Ar ² are the same as defined above. ] It is a compound represented by these. Here, examples of the carbonic acid diaryl compound include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, and bisphenol A bisphenyl carbonate.
Examples of the dialkyl carbonate compound include diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, bisphenol A bismethyl carbonate and the like. Examples of the alkyl aryl carbonate compound include methylphenyl carbonate, ethylphenyl carbonate, butylphenyl carbonate, cyclohexylphenyl carbonate, bisphenol A methylphenyl carbonate and the like. In the present invention, as the carbonic acid diester as the component (B), the above compounds are appropriately selected and used. Among these, diphenyl carbonate is preferably used.

Next, as raw materials other than the dihydroxy compound and the carbonic acid diester used in the present invention,
These include: That is, examples of diesters of dihydroxy compounds include diacetic acid ester of bisphenol A, dipropionic acid ester of bisphenol A, dibutyric acid ester of bisphenol A, and dibenzoic acid ester of bisphenol A. Examples of dicarbonic acid esters of dihydroxy compounds include bisphenol A bismethyl carbonate, bisphenol A bisethyl carbonate,
Examples thereof include bisphenyl carbonate of bisphenol A. Examples of monocarbonic acid esters of dihydroxy compounds include bisphenol A monomethyl carbonic acid ester, bisphenol A monoethyl carbonic acid ester, bisphenol A monopropyl carbonic acid ester, and bisphenol A monophenyl carbonic acid ester.

In the production method of the present invention, the terminal terminator shown below can be used, if necessary. Specific examples of such an end terminating agent include o-n-butylphenol; m-n-butylphenol; p-n-butylphenol; o-isobutylphenol; m-isobutylphenol; p-isobutylphenol; o-t-butylphenol. M-t-butylphenol; p-t-
Butylphenol; on-pentylphenol; m-
p-n-pentylphenol; p-n-pentylphenol; o-n-hexylphenol; m-n-hexylphenol; p-n-hexylphenol; o-cyclohexylphenol; m-cyclohexylphenol; p
-Cyclohexylphenol; o-phenylphenol; m-phenylphenol; p-phenylphenol; nn-nonylphenol; mn-nonylphenol; pn-nonylphenol; o-cumylphenol; m-cumylphenol; p -Cumylphenol; o
-Naphthylphenol; m-naphthylphenol; p-
Naphthylphenol; 2,6-di-t-butylphenol; 2,5-di-t-butylphenol; 2,4-di-
t-butylphenol; 3,5-di-t-butylphenol; 2,5-dicumylphenol; 3,5-dicumylphenol; formula

[0028]

[Chemical 13]

Examples of the compound represented by

[0030]

Embedded image

Examples include monohydric phenols such as compounds represented by: Of these phenols, although not particularly limited in the present invention, p-tert-butylphenol; p
-Cumylphenol; p-phenylphenol and the like are preferable. Also, the formula

[0032]

[Chemical 15]

Examples thereof include compounds represented by Furthermore, in the present invention, phloroglucin; trimellitic acid; 1,1,1-tris (4-hydroxyphenyl) ethane; 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl], if necessary. -4- [α ', α'-bis (4 "-hydroxyphenyl) ethyl] benzene; α,
α ′, α ″ -tris (4-hydroxyphenyl) -1,
3,5-triisopropylbenzene; isatin bis (o
-Cresol) or the like can be used as a branching agent.

In the production method of the present invention, the (C) tetrazole derivative is used as a polymerization catalyst during the transesterification reaction.
It is preferable to use the tetrazole derivative in combination with the nitrogen-containing organic compound (D) (excluding the tetrazole derivative). Here, various tetrazole derivatives as the component (C) can be used, and for example, the following can be used.
General formula (1)

[0035]

Embedded image

[In the formula, R ¹ and R ² are each a single bond, an alkylene group having 1 to 20 carbon atoms, an alkylidene group having 2 to 20 carbon atoms or an arylene group having 6 to 30 carbon atoms, and A is _{^{-N (r 1) 2, -N}} (r 2) 3 + X -, pyridyl group, alkyl-substituted pyridyl group having 1 to 20 carbon atoms, an aryl group substituted pyridyl group having 6 to 30 carbon atoms, the general formula (a)

[0037]

[Chemical 17]

(Where r³And r^FourEach is water
Elementary, alkyl group having 1 to 20 carbon atoms or 6 to 30 carbon atoms
Represents an aryl group of. Group represented by), -P (r^Five)₂, −
P (r⁶)₃ ⁺X^-, -S (r⁷)₂ ⁺X^-[Where r¹, r², r^Five
~ R⁷Is an alkyl group having 1 to 20 carbon atoms or 6 to
30 aryl groups, r¹, r², r^Five~ R⁷Are the same
May also be different. X is OH, halogen, B
(R)_Four, (R)₂PO_Four(Where r is hydrogen, carbon number 1 to 2
Represents an alkyl group of 0 or an aryl group of 6 to 30 carbon atoms
)], Or an azabicycloalkyl group, and B is-
H, -OY, -SY, -Nr⁸r⁹, -COOY (here
And r⁸And r⁹Is hydrogen, alkyl having 1 to 20 carbons
Group or an aryl group having 6 to 30 carbon atoms, Y is water
Elementary, N (r^Ten)_Four ⁺, P (r¹¹)_Four ⁺, B (r¹²)_Four ⁺, S (r¹³)₃ ⁺
Or a monovalent metal ion, r^Ten~ R¹³Has 1 carbon
To 20 alkyl groups, each of which is the same,
It may be different. )}
It

Here, the carbon number of R ¹ and R ² is 1 to 20.
There are many alkylene groups or alkylidene groups having 2 to 20 carbon atoms, such as a methylene group,
Ethylene group, propylene group, butylene group, amylene group,
Hexylene group, ethylidene group, propylidene group, isopropylidene group, butylidene group, pentylidene group and the like can be mentioned. Preferably, it has 4 or less carbon atoms. Examples of the arylene group having 6 to 30 carbon atoms include a phenylene group and a naphthylene group, but a phenylene group is preferable. Further, the carbon number of r ^{1 to} r ¹³ is 1 to
Examples of the alkyl group of 20 include a methyl group, an ethyl group, a propyl group, an isopropyl group, various butyl groups (n-butyl group, isobutyl group, tert-butyl group), various pentyl groups, various hexyl groups, various heptyl groups, Although various octyl groups can be mentioned, those having 4 or less carbon atoms are preferable. The same applies to the alkyl group as the substituent of the pyridyl group. Further, examples of the aryl group of r ^{1 to} r ⁹ include a phenyl group and a naphthyl group, but a phenyl group is preferable. The same can be said for the substituent of the pyridyl group. The monovalent metal in Y is an alkali metal, such as potassium or sodium.

As the azabicycloalkyl group in A, there are various ones. As alkyl, heptane,
5 to 5 carbon atoms such as hexane, octane, nonane, and decane
20. Specific examples thereof include 1-azabicyclo [2.2.1] heptane and 1-azabicyclo [2.
2.2] Octane and the like can be mentioned.

Specific examples of the compound represented by the general formula (1) include 1-methyl-N, N-dimethyl-1H-tetrazole-5-methanamine; 1-ethyl-N, N-dimethyl-1H-tetrazole. -5-methanamine; 1-phenyl-N, N-dimethyl-1H-tetrazole-5-methanamine; 1-methyl-N, N-diethyl-1H-tetrazole-5-methanamine; 1-ethyl-N, N-diethyl. -1H-tetrazole-5-methanamine; 1-phenyl-N, N-diethyl-1H-tetrazole-5-methanamine; 1-methyl-N, N-dimethyl-1H-tetrazole-5-etanamin; 1-ethyl-N. , N-dimethyl-1H-tetrazole-5-etanamin; 1-phenyl-N, N-dimethyl-1H-tetrazole-5-etanamin; 1-meth -N, N-diethyl-1H-tetrazole-5-etanamin; 1-ethyl-N, N-diethyl-1H-tetrazole-5-etanamin; 1-phenyl-N, N-diethyl-1H-tetrazole-5-etanamin ;

1-Methyl-N, N-dimethyl-1H-tetrazole-5-amine; 1-ethyl-N, N-dimethyl-1H-tetrazole-5-amine; 1-phenyl-
N, N-dimethyl-1H-tetrazol-5-amine;
1-methyl-N, N-diethyl-1H-tetrazole-
5-amine; 1-ethyl-N, N-diethyl-1H-tetrazole-5-amine; 1-phenyl-N, N-diethyl-1H-tetrazole-5-amine; 1- (4-hydroxyphenyl) -N , N-Dimethyl-1H-tetrazole-5-methanamine 1- (2-hydroxyphenyl) -N, N-dimethyl-
1H-tetrazole-5-methanamine 1- (4-hydroxyphenyl) -N, N-diethyl-
1H-tetrazole-5-methanamine 1- (2-hydroxyphenyl) -N, N-diethyl-
1H-tetrazole-5-methanamine

1- (4-hydroxyphenyl) -N, N
-Dimethyl-1H-tetrazole-5-ethanamine 1- (2-hydroxyphenyl) -N, N-dimethyl-
1H-tetrazole-5-ethanamine 1- (4-hydroxyphenyl) -N, N-diethyl-
1H-tetrazole-5-ethanamine 1- (2-hydroxyphenyl) -N, N-diethyl-
1H-tetrazole-5-ethanamine 1- (4-hydroxyphenyl) -N, N-dimethyl-
1H-tetrazol-5-amine 1- (2-hydroxyphenyl) -N, N-dimethyl-
1H-tetrazol-5-amine 1- (4-hydroxyphenyl) -N, N-diethyl-
1H-tetrazol-5-amine 1- (2-hydroxyphenyl) -N, N-diethyl-
1H-tetrazol-5-amine

5- (N, N-dimethylamino) -1H-
Tetrazole-1-acetic acid 5- (N, N-diethylamino) -1H-tetrazole-1-acetic acid 5- (N, N-dimethylaminomethyl) -1H-tetrazole-1-acetic acid 5- (N, N-diethylaminomethyl) ) -1H-Tetrazole-1-acetic acid 5- (N, N-dimethylaminoethyl) -1H-tetrazole-1-acetic acid 5- (N, N-diethylaminoethyl) -1H-tetrazole-1-acetic acid 5- (N , N-Dimethylamino) -1H-tetrazole-1-butyric acid 5- (N, N-diethylamino) -1H-tetrazole-1-butyric acid 5- (N, N-dimethylaminomethyl) -1H-tetrazole-1-butyric acid 5- (N, N-diethylaminomethyl) -1H-tetrazole-1-butyric acid 5- (N, N-dimethylaminoethyl) -1H-tetrazole-1- Butyric acid 5- (N, N-diethylaminoethyl) -1H-tetrazole-1-butyric acid 1- (4-aminophenyl) -N, N-dimethyl-1H
-Tetrazole-5-methanamine 1- (2-aminophenyl) -N, N-dimethyl-1H
-Tetrazole-5-methanamine 1- (4-aminophenyl) -N, N-diethyl-1H
-Tetrazole-5-methanamine 1- (2-aminophenyl) -N, N-diethyl-1H
-Tetrazole-5-methanamine

1- (4-aminophenyl) -N, N-dimethyl-1H-tetrazole-5-ethanamine 1- (2-aminophenyl) -N, N-dimethyl-1H
-Tetrazole-5-etanamin 1- (4-aminophenyl) -N, N-diethyl-1H
-Tetrazole-5-etanamin 1- (2-aminophenyl) -N, N-diethyl-1H
-Tetrazole-5-etanamin 1- (4-aminophenyl) -N, N-dimethyl-1H
-Tetrazol-5-amine 1- (2-aminophenyl) -N, N-dimethyl-1H
-Tetrazol-5-amine 1- (4-aminophenyl) -N, N-diethyl-1H
-Tetrazol-5-amine 1- (4-aminophenyl) -N, N-diethyl-1H
-Tetrazol-5-amine

1- (N-methyl-4-aminophenyl)
-N, N-dimethyl-1H-tetrazole-5-methanamine 1- (N-methyl-4-aminophenyl) -N, N-dimethyl-1H-tetrazole-5-methanamine 1- (N-methyl-4-amino) Phenyl) -N, N-diethyl-1H-tetrazole-5-methanamine 1- (N-methyl-4-aminophenyl) -N, N-diethyl-1H-tetrazole-5-methanamine 1- (N-methyl-4) -Aminophenyl) -N, N-dimethyl-1H-tetrazole-5-ethanamine 1- (N-methyl-4-aminophenyl) -N, N-dimethyl-1H-tetrazole-5-ethanamine 1- (N-methyl) -4-Aminophenyl) -N, N-diethyl-1H-tetrazole-5-etanamin 1- (N-methyl-4-aminophenyl) -N, N-diethyl -1H-tetrazole-5-etanamin

1- (N-methyl-4-aminophenyl)
-N, N-Dimethyl-1H-tetrazole-5-amine 1- (N-methyl-4-aminophenyl) -N, N-dimethyl-1H-tetrazol-5-amine 1- (N-methyl-4-amino Phenyl) -N, N-diethyl-1H-tetrazole-5-amine 1- (N-methyl-4-aminophenyl) -N, N-diethyl-1H-tetrazole-5-amine 1- (N-ethyl-4) -Aminophenyl) -N, N-dimethyl-1H-tetrazole-5-methanamine 1- (N-ethyl-4-aminophenyl) -N, N-dimethyl-1H-tetrazole-5-methanamine 1- (N-ethyl) -4-Aminophenyl) -N, N-diethyl-1H-tetrazole-5-methanamine 1- (N-ethyl-4-aminophenyl) -N, N-diethyl-1H-tetrazo Ur-5-methanamine

1- (N-ethyl-4-aminophenyl)
-N, N-dimethyl-1H-tetrazole-5-etanamin 1- (N-ethyl-4-aminophenyl) -N, N-dimethyl-1H-tetrazole-5-etanamin 1- (N-ethyl-4-amino) Phenyl) -N, N-diethyl-1H-tetrazole-5-ethanamine 1- (N-ethyl-4-aminophenyl) -N, N-diethyl-1H-tetrazole-5-ethanamine 1- (N-ethyl-4) -Aminophenyl) -N, N-dimethyl-1H-tetrazole-5-amine 1- (N-ethyl-4-aminophenyl) -N, N-dimethyl-1H-tetrazole-5-amine 1- (N-ethyl -4-Aminophenyl) -N, N-diethyl-1H-tetrazol-5-amine 1- (N-ethyl-4-aminophenyl) -N, N-diethyl-1H-teto Razol-5-amine

5- (N, N-dimethylamino) -1H-
Tetrazole-1-phenyl acetate 5- (N, N-diethylamino) -1H-tetrazole-1-acetic acid phenyl 5- (N, N-dimethylaminomethyl) -1H-tetrazole-1-acetic acid phenyl 5- (N, N) -Diethylaminomethyl) -1H-tetrazole-1-phenyl acetate 5- (N, N-dimethylaminoethyl) -1H-tetrazole-1-acetic acid phenyl 5- (N, N-diethylaminoethyl) -1H-tetrazole-1- Phenyl acetate 5- (N, N-dimethylamino) -1H-tetrazole-1-butyric acid phenyl 5- (N, N-diethylamino) -1H-tetrazole-1-butyric acid phenyl 5- (N, N-dimethylaminomethyl) -1H-Tetrazole-1-phenyl butyrate 5- (N, N-diethylaminomethyl) -1H-tetrazole 1-phenyl butyrate 5- (N, N- dimethylaminoethyl)-1H-tetrazol-1-phenyl butyrate 5- (N, N- diethylaminoethyl)-1H-tetrazol-1-phenyl butyrate

5- (N, N-dimethylamino) -1H-
Tetrazole-1-methanol 5- (N, N-diethylamino) -1H-tetrazole-1-methanol 5- (N, N-dimethylaminomethyl) -1H-tetrazole-1-methanol 5- (N, N-diethylaminomethyl) ) -1H-Tetrazole-1-methanol 5- (N, N-dimethylaminoethyl) -1H-tetrazole-1-methanol 5- (N, N-diethylaminoethyl) -1H-tetrazole-1-methanol 5- (N , N-Dimethylamino) -1H-tetrazole-1-ethanol 5- (N, N-diethylamino) -1H-tetrazole-1-ethanol 5- (N, N-dimethylaminomethyl) -1H-tetrazole-1-ethanol 5- (N, N-diethylaminomethyl) -1H-tetrazole-1-ethanol 5 -(N, N-Dimethylaminoethyl) -1H-tetrazole-1-ethanol 5- (N, N-diethylaminoethyl) -1H-tetrazole-1-ethanol

4- (1-methyl-N, N-dimethyl-1
H-tetrazol-5-yl) morpholine; 4- (1-
Ethyl-N, N-dimethyl-1H-tetrazole-5-
4- (1-phenyl-N, N-dimethyl-1H-tetrazol-5-yl) morpholine; 4)
-(1-Methyl-N, N-diethyl-1H-tetrazol-5-yl) morpholine; 4- (1-ethyl-N, N
-Diethyl-1H-tetrazol-5-yl) morpholine; 4- (1-phenyl-N, N-diethyl-1H-tetrazol-5-yl) morpholine; 4- [1- (4-
Hydroxyphenyl) -N, N-dimethyl-1H-tetrazol-5-yl] morpholine 4- [1- (2-hydroxyphenyl) -N, N-dimethyl-1H-tetrazol-5-yl] morpholine 4- [1 -(4-Hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl] morpholine 4- [1- (2-hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl] morpholine 4- [1- (4-aminophenyl) -N, N-dimethyl-1H-tetrazol-5-yl] morpholine 4- [1- (2-aminophenyl) -N, N-dimethyl-1H-tetrazole-5 -Yl] morpholine 4- [1- (4-aminophenyl) -N, N-diethyl-1H-tetrazol-5-yl] morpholine 4- [1- (2-a Minophenyl) -N, N-diethyl-1H-tetrazol-5-yl] morpholine

4- (1-methyl-N, N-dimethyl-1
H-tetrazol-5-yl) methylmorpholine 4- (1-ethyl-N, N-dimethyl-1H-tetrazol-5-yl) methylmorpholine 4- (1-phenyl-N, N-dimethyl-1H-tetrazole- 5-yl) methylmorpholine 4- (1-methyl-N, N-diethyl-1H-tetrazol-5-yl) methylmorpholine 4- (1-ethyl-N, N-diethyl-1H-tetrazol-5-yl) Methylmorpholine 4- (1-phenyl-N, N-diethyl-1H-tetrazol-5-yl) methylmorpholine 4- [1- (4-hydroxyphenyl) -N, N-dimethyl-1H-tetrazol-5-yl ] Methylmorpholine 4- [1- (2-hydroxyphenyl) -N, N-dimethyl-1H-tetrazol-5-yl] methylmorpholine 4- [1- (4-hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl] methylmorpholine 4- [1- (2-hydroxyphenyl) -N, N-diethyl-1H-tetrazole- 5-yl] methylmorpholine 4- [1- (4-aminophenyl) -N, N-dimethyl-1H-tetrazol-5-yl] methylmorpholine 4- [1- (2-aminophenyl) -N, N- Dimethyl-1H-tetrazol-5-yl] methylmorpholine 4- [1- (4-aminophenyl) -N, N-diethyl-1H-tetrazol-5-yl] methylmorpholine 4- [1- (2-aminophenyl) ) -N, N-Diethyl-1H-tetrazol-5-yl] methylmorpholine

4- (1-methyl-N, N-dimethyl-1
H-tetrazol-5-yl) ethylmorpholine; 4-
(1-Ethyl-N, N-dimethyl-1H-tetrazol-5-yl) ethylmorpholine 4- (1-phenyl-N, N-dimethyl-1H-tetrazol-5-yl) ethylmorpholine 4- (1-methyl -N, N-diethyl-1H-tetrazol-5-yl) ethylmorpholine 4- (1-ethyl-N, N-diethyl-1H-tetrazol-5-yl) ethylmorpholine 4- (1-phenyl-N, N) -Diethyl-1H-tetrazol-5-yl) ethylmorpholine 4- [1- (4-hydroxyphenyl) -N, N-dimethyl-1H-tetrazol-5-yl] ethylmorpholine 4- [1- (2-hydroxy Phenyl) -N, N-dimethyl-1H-tetrazol-5-yl] ethylmorpholine 4- [1- (4-hydroxyphenyl) -N, N-di Ethyl-1H-tetrazol-5-yl] ethylmorpholine 4- [1- (2-hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl] ethylmorpholine 4- [1- (4-aminophenyl) ) -N, N-Dimethyl-1H-tetrazol-5-yl] ethylmorpholine 4- [1- (2-aminophenyl) -N, N-dimethyl-1H-tetrazol-5-yl] ethylmorpholine 4- [1 -(4-Aminophenyl) -N, N-diethyl-1H-tetrazol-5-yl] ethylmorpholine 4- [1- (2-aminophenyl) -N, N-diethyl-1H-tetrazol-5-yl] Ethylmorpholine

1- (1-methyl-N, N-dimethyl-1
H-tetrazol-5-yl) piperidine 1- (1-ethyl-N, N-dimethyl-1H-tetrazol-5-yl) piperidine 1- (1-phenyl-N, N-dimethyl-1H-tetrazole-5- 1- (1-Methyl-N, N-diethyl-1H-tetrazol-5-yl) piperidine 1- (1-ethyl-N, N-diethyl-1H-tetrazol-5-yl) piperidine 1- ( 1-phenyl-N, N-diethyl-1H-tetrazol-5-yl) piperidine 1- [1- (4-hydroxyphenyl) -N, N-dimethyl-1H-tetrazol-5-yl] piperidine 1- [1 -(2-Hydroxyphenyl) -N, N-dimethyl-1H-tetrazol-5-yl] piperidine 1- [1- (4-hydroxyphenyl) -N, N- Ethyl-1H-tetrazol-5-yl] piperidine 1- [1- (2-hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl] piperidine 1- [1- (4-aminophenyl)- N, N-Dimethyl-1H-tetrazol-5-yl] piperidine 1- [1- (2-aminophenyl) -N, N-dimethyl-1H-tetrazol-5-yl] piperidine 1- [1- (4- Aminophenyl) -N, N-diethyl-1H-tetrazol-5-yl] piperidine 1- [1- (2-aminophenyl) -N, N-diethyl-1H-tetrazol-5-yl] piperidine

1- (1-methyl-N, N-dimethyl-1
H-tetrazol-5-yl) methylpiperidine 1- (1-ethyl-N, N-dimethyl-1H-tetrazol-5-yl) methylpiperidine 1- (1-phenyl-N, N-dimethyl-1H-tetrazole- 5-yl) methylpiperidine 1- (1-methyl-N, N-diethyl-1H-tetrazole-5-yl) methylpiperidine 1- (1-ethyl-N, N-diethyl-1H-tetrazol-5-yl) Methylpiperidine 1- (1-phenyl-N, N-diethyl-1H-tetrazol-5-yl) methylpiperidine 1- [1- (4-hydroxyphenyl) -N, N-dimethyl-1H-tetrazol-5-yl ] Methylpiperidine 1- [1- (2-hydroxyphenyl) -N, N-dimethyl-1H-tetrazol-5-yl] methylpiperidine 1- [1- (4-hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl] methylpiperidine 1- [1- (2-hydroxyphenyl) -N, N-diethyl-1H-tetrazole- 5-yl] methylpiperidine 1- [1- (4-aminophenyl) -N, N-dimethyl-1H-tetrazol-5-yl] methylpiperidine 1- [1- (2-aminophenyl) -N, N- Dimethyl-1H-tetrazol-5-yl] methylpiperidine 1- [1- (4-aminophenyl) -N, N-diethyl-1H-tetrazol-5-yl] methylpiperidine 1- [1- (2-aminophenyl) ) -N, N-Diethyl-1H-tetrazol-5-yl] methylpiperidine

1- (1-methyl-N, N-dimethyl-1
H-tetrazol-5-yl) ethylpiperidine 1- (1-ethyl-N, N-dimethyl-1H-tetrazol-5-yl) ethylpiperidine 1- (1-phenyl-N, N-dimethyl-1H-tetrazole- 5-yl) ethylpiperidine 1- (1-methyl-N, N-diethyl-1H-tetrazole-5-yl) ethylpiperidine 1- (1-ethyl-N, N-diethyl-1H-tetrazol-5-yl) Ethylpiperidine 1- (1-phenyl-N, N-diethyl-1H-tetrazol-5-yl) ethylpiperidine 1- [1- (4-hydroxyphenyl) -N, N-dimethyl-1H-tetrazol-5-yl ] Ethylpiperidine 1- [1- (2-hydroxyphenyl) -N, N-dimethyl-1H-tetrazol-5-yl] ethylpiperidine 1- [1- (4-hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl] ethylpiperidine 1- [1- (2-hydroxyphenyl) -N, N-diethyl-1H-tetrazole- 5-yl] ethylpiperidine 1- [1- (4-aminophenyl) -N, N-dimethyl-1H-tetrazol-5-yl] ethylpiperidine 1- [1- (2-aminophenyl) -N, N- Dimethyl-1H-tetrazol-5-yl] ethylpiperidine 1- [1- (4-aminophenyl) -N, N-diethyl-1H-tetrazol-5-yl] ethylpiperidine 1- [1- (2-aminophenyl) ) -N, N-Diethyl-1H-tetrazol-5-yl] ethylpiperidine

1- (1-methyl-N, N-dimethyl-1
H-tetrazol-5-yl) piperidine 1- (1-ethyl-N, N-dimethyl-1H-tetrazol-5-yl) piperidine 1- (1-phenyl-N, N-dimethyl-1H-tetrazole-5- 1- (1-Methyl-N, N-diethyl-1H-tetrazol-5-yl) piperidine 1- (1-ethyl-N, N-diethyl-1H-tetrazol-5-yl) piperidine 1- ( 1-Phenyl-N, N-diethyl-1H-tetrazol-5-yl) piperidine 4- [1- (4-hydroxyphenyl) -N, N-dimethyl-1H-tetrazol-5-yl] piperidine 4- [1 -(2-Hydroxyphenyl) -N, N-dimethyl-1H-tetrazol-5-yl] piperidine 4- [1- (4-hydroxyphenyl) -N, N- Ethyl-1H-tetrazol-5-yl] piperidine 4- [1- (2-hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl] piperidine 4- [1- (4-aminophenyl)- N, N-Dimethyl-1H-tetrazol-5-yl] piperidine 4- [1- (2-aminophenyl) -N, N-dimethyl-1H-tetrazol-5-yl] piperidine 4- [1- (4- Aminophenyl) -N, N-diethyl-1H-tetrazol-5-yl] piperidine 4- [1- (2-aminophenyl) -N, N-diethyl-1H-tetrazol-5-yl] piperidine 4- (1 -Methyl-N, N-dimethyl-1H-tetrazol-5-yl) methylpiperidine 4- (1-ethyl-N, N-dimethyl-1H-tetrazol-5-yl) Tylpiperidine 4- (1-phenyl-N, N-dimethyl-1H-tetrazol-5-yl) methylpiperidine 4- (1-Methyl-N, N-diethyl-1H-tetrazol-5-yl) methylpiperidine 4- (1-Ethyl-N, N-diethyl-1H-tetrazol-5-yl) methylpiperidine 4- (1-phenyl-N, N-diethyl-1H-tetrazol-5-yl) methylpiperidine 4- [1- ( 4-Hydroxyphenyl) -N, N-dimethyl-1H-tetrazol-5-yl] methylpiperidine 4- [1- (2-hydroxyphenyl) -N, N-dimethyl-1H-tetrazol-5-yl] methylpiperidine 4- [1- (4-hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl] methylpiperidine 4- [1 (2-Hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl] methylpiperidine 4- [1- (4-aminophenyl) -N, N-dimethyl-1H-tetrazol-5-yl] methyl Piperidine 4- [1- (2-aminophenyl) -N, N-dimethyl-1H-tetrazol-5-yl] methylpiperidine 4- [1- (4-aminophenyl) -N, N-diethyl-1H-tetrazole -5-yl] methylpiperidine 4- [1- (2-aminophenyl) -N, N-diethyl-1H-tetrazol-5-yl] methylpiperidine

4- (1-methyl-N, N-dimethyl-1
H-tetrazol-5-yl) ethylpiperidine 4- (1-ethyl-N, N-dimethyl-1H-tetrazol-5-yl) ethylpiperidine 4- (1-phenyl-N, N-dimethyl-1H-tetrazole- 5-yl) ethylpiperidine 4- (1-methyl-N, N-diethyl-1H-tetrazol-5-yl) ethylpiperidine 4- (1-ethyl-N, N-diethyl-1H-tetrazol-5-yl) Ethylpiperidine 4- (1-phenyl-N, N-diethyl-1H-tetrazol-5-yl) ethylpiperidine 4- [1- (4-hydroxyphenyl) -N, N-dimethyl-1H-tetrazol-5-yl ] Ethylpiperidine 4- [1- (2-hydroxyphenyl) -N, N-dimethyl-1H-tetrazol-5-yl] ethylpiperidine 4- [1- (4-hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl] ethylpiperidine 4- [1- (2-hydroxyphenyl) -N, N-diethyl-1H-tetrazole- 5-yl] ethylpiperidine 4- [1- (4-aminophenyl) -N, N-dimethyl-1H-tetrazol-5-yl] ethylpiperidine 4- [1- (2-aminophenyl) -N, N- Dimethyl-1H-tetrazol-5-yl] ethylpiperidine 4- [1- (4-aminophenyl) -N, N-diethyl-1H-tetrazol-5-yl] ethylpiperidine 4- [1- (2-aminophenyl) ) -N, N-Diethyl-1H-tetrazol-5-yl] ethylpiperidine

3- (1-methyl-N, N-dimethyl-1
H-tetrazol-5-yl) -1-azabicyclo [2.2.1] heptane 3- (1-ethyl-N, N-dimethyl-1H-tetrazol-5-yl) -1-azabicyclo [2.2. 1] Heptane 3- (1-phenyl-N, N-dimethyl-1H-tetrazol-5-yl) -1-azabicycle [2.2.1]
Heptane 3- (1-methyl-N, N-diethyl-1H-tetrazol-5-yl) -1-azabicyclo [2.2.1] heptane 3- (1-ethyl-N, N-diethyl-1H-tetrazole -5-yl) -1-azabicyclo [2.2.1] heptane 3- (1-phenyl-N, N-diethyl-1H-tetrazol-5-yl) -azabicyclo [2.2.1] heptane 3 -[1- (4-Hydroxyphenyl) -N, N-dimethyl-1H-tetrazol-5-yl] -1-azabicyclo [2.2.1] heptane 3- [1- (2-hydroxyphenyl) -N , N-Dimethyl-1H-tetrazol-5-yl] -1-azabicyclo [2.2.1] heptane 3- [1- (4-hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl -1-Azabicyclo [2.2.1] heptane 3- [1- (2-hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl] -1-azabicyclo [2.2.1] heptane 3- [1- (4-aminophenyl) -N, N-dimethyl-1H-tetrazol-5-yl] -1-azabicyclo [2.2.1] heptane 3- [1- (2-aminophenyl)- N, N-Dimethyl-1H-tetrazol-5-yl] -1-azabicyclo [2.2.1] heptane 3- [1- (4-aminophenyl) -N, N-diethyl-1H-tetrazole-5- Yl] -1-azabicyclo [2.2.1] heptane 3- [1- (2-aminophenyl) -N, N-diethyl-1H-tetrazol-5-yl] -1-azabicyclo [2.2.1] ] Heptane

3- (1-methyl-N, N-dimethyl-1
H-tetrazol-5-yl) -1-azabicyclo [2.2.2] octane 3- (1-ethyl-N, N-dimethyl-1H-tetrazol-5-yl) -1-azabicyclo [2.2. 2] Octane 3- (1-phenyl-N, N-dimethyl-1H-tetrazol-5-yl) -1-azabicycle [2.2.2]
Octane 3- (1-methyl-N, N-diethyl-1H-tetrazol-5-yl) -1-azabicyclo [2.2.2] octane 3- (1-ethyl-N, N-diethyl-1H-tetrazole -5-yl) -1-azabicyclo [2.2.2] octane 3- (1-phenyl-N, N-diethyl-1H-tetrazol-5-yl) -azabicyclo [2.2.2] octane 3 -[1- (4-Hydroxyphenyl) -N, N-dimethyl-1H-tetrazol-5-yl] -1-azabicyclo [2.2.2] octane 3- [1- (2-hydroxyphenyl) -N , N-Dimethyl-1H-tetrazol-5-yl] -1-azabicyclo [2.2.2] octane 3- [1- (4-hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl -1-Azabicyclo [2.2.2] octane 3- [1- (2-hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl] -1-azabicyclo [2.2.2] octane 3- [1- (4-aminophenyl) -N, N-dimethyl-1H-tetrazol-5-yl] -1-azabicyclo [2.2.2] octane 3- [1- (2-aminophenyl)- N, N-Dimethyl-1H-tetrazol-5-yl] -1-azabicyclo [2.2.2] octane 3- [1- (4-aminophenyl) -N, N-diethyl-1H-tetrazole-5- Yl] -1-azabicyclo [2.2.2] octane 3- [1- (2-aminophenyl) -N, N-diethyl-1H-tetrazol-5-yl] -1-azabicyclo [2.2.2] ] Octane

1- (1-methyl-N, N-dimethyl-1
H-tetrazol-5-yl) pyridinium hydroxide 1- (1-ethyl-N, N-dimethyl-1H-tetrazol-5-yl) pyridinium hydroxide 1- (1-phenyl-N, N-dimethyl- 1H-tetrazol-5-yl) pyridinium hydroxide 1- (1-methyl-N, N-diethyl-1H-tetrazol-5-yl) pyridinium hydroxide 1- (1-ethyl-N, N-diethyl- 1H-tetrazol-5-yl) pyridinium hydroxide 1- (1-phenyl-N, N-diethyl-1H-tetrazol-5-yl) pyridinium hydroxide 1- [1- (4-hydroxyphenyl) -N , N-Dimethyl-1H-tetrazol-5-yl] pyridinium hydroxide 1- [1- (2-hydroxyphenyl) -N, N- Dimethyl-1H-tetrazo. Lu-5-yl] pyridinium hydroxide 1- [1- (4-hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl] pyridinium hydroxide 1- [1- (2-hydroxyphenyl) ) -N, N-Diethyl-1H-tetrazol-5-yl] pyridinium hydroxide 1- [1- (4-aminophenyl) -N, N-dimethyl-1H-tetrazol-5-yl] pyridinium hydroxide 1- [1- (2-aminophenyl) -N, N-dimethyl-1H-tetrazol-5-yl] pyridinium hydroxide 1- [1- (4-aminophenyl) -N, N-diethyl-1H- Tetrazol-5-yl] pyridinium hydroxide 1- [1- (2-aminophenyl) -N, N-diethyl-1H-tetrazol-5-yl] pyri Umm hydroxide

1- (1-methyl-N, N-dimethyl-1
H-tetrazol-5-yl) methylpyridinium hydroxide 1- (1-ethyl-N, N-dimethyl-1H-tetrazol-5-yl) methylpyridinium hydroxide 1- (1-phenyl-N, N- Dimethyl-1H-tetrazol-5-yl) methylpyridium hydroxide 1- (1-methyl-N, N-diethyl-1H-tetrazol-5-yl) methylpyridium hydroxide 1- (1-ethyl-N, N-diethyl-1H-tetrazol-5-yl) methylpyridinium hydroxide 1- (1-phenyl-N, N-diethyl-1H-tetrazol-5-yl) methylpyridinium hydroxide 1- [1- (4 -Hydroxyphenyl) -N, N-dimethyl-1H-tetrazol-5-yl] methylpyridinium hydroxide 1- [1- (2-hydroxyphenyl) -N, N-dimethyl-1H-tetrazo. Lu-5-yl] methylpyridinium hydroxide 1- [1- (4-hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl] methylpyridinium hydroxide 1- [1- (2- Hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl] methylpyridium hydroxide 1- [1- (4-aminophenyl) -N, N-dimethyl-1H-tetrazol-5-yl] methyl Pyridinium Hydroxide 1- [1- (2-Aminophenyl) -N, N-dimethyl-1H-tetrazol-5-yl] methylpyridinium Hydroxide 1- [1- (4-Aminophenyl) -N, N -Diethyl-1H-tetrazol-5-yl] methylpyridium hydroxide 1- [1- (2-aminophenyl) -N, N-diethyl 1H-tetrazol-5-yl] methylpyridinium hydroxide 1- (1-methyl-N, N-dimethyl-1H-tetrazol-5-yl) ethylpyridinium hydroxide 1- (1-ethyl-N, N- Dimethyl-1H-tetrazol-5-yl) ethylpyridium hydroxide 1- (1-phenyl-N, N-dimethyl-1H-tetrazol-5-yl) ethylpyridinium hydroxide 1- (1-methyl-N, N-diethyl-1H-tetrazol-5-yl) ethylpyridinium hydroxide 1- (1-ethyl-N, N-diethyl-1H-tetrazol-5-yl) ethylpyridinium hydroxide 1- (1-phenyl- N, N-diethyl-1H-tetrazol-5-yl) ethylpyridinium hydroxide 1- [1- (4-hydr Kishifeniru) -N, N-dimethyl--1H- tetrazol-5-yl] ethyl pyridinium hydroxide 1- [1- (2-hydroxyphenyl) -N, N-dimethyl -1H- tetrazole. Lu-5-yl] ethylpyridinium hydroxide 1- [1- (4-hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl] ethylpyridinium hydroxide 1- [1- (2- Hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl] ethylpyridinium hydroxide 1- [1- (4-aminophenyl) -N, N-dimethyl-1H-tetrazol-5-yl] ethyl Pyridinium Hydroxide 1- [1- (2-Aminophenyl) -N, N-dimethyl-1H-tetrazol-5-yl] ethylpyridinium Hydroxide 1- [1- (4-Aminophenyl) -N, N -Diethyl-1H-tetrazol-5-yl] ethylpyridinium hydroxide 1- [1- (2-aminophenyl) -N, N-diethyl 1H- tetrazol-5-yl] ethyl pyridinium hydroxide

1- (1-methyl-N, N-dimethyl-1
H-tetrazol-5-yl) trimethylammonium hydroxide 1- (1-ethyl-N, N-dimethyl-1H-tetrazol-5-yl) trimethylammonium hydroxide 1- (1-phenyl-N, N-dimethyl- 1H-tetrazol-5-yl) trimethylammonium hydroxide 1- (1-methyl-N, N-diethyl-1H-tetrazol-5-yl) trimethylammonium hydroxide 1- (1-ethyl-N, N-diethyl- 1H-tetrazol-5-yl) trimethylammonium hydroxide 1- (1-phenyl-N, N-diethyl-1H-tetrazol-5-yl) trimethylammonium hydroxide 1- [1- (4-hydroxyphenyl) -N , N-dimethyl-1H-tetrazol-5-yl Trimethylammonium hydroxide 1- [1- (2-hydroxyphenyl) -N, N-dimethyl -1H- tetrazole. Lu-5-yl] trimethylammonium hydroxide 1- [1- (4-hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl] trimethylammonium hydroxide 1- [1- (2-hydroxyphenyl) ) -N, N-Diethyl-1H-tetrazol-5-yl] trimethylammonium hydroxide 1- [1- (4-aminophenyl) -N, N-dimethyl-1H-tetrazol-5-yl] trimethylammonium hydroxide 1- [1- (2-aminophenyl) -N, N-dimethyl-1H-tetrazol-5-yl] trimethylammonium hydroxide 1- [1- (4-aminophenyl) -N, N-diethyl-1H- Tetrazol-5-yl] trimethylammonium hydroxide 1- [1- (2 Aminophenyl) -N, N-diethyl--1H- tetrazol-5-yl] trimethylammonium hydroxide

1- (1-methyl-N, N-dimethyl-1
H-tetrazol-5-yl) methyltrimethylammonium hydroxide 1- (1-ethyl-N, N-dimethyl-1H-tetrazol-5-yl) methyltrimethylammonium hydroxide 1- (1-phenyl-N, N- Dimethyl-1H-tetrazol-5-yl) methyltrimethylammonium hydroxide 1- (1-methyl-N, N-diethyl-1H-tetrazol-5-yl) methyltrimethylammonium hydroxide 1- (1-ethyl-N, N-diethyl-1H-tetrazol-5-yl) methyltrimethylammonium hydroxide 1- (1-phenyl-N, N-diethyl-1H-tetrazol-5-yl) methyltrimethylammonium hydroxide 1- [1- (4 -Hydroxyphenyl) -N, N-di Chill -1H- tetrazol-5-yl] methyl trimethylammonium hydroxide 1- [1- (2-hydroxyphenyl) -N, N-dimethyl -1H- tetrazole. Lu-5-yl] methyltrimethylammonium hydroxide 1- [1- (4-hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl] methyltrimethylammonium hydroxide 1- [1- (2- Hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl] methyltrimethylammonium hydroxide 1- [1- (4-aminophenyl) -N, N-dimethyl-1H-tetrazol-5-yl] methyl Trimethylammonium hydroxide 1- [1- (2-aminophenyl) -N, N-dimethyl-1H-tetrazol-5-yl] methyltrimethylammonium hydroxide 1- [1- (4-aminophenyl) -N, N -Diethyl-1H-tetrazol-5-yl] methyltrimethylan Pyridinium hydroxide 1- [1- (2-aminophenyl) -N, N-diethyl--1H- tetrazol-5-yl] methyl trimethylammonium hydroxide

1- (1-methyl-N, N-dimethyl-1
H-tetrazol-5-yl) ethyltrimethylammonium hydroxide 1- (1-ethyl-N, N-dimethyl-1H-tetrazol-5-yl) ethyltrimethylammonium hydroxide 1- (1-phenyl-N, N- Dimethyl-1H-tetrazol-5-yl) ethyltrimethylammonium hydroxide 1- (1-methyl-N, N-diethyl-1H-tetrazol-5-yl) ethyltrimethylammonium hydroxide 1- (1-ethyl-N, N-diethyl-1H-tetrazol-5-yl) ethyltrimethylammonium hydroxide 1- (1-phenyl-N, N-diethyl-1H-tetrazol-5-yl) ethyltrimethylammonium hydroxide 1- [1- (4 -Hydroxyphenyl) -N, N-di Chill -1H- tetrazol-5-yl] ethyl trimethylammonium hydroxide 1- [1- (2-hydroxyphenyl) -N, N-dimethyl -1H- tetrazole. Lu-5-yl] ethyltrimethylammonium hydroxide 1- [1- (4-hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl] ethyltrimethylammonium hydroxide 1- [1- (2- Hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl] ethyltrimethylammonium hydroxide 1- [1- (4-aminophenyl) -N, N-dimethyl-1H-tetrazol-5-yl] ethyl Trimethylammonium hydroxide 1- [1- (2-aminophenyl) -N, N-dimethyl-1H-tetrazol-5-yl] ethyltrimethylammonium hydroxide 1- [1- (4-aminophenyl) -N, N -Diethyl-1H-tetrazol-5-yl] ethyltrimethylan Pyridinium hydroxide 1- [1- (2-aminophenyl) -N, N-diethyl--1H- tetrazol-5-yl] ethyl trimethylammonium hydroxide

4- (1-methyl-N, N-dimethyl-1
H-tetrazol-5-yl) pyridine 4- (1-ethyl-N, N-dimethyl-1H-tetrazol-5-yl) pyridine 4- (1-phenyl-N, N-dimethyl-1H-tetrazole-5- Yl) pyridine 4- (1-methyl-N, N-diethyl-1H-tetrazol-5-yl) pyridine 4- (1-ethyl-N, N-diethyl-1H-tetrazol-5-yl) pyridine 4- ( 1-phenyl-N, N-diethyl-1H-tetrazol-5-yl) pyridine 4- [1- (4-hydroxyphenyl) -N, N-dimethyl-1H-tetrazol-5-yl] pyridine 4- [1 -(2-Hydroxyphenyl) -N, N-dimethyl-1H-tetrazo. Lu-5-yl] pyridine 4- [1- (4-hydroxyphenyl) -N, N-diethyl-1H-tetrazol-5-yl] pyridine 4- [1- (2-hydroxyphenyl) -N, N- Diethyl-1H-tetrazol-5-yl] pyridine 4- [1- (4-aminophenyl) -N, N-dimethyl-1H-tetrazol-5-yl] pyridine 4- [1- (2-aminophenyl)- N, N-Dimethyl-1H-tetrazol-5-yl] pyridine 4- [1- (4-aminophenyl) -N, N-diethyl-1H-tetrazol-5-yl] pyridine 4- [1- (2- Aminophenyl) -N, N-diethyl-1H-tetrazol-5-yl] pyridine and the like. Also, the general formula (2)

[0067]

Embedded image

[In the formula, R ¹ , R ² , A and B are the same as defined above. ] The compound represented by these is mentioned. And for a detailed description of R ¹ , R ² , A and B,
The explanations given regarding the compound represented by the general formula (1) can be similarly applied.

As specific examples of the compound represented by the general formula (2), in all of the compounds represented by the general formula (1), the substituent at the 1-position and the substituent at the 5-position are respectively the 5-position, 1
Compounds substituted at the position may be mentioned. For example, the position of the substituent is exchanged like 5-methyl-N, N-dimethyl-1H-tetrazole-1-methanamine.

Further, the general formula (3)

[0071]

[Chemical 19]

[R ³ and R ⁴ are each a single bond, an alkylene group having 1 to 20 carbon atoms, an alkylidene group having 2 to 20 carbon atoms or an arylene group having 6 to 30 carbon atoms,
A and B are the same as above. ] The compound represented by these is mentioned. Here, for the detailed description of R ³ and R ^4, the detailed description made for R ¹ or R ² in relation to the compound represented by the general formula (1) can be similarly applied. The same applies to A or B.

Specific examples of the compound represented by the general formula (3) include 1-methyl-1'-dimethylaminomethyl-5,5'-
Bi-1H-tetrazole 1-methyl-1'-diethylaminomethyl-5,5'-
Bi-1H-tetrazole 1-methyl-1'-dimethylaminoethyl-5,5'-
Bi-1H-tetrazole 1-methyl-1'-diethylaminoethyl-5,5'-
Bi-1H-tetrazole 1-methyl-1'-dimethylamino-5,5'-bi-1
H-tetrazole 1-methyl-1'-diethylamino-5,5'-bi-1
H-tetrazole 1-ethyl-1'-dimethylaminomethyl-5,5'-
Bi-1H-tetrazole 1-ethyl-1'-diethylaminomethyl-5,5'-
Bi-1H-tetrazole 1-ethyl-1'-dimethylaminoethyl-5,5'-
Bi-1H-tetrazole 1-ethyl-1'-diethylaminoethyl-5,5'-
Bi-1H-tetrazole 1-ethyl-1'-dimethylamino-5,5'-bi-1
H-tetrazole 1-ethyl-1'-diethylamino-5,5'-bi-1
H-tetrazole

1-phenyl-1'-dimethylaminomethyl-5,5'-bi-1H-tetrazole 1-phenyl-1'-diethylaminomethyl-5,5 '
-Bi-1H-tetrazole 1-phenyl-1'-dimethylaminoethyl-5,5 '
-Bi-1H-tetrazole 1-phenyl-1'-diethylaminoethyl-5,5 '
-Bi-1H-tetrazole 1-phenyl-1'-dimethylamino-5,5'-bi-
1H-tetrazole 1-phenyl-1′-diethylamino-5,5′-bi-
1H-tetrazole 1- (4-hydroxyphenyl) -1'-dimethylaminomethyl-5,5'-bi-1H-tetrazole 1- (4-hydroxyphenyl) -1'-diethylaminomethyl-5,5'-bi -1H-tetrazole 1- (4-hydroxyphenyl) -1'-dimethylaminoethyl-5,5'-bi-1H-tetrazole 1- (4-hydroxyphenyl) -1'-diethylaminoethyl-5,5'- Bi-1H-tetrazole 1- (4-hydroxyphenyl) -1'-dimethylamino-5,5'-bi-1H-tetrazole 1- (4-hydroxyphenyl) -1'-diethylamino-5,5'-bi -1H-tetrazole

1- (2-hydroxyphenyl) -1'-
Dimethylaminomethyl-5,5'-bi-1H-tetrazole 1- (2-hydroxyphenyl) -1'-diethylaminomethyl-5,5'-bi-1H-tetrazole 1- (2-hydroxyphenyl) -1 '-Dimethylaminoethyl-5,5'-bi-1H-tetrazole 1- (2-hydroxyphenyl) -1'-diethylaminoethyl-5,5'-bi-1H-tetrazole 1- (2-hydroxyphenyl) -1 '-Dimethylamino-5,5'-bi-1H-tetrazole 1- (2-hydroxyphenyl) -1'-diethylamino-5,5'-bi-1H-tetrazole 1- (4-aminophenyl) -1'-Dimethylaminomethyl-5,5'-bi-1H-tetrazole 1- (4-aminophenyl) -1'-diethylaminomethyl-5,5'-bi-1H-tetrazole 1 (4-aminophenyl) -1'-dimethylaminoethyl-5,5'-bi-1H-tetrazole 1- (4-aminophenyl) -1'-diethylaminoethyl-5,5'-bi-1H-tetrazole 1 -(4-aminophenyl) -1'-dimethylamino-
5,5'-bi-1H-tetrazole 1- (4-aminophenyl) -1'-diethylamino-
5,5'-bi-1H-tetrazole

1- (2-Aminophenyl) -1'-dimethylaminomethyl-5,5'-bi-1H-tetrazole 1- (2-aminophenyl) -1'-diethylaminomethyl-5,5'-bi -1H-tetrazole 1- (2-aminophenyl) -1'-dimethylaminoethyl-5,5'-bi-1H-tetrazole 1- (2-aminophenyl) -1'-diethylaminoethyl-5,5'- Bi-1H-tetrazole 1- (2-aminophenyl) -1'-dimethylamino-
5,5'-bi-1H-tetrazole 1- (2-aminophenyl) -1'-diethylamino-
5,5'-bi-1H-tetrazole 1-methyl-5,5'-bi-1H-tetrazole-1 '
-Yl-morpholine 1-ethyl-5,5'-bi-1H-tetrazole-1 '
-Yl-morpholine 1-phenyl-5,5'-bi-1H-tetrazole-
1'-yl-morpholine 1-hydroxyphenyl-5,5'-bi-1H-tetrazol-1'-yl-morpholine 1-aminophenyl-5,5'-bi-1H-tetrazol-1'-yl-morpholine

1-Methyl-5,5'-bi-1H-tetrazol-1'-yl-methylmorpholine 1-ethyl-5,5'-bi-1H-tetrazole-1 '
-Yl-methylmorpholine 1-phenyl-5,5'-bi-1H-tetrazole-
1'-yl-methylmorpholine 1-hydroxyphenyl-5,5'-bi-1H-tetrazol-1'-yl-methylmorpholine 1-aminophenyl-5,5'-bi-1H-tetrazol-1'-yl -Methylmorpholine 1-methyl-5,5'-bi-1H-tetrazole-1 '
-Yl-ethylmorpholine 1-ethyl-5,5'-bi-1H-tetrazole-1 '
-Yl-ethylmorpholine 1-phenyl-5,5'-bi-1H-tetrazole-
1'-yl-ethylmorpholine 1-hydroxyphenyl-5,5'-bi-1H-tetrazol-1'-yl-ethylmorpholine 1-aminophenyl-5,5'-bi-1H-tetrazol-1'-yl -Ethylmorpholine

1-Methyl-5,5'-bi-1H-tetrazol-1'-yl-piperidine 1-ethyl-5,5'-bi-1H-tetrazole-1 '
-Yl-piperidine 1-phenyl-5,5'-bi-1H-tetrazole-
1'-yl-piperidine 1-hydroxyphenyl-5,5'-bi-1H-tetrazol-1'-yl-piperidine 1-aminophenyl-5,5'-bi-1H-tetrazol-1'-yl-piperidine 1-methyl-5,5'-bi-1H-tetrazole-1 '
-Yl-methylpiperidine 1-ethyl-5,5'-bi-1H-tetrazole-1 '
-Yl-methylpiperidine 1-phenyl-5,5'-bi-1H-tetrazole-
1'-yl-methylpiperidine 1-hydroxyphenyl-5,5'-bi-1H-tetrazol-1'-yl-methylpiperidine 1-aminophenyl-5,5'-bi-1H-tetrazol-1'-yl -Methylpiperidine

1-Methyl-5,5'-bi-1H-tetrazol-1'-yl-ethylpiperidine 1-ethyl-5,5'-bi-1H-tetrazole-1 '
-Yl-ethylpiperidine 1-phenyl-5,5'-bi-1H-tetrazole-
1'-yl-ethylpiperidine 1-hydroxyphenyl-5,5'-bi-1H-tetrazol-1'-yl-ethylpiperidine 1-aminophenyl-5,5'-bi-1H-tetrazol-1'-yl -Ethylpiperidine 1- (N, N-dimethylamino) -5,5'-bi-1H
-Tetrazol-1'-yl-acetic acid 1- (N, N-diethylamino) -5,5'-bi-1H
-Tetrazol-1'-yl-acetic acid 1- (N, N-dimethylaminomethyl) -5,5'-bi-1H-tetrazol-1'-yl-acetic acid 1- (N, N-diethylaminomethyl) -5 , 5'-bi-1H-tetrazol-1'-yl-acetic acid 1- (N, N-dimethylaminoethyl) -5,5'-bi-1H-tetrazol-1'-yl-acetic acid 1- (N, N-diethylaminoethyl) -5,5'-bi-1H-tetrazol-1'-yl-acetic acid 1- (4-pyridyl) -5,5'-bi-1H-tetrazol-1'-yl-acetic acid 1- (2-Pyridyl) -5,5'-bi-1H-tetrazol-1'-yl-acetic acid 1- (4-piperidyl) -5,5'-bi-1H-tetrazol-1'-yl-acetic acid

1- (N, N-dimethylamino) -5,
5'-bi-1H-tetrazol-1'-yl-butyric acid 1- (N, N-diethylamino) -5,5'-bi-1H
-Tetrazol-1'-yl-butyric acid 1- (N, N-dimethylaminomethyl) -5,5'-bi-1H-tetrazol-1'-yl-butyric acid 1- (N, N-diethylaminomethyl) -5 , 5'-bi-1H-tetrazol-1'-yl-butyric acid 1- (N, N-dimethylaminoethyl) -5,5'-bi-1H-tetrazol-1'-yl-butyric acid 1- (N, N-diethylaminoethyl) -5,5'-bi-1H-tetrazol-1'-yl-butyric acid 1- (4-pyridyl) -5,5'-bi-1H-tetrazol-1'-yl-butyric acid 1- (2-Pyridyl) -5,5'-bi-1H-tetrazol-1'-yl-butyric acid 1- (4-piperidyl) -5,5'-bi-1H-tetrazol-1'-yl-butyric acid

1- (N, N-dimethylamino) -5,
5'-bi-1H-tetrazol-1'-yl-phenyl acetate 1- (N, N-diethylamino) -5,5'-bi-1H
-Tetrazol-1'-yl-phenyl acetate 1- (N, N-dimethylaminomethyl) -5,5'-bi-1H-tetrazol-1'-yl-phenyl acetate 1- (N, N-diethylaminomethyl) -5,5'-Bi-1H-tetrazol-1'-yl-phenyl acetate 1- (N, N-dimethylaminoethyl) -5,5'-bi-1H-tetrazol-1'-yl-phenyl acetate 1 -(N, N-diethylaminoethyl) -5,5'-bi-1H-tetrazol-1'-yl-phenylacetate 1- (4-pyridyl) -5,5'-bi-1H-tetrazole-1'- Iyl-phenyl acetate 1- (2-pyridyl) -5,5'-bi-1H-tetrazole-1'-yl-phenyl acetate 1- (4-piperidyl) -5,5'-bi-1H-tetrazole-1 '-Yl-phenyl acetate

1- (N, N-dimethylamino) -5,
Phenyl 5'-bi-1H-tetrazol-1'-yl-butyrate 1- (N, N-diethylamino) -5,5'-bi-1H
-Phenyl tetrazole-1'-yl-butyrate 1- (N, N-dimethylaminomethyl) -5,5'-bi-1H-tetrazol-1'-yl-butyrate phenyl 1- (N, N-diethylaminomethyl) Phenyl-5,5'-bi-1H-tetrazol-1'-yl-butyrate 1- (N, N-dimethylaminoethyl) -5,5'-bi-1H-tetrazol-1'-yl-butyrate Phenyl 1 -(N, N-Diethylaminoethyl) -5,5'-bi-1H-tetrazol-1'-yl-butyrate phenyl 1- (4-pyridyl) -5,5'-bi-1H-tetrazole-1'- Phenyl I-butyrate 1- (2-pyridyl) -5,5'-bi-1H-tetrazole-1'-yl-butyrate phenyl 1- (4-piperidyl) -5,5'-bi-1H-tetrazole-1 '-Yl-phenyl butyrate

1- (N, N-dimethylamino) -5,
5'-bi-1H-tetrazol-1'-yl-methanol 1- (N, N-diethylamino) -5,5'-bi-1H
-Tetrazol-1'-yl-methanol 1- (N, N-dimethylaminomethyl) -5,5'-bi-1H-tetrazol-1'-yl-methanol 1- (N, N-diethylaminomethyl) -5 , 5'-Bi-1H-tetrazol-1'-yl-methanol 1- (N, N-dimethylaminoethyl) -5,5'-bi-1H-tetrazol-1'-yl-methanol 1- (N, N-diethylaminoethyl) -5,5'-bi-1H-tetrazol-1'-yl-methanol 1- (4-pyridyl) -5,5'-bi-1H-tetrazol-1'-yl-methanol 1- (2-Pyridyl) -5,5'-bi-1H-tetrazol-1'-yl-methanol 1- (4-piperidyl) -5,5'-bi-1H-tetrazol-1'-yl-methanol

1- (N, N-dimethylamino) -5,
5'-bi-1H-tetrazol-1'-yl-ethanol 1- (N, N-diethylamino) -5,5'-bi-1H
-Tetrazol-1'-yl-ethanol 1- (N, N-dimethylaminomethyl) -5,5'-bi-1H-tetrazol-1'-yl-ethanol 1- (N, N-diethylaminomethyl) -5 , 5'-Bi-1H-tetrazol-1'-yl-ethanol 1- (N, N-dimethylaminoethyl) -5,5'-bi-1H-tetrazol-1'-yl-ethanol 1- (N, N-diethylaminoethyl) -5,5'-bi-1H-tetrazol-1'-yl-ethanol 1- (4-pyridyl) -5,5'-bi-1H-tetrazol-1'-yl-ethanol 1- (2-Pyridyl) -5,5'-bi-1H-tetrazol-1'-yl-ethanol 1- (4-piperidyl) -5,5'-bi-1H-tetrazol-1'-yl-ethanol

1-Methyl-5,5'-bi-1H-tetrazol-1'-yl-pyridinhodroxide 1-ethyl-5,5'-bi-1H-tetrazole-1 '
-Yl-pyridinhodroxide 1-phenyl-5,5'-bi-1H-tetrazole-
1'-yl-pyridinhodroxide 1-hydroxyphenyl-5,5'-bi-1H-tetrazol-1'-yl-pyridinhodroxide 1-aminophenyl-5,5'-bi-1H- Tetrazol-1'-yl-pyridinhodroxide 1-methyl-5,5'-bi-1H-tetrazole-1 '
-Yl-methylpyridin fodroxide 1-ethyl-5,5'-bi-1H-tetrazole-1 '
-Yl-methylpyridin fodroxide 1-phenyl-5,5'-bi-1H-tetrazole-
1'-yl-methylpyridinhodroxide 1-hydroxyphenyl-5,5'-bi-1H-tetrazol-1'-yl-methylpyridinhodroxide 1-aminophenyl-5,5'-bi- 1H-tetrazol-1′-yl-methylpyridin fodroxide

1-Methyl-5,5'-bi-1H-tetrazol-1'-yl-ethylpyridinhodroxide 1-ethyl-5,5'-bi-1H-tetrazole-1 '
-Yl-ethylpyridium fodroxide 1-phenyl-5,5'-bi-1H-tetrazole-
1'-yl-ethylpyridinhodroxide 1-hydroxyphenyl-5,5'-bi-1H-tetrazol-1'-yl-ethylpyridinhodroxide 1-aminophenyl-5,5'-bi- 1H-tetrazol-1'-yl-ethylpyridinhodroxide 1-methyl-5,5'-bi-1H-tetrazole-1 '
-Yl-trimethylammonium hydroxide 1-ethyl-5,5'-bi-1H-tetrazole-1 '
-Yl-trimethylammonium hydroxide 1-phenyl-5,5'-bi-1H-tetrazole-
1'-yl-trimethylammonium hydroxide 1-hydroxyphenyl-5,5'-bi-1H-tetrazole-1'-yl-trimethylammonium hydroxide 1-aminophenyl-5,5'-bi-1H-tetrazole- 1'-yl-trimethylammonium hydroxide

1-Methyl-5,5'-bi-1H-tetrazol-1'-yl-methyltrimethylammonium hydroxide 1-Ethyl-5,5'-bi-1H-tetrazole-1 '
-Yl-methyltrimethylammonium hydroxide 1-phenyl-5,5'-bi-1H-tetrazole-
1'-yl-methyltrimethylammonium hydroxide 1-hydroxyphenyl-5,5'-bi-1H-tetrazol-1'-yl-methyltrimethylammonium hydroxide 1-aminophenyl-5,5'-bi-1H- Tetrazol-1′-yl-methyltrimethylammonium hydroxide 1-methyl-5,5′-bi-1H-tetrazole-1 ′
-Yl-ethyltrimethylammonium hydroxide 1-ethyl-5,5'-bi-1H-tetrazole-1 '
-Yl-ethyltrimethylammonium hydroxide 1-phenyl-5,5'-bi-1H-tetrazole-
1'-yl-ethyltrimethylammonium hydroxide 1-hydroxyphenyl-5,5'-bi-1H-tetrazol-1'-yl-ethyltrimethylammonium hydroxide 1-aminophenyl-5,5'-bi-1H- Examples thereof include tetrazol-1′-yl-ethyltrimethylammonium hydroxide.

In the present invention, the general formula (1) is used as the component (C).
At least one compound selected from the compounds represented by (3) to (3) is used. The addition amount of this polymerization catalyst can be arbitrarily selected, but is usually 10 ⁻¹ to 10 ⁻⁸ mol / mol, preferably 10 ⁻² to 10 with respect to the dihydroxy compound of the component (A) as a raw material. Used at a rate of ^-7 mol / mol. If the amount of the catalyst added is less than 10 ^-8 mol / mol, the catalytic effect may not be exhibited. Also, 10 ^-1
If it exceeds mol / mol, PC with excellent color tone may not be obtained. When the addition amount is within the preferred range, a PC having a more excellent color tone can be obtained and the object of the present invention can be efficiently achieved.

The nitrogen-containing organic compound (excluding the tetrazole derivative) as the component (D) of the polymerization catalyst is not particularly limited and various compounds are available. Examples thereof include aliphatic tertiary amine compounds such as trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, and dimethylbenzylamine, and aromatic tertiary amine compounds such as triphenylamine.

Further, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 4-pyrrolidinopyridine, 4-aminopyridine, 2-aminopyridine, 2
-Hydroxypyridine, 4-hydroxypyridine, 2-
Nitrogen-containing compounds such as methoxypyridine, 4-methoxypyridine, imidazole, 2-methylimidazole, 4-methylimidazole, 2-dimethylaminoimidazole, 2-methoxyimidazole, 2-mercaptoimidazole, aminoquinoline and diazabicyclooctane (DABCO). Heterocyclic compounds are mentioned.

Furthermore, tetramethylammonium hydroxide (Me ₄ NOH), tetraethylammonium hydroxide (Et ₄ NOH), tetrabutylammonium hydroxide (Bu ₄ NOH), trimethylbenzylammonium hydroxide [C ₆ H ₅ CH ₂ ( Me) ₃ NO
H] and the like, and ammonium hydroxides having an alkyl group, an aryl group, an aryl group and the like. In addition, tetramethylammonium borohydride (M
e ₄ NBH ₄ ), tetrabutylammonium borohydride (Bu ₄ NBH ₄ ), tetrabutylammonium phenylborate (Bu ₄ NBPh ₄ ), tetramethylammonium tetraphenylborate (Me ₄ NBPh ₄ ), and other basic salts. . Among these (D) components,
Trihexylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide and dimethylaminopyridine are preferably used. In addition, these components (D) have a characteristic that they do not relatively remain in the reaction system. The component (D) of the polymerization catalyst is used in combination with the component (C), and in that case, the component (D) may be used in combination of two or more kinds.

In the present invention, the amount of the component (C) and the component (D) used in combination can be arbitrarily selected, but is usually 10 ⁻ with respect to the raw material (A) the dihydroxy compound. ¹ to 10 ^-8 mol / mol, preferably 10 ^-2 to
It is added at a rate of 10 ⁻⁷ mol / mol. If the amount of the catalyst added is less than 10 ^-8 mol / mol, the catalytic effect may not be exhibited. On the other hand, if it exceeds 10 ^-1 mol / mol, PC having an excellent color tone may not be obtained. When the addition amount is within the preferable range, PC having a more excellent color tone can be obtained and the object of the present invention can be efficiently achieved.

The components (C) and (D) are not particularly limited, but usually in a mixing ratio of 0.1: 1 to 1,000: 1, preferably 1: 1 to 100: 1. Used.

The PC obtained according to the present invention may further contain known additives such as an antioxidant, a plasticizer, a pigment, a lubricant, a release agent, a stabilizer and an inorganic filler, if necessary. Can be used.

In the present invention, as the antioxidant,
For example, as the phosphorus-based antioxidant, specifically, tri (nonylphenyl) phosphite, 2-ethylhexidiphenylphosphite, trimethylphosphite,
Triethyl phosphite, tributyl phosphite, trioctyl phosphite, trinonyl phosphite, trioctadecyl phosphite, distearyl pentaerythryl diphosphite tris (2-chloroethyl) phosphite, tris (2,3-dichloropropyl) phosphite Trialkyl phosphites such as phyto, tricycloalkyl phosphites such as tricyclohexyl phosphite, triphenyl phosphite, tricresyl phosphite, tris (ethylphenyl) phosphite, tris (butylphenyl) phosphite, tris (nonyl) Phenyl) phosphite, tris (hydroxyphenyl)
Triaryl phosphite such as phosphite, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecyl phosphate, distearyl pentaerythyl diphosphate, tris (2
-Chloroethyl) phosphate, trialkylphosphates such as tris (2,3-dichloropropyl) phosphate, tricycloalkylphosphates such as tricyclohexylphosphate; triphenylphosphate, tricresylphosphate, tris (nonylphenyl) phosphate, 2-ethyl Examples include triaryl phosphates such as phenyldiphenyl phosphate. Further, the obtained PC can be blended with a polymer such as polyolefin, polystyrene, polyester, polysulfonate, polyamide and polyphenylene oxide. In particular, OH group, COOH group, NH ₂
It is effective when used in combination with a polyphenylene ether having an end group such as a group, a polyether nitrile, a terminal-modified polysiloxane compound, a modified polypropylene, and a modified polystyrene.

In the production method of the present invention, the raw materials used in the production of polycarbonate by the usual transesterification method are used. Preferably, the dihydroxy compound as the component (A) and the carbonic acid diester as the component (B) are used as described above. (C) component, a catalyst that uses a combination of (C) component and (D) component,
PC with excellent quality can be obtained by carrying out the transesterification reaction using a terminal stopper or a branching agent. Specifically, the reaction may be carried out according to a known transesterification method. The procedure and conditions of the preferred production method of the present invention will be specifically shown below. This does not limit the invention. First, the dihydroxy compound of the component (A) and the carbonic acid diester of the component (B) are subjected to transesterification reaction at a ratio such that the carbonic acid diester is 1 to 1.5 times the mol of the dihydroxy compound. Depending on the situation, the amount of the carbonic acid diester is preferably 1.02 to 1.20 times the molar amount of the dihydroxy compound, which is slightly excessive. In the above transesterification reaction, the amount of the terminal terminator composed of the monohydric phenol or the like is 0.05 mol% to 1 mol based on 1 mol of the dihydroxy compound which is the component (A).
When it is in the range of 0 mol%, the hydroxyl group terminal of the obtained polycarbonate is sealed, so that a polycarbonate having excellent heat resistance and water resistance can be obtained. The total amount of such a terminal terminator composed of the monohydric phenol may be added to the reaction system in advance. Further, it may be added in part to the reaction system in advance and the rest may be added as the reaction progresses. Further, in some cases, the whole amount may be added to the reaction system after the transesterification reaction of the dihydroxy compound (A) and the carbonic acid diester (B) partially proceeds.

In carrying out the transesterification reaction according to the production method of the present invention, the reaction temperature is not particularly limited but is usually in the range of 100 ° C to 300 ° C, preferably 130 ° C to 280 ° C. If the temperature of the transesterification reaction is less than 100 ° C, the reaction rate becomes slow, while if it exceeds 300 ° C, a side reaction may occur, or the produced polycarbonate may be colored, which is not preferable. is there. Also, the reaction pressure is
It is set according to the vapor pressure of the monomer used and the reaction temperature. This is not limited as long as it is set so that the reaction is efficiently performed. Usually, in the initial stage of the reaction, the atmospheric pressure (normal pressure) up to 1 to 50 atm (760 to 38,000 torr) or the pressurized state is maintained, and in the latter stage of the reaction, the reduced pressure state, preferably finally 0.01 ~
It is often 100 torr. Further, the reaction time may be such that it reaches the target molecular weight, and is usually about 0.2 to 10 hours.

The above transesterification reaction is carried out in the absence of an inert solvent, but may be carried out in the presence of 1 to 150% by weight of the obtained PC in the inert solvent, if necessary. . Here, examples of the inert solvent include aromatic compounds such as diphenyl ether, halogenated diphenyl ether, benzophenone, polyphenyl ether, dichlorobenzene, methylnaphthalene, gases such as carbon dioxide, dinitrogen monoxide and nitrogen, and chlorofluorohydrocarbons. Examples thereof include alkanes such as ethane and propane, cyclohexane, tricyclo (5.2.10) decane, cycloalkanes such as cyclooctane and cyclodecane, and various olefins such as ethylene and propylene.

In the present invention, as the reaction proceeds, phenols corresponding to the carbonic acid diester used,
Alcohols or their esters and inert solvent are desorbed from the reactor. These desorbed substances can be separated, purified and recycled for use, and it is preferable to have a facility for removing them. And, the present invention can be carried out batchwise or continuously, and any equipment can be used. In the case of continuous production, it is preferable to use at least two reactors and set the above reaction conditions. The material and structure of the reactor used in the present invention are not particularly limited, but it is sufficient that the reactor has a normal stirring function. However, since the viscosity increases in the latter stage of the reaction, it is preferable to have a high-viscosity stirring function. Further, the shape of the reactor is not limited to a tank type, and may be an extruder type reactor or the like.

[0100]

The present invention will be further described in detail with reference to Examples and Comparative Examples. The present invention is not limited to the examples below. Examples 1 to 10 and Comparative Examples 1 and 2 22.8 g (0.10%) of bisphenol A (BPA) was added to a Ni steel autoclave (with a stirrer) having an internal volume of 100 ml.
Mol), 23.5 g (0.11 mol) of diphenyl carbonate, the tetrazole derivative shown in Table 1 and / or a nitrogen-containing organic compound, and nitrogen substitution was carried out 5 times. The mixture was heated to 180 ° C. and reacted for 30 minutes under an argon atmosphere. Next, the temperature is raised to 210 ° C., the degree of vacuum is gradually raised to 100 mmHg, and the reaction is performed for 30 minutes. Then, the temperature was set to 270 ° C., the vacuum degree was set to 0.3 mmHg, and the reaction was performed for 1 hour. Finally, a viscous and transparent condensate remained in the autoclave. This material was dissolved in methylene chloride and the viscosity average molecular weight was measured.
Further, the obtained viscous and transparent condensate was crushed, press-molded, and the hydrolysis resistance was measured. The results are shown in Table 1.

In Table 1, the tetrazole derivatives used are as follows. (1) 1-phenyl-N, N-dimethyl-1H-tetrazole-5-methanamine (2) 5-phenyl-N, N-dimethyl-1H-tetrazole-1-methanamine (3) 4- (5-phenyl- 1H-tetrazole-1-
Yl) pyridine (4) 3- (1-methyl-1H-tetrazol-5-yl) -1-azabicyclo [2.2.1] heptane (5) 5- (4-aminophenyl) -N, N-diethyl -1H-Tetrazole-Ethanamine (6) 5- (N, N-dimethylaminomethyl) -1H-
Tetrazole-1-acetic acid (7) 1- (4-hydroxyphenyl) -N, N-dimethyl-1H-tetrazole-5-methanamine

[0102]

[Table 1]

[0103]

[Table 2]

* 1 Unit: mol / mole BPA * 2 19.99 wt% aqueous solution manufactured by Nippon Special Chemical Industry Co., Ltd. Metal content Na <1ppb, K <1ppb, Ca <
1 ppb. * 3 Intrinsic viscosity [η] at 20 ° C was measured in methylene chloride, and [η] (dl / g) = 1.23 × 10 ^-5 M _v ^0.83
Calculated from * 4 Plate (thickness 3 mm) 4 for steam at 121 ° C
Visually judge the condition after exposure for 8 hours.

[0105]

According to the present invention, it is possible to efficiently produce a PC having an excellent color tone while improving the reaction rate, having a small amount of residual catalyst, and not impairing hydrolysis resistance. Therefore, the PC obtained by the method of the present invention is suitably used as a material for electric / electronic parts, mechanical parts, automobile parts, and the like.

Claims (4)

[Claims] 1. A method for producing a polycarbonate, which comprises using a tetrazole derivative (C) as a catalyst when producing a polycarbonate from a dihydroxy compound (A) and a carbonic acid diester (B) by a transesterification method. 2. The method for producing a polycarbonate according to claim 1, wherein (C) a tetrazole derivative and (D) a nitrogen-containing organic compound (excluding the tetrazole derivative) are used as catalysts. 3. The (C) tetrazole derivative has the general formula
(1) [Chemical formula 1]{In the formula, R¹And R²Are single bond and carbon number 1 respectively
~ 20 alkylene group, C2-20 alkylidene
A group or an arylene group having 6 to 30 carbon atoms, A is
-N (r¹)₂, -N (r²)₃ ⁺X^-, Pyridyl group, carbon number 1
~ 20 alkyl-substituted pyridyl groups, C6-30 alkyl groups
Reel group-substituted pyridyl group, general formula (a):(In the formula, r³And r^FourAre hydrogen and 1 to 1 carbon atoms, respectively.
20 alkyl groups or aryl groups having 6 to 30 carbon atoms
Show. Group represented by), -P (r^Five)₂, -P (r⁶)
₃ ⁺X^-, -S (r⁷)₂ ⁺X^-[Where r¹, r², r^Five~ R
⁷Is an alkyl group having 1 to 8 carbon atoms or 6 to 30 carbon atoms
An aryl group of¹, r², r^Five~ R⁷Are the same
Or it may be different. X is OH, halogen,
B (r)_Four, (R)₂ PO_Four(Where r is hydrogen and carbon number 1
~ 20 alkyl group or C6 ~ 30 aryl group
, Or an azabicycloalkyl group, B
Is -H, -OY, -SY, -Nr⁸r⁹, -COOY
Where r⁸And r⁹Are hydrogen and 1 to 20 carbon atoms, respectively.
Represents an alkyl group or an aryl group having 6 to 30 carbon atoms.
, Y is hydrogen, N (r^Ten)_Four ⁺, P (r¹¹)_Four ⁺, B (r¹²)_Four ⁺,
S (r¹³)₃ ⁺Or a monovalent metal ion, r^Ten~ R¹³
Represents an alkyl group having 1 to 20 carbon atoms, each of which is the same.
It can be different or different. )} Compounds
Thing, general formula (2)[Wherein, R¹, R², A and B are the same as above.
It ] And a compound represented by the general formula (3):[R³And R^FourAre a single bond and 1 to 20 carbon atoms, respectively.
Alkylene group, alkylidene group having 2 to 20 carbon atoms,
Is an arylene group having 6 to 30 carbon atoms, and A and B are
Same as above. ] Selected from compounds represented by
A compound which is at least a kind of compound.
Alternatively, the method for producing a polycarbonate according to claim 2. 4. The method for producing a polycarbonate according to claim 2, wherein the nitrogen-containing organic compound (excluding the tetrazole derivative) (D) is a pyridine compound, an ammonium hydroxide compound or an ammonium borohydroxide compound.