JPS636540B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel compound having a substituted amino group and a method for producing the same.

Hardening agents for epoxy resins and the like can be broadly classified into amines such as aliphatic polyamines and aromatic polyamines, acid anhydrides including phthalic anhydride, polyamide resins, polysulfide resins, and the like. The physical properties of the resin vary depending on the type of curing agent used, and one of the most commonly used curing agents is polyamine.

Against this background, the present inventors developed a basic compound represented by the following structural formula () [hereinafter referred to as
``Compound ()''] was discovered.

(In the formula, X represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a halogen or a nitro group, and m and n represent integers of 1 to 4.) This is a novel basic compound represented by the formula (wherein, X, m and n have the same meanings as above).

A preferred embodiment of m and n in compound () is that (m+n) is an integer from 2 to 5.
Preferred embodiments of X include hydrogen, methyl group,
It is an ethyl group or a chloro group.

Further, the present invention is characterized in that an amine represented by the following structural formula () is reacted with a styrene substituted product () in the coexistence of an alkali metal amide represented by the corresponding structural formula (). This is a method for producing a novel basic compound represented by the structural formula ().

(In the formula, X represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a halogen or a nitro group, and m and n represent integers of 1 to 4.) One of the preferred embodiments for the alkali metal amide () is lithium amide. be.

One of the preferred reagents for reacting the amine represented by the structural formula () to lithium amide is an alkyl lithium, and one of the preferred reagents as the alkyl lithium is n-butyl lithium.

This reaction can also be carried out in the presence of an inert organic liquid. As an inert organic liquid, hexane, cyclohexane, tetrahydrofuran, ether, benzene, toluene, or 2
It is desirable to use a mixture of more than one species of liquid.

One of the preferred reaction methods is to add a styrene substitute to a mixture of an amine represented by the structural formula () and an alkyl lithium.

Examples of general methods for producing compound () are shown below.

This reaction is performed using an amine represented by the following structural formula () [hereinafter referred to as "amine ()" or simply "amine"]
] is reacted with a styrene substituted product () in the coexistence of the corresponding alkali metal amide ().

As the alkali metal, lithium is preferred due to its high reactivity and ease of reaction operation. A preferred method for preparing lithium amide is to react an amine with alkyl lithium, phenyl lithium, aluminum lithium hydride, lithium hydride, etc. Among these, alkyl lithium is used because of its solubility in solvents, operability, etc. It is particularly preferable to do so. The lithium amide corresponding to the compound () will be simply referred to as "lithium amide" hereinafter.

Examples of styrene substitutes include styrene, alkylstyrenes such as methylstyrene and ethylstyrene, halogenated styrenes including chlorostyrene and bromostyrene, and nitrated styrenes. Among these, one example of a more preferred embodiment is styrene and chlorostyrene.

As a preferable example of the amine, (m+n) is 2
Starting with diethylenetriamine, (m
+n) are 3, 4 and 5 amines.

In this reaction, lithium amide () acts as a catalyst. This is one of the major features of this reaction. That is, it is sufficient to use lithium amide () in an amount equal to or less than the molar amount of the styrene substituted product, preferably 0.001 to 0.5 times the molar ratio, and more preferably 0.01 to 0.2 times the molar ratio.
It's double the amount. At this time, it should be kept in mind that the concentration of lithium amide () controls the reaction rate.

Lithium amide () contains water coexisting in the reaction system,
Since it is deactivated by reacting with substances containing active hydrogen such as alcohols and acids, it is preferable that the raw materials and solvents used be purified by dehydration in advance, but if it is unavoidable,
When these active hydrogen-containing substances are mixed, it is desirable to use more than the intended amount of lithium amide. As already mentioned, lithium amides can be easily prepared, for example, by reacting an alkyllithium with an amine. As the alkyl lithium, methyl lithium, ethyl lithium, butyl lithium, etc. can be used, but among these, n-butyl lithium, which is also produced industrially, is particularly preferred from the viewpoint of easy availability.

The amount of amine () to be used relative to the styrene substituted product is preferably 0.5 to 5 times, more preferably 0.8 to 2 times, in terms of molar ratio. If the amount of amine () is too small, the yield of product () will decrease and at the same time the amine will contain two (m=n=
In the case of I, it is not preferable because there is a possibility that by-products having three or more styrene substituents (represented by the following structural formula ()) or to which three or more styrene substituents are added may be produced.

There are, for example, the following two methods for reacting the mixture of lithium amide () and amine () with the styrene substitute. The first method is to add a mixture of the former to the styrene substituted product. The second method is to add a styrene substitute to a mixture of lithium amide and amine.

The first method has the disadvantage of increasing the production of by-products (), whereas the second method requires only one reaction vessel and the need to transfer the lithium amide solution. The second method is more recommended because it has advantages such as not requiring any additional operations.

The reaction in the present invention can also be carried out in the presence of an inert solvent. Examples of solvents include aliphatic hydrocarbons such as pentane, hexane, cyclohexane, heptane, and octane, aromatic hydrocarbons such as benzene, toluene, and xylene, ethers such as diethyl ether, dibutyl ether, dioxane, and tetrahydrofuran, dimethyl sulfoxide, N・N-
Liquids that do not react with lithium amide under the reaction conditions can be used, such as aprotic polar solvents such as dimethylformamide and hexamethylphosphoric triamide. Among these, hexane, cyclohexane, benzene, tetrahydrofuran, ether, toluene and the like are more preferred. Aliphatic hydrocarbons such as hexane are commonly used as completely inert solvents.

The amount of solvent used is the volume of the styrene substituted product.
Preferably 0.1 to 50 times, more preferably 0.5
It is 20 to 20 times larger.

The temperature at which the reaction of the present invention is carried out is not particularly limited, but is preferably -10°C to 150°C, more preferably 20°C to 80°C. When carrying out the reaction above the boiling point of the solvent, it is necessary to use a pressure vessel. It is also preferred that the reaction mixture be stirred or shaken.

Although there is no restriction on the reaction time, it is preferably 1 minute to 10 hours, more preferably 5 minutes to 6 hours.
The reaction rate depends on temperature, type of amine, concentration of raw materials,
The reaction time should be set depending on the conditions, as it is largely controlled by the type of solvent, etc., but during the reaction,
It is recommended that the end time of the reaction be determined by sampling at regular intervals and quantifying the raw materials and products using gas chromatography, liquid chromatography, etc. In order to stop the reaction, it is necessary to deactivate the lithium compound with an alcohol such as methanol or ethanol, water, or the like.

In order to isolate the product compound (), general organic chemical separation methods such as recrystallization, column chromatography, extraction, etc. can be used. There is also a method of precipitating the compound () as a hydrochloride salt by adding hydrochloric acid or hydrogen chloride gas.

The compound () obtained by the present invention can be used as a curing agent for epoxy resins and the like.

Examples of the present invention will be shown below, but the present invention is not limited to the scope of these Examples.

Example 1 Tetrahydrofuran 356 dried and distilled over sodium metal was placed in a pressure-resistant glass container with an internal volume of 800 ml.
After adding ml, diethylenetriamine 149g
(1.44 mol) was added, and the inside of the container was purged with nitrogen. Next, 44.6 ml (0.072 mol) of n-butyllithium
74.8g of styrene dried and dehydrated with synthetic zeolite after introducing 15% n-hexane solution
(0.72 mol) was introduced.

The reaction vessel was placed in a water bath at 40° C., and stirring was continued for 3 hours, and then 100 ml of methanol was added to the reaction mixture to stop the reaction. When acetone was added in Step 5, a precipitate formed, so after removing this, the object was thoroughly washed with acetone and dried in a vacuum dryer.137
g of reaction product was obtained.

This reaction product was further dissolved in methanol (1), added with acetone (5), reprecipitated, filtered, washed with acetone, and dried in a vacuum dryer to yield 126 g (85%). A reaction product was obtained.

As a result of analyzing this reaction product using a general organic chemical analysis method, it was found that the product had the following structure.

The results of the analysis are shown below.

Elemental analysis; C69.57 (69.52), H10.14 (10.21),
N20.29 (20.27) However, the numbers in parentheses here indicate the theoretical values.

Mass spectrum (M ⁺ /e); 207 (M ⁺ ), 130,
102, 77 and other infrared absorption spectra (cm ^-1 ); 690, 742, 1038,
Around 1360, 1450, 1492, 1601, 2805, 3300 (wide range) Nuclear magnetic resonance spectrum (δ-value); around 7.2 (multiplet, 5H), 2-3.5 (multiplet, 12H), 1.10 (singlet, 4H) ) Example 2 Tetrohydrofuran 356 dried and distilled over sodium metal was placed in a pressure-resistant glass container with an internal volume of 800 ml.
After adding ml, diethylenetriamine 112g
(1.09 mol) was added, and the inside of the container was purged with nitrogen. Then 45 ml (0.072 mol) of n-butyllithium 15
75 g (0.72 mol) of styrene dried and dehydrated with synthetic zeolite after introducing %n-hexane solution
introduced.

The reaction vessel was placed in a 20°C water bath, and stirring was continued for 5 hours. The product was isolated from the reaction mixture in the same manner as in Example 1, yielding 118 g (79%) of a colorless solid. It was confirmed from liquid chromatography and infrared spectroscopy that this substance was the same as the substance obtained in Example 1.

Example 3 Tetrahydrofuran 356 dried and distilled over sodium metal was placed in a pressure-resistant glass container with an internal volume of 800 ml.
After adding ml, diethylenetriamine 149g
(1.44 mol) was added, and the inside of the container was purged with nitrogen. Next, 29.8 ml (0.048 mol) of n-butyllithium
After introducing a 15% n-hexane solution, 49.9 g (0.48 g) of styrene was dried and dehydrated using synthetic zeolite.
mol) was introduced.

The reaction container was placed in a water bath at 60° C., and stirring was continued for 2 hours, and then 1 part of methanol was added to the reaction mixture to stop the reaction.

This reaction mixture was distilled to remove raw materials such as styrene and diethylenetriamine, leaving a residue of 95%.
g (95%) was obtained. After dissolving this residue in 100ml of methanol and blowing hydrogen chloride gas into it,
This was rejected because a precipitate formed. After adding 400 ml of 4N-NaOH to the obtained product and dissolving it, the mixture was passed through a cation exchange resin and concentrated to obtain 81 g (81%) of a reaction product.

This reaction product was found to be the same product as in Example 1 from the results of liquid chromatography and infrared spectroscopy.

Example 4 390 ml of benzene dried and distilled over sodium metal was placed in a pressure-resistant glass container with an internal volume of 800 ml, and then 149 g (1.44 mol) of diethylenetriamine was added, and the inside of the container was purged with nitrogen. Then 45ml (0.072
After introducing a 15% n-hexane solution of n-butyllithium (mol), drying with synthetic zeolite,
Dehydrated p-chlorostyrene 99.8g (0.72mol)
introduced.

The reaction vessel was placed in a water bath at 40° C., and stirring was continued for 4 hours, followed by isolation from the reaction mixture in the same manner as in Example 1 to obtain 139 g (80%) of the reaction product.

As a result of analyzing this reaction product using a general organic chemical analysis method, it was found that the product had the following structure.

The results of the analysis are shown below.

Elemental analysis; C59.63 (59.62), H8.28 (8.34), N17.39
(17.38), Cl14.70 (14.66) However, the numbers in parentheses indicate theoretical values.

Mass spectrum; 241 (M ⁺ /e), 206 (M-Cl),
130 (M-C ₆ H ₄ Cl), 111 (C ₆ H ₄ Cl), 102
(C ₄ H ₁₂ N ₃ ) Infrared absorption spectrum (cm ^-1 ); 690, 742, 830,
1038, 1360, 1450, 1492, 1601, 2805, around 3300 (wide range) and others Example 5 200 equipped with a reflux vessel, dropping funnel and stirring bar
100 ml of benzene dehydrated over sodium metal and 11.6 g (0.05 mol) of pentaethylenehexamine are placed in a 3-necked flask. After purging the inside of the container with nitrogen, 3.1 ml (0.005 mol) of a 15% hexane solution of n-butyllithium was added with stirring. Next, 7.45 g (0.05 mol) of meta-nitrostyrene was dissolved in 30 ml of benzene and introduced into the reactor through the dropping funnel for about 10 minutes while stirring. After that, stirring was continued for about 8 hours at the reflux temperature of benzene, and then 10 ml of methanol was added to the reaction mixture to stop the reaction. After concentrating 1/10 of the total volume of the reaction mixture and separating it by column chromatography, 0.65 g (calculated as 34%) of the product was obtained. Analysis by liquid chromatography showed that the product was a mixture of two components in approximately equal amounts. As a result of analysis, these substances are 1,14-diamino-N ³ -{2
-(m-nitrophenyl)ethyl}-3.6.9.
12-tetraaza-n-tetradecane (m=1, n
=4 or m=4, n=1) and 1,14-diamino- ^N6- {2-(m-nitrophenyl)ethyl}
It was found to be -3,6,9,12-tetraaza-n-tetradecane (m=2, n=3 or m=3, n=2). The analysis results are as follows.

Elemental analysis; C56.42 (56.67), H9.29 (9.25), N25.98
(25.70) Infrared absorption spectrum (unit cm ^-1 ); 742, 830,
Around 1038, 1332, 1450, 1530, 1601, 2805, 3300 (wide range) and others Example 6 100 ml of dehydrated benzene was placed in a 200 ml three-necked flask equipped with a reflux, dropping funnel, and a stirring bar sealed with liquid paraffin. and 8.03g (0.055
mol) of triethylenetetramine was added, and then 3.1 ml (0.005 mol) of a 15% hexane solution of n-butyllithium was added with stirring using a syringe. Next, 8.0 g (0.05 mol) of para-n-butylstyrene was dissolved in 30 ml of benzene and added through the dropping funnel. After continued stirring for 8 hours at the reflux temperature of benzene, the reaction was stopped with 2 ml of methanol. In the same manner as in Example 5, 1.09 g (71% in terms of conversion) of a product was obtained. Analysis by liquid chromatography showed that the product consisted of a single component. From the analysis results below,
This product is 1,8-diamino-N ³ -{2-(para-n-butyl)ethyl}-3,6-diaza-n-
Turns out it's octane. The analysis results are as follows.

Elemental analysis; C70.31 (70.54), H11.35 (11.18),
N18.45 (18.28) Infrared absorption spectrum (unit cm ^-1 ); 742, 830,
Around 1038, 1450, 1601, 2804, 3300 (wide range)
other

Claims (1)

[Claims] 1 Structural formula () (wherein, X represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a halogen or a nitro group, and m and n represent integers of 1 to 4). 2. The basic compound according to claim 1, wherein (m+n) is an integer from 2 to 5. 3. The basic compound according to claim 1 or 2, wherein X is hydrogen, methyl group, ethyl group, or chloro. 4 Structural formula () (In the formula, m and n represent integers from 1 to 4.) An amine represented by the corresponding structural formula () (In the formula, m and n represent integers from 1 to 4.) In the coexistence of an alkali metal amide represented by the structural formula () (In the formula, X represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a halogen, or a nitro group.) (In the formula, X represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a halogen or a nitro group, and m and n represent integers of 1 to 4.) 5. The method for producing a basic compound according to claim 4, using lithium amide as the alkali metal amide (). 6. A method for producing a basic compound according to claim 4, using a lithium amide prepared from an amine represented by the structural formula () and an alkyl lithium. 7. The method for producing a basic compound according to claim 4, using n-butyllithium as the alkyllithium. 8. A method for producing a basic compound according to any one of claims 4 to 7, wherein the reaction is carried out in the presence of an inert organic liquid. 9. The method for producing a basic compound according to claim 8, wherein any one of hexane, cyclohexane, tetrahydrofuran, ether, benzene, toluene, or a mixture of two or more thereof is used as the inert organic liquid. 10. The method for producing a basic compound according to any one of claims 4 to 9, which comprises adding a styrene substitute () to a mixture of an amine represented by the structural formula () and an alkyl lithium.