JPS5883655A - Novel tertiary amine and its preparation - Google Patents

Abstract

NEW MATERIAL:The tertiary amine of formulaI(n is 1 or 2). EXAMPLE:Di(8-dimethylaminooctyl)methylamine. USE:Epoxy resin curing catalyst, polyurethane resin curing catalyst, rubber chemicals, intermediate for agricultural chemicals, and intermediate for pharmaceuticals. Since it has high boiling point and low vapor pressure at normal temperature, it can be handled easily, and exhibits little undersirable effect to the human body. PROCESS:To prepare the tertiary amine of formulaIis prepared by reacting the active hydrogen atoms of the polyoctamethylene polyamine of formula II with formaldehyde and formic acid, thereby methylating all active hydrogen atoms in the polyamine molecule. As the formaldehyde molecule is used in the formation of C-N bond, and formic acid acts as the reducing agent of N-methylol compound, it is necessary to use 5mol each of formaldehyde and formic acid per 1mol of the triamine when n in the formulaIis 1, and 6mol each when n is 2. For the formation of amine and salt, 3mol or 4mol of additional formic acid is added to the reaction system corresponding to triamine or tetramine, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel 3
amines.

The present inventors have developed the agricultural and horticultural fungicide guazatine (Gt+ms
9-aza-1,17-diaminohebutadecane (also referred to as dioctamethylenetriamine, hereinafter simply referred to as triamine), which is an intermediate of +atin・), is also referred to as 1,8-diamyloctane C octamethylenediamine, Hereinafter, it will simply be referred to as diamine. ) Polyoctamethylene polyamine c, which is produced in large quantities by the deammonia dimerization reaction, is an industrial waste that is undesirable from the viewpoint of boria countermeasures, and as a result of extensive research,
The above-mentioned novel tertiary amine represented by the formula (11) can be isolated as an industrially useful liquid substance, and can be effectively methylated by reductively methylating the active hydrogen of the polyamine mixture in the presence of formaldehyde. A method for producing the above tertiary amine was discovered, and the present invention was completed.

Substances with n = 1 in (112), 7 i.e. diC8-dimethylaminooctyl)methylamine and n
= 2 substances, that is, N,N'-bis(8-dimethylaminooctyl)-N,N'-1,8-dimethylamino-octane, are both liquid at room temperature, novel substances in themselves, and have a boiling point of It is a substance that has a high vapor pressure and a low vapor pressure at room temperature, so it is easy to handle and has little adverse effect on the human body.It can be used alone or as a mixture as an epoxy resin curing catalyst,
It can be used in polyurethane resin curing catalysts, rubber drugs, agricultural chemical intermediates, pharmaceutical intermediates, etc. Furthermore, the compound of the present invention can be used as a raw material for synthesizing a compound similar to the fiber softening agent described in JP-A-55-76168, for example.
The quaternary ammonia salt obtained by reacting a long-chain alkyl halide with the tertiary amine of the present invention can be used as a water repellent for fibers. The water repellent treatment is performed by immersing the fibers in an aqueous solution of the above ammonium salt and treating the fibers with an aqueous sodium silicate solution.

The parent regular 6-ary amine of the present invention represented by the above intermediate formula is:
For example, Organlc 8ynthesig Vol. 25, p. 89, J, Aml.

Cbm, See, j$55, page 4571, same no.6
Described in Vol. 2, p. 161, Vol. 62, p. 1964, Vol. 64, p. 2265, Vol. I 75 @ p. 6038, B@r, Vol. 58, p. 880, U.S. Patent No. 2,566,554, and others. It is obtained by substantially complete methylation in the presence of formaldehyde, which is an active hydrogen bonded to the amine nitrogen of the primary and secondary amines of a polyamine, by the "Ks@hv.il@r C1ark reaction".

A more advantageous method for producing the novel tertiary amine of the present invention is to add 1 gram of amino (-NHR) and imino (=NH) active hydrogen to the polyamine residue that is produced as a by-product during the deammonization dimerization reaction of diamine. This is a method in which 1 mol of formaldehyde and 1 mol of formic acid are reacted per atom to methylate all active hydrogens in polyamine molecules and convert them into tertiary amines. Here, formaldehyde is used to form a 1-f-4L monocarbon bond, and formic acid is
Acts as a reducing agent for N-methylol. Therefore, in the intermediate formation, when n = 1, 5 moles of formaldehyde and 5 moles of formic acid are required per mole of triamine, and n =
2, 6 formaldehyde per mole of tetramine
It takes 6 moles of formic acid and 6 moles of formic acid to form the amine and salt, so in the case of the triamine, an additional 3 moles are required.
In the case of molar tetramine, 4 moles of formic acid must be added. Of course, since the polyamine mixture contains various higher order condensates in addition to triamine and tetramine, it is necessary to measure the active hydrogen equivalent and 757 valence in advance, and use the necessary amounts of formaldehyde and formic acid in the reaction. Here, the active hydrogen equivalent of KX is a value expressed in molecular weight units of the amount equivalent to one hydrogen atom of all the 1NH, groups and =NH groups contained in the polyamine mixture.

In this reaction, polyamine formate can be reacted with formaldehyde in the presence or absence of a solvent such as water or alcohol, or polyamine can be reacted with a mixture of formic acid and formaldehyde. May be added. Examples of solvents for polyamines include isopropanol,
Alcohols such as isobutanol, 1.C-butanol, and n-butanol; seisosols such as methyl cellosolve, ethyl cellosolve, and n-butyl cellosolve; acid amides such as dimethylacetamide and dimethylacetamide; and dioxane and dibutyl ether. Ethers and the like can be used, and the formaldehyde used may be a polymer such as paraform or an aqueous solution such as formalin.

When an amine reacts with formaldehyde and formic acid, a large amount of carbon dioxide gas is generated, so it is necessary to add the amine or formaldehyde to the reaction system while controlling the foaming state of the reaction solution. After the addition is complete, methylation is carried out by heating under reflux until the reaction is completed. Next, the organic solvent is removed under compensated pressure, the remaining methylated polyamine formate mixture is neutralized with caustic alkali or aqueous ammonia, and extracted with toluene, xylene, ethyl ether, etc. After this is removed, the remaining oil is removed dropwise under reduced pressure to separate a distillate containing the tertiary amine represented by the above general formula as a main component.

The advantages and features of the above production method are that a new industrially useful tertiary amine compound can be produced in a simple manner using the economically worthless nonvolatile polyamine mixture produced as a by-product of guazatine production 1* as a raw material. Good yield (in that it can be recovered), which makes it possible to greatly reduce the large amount of industrial waste generated during guazatine production, and therefore, we have found a method that is extremely advantageous in reducing production costs. .

In addition, as a method for producing a tertiary amine other than the above, there is a method in which a polyamine is reacted with formalin in methanol 111+111 to methylate it, and then catalytically reduced.

The present invention will be explained in more detail with reference to Examples below, but of course the gist and scope of the present invention are not limited by these Examples.

゛ Example 1 When producing triamine by diamine dimerization reaction, klli
A non-volatile polyamine with no droplets (boiling point 200℃)
/ 1 Dark pitch-like polyamine compound with wmHI or higher, melting point 63-67°C, amine content 105.0, active hydrogen equivalent 69'5, triamine about 10, tetramine about 5
Contains 0-. ) 138.61 and a@e-butanol 120- to a mixture of 127.9 # of 90 formic acid, 65.2 # of 92-paraform, and 101 # of water.
The mixture was gradually added over 15 hours while stirring at 100°C. Then 90 mol formic acid 43. θI was added in 15 minutes and the mixture was stirred at 90-100° C. for 10 hours. From this reaction solution, s@c-butanol was extracted under reduced pressure, and 250 d of water was extracted.
While stirring, aqueous ammonia was gradually added to adjust the pH to 10, and a dark brown viscous oil was separated into an upper layer. Add 250% of toluene to this to remove the aqueous layer, and then remove the organic layer.
It was shaken and washed three times with 250-g water. The organic layer was then separated and the toluene removed, yielding a black oily methylated 6-acid polyamine mixture 15a2jl. When this black corrugated material was removed dropwise under a reduced pressure of tt[LO 2 mH, 9, 112.4 JF of a pale yellow transparent oily tertiary amine mixture distilled out with a boiling point of 75 to 214° C. was obtained.

This oily tertiary amine mixture 110I was added to α02mH again.
Dropless fractionation was carried out under reduced pressure at a boiling point of 137-1.
Di(8-dimethylaconoctyl)methylamine 7.5 JF at 40°C.

N,N'-bis(8-dimethylaminooctyl)-NtN' 1s8-dimethylamino-octane 54LOJI was obtained with a boiling point of 210-212<0>C.

The analysis values for each are as follows.
Theoretical value as 1 = 12.1 h) O mass spectrometry m/e 341 (M+) O refractive index nD = t4576 (21N, N'-bis(8-dimethylaminooctyl)
-N,N' -1,8-dimethylamino-octane l-
---People ^ 1 Example 2 A mixture of the polyamine dropless residue of Example 1, f1!15B, 61 and inbutanol 100-90 thiformic acid 127.9
L-paraform (contains 92 HΦCHO).

) 90 to 100 in a mixture of 65.2 N and 201 N of water.
The mixture was added gradually over 1 hour while stirring at °C. Then add 90 sachets of formic acid 4&OJI for 15 minutes and mix the reaction.
The mixture was heated to reflux with stirring for 6 hours. The mixture was heated under reduced pressure to distill off the isobutyl alcohol, and the water
011J1''1yil! was dissolved, and aqueous ammonia was gradually added with stirring to adjust the pH to 10, and a dark brown viscous oil was separated into the upper layer. 200d of ether was added to this, the aqueous layer was removed, and the organic layer was separated. -250- was shaken and washed three times with water, then the organic layer was separated and the ether was distilled off, resulting in a methylated tertiary polyamine mixture of 147.
5M was obtained as a black viscous oil. This mixture S
When @amine was added dropwise to a, 02■ HII under reduced pressure, pale yellow transparent oil 51 was distilled out with a boiling point of 75-214°C.
1 to obtain an amine mixture 1 (nutl-).

As a result of gas chromatography and mass spectrometry, this contained di(8-dimethylaminooctyl)methylamine zoy.

N, N'-bis(8-dimethylaminooctyl)-N,
It was found that it contained N'-1,8-dimethylamino-octane 6αlt-. Also, the black tar-like non-drop residue is 3
2. ON, the residue of Arichito is 2 of the raw material polyamine mixture.
&o corresponds to % by weight.

Example 3 Industrial triamine 7599 and C-butanol 100m
A mixture of 87% formic acid 129.5N, 9211pj7)
C Ru A49.01.551*Rules/42.9j+
was gradually added to a mixture of 10 ml of water over 1 hour while stirring at 80 to 90°C, and then stirred at 90°C for 10 hours. C-butanol was removed from the reaction solution under reduced pressure, 100 ml of water was added, and aqueous ammonia was gradually added with stirring to adjust the pH to 10, and a pale yellow oil was separated into an upper layer. The aqueous layer was then extracted twice using 100 d each of ether, and the ether was removed to give 92.1 of a pale yellow oil containing a methylated tertiary amine. When this was analyzed by gas chromatography, di(8-dimethylaminooctyl)
This pale yellow oily substance, which was found to contain methylamine 54214', was then treated with 3■H! Fractionation was carried out under reduced pressure of 1 to obtain di(8-dimethylaminooctyl)methylamine 4&2#t' with a boiling point of 202 to 204°C.

Claims (1)

[Scope of Claims] t A novel tertiary amine represented by the general formula: (wherein n represents 1 or 2). The active hydrogen of a polyoctamethylene polyamine represented by the general formula 2, (in the formula, the cage indicates 1 or 2) is reductively methylated in the presence of formaldehyde to form the general formula, (in the formula, n is 1). or 2.) A new 3 represented by
A method for producing a novel tertiary amine, which comprises converting it into a tertiary amine.