FI82445C - Bis (2,2-dimethyl-3-oxopropyl) amine, its functional derivatives and methods for preparing them, and their use - Google Patents

Description

82445

Bis (2,2-dimethyl-3-oxopropyl) amine, its functional derivative and methods of preparing them, and the use of these Bis (2,2-dimethyl-3-oxopropylyl) amine, since the functionaliset johdannaiset ja menelmelmä nuiden käyttö

The invention relates to new compounds having several uses and a method for preparing them.

In the literature, there is an example of attempts to condense ammonium chloride, isobutyraldehyde and formalin, but the reaction product was only an undefined tar. (R. J. Jacobson, J. Am.Chem.Soc.67.

15 (1945), 1999). The author's purpose was to produce in a "one pot" process a known Mannich base 2,2-dimethyl-3-aminomethylpropanal. The intention was to first transfer formaldehyde in methylamine hydrochloride:

2CH 2 O + NH 4 Cl -> NH 2 - CH, «HCl + HCOOH

Which would add another mole of formaldehyde "in situ" and one mole of isobutanal: CH 2 - NH 2 -HCl + CH 2 O + (CH 3) 2 CHCHO -> CH 3 - NH - CH, C (CH 3): - CHO + H-, 2,2-dimethyl-3-aminomethylpropanal.

This process has proved unworkable in practice. Probably, under the catalytic action of the formed formic acid, a variety of polycondensation and ring formation reactions were developed (see, for example, Walker "Formaldehyde" Chapter 9.14), which proceeds faster than the Mannich reaction.

By using a large excess of formaldehyde, about 220 mol% to the other reactants, very favorable conditions have been established for the development of various polycondensation processes and in addition, two immiscible phases were formed. The aqueous phase contained ammonia in uin chloride, formaldehyde and the formic acid formed, while the organic phase was water-insoluble isobutyraldehyde. Under such conditions, formation of a uniform reaction product was hardly possible.

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Otherwise, the literature only finds descriptions of reactions between isobutyraldehyde, formaldehyde and secondary and primary amines, but not with ammonia and resp. its salts. SA eg in a reaction between isobutyraldehyde, formaldehyde and dimethylamine, the 3-dimethylamino-2,2-dimethylpropanal is formed (EP 46 288). A similar synthesis has been described in the 1930s by Mannich, Lesser and Silten (Ber. £ 6, (1932), 378). The reaction processes between the primary amines, formaldehyde and isobutyraldehyde have been carefully investigated by H. Möhrle and D. Schnädelbach (Arch. Pharmaz. 308/75 p. 352), who have proven that at all times a cyclic compound is formed according to the following mechanism. : RNH2 + 2CHOH + CH (CH2), CH0 -> R - N - CH2 + H, 0CH2 C (CH3) 2 V /

15. "" Uh

In the literature, a number of descriptions of condensation reactions between ketones, formalin and ammonia are also found. But then either cyclic compounds or ketoamines are formed. (See, e.g., C. Mannich, S. M. Abdullach, Ber. 68, (1935), 113, H. K. Hall, J. Am. Chem. Soc. 79, (1957), 5444.)

During the past few years, there have been published several patents and journal articles describing various preparation methods of amines, starting from ammonia and aldehydes. According to German Offenlegungsschrift 2327510, tertiary amines are produced from aldehydes, ammonia and hydrogen. The process proceeds in the presence of a heterogeneous catalyst under a pressure of between 80 and 250 kp / cm 2 and at a temperature of 60-30 180 ° C. Since alkyl radicals of the tertiary amines formed do not contain any other functional groups, the use of the product is rather limited.

European Patent Application 0200917 discloses the synthesis of di (tert-butanol) amine. This substance is formed upon hydrogenation of 2 (1-hydroxy-1-methyl-ethyl) -5,5-dimethyl-1,3-oxazoline.

II

3 82445 CH, H N. H, CH,

11 / i

CH1 - C - C1-6 CH -> NH (CH2 - C - OH) 2 j cat j OH O - C - CH, CH, l CH

The process runs at a pressure between 30 and 200 bar and at a temperature of 50-150 ° C.

The aforementioned oxazoline derivative is obtained by aminoniac treatment of alpha hydroxy isobutyraldehyde, respectively. its acetal. In the author's opinion, di (tert-butanol) amine can be used as an absorbent agent for acid gases and, respectively. as starting material for various syntheses. Limited availability of raw material, a manufacturing process consisting of three different reactions, the need for an expensive hydrogenation equipment limits the technical value of this invention. In addition, derivatives of a tert. hydroxy group (eg esters, ethers) are usually chemically unstable.

One way to make tart. amines which in their structure contain three hydroxy ester groups are described in US Pat. These substances are synthesized by a reaction between monohydroxyalkyl acrylates and ammonia. Thanks to the presence of an alkaline group, they can be used for the absorption of acid gases. The three hydroxy groups can also be used as crosslinking agents. It is easy to see that the patent comprises a very limited group of compounds.

From this literature review and market analysis, it is concluded that there are quite few technically available, versatile higher amines containing in their structure a reactive amine group and two additional functional groups linked to the amine alkyl radicals. It is easy to see that such compounds can have many important technical applications such as e.g. monomers, plasticizers, corrosion and degradation inhibitors, surfactants and more. We have produced such an interesting substance, starting from cheap and easily accessible foxes.

We have now invented a method of condensing ammonia salt (AM), formaldehyde (FOR) and isobutyraldehyde (IBA) to form a compound 82445 hitherto unknown, which in turn can be transferred into a number of hitherto unknown derivatives with valuable technical characteristics.

The compounds of the invention are characterized in that they are bis (2,2-5 dimethyl-3-propyl-functional) amines of the general formula CH

H - N (CH - C - Z) 2 I

CH, where Z is an aldehyde group of formula -CHO, or a carboxyl group of formula -C00H, or an ester group of formula -C00R, or an alcohol group of formula -CH2-OH, or an amine group of formula -CH2 -NH, or -CH 2 -NHR, or an ether group of the formula -CH 2 -OR, and R is a lower alkyl radical or lower alkenyl radical.

The process for preparing the compounds of the invention is characterized in that isobutyraldehyde, formaldehyde and an ammonia salt react in the advantageous molar ratio between 1: 1.5: 1.5 and 1: 4: 4, the reaction being carried out so that the reactants come into intimate contact through intensive contact. stirring at the favorable temperature of 60 to 90 ° C to give bis (2,2-dimethyl-3-oxopropyl) amine, which may be reduced to bis (2,2-dimethyl-3-hydroxypropyl) amine or oxidized if desired. to bis (2,2-dimethyl-3-propionic acid) amine or to amine to bis (2,2-dimethyl-3-aminopropyl) amine or to bis (2,2-dimethyl-3-alkyl-aminopropyl) amine.

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The reaction carried out between the starting materials isobutyraldehyde, formaldehyde and ammonium salt can be described by the reaction similarity, CH1.3 NH2X + 2CH0H + 2CH (CH2) 2CHO -> H-N (CH2 - C - CH0) 2 + HX + 2H

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5 82445

The oxidation, reduction and amination can be described with the reaction similarities to esters 5 CH 3 polyesters H - N (CH

CH ·, CH, esters I \ H - N (CH2-C-CHO) 2 oxidation y H - N (CH2-C-COOH) 2 -> polyesters CH3 CH3 amides \ amination polyamides n.

GH3 polyamides H - N (CH2-C-CH2NH2) 2 -> isocyanates CH3 The compounds of the invention are di. trifunctional because the hydrogen atom bound with nitrogen can also participate in a variety of reactions. They show a completely different chemical nature than the compounds that previously formed the reaction product in condensation reactions of the same kind. Previously, neither the bis-aldehyde nor its derivatives are known.

The compounds can be used as various kinds of monomers, as emulsifiers, as detergents, as metal complexing agents or corrosion inhibitors. They can also act as plasticizers in PVC or as starting materials for the production of plasticizers, and they can improve the thermostability of PVC. In addition, esters and ethers can be formed by the compound, which can be used i.a. in dyes and varnishes.

In the synthesis we have invented, the formaldehyde can be used either in the form of a solution or as a solid polymer (paraformaldehyde).

Amrooniak is used in the form of its salts, e.g. ammonium chloride. Isobutyraldehyde may contain its trimer, (2,4,6-tri-isopropyl-1,3,5-trioxane), which is formed, inter alia, during a longer storage or resp. in the presence of 6,82445 certain catalysts. Nor does the presence of water or impurities in the form of organic acids negatively affect the course of condensation.

The rate of condensation is strongly dependent on the temperature. The reaction proceeds at a noticeable rate already at about 50 ° C, while at the use of the reflux temperature it can be completed after about 4 hours. It is possible to further increase the reaction rate by heating under pressure. The molar ratio of the reactants may vary within certain limits. From the reaction similarity, it is seen that the stoichiometric ratio AM: FOR: IBA is equal to 1: 2: 2, but also in other quantitative ratios one can obtain BIS as the reaction main product. The optimal ratio of the reagents is between 1: 1.5: 1.5 and 1: 4: 4, but even at a ratio of 1:10:20 and 1: 0.4: 0.3, a certain amount of BIS.

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There are various opportunities to introduce the reagents into the reactor. One can, for example, introduce all three substances and the catalyst into the reaction vessel at the same time and then, under intense stirring, start heating. In such a process, the condensation proceeds both with satisfactory speed and selectivity. This process presents difficulties in removing the heat of reaction because the reaction is exothermic. Formaldehyde can also be dosed in a reactor containing isobutyraldehyde, aqueous ammonia salt and catalyst, respectively. dosing both formaldehyde and isobutyraldehyde in a reactor containing aqueous solution of an ammonia compound and catalyst. On the other hand, a mixture of formaldehyde and ammonia salt should be avoided in the absence of isobutyraldehyde, since a side reaction is developed in which methylamine is formed and the formed methylamine can react further with formaldehyde and isobutyraldehyde to form different by-products. . The process can also be carried out in a continuous manner. Then all reactants and the catalyst are continuously introduced into the reaction zone consisting of one or more reactors. You can use both tank and pipe reactors. The latter form of reactor is particularly favorable when all reactants are in liquid phase, e.g. formaldehyde as formalin and ammonium chloride dissolved in water. The condensation reaction may proceed in the absence or presence of catalysts.

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It is significantly accelerated under the catalytic effect of organic and inorganic acids, various types of salts, Lewis acids and acidic ion exchangers.

Among the inorganic acids, hydrochloric acid and hydrobromic acid are particularly suitable. Sulfuric acid and phosphoric acid may also be used, but they may cause some discoloration of the final product. Among the organic acids, aliphatic and aromatic sulfonic acids are particularly active. In the Lewis Syracuse group, zinc dichloride which shows a very high catalytic capacity. In the ion exchange group there is the highest catalytic activity of macroporous polymers containing free sulfone groups.

At the first stage, the condensation process is very intensive and there is no catalyst needed. Over time, however, the reaction rate decreases and then it is favorable or necessary to introduce the catalyst. If a sufficiently efficient cooling device is available, you can, with a certain time gain, introduce the catalyst at the beginning of the process.

The necessary measures to achieve the intended effect are thus, firstly, an intimate contact between the two and the other. three phases, so intense stirring is necessary. A proper molar relationship between the reactants is also very important, referring to patent claim 3 and the discussion on the first page of the patent, which is why Jacobsson has failed in his experiment. Other important factors are the right temperature with the optimum between 60 and 90 ° and the right dosage method to avoid the formation of by-products, as well as the right vai and the right amount of catalyst. Interaction between the above five conditions is crucial for the process's exchange and selectivity, which the applicant with this invention has succeeded with.

Preparation of pp (2,2-dimethyl-5-hydroxyhydroethylamine) To reduce the formed dialdehyde to the corresponding diol (see reaction similarity), various types of reducing agents such as hydrogen, lower aldehydes, hydrides, alcoholates, amalgam can be used. Undoubtedly, it is the catalytic hydrogenation of hydrogen gas that is most important from the economic point of view. Depending on the activity of the catalyst, the temperature can vary between room temperature and 150 ° C, since the pressure can vary between 101.3 kPa and 35.4 MPa (1 and 350 at). The technically optimal conditions are in a pressure range between 304 kPa and 7 MPa (3 and 70 at) and a temperature range between 40 and 70 ° C. The latter pressure and temperature conditions can be used of a nickel catalyst either in the form of Raney nickel or in the form of metallic nickel on a support. It is also possible to use different types of platinum metals, but then one must choose the catalyst type very carefully, since many of them show a strong degradation ability. The same applies to chromite and some cobalt catalysts. At all times, the use of BIS in the form of salts gives significantly better yield of DIOL than the use of the free aminoaldehyde. The reduction is very easy in the presence of sodium borohydride. The reaction rate is high and the yield satisfactory. The reduction process can proceed both continuously and continuously.

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The formed amino diol can be used directly e.g. for the preparation of surfactants by neutralization with higher fatty and sulfonic acids. as a corrosion inhibitor. It can also be further refined by esterification, etherification, polycondensation, etc.

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Preparation of bis (2,2-dimethyldropionic acid) amine BIS can be transferred into the corresponding carboxylic acid (BIA) using a large amount of oxidizing agent such as e.g. oxygen, ozone, various organic and inorganic peroxides, hypohalides, permanganate, chromate and dichromate, nitric acid and others. For economic reasons, nitric acid, hydrogen peroxide and oxygen (air) are particularly interesting. Of these three substances, the nitric acid is least favorable. because the oxidation product is usually contaminated by hard-separable nitrates and, above all, because of the danger of forming highly hazardous nitrosoamines. In use 9 82445 of oxygen gas, respectively. hydrogen peroxide if you get a product with fairly low levels of inorganic additives.

Oxidation with oxygen (possibly air) is most easily carried out in a vertical tube reactor 5 equipped with a cooling or cooling system. a heat jacket, a reflux condenser and a gas distribution device at the bottom. The oxidation can occur both at atmospheric pressure and under high pressure. For economic reasons, 2 MPa (20 at) is not exceeded. Both pure oxygen and air can be used. The oxidation process can also proceed in a tank reactor equipped with a stirrer 10 as well as a cooling and heating jacket. Oxygen under pressure is continuously introduced into the reactor. The oxidation can be carried out both in the presence and absence of catalyst. The use of catalysts significantly facilitates the oxidation process. A sufficient efficiency shows salts of polyvalent metals e.g. manganese and cobalt. The oxidation temperature is mainly dependent on the pressure of the oxygen and the amount and type of the catalyst. It can vary within a range between 60 and 120 ° C. Some pollutants can greatly inhibit the process. The dialdehyde can be oxidized either in free form or in the form of the salt, e.g. hydrochloride. The last alternative is simpler because salts are very easily soluble in water.

In addition, at the condensation step (see similarity), the BIS aldehyde is obtained in the form of a site, so that it can be used directly for oxidation without any intermediate treatment. It should also be noted that the oxidation of the rA condensation product with oxygen or air runs slowly, especially at atmospheric pressure.

Also, when using hydrogen peroxide, it is more favorable to proceed from rA reaction mixture from the condensation process. DA produces a homogeneous aqueous solution that is not combustible and easy to handle. In contrast, the free amine is insoluble in water, requiring the use of organic solvents. The oxidation product is most easily separated by the production of water and recrystallization of the Ater residue. Oxidizing rA reaction mixture from the condensation step (similarity) gives ΒΙΑ in the form of amine salt while two carboxyl groups are free and can be further refined e.g. through esterification. The esterification proceeds readily in a homogeneous phase since the above compound is soluble in a variety of alcohols and polyols. Just as easily, BIAs amine salt can be converted into amides and their derivatives e.g. by reaction with anhydrides, respectively. chlorides of organic acids. By treating DIAs amine salt with strong alkalis e.g. NaOH can partially or completely neutralize the two free carboxyl groups. To reduce the amount of hydrogen peroxide, one can combine the two oxidation processes described. One can first oxidize the raw material with air and then terminate with hydrogen peroxide or introduce both oxidants at the same time. The oxidation process can be carried out both discontinuously and continuously.

10 Aminerine of BIS

The transfer of bis (2,2-dimethyl-3-oxopropyl) amine into the corresponding diamine can be effected by two different methods. The first is based on the transfer of BIS to the corresponding dioxime, leaving the dialdehyde real with hydroxylamine to form the corresponding oxime, which, under the influence of hydrogen in the catalyst's presence, is reduced to the corresponding amine.

CH3 nh2oh ch3 h2 ch3 H-N (CH2-C-CHO) 2 -> H-N (CH2-C-C-N-OH) 2 -> H-N- (CH2-C-CHNH2) 2 CH3 CH3 cat CH3

The reaction between dialdehyde and hydroxylamine proceeds rapidly and with almost quantitative yield. One can freely start from free amine or its salt. The hydrogenation to amine is accompanied by the formation of higher condensation products in the form of secondary amines. The formation of these by-products can be restricted by conducting the hydrogenation in the presence of ammonia. As the hydrogenation catalyst, nickel is used either in the form of Raney nickel or as a metal on a support. Also cobalt and precious metals are catalytically active. The hydrogenation temperature and pressure depend on the activity of the catalyst. You can make use of a print. which lies between 20 and 350 at, while optimum is between 50 and 150 at. The temperature can vary between 40 and 120 ° C.

The second method consists of only one step. DA introduces in a pressure reactor a solvent, a catalyst, BIS and ammonia, the latter in 82445 best in liquid form. While stirring, the hydrogen gas is pressurized and the reaction mixture heated. The same catalysts can be used as in the hydration of oximes. The reaction proceeds as follows: 5 H3 cat CH3 H-N (CH2-C-CHO) 2 + 2NH3 + 2H2 -> H-N (CH2-C-CH2NH2) 2 + 2H2O

I I

CH3 ch3 Hydrogen pressure can be within a range of 3-35 MPa (30-350 at), best between 7 and 15 MPa (70 and 150 at). Also in this process, by-products are formed in the form of secondary amines, but for the above-described application this is not disturbing. If instead of ammonia, a primary amine is used, then a secondary amine group is formed in position 3: CH3 cat CH3 I 3 I 3 HN (CH2-C-CH0) 2 + 2RNH2 + 2 H2 -> HN (CH2- C-CH 2 NH-R 2 + 2 H 2 O 3 Ch 3 Ch 3 The amination process can proceed both continuously and discontinuously.

Below we give a few examples which describe in detail the method invented by us, but of course these are not intended to limit the invention to the details thereof.

Example 1

Synthesis of bis (2,2-dimethyl-3-oxopropyl) lamin 30 without the use of catalyst (Z - - C - O)

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Into a 1-liter flask equipped with a stirrer, reflux condenser and contact thermometer for temperature control were introduced 67 g of ammonium chloride, 95 35 g of p-formaldehyde, 50 g of water and 220 g of isobutyraldehyde. The mixture was heated under intense stirring to the boiling point, i.e. 61 ° C. After heating for 10 minutes at boiling temperature, the condensation reaction became sufficiently intense that the reaction mixture was in a boiling state without any external heat addition. After about 15 minutes, it became necessary to switch on the heating device.

With continued heating, the turbid reaction mixture gradually became clearer in appearance and the temperature rose to 80 ° C. The heating was continued at this temperature and chromatographically controlled the course of the reaction. The heating was terminated when two consecutive chromatograms did not show any changes in the yield of the products. The reaction procedure is described below:

Heating reaction mixture to boiling point 20 min

Heating reaction mixture at boiling point 10 min

Autothermal process 15 min 15 Heating from 60 ° C to 80 ° C 90 min

Heating at 80 ° C 300 min

The end product was a viscous, yellowish, homogeneous liquid. It was clean enough to be used directly for further processing, e.g.

Oxidation, reduction, amination.

Experience shows that cleaning of the processing product is significantly easier than cleaning aminoaldehyde. We have not succeeded in recrystallizing the solid aminoaldehyde in the form of hydrochloride with a good yield, nor have we succeeded in separating the free aminoaldehyde by destination.

A method for separating and characterizing the substance obtained is described below.

30. Separation and characterization of amino aldehyde 100 g of the obtained reaction mixture was evaporated for 20 hours under 30 mm Hg vacuum with gradual increase in temperature to 70 ° C. A transparent, glassy, brittle substance was obtained, soluble in water and ethanol, insoluble in petroleum ether, and m.p. 107-110 ° C. 10 g of the glass-like substance was dissolved in 40 ml of water and the resulting solution was extracted 3 ginger, each ging with 25 ml of petroleum ether. The ether extract containing forging quantities of extracted organic neutral substances was discarded. Aqueous solution and 60 ml of diethyl ether were introduced into a flask and, with stirring and ice-cooling, a very 10% solution of NaOH was dosed to make the aqueous phase clearly alkaline. They contained the main amount of the aldehydoamine in the ether layer while the hydrophilic contaminants remained in the aqueous layer. Half of the ether layer was taken for analysis and the remainder was introduced into a flask while ice-cooling and stirring gently added 7% hydrochloric acid until the aqueous phase became clearly acidic. 1 and with the acidification, the amino aldehyde passed to the aqueous phase in the form of its hydrochloride, which is considerably more stable in the free aldehyde. The aqueous phase was evaporated and dried for 12 hours at 30 mm Hg, gradually increasing the temperature to 70 ° C. The final product was a white powder with sp 139-141 ° C.

The taken sample of the aminoaldehyde ether solution was dried over MgSO 4 and then evaporated under vacuum at room temperature. The evaporator iterate was a quadruple, viscous Welsh. Chromatographic analysis showed that the substance was pure and contained only smudges of brewing substance, probably solvent residues. IR and NMR spectrum of · aldehydoamine are attached (ANNEX 6 and ANNEX 7). Pi IR clearly shows a carbonyl peak at about 1720 and two characteristic aldehyde peaks at about 2720 and 2940. The peak 2810 characterizes the structure of the secondary frame 25 - CH 2 - NH - CH 2 - (see eg Sadtler "Handbook of Infrared Spectra").

Equally clear image of the structure gave NMR spectrum: δ (CDClj) 0,5 0.5 (S, 6H, CH,); 2.6 (S, 2H, CH 2) 9.4 (S, 1H, CHO) ppm

To more accurately characterize the aminoaldehyde synthesized by us, we determined melting points for a range of its derivatives: bis (2,2-dimethyl-3-oxopropyl) amine hydrochloride 139-141 ° C

oxime of bis (2,2-dimethyl-3-oxopropyl) amine 107-108 ° C

oxime of bis (2,2-dimethyl-3-oxopropyl) amine hydrochloride 208-210 ° C

2.4 dinitrophenyl hydrozone of

bis (2,2-dimethyl-3-oxopropyl) amine hydrochloride 197-198 ° C

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Elemental analysis of oxime hydrochloride gave the following results C: f 47.6% theory 47.8% H: f 8.75% theory 8.76% 0: f 12.9% theory 12.75% N: f 16.6 % Theor 16.7%

Further analytical data are provided in Examples 5 and 11.

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Example 2

Catalytic synthesis of bis (2,2-dimethyl-3-oxopropyl) amine hydrochloride from paraformaldehyde (Z - - C - O)

15 H

Due to the large oxidation propensity of the isobutyraldehyde, the entire process was carried out under nitrogen gas protection. Into a 1 liter flask equipped with a stirrer, efficient reflux condenser and contact temperature control for temperature control was introduced 67 g of anunonium chloride, 95 g of parafonnaldehyde, 50 g of water, 220 g of isobutyraldehyde and 1 ml of wife. hydrochloric acid. The mixture was heated under intense stirring. At about 60 ° C, an intense reaction began to take place. Despite switching off the heating, an intense reflux continued for about 30 minutes. As the intensity of the reaction decreased, the mixture was warmed slowly to 80 ° C. The initially cloudy reaction mixture became clearer over time. The heating at 80 ° C continued for about 2 hours so that the entire synthesis lasted about 4.5 hours (counted from the beginning of the intense reaction). The end product was a viscous, yellowish homogeneous liquid. The yield was 424 g.

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A sample of the reaction mixture was first dried in vacuo at room temperature. perature and later with a gradual rise in temperature to 60 ° C. A glassy brittle colorless Ather residue was obtained, which partially melts at about 56/60 ° C. By reaction with hydroxylamine, it can be transferred to an oxime having a melting point of 208-210 ° C.

n is 82445

Example 3

Hydration of bls (2,2-dimethyl-3-oxooropyl) amine hydrochloride to bis (2,2-dimethyl-3-hydroxypropyl) amine (Z - CH 2 OH) 500g of the reaction mixture was neutralized to a pH between 5 and 6 and introduced into a hydrogenation reactor. . Raney nickel (4 g) was added and the hydrogenation proceeded for 4 hours at 5 MPa (55 at) pressure and at a temperature between 70 and 75 ° C. After removal of the catalyst, a clear, greenish solution was obtained. The free bis (2,2-dimethyl-3-hydroxy-propyl) amine was separated by alkalization and extraction. The hydration yield was about 80%.

Example 4 15

Synthesis of bis (2,2-dimethyl-3-oxoorodyl) amine hydrochloride starting from formalin (Z - - C - 0)

hrs

In a 1 liter flask equipped with an effective stirrer, water cooler and ν '; thermometer introduced 53.5 g (1 mole) of ammonium chloride, 237.6 g (3.3 mole) of isobutyraldehyde, 267.6 g of a 37% solution of formaldehyde (3.3 mole), and 2 ml of concentrated hydrochloric acid. The mixture was heated with stirring. At about 62 ° C, intense cooking began to agitate. The reflux was continued for 5 hours and the temperature gradually increased to 76 ° C. The strongly cloudy solution became much clearer over time. The contents of the flask were cooled to room temperature. The entire synthesis was performed under the protection of nitrogen gas.

Example 5

Reduction of bis (2,2-dimethyl-3-oxopropyl) amine hydrochloride to bis (2,2-dimethyl-3-hydroxypropyl) amine (Z - CH 2 OH) In a 2.5 liter 3-neck flask equipped with an effective stirrer and in an ice bath 450 ml of methanol, 100 g of a 50% solution of sodium hydroxide and 34 g of sodium borohydride were introduced. Under protection of nitrogen gas and intense stirring, the pure condensation product was dosed at such a rate that the temperature of the coke did not exceed 20 ° C.

After completion of dosing, stirring was continued for 1 hour at 20 ° C temperature. To remove methanol, the reaction mixture was evaporated until it became almost solid and diluted with 500 ml of water. The resulting solution was stirred at 60 ° C until two layers formed. The upper organic layer was separated in a separatory funnel and the aqueous phase was extracted with ether. The ether extract was added to the organic phase.

The organic phase was first distilled without vacuum and then in vacuo. The main product was distilled as a fraction in 127 ... 130 ° C / 3 mmHg in the form of a viscous liquid which over time solidified to a white mass, melting at 32/34 ° C. The yield was 50%. The product's IR spectrum 15 is attached as Appendix 1 and its mass spectrum as Appendix 2.

Example 6

Alloying of bis (2,2-dimethyl-3-hydroxypropyl) amine (Z - CiL, - 0 - R) In a flask provided with a heating coil, stirrer, reflux condenser, dosing device and bottom tap, 58.8 g of bis ( 2,2-dimethyl-3-hydroxy-propyl) amine, 171 g of 50% sodium hydroxide, 7 g of tetrabutyl ammonium hydrogen sulfate (catalyst), 3 g of sodium iodide and 86 ml of toluene.

The mixture was heated to 60 ° C and 65.2 g of allyl chloride was introduced at this temperature for 2.5 hours. Stirring was continued for an additional 2 hours. Then, in very hot water, the whole sodium chloride precipitate was added to dissolve. The stirrer was stopped and the aqueous phase removed. The wash was repeated 3 ginger, each time with 70 ml of warm (60 ° C) water. The last portion of the wash phase showed a neutral pH. ·· All water portions were combined and the chloride content was determined. The conversion rate of allyl chloride was 80%.

The organic phase was dried over magnesium sulfate and roll evaporated under vacuum (final temperature 60 ° C). The residue was a moving yellowish 82445 vdtska. Its IR spectrum shows that both hydroxy groups have been enriched (Appendix 3).

Example 7 5

Is synthesized by bis-dimethyl-5-oxoprotein N-amine hydrobromide (Z - - C-O)

hrs

The condensation reacton described in Example 2. was repeated. The only difference was that an equivalent amount of ammonium bromide was used in the ammonium chloride broth and 1 ml of concentrated hydrobromic acid was used. The condensate solution process was similar to that of Example 2.

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Example 8

Was synthesized by blsf2,2-dimethyl-3-oxopropyl) amine hydrochloride using acidic solvent as catalyst (Z - - C - 0)

20 H

The condensation reaction was described as described in Example 2. The difference was that in the hydrochloric acid solution, 10 g of an acidic ion exchanger Levatit SC 10 was used as catalyst. The condensate solution process was similar to that of Example 2.

Example 9

Oxidation of bis (2,2-dimethyl-3-oxopropyl) amine hydrochloride to bis (2,2-dimethyl-propionic acid) amine hydrochloride (Z - - COOH)

The condensation reaction described in Example 2 was repeated, comprising 110 g of isobutyraldehyde, 47.5 g of paraformaldehyde, 33.5 g of ammonium chloride, 25 ml of water and 1 ml of wife. hydrochloric acid. 213.2 g of a clear viscous greenish solution were obtained. The solution was heated to 65 ° C and, at this temperature (+ 5 ° C), dosed with cooling for 1.5 hours 130 i 82445 g of 47% hydrogen peroxide. After dosing, stirring was continued for 3 hours at 70 ... 75 ° C. Thereafter, the residual amount of hydrogen peroxide was destroyed by adding a decomposition catalyst and the filtered solution. The reaction mixture was evaporated to give 187 g of a glass clear mass. This mass was recrystallized from 250 ml of isobutanol and 25 ml of toluene to give 160 g of a white precipitate consisting of a mixture of bis (2,2-dimethylpropionic acid) amine hydrochloride and its isobutyl ester. The object is to prepare isobutyl ester or a mixed ester, so the presence of ester substance in the recrystallization product is very favorable. Of course, instead of isobutanol, a number of other alcohols can be used.

Exempel._j, P

Preparation of Pure Bis (2,2-Dimethyl-Proplonic Acid) Amine Hydrochloride

Identical oxidation procedure as in Example 9, but to obtain a pure bis derivative free from esters, the crude oxidation product was recrystallized from a mixture of butanone and toluene (3: 1). DA obtained a snow-white powder which, when heated, shrinks at about 165 ° C and melts with partial decomposition at 175/177 ° C. The next recrystallization gives a product of melting point 188/190 ° C. The product's IR spectrum is attached as Appendix 4 and its mass spectrum as Appendix 5.

Example 11 Pre-step of bis 2,2-dimethyl-propionic acid amine hydrochloride with butanol (Z - C00R) As a reactor, a 250 ml 3-neck flask equipped with a Dean-Stark staircase for water separation plus a thermometer and a magnetic stirrer was used. Into the coke was added 120 ml of butanol and 25.3 g of bis (2,2-dimethylpropionic acid) amine hydrochloride recrystallized two times from ethyl methyl ketone-toluene mixture (3: 1) with the melting point at 192/194 ° C . The flask contained was heated to boiling temperature and then 2 ml of 37% hydrochloric acid was introduced.

: Separation of water in the stairs was started immediately. The synthesis proceeded for 8 hours. Every 2 hours, 2 ml of 37% HCl was added. During the separation process, 5.9 g of water was separated (water derived from the hydrochloric acid extraction). Theoretically, 3.6 g of H2 O should be formed, but when HCl reacts with butanol to form butyl chloride, water is also formed and in addition a certain amount of butanol is dissolved in the aqueous phase.

To remove the excess of butanol, the reaction product was evaporated in a vacuum evaporator at 70 ° C and 40 mm Hg. The residue was a yellow rather viscous liquid. This liquid was treated with ice-cooling and intensive stirring with 10% NaOH until the aqueous solution showed a clear alkaline reaction. In this way, the amine hydrochloride group was transferred into free amine. Then, 100 ml of ether was added and the whole mixture was poured into a separating funnel. The lower aqueous layer was separated. The upper organic layer was shaken 3 times with 25 ml of water and dried over 15 MgSOv. After drying and separation of desiccant, the ester was treated with 0.5 g of pale soil. The final product was 28.2 g of a viscous liquid. Chromatographic analysis showed that the product was about 95%. This means that the yield was 86%. Vacuum distillation (fraction 137-143 / 4 mm Hg) gave a clear, colorless product with a high degree of purity. The product 20 has a variety of uses as a polyester monomer and as a plastic stabilizer. After benzoylation of the amine group with benzoyl chloride, a full plasticizer for PVC plastics is obtained.

Example 12

Preparation of bis (2,2-dimethyl-3-tert-butylamine propane) amine. (Z - -CH 2 - NHR)

The reaction proceeds according to the following scheme: CH, NH (CH 2 -C-CH-O) j + 2H 2 N-C (CH 2) 3 -> 1 35:: CH 3

I I I

-> NH (CH2-C-CH-N-C (CH,),) 2 -> HN (CH2-C-CH2-NH-C-CH3) 2 * CH, CH, CH,

Schiffbas 5

The synthesis proceeds in an anhydrous environment and under nitrogen gas protection. 36.6 g of aminoaldehyde was separated from its hydrochloride, as described in Example 1, liberated from the rest of the water at 40 ° C under vacuum. The anhydrous amino aldehyde was dissolved in 150 ml of dry ether and the solution was introduced into a 1 liter 3 neck flask equipped with a magnetic stirrer. 90 g of tert-butylamine was added under magnetic stirring at such a rate that the temperature did not exceed 30 o. Then stirring was stopped and 100 g of mole sieve A3 was introduced into the coif. The reaction mixture was stored for two days at a temperature of 26-30 ° C. DA and dA were easily shaken the contents of the piston. Then the mole sieve was filtered off and the liquid organic phase was liberated under vacuum from ether. The resulting disk base was dissolved in 200 ml of dry methanol and placed in a 3-neck flask equipped with a stirrer and a thermometer. During cooling, 16.4 g of sodium borohydride were added portionwise to the coke at such a rate that the temperature was between 15 and 25 ° C. The dosing time was about 40 minutes. Stirring was continued for a further 30 minutes and finally the reaction mixture was heated to the boiling point for 20 minutes.

: When the flask contained calinate, the methanol was evaporated under vacuum and the solid residue was treated with 100 ml of water. The emulsion formed was transferred to a separatory funnel. To facilitate the separation, 80 ml of ether was added. The aqueous phase was shaken with an additional 50 ml of ether, both ether extracts were combined and dried over MgSO After removal of the desiccant and evaporation of the ether, the final product was obtained in the form of a water-clear rather viscous liquid. The yield was 37.7 g, purity 90%. A purer product is obtained by recrystallization of trihydrochloride. The recrystallized trihydrochloride melts under intense decomposition at 145-147 ° C. By gentle neutralization one can also A · fA a symmetrical dihydrochloride, which melts with degradation at 199-200 ° C. The structure of bis (2,2-dimethyl-3-tert-butylamine propane) amine has been demonstrated by NMR of both free amine and symmetric dihydrochloride. Corresponding diagrams form the annex to the patent application (Appendices 8 and 9).

Claims (8)

Compounds characterized in that they are bis (2,2-dimethyl-3-propyl functional group) amines of the general formula CH3 H - N (CH2 - C - Z) 2 ch3 10 wherein Z is an aldehyde group of the formula -CHO, or a carboxyl group of the formula -COOH, or an ester group of the formula -COOR, or an alcohol group of the formula -CH2-OH, or an amine group of the formula -CH2-NH2 or -CH2- NHR, or an ether group of the formula -CH2-OR, and R is a lower alkyl radical or a lower alkenyl radical. Process for the preparation of compounds according to Claim 1, characterized in that the isobutylaldehyde, formaldehyde and ammonia salt are reacted in such a way that the molar ratio is preferably between 1: 1.5: 1.5 and 1: 4: 4, the reaction being carried out as follows: that the reactants come into close contact with each other by vigorous stirring at 60-90 ° to form bis (2,2-dimethyl-3-oxopropyl) -25 amine, which can be reduced to bis (2,2-dimethyl-3-hydroxypropyl) amine if desired, or oxidize to bis (2,2-dimethyl-3-propionic acid) amine or aminate bis (2,2-dimethyl-3-aminopropyl) amine or bis (2,2-dimethyl-3-alkylaminopropyl) amine i. 30 Process according to Claim 2, characterized in that the formaldehyde is used in the form of paraformaldehyde or a solution. Process according to one of Claims 2 to 3, characterized in that the bis (2,2-dimethyl-3-oxopropyl) amine is oxidized to the bis (2,2-282445 dimethyl-3-propionic acid) amine in the form of the free amine or a salt thereof. using typical oxidizing agents. Process according to one of Claims 2 to 3, characterized in that the bis (2,2-dimethyl-3-oxopropyl) amine is reduced to bis (2,2-dimethyl-3-hydroxypropyl) amine in the form of the free amine or its salts using hydrogen gas. , hydrides and other conventional reducing agents. Process according to one of Claims 2 to 3, characterized in that the bis (2,2-dimethyl-3-oxopropyl) amine is aminated to bis (2,2-dimethyl-3-aminopropyl) amine or bis (2,2-dimethyl- 3-alkylaminopropyl) amine by the action of ammonia and hydrogen gas or alkylamine and hydrogen gas in the presence of a catalyst. 15 Process according to any one of Claims 2 to 3, characterized in that the bis (2,2-dimethyl-3-oxopropyl) amine is aminated to bis (2,2-dimethyl-3-aminopropyl) amine by converting said dialdehyde into the corresponding oxime and by carrying out this catalytic hydrogenation. Use of the compounds according to claim 1 as a monomer for the preparation of polycondensation monomers which can be made water-soluble, as surfactants by neutralizing the compounds with fatty acids or higher sulfonic acids, as corrosion inhibitors and the like. due to the presence of an amino group and two branched atomic chains.