DE203082C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

PATENT LETTERING

CLASS Uq. GROUP

in Paris.

Process for the preparation of amino alcohols.

Addendum to patent 199148 of March 7, 1905.

Patented in the German Empire on June 22, 1905. Longest duration: March 6, 1920.

The main patent 199148, class 12 q, concerns a method of preparing secondary and tertiary amino alcohols of the composition :

R ₁ - CO H

I ■

2

( R ₁ = alkyl or aryl or aralkyl; R _{2 the} same; J? G = alkyl; R _t = alkyl or hydrogen) by the action of primary or secondary aliphatic amines on ethylene oxides of the structure

CH ₂
/ \

Ri-C-O

(R ₁ = alkyl or aryl or aralkyl; R _{2 the} same).

In contrast, the present Veras concerns the representation of the primary amino alcohols

CH, -NH ₀

iv, - C - OH

R,

as well as bodies of composition

-OH

NH -C (~ 0H

35

40

(in both formulas means: .R ₁ = alkyl or aryl or aralkyl; R _{2 is the} same) by the action of ammonia on the same ethylene oxides as those used according to the method of the main patent 199148.

It has been found that ammonia reacts to ethylene oxides just like the primary or secondary aliphatic amines according to the main patent 199148, class 12 q. However, when ammonia is used, two bases are formed, one of which as a result the result is that ammonia acts on one molecule of ethylene oxide, while the other base is affected by the action of ammonia forms ethylene oxide on two molecules.

In this case, however, the secondary base is obtained in a larger amount, while only very much little primary base - even in the presence of a large excess of ammonia - arises. .

The technically valuable properties of the pri-

mary amino alcohols result from the patent 189481, cl. 12 q, which the representation the same end products, but using a different process, to the objects Has.

B is ρ i el i.
Representation of the aminodimethylisoamylcar-

binols

CH ₂ -NH ₂

C ₅ H ₁₁ -C- OH

CH _S

and iminobisdimethylisoamylcarbinol

NH

C H. Cf-O H

CH ₂ -c (~ OH

\ ci /

100 g methyl isoamylethylene oxide (Methäthenylisopentanoxyd)

CH ₉
/ \ "

C ₅ H ₁₁ - C - O

I.
CH ₃

are heated to 100 ° in a closed tube in a pressure vessel for 5 hours. The excess ammonia is driven off by boiling and the residue is treated with dilute hydrochloric acid. As soon as the liquid reacts acidic, a white body falls out. The precipitate is centrifuged out and washed out with water. A yield of 90 g is obtained. The body recrystallized from boiling water melts at 187 ^° ; the chlorine determination is 11.3 percent. For the body created by the action of ammonia on two molecules of ethylene oxide, 11.0 percent chlorine is calculated.
The finely powdered chlorine hydrate is crushed in a mortar together with caustic soda and then the mass is leached with ether. The essential solution is after being annealed with. Sodium sulfate has been dried, evaporated and the residue distilled in vacuo. The secondary base having a syrupy texture, distilled at 206-207 ⁰ mm under pressure 46 and solidifies after a short time into a solid mass. The primary base, which is formed in smaller quantities, is in the acidic mother liquor, from which the hydrochloride of the secondary base was precipitated. It is set free with caustic soda and extracted with ether. The body is obtained in an amount of 6g; it boils at 125 ⁰ under 68 mm pressure. Its hydrochloride is hygroscopic and easily soluble in water.

Example 2.

Aminodimethylethylcarbinol

CH ₂ -NH ₂

C ₂ H ₅ -C-OH

CH

and iminobisdimethylethylcarbinol

y C ₂ fi _s

CH ₂ -C (-OH / ^ CH ₃

NH

CH ₂ -C (-OH

The two bases are obtained at the same time when one uses methylethylethylene oxide (Metihäthenyläthanoxyd)

CH ₀

C ₂ H ₅ -CO

I.
CH

Allow excess ammonia to act.

The secondary base is formed almost exclusively, just like that in the previous example described is set in freedom, with the only difference that after the product of the action has been treated with dilute hydrochloric acid, the acidic solution is completely evaporated in vacuo. The syrupy residue is then washed with caustic soda treated to set the secondary base free. This also creates the primary base, but in a smaller amount. The mixture of the two bases is im Vacuum fractionated.

The main component, which consists of the secondary base, distills off at 145 to 147 ⁰ and 25 mm pressure.

The secondary base forms a hydrochloride which crystallizes in non-hygroscopic flakes, which are much less soluble in water than the hydrochloride are usually. The chlorohydrate melts at 144 ⁰ .

The. The primary base, in turn, forms a hygroscopic hydrochloride, which in leaflets crystallized, which melt at 85 °.

Example 3.
Aminodimethylphenyl carbide oil

CH ₂ -NH ₂

C ₆ H ₅ -C-OH

CH,

ίο and iminobisdimethylphenylcarbinol
CH-cCOH

NH

/ ^C 6 ^H i

CH ^ 'Ck-O H

These bodies are done in exactly the same way as in the previous example Effect of excess ammonia on methylphenylethylene oxide (Methäthenylpfhenoxyd)

CH

C ₆ H ₆ -CO

CH,

obtain.

The largest part of the product of the action consists of secondary base.

After the excess ammonia has evaporated, dilute hydrochloric acid is added, which brings the chlorohydrate of the secondary base almost completely to precipitate, after which the base from the chlorohydrate; precisely as indicated in Example 1, is isolated.

The secondary base boiling at 258 ⁰ and 40 mm pressure; Their chlorine hydrate, which is almost insoluble in water, is recrystallized from absolute alcohol, from which it crystallizes ^{in beautiful leaves that melt at 228 to 229 0.}

The primary base remains in the mother liquor from which the hydrochloride of the secondary base has been removed; it boils at 175 ⁰ and 40 mm pressure.

In a similar way, one can, for example, aminomethyl diethyl carbinol and iminobis diethyl methyl carbinol, Aminodimethylpropylcarbinol and iminobisdimethylpropylcarbinol, aminodimethylisobutylcarbinol and iminobisdimethylisobutylcarbinol, Represent aminodimethylbenzylcarbinol and iminobisdimethylbenzylcarbinol.

Claims (1)

Patent claim: Further development of the process protected by patent 199148, consisting in that one here for the purpose of representing amino alcohols of the composition CH-NH ₂
. 'I "
R, - C - OH and CH ₂ - C (- OH NH CH ₂ , R ₁ -OH (R ₁ = alkyl or aryl or aralkyl; R _{2 the} same) instead of the primary or secondary aliphatic amines ammonia on ethylene oxides of the structure CH ₂ / \
R ₁ -CO can act.