DE1445936B1 - Process for the preparation of mixtures containing 1,4-diazabicyclo [2.2.2] octanes - Google Patents

Description

1 2

It is already known, heterocyclic compound ammonia throughput of 0.59 g / cm ³ catalyst / fertilize the piperazine or diazabicyclo [2.2.2] hour. All of the octane type emerging from the reactor through the reaction of ethylenediamine, Gut was condensed in a flask, which is immersed in a diethylenetriamine, triethylenetetramine or N-amino dry ice acetone bath and with an ethyl piperazine with ammonia in the presence of 5 dry ice -Acetone cooler was connected. The ProMetall or acidic metal oxide catalyst was produced by distillation up to the temperature. The results obtained are, however, not entirely satisfactory for the N-aminoethylpiperazine (boiling point 222 ° C.) for a number of reasons. has gone into a passing fraction and a So, for example, those in connection with the residue fraction are broken down. The overriding Frakbisher used catalysts to achieve io tion was analyzed by vapor phase chromatography of a good cyclization required reaction, whereby the following results obtained conditions usually so sharp that also cleavage were:
and condensation reactions of the starting materials and ^. _m j _no äthvlr »iDerazin
of the desired reaction products are promoted conversion "... 83 percent by weight

It is also known that N-Aminoathylpiperazm by 15 pi _pe razine yield 40

KysXen ^ irTdef ^ ΤρΙίί ^ ΤΪDkzabt Triäthylenediamine yieldV "39

transferring cyclo [2.2.2] octane. The starting material example 2
however, it is not fully implemented, and the

The yields achieved are quite low. 20 In the middle of a cylindrical reaction vessel

The subject of the invention is now a with-higher made of corrosion-resistant steel were about 100 ml

Yields proceeding process for the production of aluminum phosphate catalyst on support equipment

of 1,4-diazabicyclo [2.2.2] octane of the general line attached. The room above the cataly- Λ

Formula _, sators served as a preheating section. N-hydroxyethyl- ^

CHR CHR ₂₅ 3-methylpiperazine was added to the weight

/ j related throughput rate of 0.35 / hour

Γ " ² CH ₂ -NI _unc j ammonia was added to the weight

\ ~, _up / -up related throughput rate of 0.1 / hour

^CHR CHR introduced _{at the} top of the reaction vessel,

wherein R is a hydrogen atom or an alkyl group having ³ ° ff ^at 400 ⁰ C and atmospheric pressure was maintained.

Represents 1 to 12 carbon atoms, containing The material emerging from the reaction vessel was

Mixtures by reacting piperazines which were distilled and after removal of the water

general formula ^one rich in 2-methyl-1,4-diazabicyclo [2.2.2] octane

CHR CHR fraction with a boiling range from 100 to about

/ \ 35 200 ⁰ C collected. Then it was on to the column

χ _ QH Qn ν NH II vacuum applied to remove the unreacted feed

^{2 2} \ / kung to remove. These factions were through

QHR CHR gas phase chromatography analyzed.

The following results were obtained:

wherein X represents a hydroxy or amino group, 40 _N fjvdroxväthvl

of catalysts in the gas phase with increased tem- 3-methylpiperazine

temperature, which is characterized in that conversion 100%

the reaction at a temperature of about 250. prey

to 550 ⁰ C in the presence of about 1 to 15 mol - Meth 1 14 diaz hi Λ

Ammonia / mole of starting material using 45 ' _cyc lo [2 ~ 2.2] octane. ".... 50 percent by weight *

of aluminum phosphate as a catalyst. 1 4 TT b 1 Γ2 2 21-

Examples of usable starting materials are '"' ⁰ ^ L>> J

N-Aminoäthylpiperazin, N-Hydroxyäthylpiperazin ..., '\ _

and mixtures thereof. ρ. low

The implementation is preferably at Atmo- 50 ^{y gg}

In the following examples 3 to 6, the transfer printing up to about 0.1 atmospheres was used with the reaction specified therein, which are used to achieve the best results in the conditions and otherwise as in example 2. Vapor phase are preferred. One can also give performed at; the conversion of the initial overpressure work, but this is with the practical 55 materials was also 100%. The yields of carrying out the process according to the invention are listed below,
not necessary. The reaction temperature is preferred. .
wise between about 270 and 550 ° C. Example 3

The invention is illustrated by the following examples: N-hydroxyethyl-3-ethylpiperazine;

explained in more detail. 60 reaction conditions: 400 ° C .; Throughput speed

Example 1 speed of loading 0.5 / hour and throughput

rate of ammonia 0.1 / hour.

N-Aminoäthylpiperazin was about 50 cm ^{3 of} aluminum phosphate with a sieve opening of 4.76 to Yields: weight percent 2.36 mm corresponding particle size (4 to 8 mesh) 65 2-ethyl-1,4-diazabicyclo [2.2.2] octane .. 50

reacted under the following conditions: 375 ° C, ethyl piperazine 2

1 atmosphere pressure, N-aminoethylpiperazine by 1,4-diazabicyclo [2.2.2] octane 2

rate of 1.15 g / cm ³ catalyst / hour and a residue 7

Example 4

Charge: N-hydroxyethyl-2,5-dimethylpiperazine; Reaction conditions: 380 ^° C., throughput rate of the charge 0.48 / hour and throughput rate of ammonia 0.03 / hour.

In addition, hydrogen was also used at a throughput rate of 3440 cm ³ / cm ³ catalyst per hour.

Yields: ".,

Weight percent

2,5-dimethyl-1,4-diazabicyclo [2,2,2] -

octane 29

Backlog 10

2,5-dimethylpiperazine 18

Example 5

Charge: N-hydroxyethyl-2,6-dimethylpiperazine; Reaction conditions: 388 ^° C. throughput rate of the charge 0.5 / hour and throughput rate of ammonia 0.1 / hour.

Yields: percent by weight

2,6-dimethyl-1,4-diazabicyclo [2,2,2] -

octane 19

2,6-dimethylpiperazine 15

Vinyl-3,5-dimethylpiperazine 3

Backlog 6

Example 6

Feed: N-hydroxyethylpiperazine; Reaction conditions: 400 ^° C., throughput rate of the charge 0.55 / hour and throughput rate of ammonia 0.1 / hour.

Yields:. Weight percent

1,4-diazabicyclo [2.2.2] octane 33

Piperazine 9

Backlog 17

Claims (1)

Claim: Process for the preparation of 1,4-diazabicycloF_2,2,2] octane the general formula CHR- CHR N-CH ₂ CH ₂ -NI CHR-CHR wherein R represents a hydrogen atom or an alkyl radical having 1 to 12 carbon atoms Mixtures by reacting piperazines of the general formula X —CH, -CH, -N CHR-CHR CHR- CHR NH wherein X represents a hydroxyl or amino group on catalysts in the gas phase at elevated temperature, characterized in that the reaction is carried out at a temperature of about 250 to 550 ⁰ C in the presence of about 1 to 15 mol of ammonia / mol of starting material using Performs aluminum phosphate as a catalyst.