DE1593820A1 - Process for the production of diamines - Google Patents

Description

Troisdorf, the 13th Harz 1967

DYNAIiIIT NOBEL AXTIMGESFILLSCHAFT Troiadorf / Bez. Cologne

Process for the production of diamines (addendum to patent application D 49 966 IVb / 12 qu)

The main patent is a method for

Production of diamines of the general formula

OH ₃ R 'R "

H ₂ N- (CH ₂ ) -j -C-OH ₂ -OH-OH-NH ₂ , CH ₃

in which R ¹ and R "hydrogen, alkyl, cycloalkyl or aryl radicals" and R ¹ and R "can also form a common carbon-containing ring, which is characterized in that there are α, ß-unsaturated, carbonyl-containing nitriles of the general formula

OH ₃ R'R »

NC-OH ₂ -OH ₂

^r 1 ι

-0-OH = C-O = O,

OH ₃

in which R ¹ and R "as defined above, in the presence of at least a stoichiometric amount of ammonia, is hydrogenated by means of known per se hydrogenation catalysts with Y / on Hydrogen The hydrogenation is carried out at 50 -. 200 ⁰ C, ■ preferably at 70 to 130 ⁰ G, carried out.

In this process for the production of diamines from α, β-unsaturated nitriles containing carbonyl groups .be the hydrogenation of the 3 stages in one operation carried out, namely the hydrogenation of the carbon

0Q98S0 / 2O57 bad original,

double bond, the hydrogenation of the nitrile group to primary amino group and the aminating hydrogenation. the carbonyl group to the primary amino group. the Yields of the diamines prepared by this process are in the single-stage hydrogenation Range from 66 - 88 #. The manufactured as described Contains diamines, but by slemental analysis Impurities that are barely detectable, which are caused by rapid discoloration of the product make them uncomfortable when standing. In addition, the impurities it contains are for it that is responsible for the condensation of the diamines Polyamides only discolored with carboxylic acids or their derivatives are not sufficient for technical purposes high molecular weights can be produced. The removal of these impurities nqch known cleaning processes are extremely complex and lossy.

In a modification of this process, it has now surprisingly been found that the diamines are in greater yields and can be produced without the troublesome impurities that tend to discolour, whereby the The diamines either no longer contain impurities or only contain very small amounts, so that they are more suitable for making high molecular weight polyamides by using the method of making

the diamines according to the main patent (file number

D 49 966 IVb / l2 qu) by catalytic hydrogenation the α, β-unsaturated nitriles containing carbonyl groups is carried out in 2 stages in such a way that these are first carried out

^f '^ 009850/205 ^! j bad original.

_ 3 -

ir the 1st hydrogenation stage by hydrogenation in the absence of ammonia "at temperatures from -20 to" +70 ⁰ C in saturated, carbonyl-containing nitriles and then in the 2nd stage in the presence of at least a stoichiometric amount of ammonia at 50 - 20 ° C, preferably at 70-130 ° C, further hydrogenated to diamines.

The stepwise hydrogenation of the α, β-unsaturated, carbonyl group-containing nitriles is carried out according to the present invention in the manner that in the first reaction step the carbon double bond is first selectively hydrogenated with a noble metal catalyst in the absence of ammonia. Suitable Ecielmetall-Hydrter catalysts are those obtained by reducing the oxides. Metals, such as platinum or palladium, the metals applied to carrier substances, such as is.B. Palladium on calcium carbonate or barium sulfate to further Pt on carbon and the like. The first hydrogenation stage may proceed at temperatures from -20 to + 7O ⁰ C, preferably carried out between 0 and 4O ^e C, with no reduction of the carbonyl or nitrile group takes place . This selective hydrogenation of the carbon double bond does not require an excessively high hydrogen pressure. It can also be carried out without excess hydrogen pressure, but a pressure of up to about 50 atmospheres is preferred to achieve a high rate of hydrogenation. On a case-by-case basis, higher pressures may be used, but some

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BATH

are not required. As a solution or dilution medium can be those described in the main patent be used. The saturated carbonyl-containing nitriles are obtained in almost quantitative yield. To transfer the saturated, carbonyl-containing Nitriles in the diamines is the hydrogenation in the second reaction stage according to the information of the Main patent ......... (file number D 49 966 IVb / 12 qu) carried out in the presence of at least a stoichiometric amount of ammonia.

The 2-step process can be used just like the 1-step be carried out continuously, in which case it is expedient to use fixed hydrogenation catalysts be used"

The method according to the present invention will illustrated by the examples belowί

- 5 - " 009860 / 2ÖS7

"Example 1:

15 g of Pd on CaCO ₃ (Pd content 5 1 °) were filled under nitrogen in 1 liter of methanol into a 5 1 autoclave and "activated at room temperature with 10 atmospheric hydrogen at room temperature" for 10 minutes. After the addition of a solution of 1485 g of 5,5-dimethyl-7-cyanhepten-3-one-2 and 500 ml of CH ₃ OH, the autoclave was briefly flushed again with hydrogen and 40 atmospheres of hydrogen were injected with the stirrer stopped the pressure immediately to 10 atm, and the temperature rose to 25 ⁰ C. By pressing 7 / hydrogen 6 times up to. 40 atm, the loss of pressure caused by the hydrogen uptake was compensated. The temperature rose slowly to 4O ⁰ C. The hydrogenation was complete after 10 minutes. The excess hydrogen was slowly let off, and the contents of the autoclave were filtered off from the catalyst under nitrogen. Methanol is distilled off and the residue over a 30 cm. igreux column fractionated in vacuo. After a first run of 28 g at 112-114 ° C / 0.2 Torr, the bulk of 5,5-dimethyl-7-cyanheptanone- (2) boils uniformly at 114-115 ° C / £ Torr, yield: 1459 g (97 ^c / ° d. Th.).

C ₁₀ H ₁₇ KO (MoI-GeW. 167) Calc. C: 71.98 %, H: 10.17? I, N: 8.37? &,

O: 9.5ö? O, ■

n * ^r ': 1.4520 Found .0: 71.82 $, H: 1C, 15 ^, ff: 8.58 ^,

O: 9.71? B.

1459 g of 5,5-dimethyl ~ 7-cyanoheptanon- (2) vairden together with 1 About ethanol and 200 g of iickel-Eieselgur catalyst

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(Girdler G 49 A) is filled into an autoclave previously flushed with nitrogen and 600 ml of liquid ammonia are added from a dosing vessel. A hydrogen pressure of 80 atmospheres was applied and the mixture was heated with stirring. The V / asserstoffaufnahme set at 80 - 100 ^0C a very strong, the pressure loss must be compensated by continuous addition of hydrogen, the temperature of ■ even at 130 - 14O ⁰ C increase. The Y / ass only took off was over after 1 1/2 hours. After cooling, the catalyst was filtered off and washed out with alcohol. liach distilling off ammonia and solvent, the residue was fractionated over a 30 cm Vigreux column in vacuo. The yield of 4> .4-dimethyl-1,7-diaminooctane, bp. _15: 120-122 ⁰ C was 1361 g (90.5 # d Th..).

Based on the 5,5 ~ dimethyl-7-cyano-hepten-3-one-2 used, the yield of diamine was 88%. The thief remained colorless even after standing for several weeks. In the one-step process, the yield was maxier. 1 70 <f and the diamine was already colored yellow after 3 days.

i
Example 2:

165 g of 5 »5-DimHth.yl-7-cyano-hepten-3-one ~ 2, 500 ml ethanol and Y 2 g of platinum on carbon (5 wt, $ Pt) were placed in a stirred autoclave at 30 - 40 atm and 25 - 35 ⁰ C subjected to the action of hydrogen. The calculated amount was consumed after 2 hours. After removal

BADORiG- ⁵ NAL

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the ^ i ^ tin catalyst was further hydrogenated with the addition of 50 g GirdIer catalyst G 49 A after pressing * of 2 atmospheres FH, with a hydrogen pressure of 100 atmospheres. The Hvdriertemperatur "was 80 - 10O ⁰ C. The Wasserst off uptake was complete after one hour, liach Abkühlen- was filtered and the diamine after distilling off excess ammonia and alcohol over a 30 cm Vigreux column under vacuum fractionated to Die.Ausbeute. A , 4-Dimethy1-1,7-diaminooctane was 154.8 g (90.0 *; i.d.) The diamine remained colorless even after standing for several weeks.

The diamines listed in the table below were prepared in analogy to Example 1. A comparison of the yield and the behavior in the light shows the advantage of the two-stage hydrogenation process over the ¹ - *, one-step, en of the main patent. .

■> "■" "■" / '■' ■ ". ■; ■ '■' BAD ORIGINAL

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Tabellp;

Oiamine Hydrogenation
- method yield , $ 9 behavior .3 at the light still stains 4,4,6-Trim ^ thy1- single stage 67 , $ 5 after 3 VJI Days yellow colorless 1,7-α j ami no ο c tan two-stage .88 , 5-ic ti 5 Il still _ffe r « _rbt A , L ,> · -Tr? r ¹ e thy 1- single stage 70 , 0 ψ " " colorless 1,7-cn aniηononane two-stage 92 Il Il Dior-jn ptis dem K01 ". Ί £: 1 P? -. 1 ^{Ί <} OT S- VJl yellow pronuct ο, α- 8 io VJl still ■ ^ ows butyralcehyd single stage 87 ι io Il Il - i'ar) go u? id. "" ethyl-i so- two-stage 96, It 10 Il 19lD butvi ice ton ο io 10 still - »colors A , / -— ~ in ^t et ^> vl — 7— single stage 67, 9 io Il 3 ti yellow colorless phenyl-1,7- two-stage 89 5 ok It 3 dd still colored 4,4- ^T ) irr.ethyl-1,7- single stage 66 8 io Il Il colorless diaminol.ej tan two-stage
I. 85 Il Il

bad -am:

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Claims (1)

Pat ent s award Modification of the process for the production of diamines according to the main patent "...... (file number D 49 966 IVc / 12 qu). characterized in that the catalytic hydrogenation of the α, β-uns9that-te ^, carbonyl-ruopen-containing nitriles is carried out in 2 stages in such a way that these are first carried out in the 1st hydrogenation stage by hydrogenation in the absence of ammonia at temperatures from -20 to + 7O ⁰ O in saturated, carbonyl group-containing -; - ·? Nitriles converted and these then in the 2nd stage in the presence of an at least stoichiometric amount of ammonia at 50-20 ° C, preferably at ^{70-130 0} C, further hydrogenated to diamines. pat.-dept.
Dr Kni, / Frv '-. BAD OR! Gff> IÄL QQ9850 / 2067