DE2038956A1 - Process for the preparation of nitrogen-containing derivatives of 1,12-dodecanedicarboxylic acid - Google Patents

Description

rY ΒΓ OiIiDICAIw UEIIIBD, Britannic House, Kobr Lan « - ₉ - ■ London ß» 0.2,

Process for the preparation of nitrogen-containing derivatives of !, IS-dodecanedicarboxylic acid. . ..

The present invention relates to the production of nitrogen-containing derivatives of alkane-alphatomega-dicarboxylic acids which the nitrogen is bound to the omega carbon atom let, and represents an improvement or modification of the process described in the German patent application P 16 43 6 * 0.1 and the Belgian patent specification 702 603 is described. The latter relate to a method of manufacture of derivatives of alkane-alpha, omega-dicaj? bonic acids with nitrogen bonded to the omega carbon atom and the process consists essentially in heating a compound the formula

³ O ⁰

where Σ and X »represent divalent aliphatic radicals, which can be the same or different. In particular, the preparation of ll-cyanundecanoic acid and / or decan ~ l, 10 ~ dicarbonimide by heating l, l'-peroydicyolohexylamine is described.

The invention relates to a process for the preparation of derivatives of l, 12 ~ dodecanedicarboxylic acid with am 12-carbon

109816/2269

atom-bound nitrogen and the process. in the form of liquid droplets in one under the absorption conditions
introduces inerbes gas, which at increased temperature xvoA b-jl a pressure in the range 3GO mm Hg bia 3 ata kept m rcU

"l ^f ~ Feroxydicyclohe: xylamine and process au ocinex · production are described in the German patent application 16 70 246.8 and in the Belgian patent 01 _{327- l f} l '~ Pej> oxydicyelohexylaiain is referred to below as peroxyamine.

The derivative of dodelcrm-l ^ ll'-dicarboxylic acid produced will depend on the reaction conditions. Higher temp and longer residence times favor the formation of ll-gycinim-decaiic acid, while lower temperatures nr-Λ küx-zeve 7c; .i: - sometimes the formation of decane-1,10-di.carbonimid bog'Ji. ^ run.

The gas in the welchea Plüssiglceitströpfchen einge.Cühr "t nev- · be the may be any gas which _unt;? He the Re isbedlngungen .lctior> inert int examples goeigneber Gi ^ e are nitrogen, steam and Verbrennungegas (. annulment by burning distillate ff),

The peroxyamine can by any iuaagoude Llelhoile
in the form of droplets of liquid. These droplets can essentially only consist of the leroxyamine, but they can also contain other substances;
that it is sprayed into the reactor in the liquid phase.

For example, the peroxyamine in the liquid phase can be transformed into a drip »by flowing the peroxyamine in the liquid phase through the action of an elevated temperature.

109816/2269 bad original

temperature maintained gas stream atomized. Atomization is in the same way as a fragrance spray obtained and suitable Nebulizers are known to those skilled in the art. But Kan can also generate the liquid droplets by using the peroxyamine in the liquid phase through suitable spray nozzles, without the need for a gas stream to be involved in atomization were. Other types of atomizers, e.g. örehnapf * atomizers, can also be used.

The feroxyamine in liquid phase, which turns into droplets may be in molten form or in the form of a solution in a solvent. Use is preferred of solutions of peroxyarain in cyclohexanone and in the process for the production of peroxyamine according to German Patent application P 16 70 246.8 and Belgian patent specification 701 327 fall the peroxyamine often in the form of a solution in cyclohexanone at. These solutions can be used with or without additional amounts Cyclohexanones carried out the process according to the invention will.

The implementation is at a pressure of $ 00 mm Hg to 3 ata executed. It is preferred to use atmospheric pressure or a pressure close to atmospheric pressure, e.g. 0.9 to 1.3 atmospheres.

The temperature at which the gas is maintained in the reactor can vary over a moderately wide range. So can temperatures can be used in the range 250 ° C - 1000 ° 0. The lower temperature limit is preferably 300 ° G, the upper one preferably 600 ° G. It should be noted that these temperature specifications concern the reaction zone and not the temperatures of a gas stream before it enters this zone.

103816/2269 BADORIQfNAL

The residence time of the peroxyainine in the reactor can vary over a moderately wide range. Examples of suitable times are those in the range 0.05 to ¹ } seconds. '

With a residence time of about 0.5 seconds, reaction temperatures "favor" above 360 ° C the formation of ll-qyanundecanoic acid, with a residence time of about 4 seconds II-cyanundecanoic acid is the main product at reagent temperatures above 300 ° G.

* The gas, which is inert under the reaction conditions, becomes the reaction zone preferably at such a speed supplied that the molar ratio of inert gas to the Peroxy-amine in the range 5 * 1 to 500 * 1 was

The reaction can be carried out in any suitable reaction system, but is preferably carried out in a nicely packed reactor which is essentially adiabatic, ie a reactor in which no significant amount of heat passes through the reactor walls from the interior of the reactor is transferred and which (5 has a low surface: volume ratio _f e.g. «less than 1 cm«

The use of thicknesses in the range of 300 mm Hg to 3 atmospheres and, in particular, the use of pressures close to atmospheric pressure allow a simplification of the construction of the reactor system and a strong reduction in the need for rags, etc., compared to working at pressures wn 0 , 1 to 300 mm Hg.

The invention will be explained in more detail with the aid of the following examples.

Ί LJ 8 1 6/2 2 6 9 ^ ⁰ ° ™ ^QINAL

Jenn in the examples stated that in a "2x3" reactor was worked, then the reactor used was finished from a 0.61 m (2 ft.) long stainless steel pipe with an outside diameter & r Υ.Φ * | 7 »ζ? cm (3 in.) and an inside diameter from 7 * 0 ciüMüie atomizing nozzle was in the upper Flange of the reactor housed. The reaction products became a condensation and condensation at the bottom of the reactor Game system deducted. A cross section of the reactor is made shown in the accompanying drawing * I

Two electrical © heating elements were outside around the reaction »- zone winding, to compensate for V / arine losses through the Jände. The!,! • Peroxydicyclohexylamine v / urde in the Inlet 1 inserted through a small filter on atomizing nozzle 2. Superheated steam introduced through inlet 3 caused atomization of the PeroxyamiBS and performed it the reaction zone * Sin side arm 4 was intended to go through what extra steam, if necessary, can be supplied could "The products were withdrawn through the outlet pipe · 5" Pockets 6, 7 and 8 were intended for the attachment of thermocouples.

The "2x2" reactor had an internal diameter of 4.4 cm and was also wrapped with two heating elements * In each other With regard to this, it ötimiiite with the "23c3" - "Boaktor.

example 1

4000 g of the crude reaction product, obtained according to German patent application P 16 7 ^Ü 246 # 8 or Belgian patent specification 701 327, containing 3560 g of peroxyain and 400 g of cyclohexanone, were over a period of 80 minutes

BATH

10U81S / 2269,

2 O; 8 9 5

with 5000 liters hour ben Bulb temperature steam at about 0 ° 0 ^ introduced / through an atomizing nozzle into a 2x2 ⁿ "-Reakfcor, which was maintained at 500 ° 0 and atmosphärischein pressure. Dia .Reaktionsprodukte were condensed and the two phases separated. The The organic phase contained, as was shown by gas chromatography analysis, 1804 g of II-cyanodecanoic acid · »284 g of caprolacbam and 756 β cyclohexanone. The aqueous phase contained a further 180 g of caprolaotam and 116 g of cyclohexanone.

Example 2

5CCO g of the crude peroxide containing 4172 g of peroxyaiain and 600 g of cyclohexanone, were over a period of 100 Minutes with 3300 liters / hour of superheated steam through a Atomizing nozzle inserted into a "2x2" reactor, which was kept at 500 ° C and atmospheric pressure, the reaction products were condensed and the two phases were separated «, The organic phase contained 2286 g ll-oyanundecanoic acid, M5 g of oaprolactam and 1023 6 cyclohexanone. The watery Phase contained a further 160 g of caprolactam and 99 g of cyclohexanone.

200 g of the crude peroxide containing 144 g Peroxyaiain, were {jtoar a period ron 16 minutes 1860 liters / hour in a Daiüpf ⁿ 5jt2 "-ßeaktor

· was introduced, which is held at 300 ° C and Atnospharendrüek The Realrbionsprodiikta were eier.tj condensate "and filtered to give 48 g of dodecane ~ l _t 10 dicarbonimidi yielded. The filtrate was with; Diethyl ether is preferred. The Kxbrakta were dried, the ether was distilled off and

109816 / 226ä ^BA D- ORIGINAL

91 × 2 g of residue remained, which contained 17.5 g of 11-cyanundecanoic acid and 7.7 g of dodecane l, 10-dicarboniraid contained.

Example 4

1200 g of the raw reaction egg product, originating from the process according to German patent application P 16 70 246.8 or * Belgian patent 701 527 * containing 9 * 2 g of peroxyamine and 152 β cyclohexanone, were used over a period of 24 minutes together with 1860 liters / hour of superheated steam through | introduced a nebulizer into a "2x2" reactor. By additional ■ [ '■ a Seitenana VAirden 4000 liters / hour exceeded ΐ; heated steam is introduced into the reactor. The reaction temperature was 500 ° 0, the residence time 0.18 seconds. The reaction products are condensed, the organic and aqueous phases are separated.

Example., Ty

400 g of crude peroxide in the form of a 312 g of reroxyaiain containing Oils were vaporized over a side space of 57 minutes with 1860 liters / hour of superheated steam by an atomizer introduced into a "2x2" reactor. An additional 6000 liters / otunde of superheated steam was introduced into the through the side arm Reactor introduced. The reaction temperature was 500 ° C, the time is 0.14 seconds. The reaction products were condenses »the organic and the aqueous phase separate The organic phase contained 156 g of 11-cyanundecanoic acid

BATH ORIGINAL

109816/2269

2 O Ί: 8 3 5

HOO g don raw peroxides containing VJI g Peroxymain were lünuten over a period of H ^ with I860 liters / Stun "de üuerhJt Estonians steam π by a Zeratihiber in a" 2x3 "," · Realttor introduced '' By ÖON ßuitoiiöPin Buoiitz3ioho were ^ 000 liter / hour iiborhi i ßßii steam fl 3η <1 <5X3]? Enktor Ginß (? ~ Fiüirt «Die Röalifcionntmrtparatijp Ijetniß 37 $ ° 0 _f die Vnrwoil» Knit 0.54 IJelsTmdien »Die l {ondßnßiei ^l tcn fil» wwrd trlort, where eich I ⁷ I, ^ β Dodolian «·!, lO-dlcarbonimid erßalxm, w \ ä the organioche and the wholesome phase of the S ¹ 13 were separated. The Orßandscho 3 ⁵ JiMSe released 31j 48 _% 7 β 13- Cyanundoltanic acid and 22.3 G 1) odol: an-3 ₁ 3O-dicarbonin3df.

Example 7

The same Keafctionsbedineungen as in Example ^l \ angowondet * Inoßoßniat were 21 lig raw Peroxydn _f © ntlial · tend 36.9 leg Peroxyamin, ü "over a Äedtrawm of '? _F? Introduced three hours," Hur 8 g tar were after this ryro3yr? e found in the reactor.

JBAD OHJQINAL

Claims (12)

Claims Process for the preparation of derivatives of 1,12-dodecanedicarboxylic acid with nitrogen bound to the 12-carbon atom, characterized in that one!, l'-Peroxydicyclohesylamine introduced in the form of liquid droplets into a gas which is inert under the reaction conditions, which is maintained at an elevated temperature and at a pressure in the range of 300 mm Hg to 3 ata. 2. The method according to claim I _1, characterized in that the derivative of 1,12-dodecanedicarboxylic acid is heard in a nichtgepaeliten, essentially adiabatic Heakbor. 3. Method according to claim 1, characterized in that 11-Oyanundecanoic acid the derivative of 1,12-dodecanedicarboxylic acid produced is· 4. The method according to claim 1 _9, characterized in that decane-l, 10-dicarbonimide is the derivative of 1,12-dodecanedicarboxylic acid produced. 5. The method according to any one of the preceding claims, characterized characterized in that the gas into which the liquid droplets of l, l'-peroxydicyclöheatylamine are introduced from nitrogen, steam or combustion gas or mixtures thereof. 6. The method according to any one of the preceding claims, characterized in that the liquid droplets of I, l'-Pero3qjrdicyclohe3 £ 3rlamin from geochiaolaenem Ι, Ι'-Ρθγ-oxydicyclohexylamine exist. 109816 / 226'tr 7. Process according to one of Claims 1-5, characterized in that the liquid droplets of l, l '~ peroxydieyelohesylamine, which are introduced into an inert gas, consist of a solution of!, IVPerox ^ dlcyclohesylamine in a solvent * 8. The method according to claim 7, characterized in that Cyclohcacanone is the solvent. Process according to one of the preceding claims, characterized in that the temperature of the inert gas into which the liquid droplets of i, l ^f -peroxydicyclokexylaiain are introduced is in the range from 250 ° G to 1000 ° C. 10. The method according to claim 9 _S, characterized in that the temperature of the inert Gasee in the range. 300 ° 0 to 600 ° C. 11. The method according to any one of the preceding claims, characterized in that the residence time of l, l '~ peroxydicyelohexylamine in the header in area C, 05 to 5 seconds lies. 12. The method according to any one of the preceding claims, characterized in that the reactants in the Reakbor at a pressure in the range of 300 mm Hg to 3 ata be halved » 15 * The method of any preceding claim, characterized in that the llol-Verhälfcnlß dee inert gas sub-l.l' Peroxjdicyclohexylamin in Heaktor in the range 5tl to 500 * 1 is in accordance. 109ÖIÖ / 2269 EAD 2038356 Decay according to one of the standards 2 to 131, characterized in that the Eeakfcor has a surface / volume ratio of less than 1 cm "" β 1098 13/2269 Blank page