DE896347C - Process for the production of N-substitution products of 2-aminobutadiene-1,3 - Google Patents
Process for the production of N-substitution products of 2-aminobutadiene-1,3Info
- Publication number
- DE896347C DE896347C DEB6483D DEB0006483D DE896347C DE 896347 C DE896347 C DE 896347C DE B6483 D DEB6483 D DE B6483D DE B0006483 D DEB0006483 D DE B0006483D DE 896347 C DE896347 C DE 896347C
- Authority
- DE
- Germany
- Prior art keywords
- aminobutadiene
- substitution products
- production
- aminobutyne
- phenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000006467 substitution reaction Methods 0.000 title claims description 6
- 238000000034 method Methods 0.000 title claims description 3
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims description 8
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- BLRXYTIIKIPJQL-UHFFFAOYSA-N dicarbide(1-) Chemical class [C-]#C BLRXYTIIKIPJQL-UHFFFAOYSA-N 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 150000003141 primary amines Chemical class 0.000 claims description 2
- 150000003335 secondary amines Chemical class 0.000 claims description 2
- 238000009835 boiling Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- BUNYBPVXEKRSGY-ONEGZZNKSA-N (1e)-buta-1,3-dien-1-amine Chemical compound N\C=C\C=C BUNYBPVXEKRSGY-ONEGZZNKSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- -1 aluminum hydroxide-iron hydroxide Chemical compound 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
Verfahren zur Herstellung von N-Substitutionserzeugnissen des 2-Aminobutadien-1, 3 Es wurde gefunden, daß man N-Substitutionserzeugnisse des 2-Aminobutadien-i, 3 erhält, wenn man die N-Substitutionserzeugnisse des 2-Aminobutin-3, die durch Umsetzen von Acetylen mit primären oder sekundären Aminen in Gegenwart von Acetyleniden der Schwermetalle der i. und 2. Gruppe des Periodischen Systems bei Temperaturen bis etwa no° zugänglich sind, in der Gasphase erhitzt.Process for the production of N-substitution products of 2-aminobutadiene-1, 3 It has been found that N-substitution products of 2-aminobutadiene-i, 3 obtained when the N-substitution products of 2-aminobutyne-3 are obtained by reaction of acetylene with primary or secondary amines in the presence of acetylenides of the Heavy metals of the i. and 2nd group of the periodic table at temperatures up to about no ° are accessible, heated in the gas phase.
Die Leichtigkeit, mit der die Umwandlung vor sich geht, ist je nach der Art der Substituenten in der Aminogruppe des Aminobutins verschieden. Dementsprechend sind auch die anzuwendenden Umsetzungsbedingungen verschieden. So genügt es beispielsweise zur Herstellung von N-Phenyl-2-aminobutadien-i, 3 oder dessen im Phenylkern substituierten Abkömmlingen, den Ausgangsstoff einige Zeit lang über seinen Siedepunkt (z. B. io bis 30° darüber) zu erhitzen, beispielsweise indem man ihn durch ein über den Siedepunkt erhitztes leeres Rohr leitet. Bei anderen Verbindungen sind höhere Temperaturen oder längere Verweilzeiten oder beides erforderlich. Die Erhitzungsdauer wird in jedem Fall so bemessen, daß einerseits zumindest ein Teil des Aminobutins in Aminobutadien umgewandelt wird, andererseits aber Zersetzungen der Ausgangs- und Endstoffe vermieden werden.The ease with which the conversion takes place is dependent on the nature of the substituents in the amino group of the aminobutine differs. Accordingly the applicable implementation conditions are also different. So it is enough, for example for the preparation of N-phenyl-2-aminobutadiene-i, 3 or its substituted in the phenyl nucleus Derivatives, the starting material for some time above its boiling point (e.g. io up to 30 ° above), for example by putting it through a boiling point heated empty pipe conducts. With other connections are higher temperatures or longer residence times or both are required. The heating time is in in each case so dimensioned that on the one hand at least part of the aminobutine in aminobutadiene is converted, but on the other hand, decomposition of the starting and end materials is avoided will.
Der Umsatz läßt sich wesentlich verbessern, wenn man das Erhitzen in Gegenwart von Katalysatoren ausführt. Als solche eignen sich großoberflächige Stoffe, wie Kieselgel, Bimsstein, oder auch Metalloxyde, z. B. Aluminiumoxyd. Dessen Wirkung kann durch Zusätze, beispielsweise von Eisen-, Titan-, Chrom-, Molybdän-, Wolfram-, Uran- und Vanadiumverbindungen, erhöht werden.The conversion can be improved significantly if the heating is used in the presence of catalysts executes. As such are suitable Large-surface substances, such as silica gel, pumice stone, or metal oxides, e.g. B. Aluminum oxide. Its effect can be increased by additives such as iron, titanium, Chromium, molybdenum, tungsten, uranium and vanadium compounds are increased.
Die Umsetzungstemperaturen liegen zweckmäßig zwischen etwa Zoo und 35o°. Bei einem Durchsatz von etwa 3o bis 8o g auf den Liter Umsetzungsraum betragen innerhalb dieser Temperaturgrenzen die Umsätze bei Verwendung von Katalysatoren 6o bis 9o °/o, ohne Katalysatoren weniger.The reaction temperatures are expediently between about zoo and 35o °. With a throughput of about 30 to 80 g per liter of conversion space within these temperature limits, the conversions when using catalysts 60 to 90 per cent, less without catalysts.
Die nach der Erfindung erhaltenen Erzeugnisse unterscheiden sich von den entsprechenden Aminobutinen durch verschiedene Siedepunkte, Dichten, Brechungsindizes und Molrefraktionen. Sie eignen sich als Ausgangsstoffe für weitere chemische Umsetzungen.The products obtained according to the invention differ from the corresponding aminobutines through different boiling points, densities, and refractive indices and molar refractions. They are suitable as starting materials for further chemical reactions.
Beispiel z Durch ein elektrisch beheiztes Rohr aus Porzellan von 75 cm Länge und 2,8 cm Durchmesser wird bei 25o bis 255° 2-Phenylaminobutin-3 über einen Katalysator geleitet, der durch Fällen von Aluminiumhydroxyd in Gegenwart von r °/o Eisenhydroxyd aus einer kolloidalen Aluminiumhydroxyd-Eisenhydroxyd-Lösung mittels Alkalihydroxyd, Auswaschen mit Wasser, Peptisieren durch sehr verdünnte Salpetersäure und Formen zu Körnern von q. bis 6 mm Größe hergestellt worden ist. Der Durchsatz beträgt 6o g 2-Phenylaminobutin-3 in der Stunde auf 11 Kontakt. Durch Kondensation der Dämpfe erhält man eine Flüssigkeit, aus der sich durch Vakuumdestillation in 7o bis 8o°/oiger Ausbeute das 2-Phenylaminobutadien-z; 3 als bei zo mm Drück bei 112 bis 1z5° siedende Flüssigkeit abtrennen läßt. über mit Eisenoxyd aktiviertes Aluminiumoxyd. Das erhaltene N-Methyl-N-phenyl-2-aminobutadien-z, 3 ist eine helle, nicht kristallisierende Flüssigkeit vom Siedebereich 25o bis 26o° bei 76o mm bzw. r2o bis z28° bei ro mm Druck.Example z Through an electrically heated pipe made of porcelain 75 cm long and 2.8 cm in diameter, 2-phenylaminobutyne-3 is passed at 25o to 255 ° over a catalyst which, by precipitating aluminum hydroxide in the presence of r% iron hydroxide from a colloidal aluminum hydroxide-iron hydroxide solution by means of alkali hydroxide, washing out with water, peptizing with very dilute nitric acid and shaping into grains of q. up to 6 mm in size. The throughput is 6o g of 2-Phenylaminobutin-3 hour to 1 1 contact. By condensing the vapors, a liquid is obtained from which, by vacuum distillation, the 2-phenylaminobutadiene-z is obtained in a yield of 70 to 80%; 3 than at zo mm pressure at 112 to 15 ° can separate boiling liquid. via aluminum oxide activated with iron oxide. The N-methyl-N-phenyl-2-aminobutadiene-z.3 obtained is a pale, non-crystallizing liquid with a boiling range of 25o to 26o ° at 76o mm or r2o to z28 ° at ro mm pressure.
In entsprechender Weise erhält man aus N-Äthyl-N-phenyl-2-aminobutin-3 bei 26o bis 27o° in einer Ausbeute von 7o bis So % das N-Äthyl-N-phenyl-2-aminobutadien-r, 3 (Kplo = 125 bis z35°).Similarly, N-ethyl-N-phenyl-2-aminobutyne-3 is obtained from N-ethyl-N-phenyl-2-aminobutyne-3 at 26o to 27o ° in a yield of 70 to 70 % = 125 to z35 °).
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB6483D DE896347C (en) | 1939-12-17 | 1939-12-17 | Process for the production of N-substitution products of 2-aminobutadiene-1,3 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB6483D DE896347C (en) | 1939-12-17 | 1939-12-17 | Process for the production of N-substitution products of 2-aminobutadiene-1,3 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE896347C true DE896347C (en) | 1953-11-12 |
Family
ID=6954668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB6483D Expired DE896347C (en) | 1939-12-17 | 1939-12-17 | Process for the production of N-substitution products of 2-aminobutadiene-1,3 |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE896347C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3359319A (en) * | 1965-05-07 | 1967-12-19 | Du Pont | 2-[bis(perfluoroalkyl) amino]-1, 3-butadienes and process of preparation |
-
1939
- 1939-12-17 DE DEB6483D patent/DE896347C/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3359319A (en) * | 1965-05-07 | 1967-12-19 | Du Pont | 2-[bis(perfluoroalkyl) amino]-1, 3-butadienes and process of preparation |
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