DE1233411B - Process for the preparation of 3, 4-dihydropyranyl-2-methyl-amines - Google Patents
Process for the preparation of 3, 4-dihydropyranyl-2-methyl-aminesInfo
- Publication number
- DE1233411B DE1233411B DEF40843A DEF0040843A DE1233411B DE 1233411 B DE1233411 B DE 1233411B DE F40843 A DEF40843 A DE F40843A DE F0040843 A DEF0040843 A DE F0040843A DE 1233411 B DE1233411 B DE 1233411B
- Authority
- DE
- Germany
- Prior art keywords
- parts
- weight
- methyl
- dihydropyranyl
- hydrogen
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 19
- 238000005984 hydrogenation reaction Methods 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- NPWYTMFWRRIFLK-UHFFFAOYSA-N 3,4-dihydro-2h-pyran-2-carbaldehyde Chemical compound O=CC1CCC=CO1 NPWYTMFWRRIFLK-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- -1 formyl compound Chemical class 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 235000011118 potassium hydroxide Nutrition 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- WOXFMYVTSLAQMO-UHFFFAOYSA-N 2-Pyridinemethanamine Chemical compound NCC1=CC=CC=N1 WOXFMYVTSLAQMO-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 1
- JZFPYUNJRRFVQU-UHFFFAOYSA-N Niflumic acid Chemical compound OC(=O)C1=CC=CN=C1NC1=CC=CC(C(F)(F)F)=C1 JZFPYUNJRRFVQU-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003927 aminopyridines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 150000002084 enol ethers Chemical class 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical class ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 1
- 150000005002 naphthylamines Chemical class 0.000 description 1
- NYGCBQKDTGBHSC-UHFFFAOYSA-N oxan-2-ylmethanamine Chemical compound NCC1CCCCO1 NYGCBQKDTGBHSC-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D309/20—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hydrogen atoms and substituted hydrocarbon radicals directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/141—Amines; Quaternary ammonium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von 3 ,4-Dihydropyranyl-2-methyl-aminen Die Erfindung betrifft ein Verfahren zur Herstellung von 3,4-Dihydropyranyl-2-methyl-aminen der allgemeinen Formel in der R ein Wasserstoffatom, einen Alkyl- oder Alkenylrest, einen gegebenenfalls durch ein Halogenatom eine Alkyl- oder die Hydroxylgruppe substituierten Phenylrest oder den Naphthylrest sowie den Pyridyl- oder Methylpyridylrest bedeutet.Process for the preparation of 3,4-dihydropyranyl-2-methyl-amines The invention relates to a process for the preparation of 3,4-dihydropyranyl-2-methyl-amines of the general formula in which R denotes a hydrogen atom, an alkyl or alkenyl radical, a phenyl radical optionally substituted by a halogen atom, an alkyl or hydroxyl group, or the naphthyl radical and also the pyridyl or methylpyridyl radical.
Aus der USA.-Patentschrift 3 008 964 ist die Hydrierung von 2, 5-Dialkyl-2-formyl-3,4-dihydro-pyranen mit Ammoniak in Gegenwart von Wasserstoff und einem Hydrierkatalysator bekannt. Diese Hydrierung wird in zwei Stufen durchgeführt, wobei in einer ersten Stufe bei Temperaturen von 30 bis 1800C und einem Druck von etwa 4 bis 140 at die entsprechenden 2,5-Dialkyl-3,4-dihydropyranyl-2-methyl-amine erhalten werden und wobei in einer zweiten Stufe bei Temperaturen von 160 bis 250"C und einem Druck von etwa 140 bis 350 at die 3,4-Dihydropyranyl-2-methyl-amine zu den entsprechenden Tetrahydroverbindungen hydriert werden. Aus der USA.-Patentschrift 3 008 964 geht jedoch weiterhin hervor, daß bei der Reaktion von dimerem Acrolein mit Ammoniak in Gegenwart von Wasserstoff die Doppelbindungen des Pyranrings gesättigt werden, unter Bildung von Tetrahydropyranyl-2-methyl-amin. Man kann also nach der genannten Patentschrift 3,4-Dihydropyranyl-2-methyl-amine aus 2-Formyldihydropyranen und Ammoniak in Gegenwart von Wasserstoff nur dann herstellen, wenn ein Kohlenstoffatom an der Doppelbindung des Pyranrings substituiert ist, wenn also z.B. 2,5-Dialkyl-2-formyl-3,4-dihydropyrane wie etwa das durch Diels-Alder-Reaktion gebildete Dimere des os-Methacroleins verwendet wird. US Pat. No. 3,008,964 describes the hydrogenation of 2,5-dialkyl-2-formyl-3,4-dihydro-pyrans known with ammonia in the presence of hydrogen and a hydrogenation catalyst. This hydrogenation is carried out in two stages, with in a first stage at Temperatures of 30 to 1800C and a pressure of about 4 to 140 at the corresponding 2,5-Dialkyl-3,4-dihydropyranyl-2-methyl-amines are obtained and in one second stage at temperatures of 160 to 250 "C and a pressure of about 140 to 350 at the 3,4-dihydropyranyl-2-methyl-amines to the corresponding tetrahydro compounds be hydrogenated. However, US Pat. No. 3,008,964 also shows that that in the reaction of dimeric acrolein with ammonia in the presence of hydrogen the double bonds of the pyran ring are saturated, with the formation of tetrahydropyranyl-2-methyl-amine. So you can use the patent mentioned 3,4-dihydropyranyl-2-methyl-amine from 2-formyldihydropyrans and ammonia in the presence of hydrogen only produce when a carbon atom on the double bond of the pyran ring is substituted when e.g. 2,5-dialkyl-2-formyl-3,4-dihydropyrans such as the one produced by the Diels-Alder reaction formed dimers of the os-methacrolein is used.
Es sollte demnach nicht möglich sein, durch Reaktion von 2-Formyl-3,4-dihydropyran mit Aminen in Gegenwart von Wasserstoff und Hydrierkatalysatoren an der Doppelbindung des Pyranrings unsubstituierte 3,4-Dihydropyranyl-2-methyl-amine herzustellen.It should therefore not be possible by reacting 2-formyl-3,4-dihydropyran with amines in the presence of hydrogen and hydrogenation catalysts on the double bond of the pyran ring to produce unsubstituted 3,4-dihydropyranyl-2-methyl-amines.
Es wurde nun gefunden, daß man 3,4-Dihydropyranyl-2-methyl-amine dadurch erhält, daß man 2-Formyl-3,4-dihydropyran mit mindestens der äquivalenten Menge Ammoniak oder primärem Amin der allgemeinen Formel R - NH,, in der R einen Alkyl-oder Alkenylrest, einen gegebenenfalls durch ein Halogenatom, eine Alkyl- oder die Hydroxygruppe substi- tuierten Phenylrest oder den Nyphthylrest sowie den Pyridyl- oder Methylpyridylrest bedeutet, in Gegenwart von Wasserstoff und einem Hydrierkatalysator bei Temperaturen von 0 bis 150"C und einem Wasserstoffdruck von 5 bis 100 at, gegebenenfalls in Anwesenheit eines inerten organischen Lösungsmittels zu den Verbindungen der allgemeinen Formel in der R die oben angegebene Bedeutung besitzt oder ein Wasserstoffatom darstellt, umsetzt.It has now been found that 3,4-dihydropyranyl-2-methyl-amines are obtained by adding 2-formyl-3,4-dihydropyran with at least the equivalent amount of ammonia or primary amine of the general formula R - NH ,, in R denotes an alkyl or alkenyl radical, a phenyl radical, optionally substituted by a halogen atom, an alkyl or hydroxyl group, or the nyphthyl radical and the pyridyl or methylpyridyl radical, in the presence of hydrogen and a hydrogenation catalyst at temperatures from 0 to 150.degree and a hydrogen pressure of 5 to 100 atm, optionally in the presence of an inert organic solvent, to give the compounds of the general formula in which R has the meaning given above or represents a hydrogen atom.
Die in der USA.-Patentschrift 3 008 964 behauptete Unmöglichkeit dieser Reaktion erweist sich somit als ein technisches Vorurteil, das durch das erfindungsgemäße Verfahren überwunden wird. The impossibility claimed in U.S. Patent 3,008,964 This reaction thus proves to be a technical prejudice, which is caused by the inventive method is overcome.
Das erfindungsgemäße Verfahren wird im allgemeinen so durchgeführt, daß man das 2-Formyl-3,4-dihydropyran in einem inerten organischen Lösungsmittel löst, 0,1 bis 10 Gewichtsprozent eines Hydrierkatalysators zusetzt und das Gemisch zusammen mit einer äquivalenten Menge oder einem Überschuß eines entsprechenden primären Amins oder Ammoniak in einem Autoklav hydriert. Vor der Hydrierung wird der Autoklav auf die erforderliche Reaktionstemperatur gebracht. Nach der Aufnahme von 1 Mol Wasserstoff pro Mol der eingesetzten Formylverbindung ist die Hydrierung beendet. Das Reaktionsprodukt kann nach dem Abfiltrieren des Katalysators und Verdampfen des Lösungsmittels, gegebenenfalls im Vakuum, durch Rektifrkation bzw. durch Umkristallisation gereinigt werden. The process according to the invention is generally carried out in such a way that that the 2-formyl-3,4-dihydropyran in an inert organic solvent dissolves, 0.1 to 10 percent by weight of a hydrogenation catalyst is added and the mixture together with an equivalent amount or an excess of a corresponding one primary amine or ammonia hydrogenated in an autoclave. Before the hydrogenation is the autoclave is brought to the required reaction temperature. After the recording of 1 mole of hydrogen per mole of the formyl compound used is the hydrogenation completed. The reaction product can after filtering off the catalyst and evaporating of the solvent, optionally in vacuo, by rectification or by recrystallization getting cleaned.
Bei der Umsetzung mit Ammoniak wird das Ammoniak vorzugsweise in flüssiger Form in den Autoklav eingebracht. When reacting with ammonia, the ammonia is preferably in liquid form introduced into the autoclave.
Als primäre Amine lassen sich aliphatische Amine wie Methyl-, Butyl-, Cetylamin oder aromatische Amine wie Anilin, Toluidine, Naphthylamine, Chloraniline, Aminophenole und heterocyclische Amine wie Aminopyridine und Pyridylmethyl-amin verwenden. As primary amines, aliphatic amines such as methyl, butyl, Cetylamine or aromatic amines such as aniline, toluidines, naphthylamines, chloranilines, Aminophenols and heterocyclic amines such as aminopyridines and pyridylmethyl-amine use.
Als inerte organische Lösungsmittel sind z. B. As inert organic solvents are, for. B.
Methanol, Äthanol, Dioxan, Benzol und Tetrahydrofuran geeignet. Als Katalysatoren können die üblichen Hydrierkontakte, wie Raney-Nickel oder Raney-Kobalt, verwendet werden. Der Zusatz von Substanzen, die die Wirksamkeit der Hydrierkatalysatoren herabsetzen, wie Eisensulfat, kann von Vorteil sein.Methanol, ethanol, dioxane, benzene and tetrahydrofuran are suitable. as Catalysts can use the usual hydrogenation contacts, such as Raney nickel or Raney cobalt, be used. The addition of substances that affect the effectiveness of the hydrogenation catalysts Decrease, such as iron sulfate, can be beneficial.
Die erfindungsgemäß hergestellten Verbindungen sind technisch wertvolle Produkte. Sie sollen insbesondere als Korrosionsschutzmittel für Wasserkühler und als Zusätze zu Anstrichmitteln verwendet werden. The compounds prepared according to the invention are technically valuable Products. They are intended in particular as an anti-corrosion agent for water coolers and used as additives to paints.
Beispiel 1 112 Gewichtsteile 2-Formyl-3,4-dihydropyran werden zusammen mit 300 Gewichtsteilen n-Butylamin und 10 Gewichtsteilen Raney-Kobalt bei 60"C unter einem Wasserstoffdruck von 100 at hydriert. Nachdem das Reaktionsgemisch innerhalb von 100 Minuten je Mol des Dihydropyrans 1 Mol Wasserstoff aufgenommen hat, wird das Gemisch abgekühlt, der Katalysator abfiltriert und das überschüssige n-Butylamin abdestilliert. Durch anschließende Destillation des Rückstandes werden 80 Gewichtsteile 3,4-Dihydropyran-2-N-n-butylmethyl-aminvomlKp.l5 108 " C; n2no =1,4628 erhalten. Äquivalentgewicht: berechnet 169,3; gefunden 169. Example 1 112 parts by weight of 2-formyl-3,4-dihydropyran are combined with 300 parts by weight of n-butylamine and 10 parts by weight of Raney cobalt at 60 "C below hydrogenated under a hydrogen pressure of 100 at. After the reaction mixture within has absorbed 1 mole of hydrogen per mole of dihydropyran for 100 minutes, is the mixture is cooled, the catalyst is filtered off and the excess n-butylamine distilled off. Subsequent distillation of the residue gives 80 parts by weight 3,4-Dihydropyran-2-N-n-butylmethyl-amine obtained from I.B. 15 108 "C; n2no = 1.4628. Equivalent weight: calculated 169.3; found 169.
Beispiel 2 3,4-Dihydropyranyl-2-methyl-amin 112 Gewichtsteile dimeres Acrolein werden zusammen mit 10 Gewichtsteilen eines eisenhaltigen Raney-Kobalt-Katalysators, 100 Gewichtsteilen Tetrahydrofuran und 200 Volumteilen flüssigem Ammoniak bei 100"C und 100 at Wasserstoffdruck hydriert. Example 2 3,4-Dihydropyranyl-2-methyl-amine 112 parts by weight of dimeric Acrolein are used together with 10 parts by weight of an iron-containing Raney cobalt catalyst, 100 parts by weight of tetrahydrofuran and 200 parts by volume of liquid ammonia at 100 "C and hydrogenated at 100 at hydrogen pressure.
Nachdem die lebhafte Wasserstoffaufnahme nach 70 Minuten beendet ist, wird das Reaktionsgemisch abgekühlt und vom Katalysator befreit. Die zurückbleibende Lösung wird mit Kaliumhydroxid getrocknet und dann destilliert. Es werden 94 Gewichtsteile P-Dihydropyranyl -2-methyl- amin vom Kr.12 58 bis 59"C, n2D = 1,4791 erhalten. Der Gehalt an Tetrahydropyranylmethal-amin beträgt 0,7 O/o.After the lively hydrogen uptake has ended after 70 minutes, the reaction mixture is cooled and freed from the catalyst. The one left behind Solution is dried with potassium hydroxide and then distilled. It becomes 94 parts by weight P-dihydropyranyl -2-methyl-amine of Kr.12 58 to 59 "C, n2D = 1.4791. Der Tetrahydropyranylmethalamine content is 0.7%.
Beispiel 3 3,£Dihydropyranyl-2-N-methyl-methyl-amin Ein Autoklav aus rostfreiem Stahl wird mit 112 Gewichtsteilen dimerem Acrolein, 10 Gewichtsteilen eines eisenhaltigen Raney-Kobalt-Katalysators und 300 Volumteilen flüssigem Methylamin gefüllt. Unter Rühren wird der Autoklav auf 90"C erhitzt und wiederholt Wasserstoff bis zu einem Druck von 100 at eingepreßt, bis die aus dem Druckabfall berechnete Menge Wasserstoff 22400 Volumteile (bei Normalbedingungen) beträgt. Dann ist die Wasserstoffaufnahme beendet. Anschließend wird das Reaktionsgemisch abgekühlt und der Autoklav langsam entspannt. Der Katalysator wird abfiltriert, das zurückbleibende Gemisch getrocknet und destilliert. Es werden 89 Gewichtsteile 3,4-Di- hydropyranyl-2-N-methyl-methyl-amin vom Kr.13 65 bis 67"C Qz2no = 1,4683, Äquivalentgewicht gefunden 127, berechnet 127) neben 26 Gewichtsteilen Rückstand erhalten. Example 3 3, £ Dihydropyranyl-2-N-methyl-methyl-amine An autoclave stainless steel becomes 112 parts by weight of dimeric acrolein, 10 parts by weight an iron-containing Raney cobalt catalyst and 300 parts by volume of liquid methylamine filled. The autoclave is heated to 90 ° C. with stirring and hydrogen is repeated pressed in up to a pressure of 100 at, until the one calculated from the pressure drop Amount of hydrogen is 22400 parts by volume (under normal conditions). Then it is End of hydrogen uptake. The reaction mixture is then cooled and the autoclave slowly relaxes. The catalyst is filtered off, the remaining one Mixture dried and distilled. There are 89 parts by weight of 3,4-di- hydropyranyl-2-N-methyl-methyl-amine vom Kr.13 65 to 67 "C Qz2no = 1.4683, equivalent weight found 127, calculated 127) obtained in addition to 26 parts by weight of residue.
Beispiel 4 3,4-Dihydropyranyl-2-N-oleyl-methyl-amin 56 Gewichtsteile 3,4-Dihydro-2-formyl-2 werden in 200 Volumteilen Tetrahydrofuran und 135 Gewichtsteilen Oleylamin in Gegenwart von 10 Gewichtsteilen Raney-Kobalt bei 90"C und 100 at Wasserstoffdruck in einem Stahlautoklav so lange gerührt, bis das Reaktionsgemisch 11 200 Volumteile Wasserstoff aufgenommen hat. Dann wird die Lösung vom Katalysator befreit und im Vakuum eingedampft. Als Rückstand werden 179 Gewichtsteile eines Rohproduktes (n2D0 = 1,4770) erhalten. Das Infrarotspektrum zeigt die für Enoläther charakteristische Bande bei 1240 cm-und die der trans-Konfiguration bei 962 cm-l. Example 4 3,4-Dihydropyranyl-2-N-oleyl-methyl-amine 56 parts by weight 3,4-Dihydro-2-formyl-2 are in 200 parts by volume of tetrahydrofuran and 135 parts by weight Oleylamine in the presence of 10 parts by weight of Raney cobalt at 90 ° C. and 100 atmospheres hydrogen pressure Stirred in a steel autoclave until the reaction mixture is 11,200 parts by volume Has absorbed hydrogen. Then the solution is freed from the catalyst and im Evaporated in vacuo. 179 parts by weight of a crude product (n2D0 = 1.4770). The infrared spectrum shows the characteristic of enol ethers Band at 1240 cm-l and that of the trans configuration at 962 cm-l.
Das Rohprodukt enthält 800/o an 3,4-Dihydropyranyl-2-N-oleyl-methylamin . The crude product contains 800 / o of 3,4-dihydropyranyl-2-N-oleyl-methylamine .
Beispiel 5 3,4-Dihydropyranyl-2-N-dodecyl-methyl-amin Werden 56 Gewichtsteile 2-Formyl-3,4-dihydropyran mit 93 Gewichtsteilen Dodecylamin analog Beilpiel 4 umgesetzt, so erhält man durch Destillation des nach Abdampfen des Lösungsmittels zurückbleibenden Rückstandes 112 Gewichtsteile 3,4-Dihydropyranyl-2-N-dodecyl-methyl-amin vom Kp.0,08 140 bis 145"C. Example 5 3,4-Dihydropyranyl-2-N-dodecyl-methyl-amine becomes 56 parts by weight 2-Formyl-3,4-dihydropyran reacted with 93 parts by weight of dodecylamine analogously to Example 4, in this way, what remains after evaporation of the solvent is obtained by distillation 112 parts by weight of 3,4-dihydropyranyl-2-N-dodecyl-methyl-amine with a boiling point of 0.08 140 to 145 "C.
Molgewicht: berechnet281,5, gefunden (titrimetrisch) 283.Molecular weight: calculated 281.5, found (titrimetrically) 283.
Beispiel 6 3,4-Dihydropyranyl-2-N-phenyl-methyl-amin 56 Gewichtsteile dimeres Acrolein werden im Gemisch mit 100 Gewichtsteilen Tetrahydrofuran und 250 Gewichtsteilen Anilin in Gegenwart von 10 Gewichtsteilen Raney-Kobalt-Katalysator bei 100"C und 100 at Wasserstoffdruck hydriert, bis 11 200 Volumteile Wasserstoff aufgenommen sind. Dann wird der Katalysator abfiltriert, die zurückbleibende Lösung mit Kaliumhydroxyd getrocknet und destilliert. Es werden 70 g 3,4-Dihydropyranyl-2-N-phenyl-methylamin vom Kpoo 09 109"C (nD = 1,5710) erhalten. Das Infrarotspektrum zeigte die charakteristische Frequenz für Enoläther bei 1235 cm-l. Example 6 3,4-Dihydropyranyl-2-N-phenyl-methyl-amine 56 parts by weight dimeric acrolein are mixed with 100 parts by weight of tetrahydrofuran and 250 Parts by weight of aniline in the presence of 10 parts by weight of Raney cobalt catalyst Hydrogenated at 100 "C and 100 at hydrogen pressure, up to 11,200 parts by volume of hydrogen are included. Then the catalyst is filtered off, the remaining solution dried with potassium hydroxide and distilled. There are 70 g of 3,4-dihydropyranyl-2-N-phenyl-methylamine obtained from Kpoo 09 109 "C (nD = 1.5710). The infrared spectrum showed the characteristic Frequency for enol ethers at 1235 cm-l.
Beispiel 7 In einem stehenden Rührautoklav aus rostfreiem Stahl werden 15 Gewichtsteile eines Raney-Kobalt-Katalysators, 50 Volumteile Tetrahydrofuran und 5 Volumteile einer 0,5 molaren wäßrigen Ferrosulfatlösung vorgelegt. Dann werden 100 Volumteile flüssiges Ammoniak eingepreßt und darauf eine Lösung von 112 Gewichtsteilen dimerem Acrolein in 50 Volumteilen Tetrahydrofuran unter Rühren eingepumpt. Example 7 In a standing stainless steel stirred autoclave 15 parts by weight of a Raney cobalt catalyst, 50 parts by volume of tetrahydrofuran and 5 parts by volume of a 0.5 molar aqueous ferrous sulfate solution. Then will Injected 100 parts by volume of liquid ammonia and then a solution of 112 parts by weight dimeric acrolein in 50 parts by volume of tetrahydrofuran is pumped in with stirring.
Unter einem Wasserstoffdruck von 10 at wird der Autoklav auf 140°C erhitzt und bei dieser Temperatur, unter Ausnutzung des Intervalls 60 bis 80 atü Wasserstoffdruck, die Hydrierung durchgeführt. Nach 70 Minuten wird die Reduktion abgebrochen, das Reduktionsprodukt durch Filtration vom Katalysator befreit, dieses mit Ätzkali getrocknet und dann destilliert. Es werden 67 Gewichtsteile einer Fraktion vom Kp.20 61 bis 71"C, n2D0 = 1,4799 (Äquivalentgewicht durch Titration = 113), erhalten. Nach der Analyse mittels Gaschromatogramm besteht diese Fraktion zu 97,4 °/0 aus 3 ,4-Dihydropyranyl-2-methyl-amin.The autoclave is heated to 140 ° C. under a hydrogen pressure of 10 atm heated and at this temperature, using the interval 60 to 80 atm Hydrogen pressure, the hydrogenation carried out. After 70 minutes the reduction canceled, the reduction product freed from the catalyst by filtration, this dried with caustic potash and then distilled. There are 67 parts by weight of a fraction from bp 20 61 to 71 "C, n2D0 = 1.4799 (equivalent weight by titration = 113), obtain. After the analysis using Gas chromatogram consists of this 97.4% fraction from 3,4-dihydropyranyl-2-methyl-amine.
Beispiel 8 In einem stehenden Rührautoklav aus rostfreiem Stahl werden 15 Gewichtsteile Raney-Nickel, 50 Volumteile Tetrahydrofuran und 100 Volumteile flüssiges Ammoniak vorgelegt. Dann wird eine Lösung von 112 Gewichtsteilen dimerem Acrolein in 50 Volumteilen Tetrahydrofuran unter Rühren eingepumpt und unter einem Wasserstoffdruck von 10 Atmosphären auf 40"C erhitzt. Hierauf wird bei dieser Temperatur der Wasserstoffdruck auf 100 Atmosphären gebracht und in einem Druckintervall von 80 bis 100 Atmosphären hydriert. Nach 32 Stunden ist die Hydrierung beendet. Anschließend wird gemäß Beispiel 7 aufgearbeitet, wobei 36 Gewichtsteile einer Fraktion vom Kr.17 75 bis 82"C erhalten werden, deren Analyse mittels Gaschromatogramm einen Gehalt von 72,4 0/o 3,4-Dihydropyranyl-2-methyl-amin ergibt. Daneben erhält man noch eine Fraktion vom Kr.17 154 bis 160"C. Der Anteil an Tetrahydropyranylmethyl-amin beträgt unter 1ozon Beispiel 9 N-(3 ,4-Dihydropyranylmethyl)-oc-picolylamin 53,5 Gewichtsteile ol-Picolylamin und 56 Gewichtsteile dimeres Acrolein werden zusammen mit 300 Volumteilen Tetrahydrofuran in Gegenwart von 20 Gewichtsteilen eines eisenhaltigen Raney-Kobalt-Katalysators bei 90"C in einem Rührautoklav unter 100 at Wasserstoffdruck hydriert. Die Wasserstoffaufnahme ist nach 2,5 Stunden beendet. Das Reaktionsprodukt wird dann durch Filtration vom Katalysator befreit Hierauf mit Ätzkali getrocknet und destilliert. Es werden 24 Gewichtsteile N-(3,4-Dihydropyranyl-methyl)-o;-picolylamin vom Kp.0,2 105 bis 115"C erhalten. Example 8 In a standing stainless steel stirred autoclave 15 parts by weight of Raney nickel, 50 parts by volume of tetrahydrofuran and 100 parts by volume submitted liquid ammonia. Then a solution of 112 parts by weight of dimeric Acrolein in 50 parts by volume of tetrahydrofuran is pumped in with stirring and under a Hydrogen pressure of 10 atmospheres to 40 "C. This is followed by at this temperature the hydrogen pressure is brought to 100 atmospheres and in a pressure interval of Hydrogenated 80 to 100 atmospheres. The hydrogenation has ended after 32 hours. Afterward is worked up according to Example 7, with 36 parts by weight of a fraction from Kr.17 75 to 82 "C are obtained, the analysis of which by means of a gas chromatogram shows a content of 72.4% gives 3,4-dihydropyranyl-2-methyl-amine. You also get another one Fraction from Kr.17 154 to 160 "C. The proportion of tetrahydropyranylmethyl-amine is under 1ozon Example 9 N- (3,4-dihydropyranylmethyl) -oc-picolylamine 53.5 parts by weight ol-picolylamine and 56 parts by weight of dimeric acrolein are used along with 300 parts by volume Tetrahydrofuran in the presence of 20 parts by weight of an iron-containing Raney cobalt catalyst hydrogenated at 90 "C. in a stirred autoclave under 100 atm. hydrogen pressure. The hydrogen uptake is finished after 2.5 hours. The reaction product is then filtered off from the Catalyst freed Then dried with caustic potash and distilled. It will be 24 Parts by weight of N- (3,4-dihydropyranyl-methyl) -o; -picolylamine with a boiling point of 0.2 105 to 115 "C obtain.
Molgewicht: berechnet 204,3, gefunden (titrimetrisch) 207.Molecular weight: calculated 204.3, found (titrimetric) 207.
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