DE1795325C3 - 3,3-dialkyl-tetrahydroquinoxaline and a process for their preparation - Google Patents

3,3-dialkyl-tetrahydroquinoxaline and a process for their preparation

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Publication number
DE1795325C3
DE1795325C3 DE19681795325 DE1795325A DE1795325C3 DE 1795325 C3 DE1795325 C3 DE 1795325C3 DE 19681795325 DE19681795325 DE 19681795325 DE 1795325 A DE1795325 A DE 1795325A DE 1795325 C3 DE1795325 C3 DE 1795325C3
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Germany
Prior art keywords
dimethyl
methyl
dialkyl
tetrahydroquinoxaline
hydrogen
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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
Application number
DE19681795325
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German (de)
Other versions
DE1795325B2 (en
DE1795325A1 (en
Inventor
Roland Dr. 4047 Dormagen Nast
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Bayer AG
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Bayer AG
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Priority to DE19681795325 priority Critical patent/DE1795325C3/en
Priority to ES371364A priority patent/ES371364A1/en
Priority to US856796A priority patent/US3661905A/en
Priority to CS6200A priority patent/CS161093B2/cs
Priority to FR6931088A priority patent/FR2018055A1/fr
Priority to BR21242169A priority patent/BR6912421D0/en
Priority to NL6913937.A priority patent/NL156694B/en
Priority to GB41353/69A priority patent/GB1285060A/en
Publication of DE1795325A1 publication Critical patent/DE1795325A1/en
Publication of DE1795325B2 publication Critical patent/DE1795325B2/en
Application granted granted Critical
Publication of DE1795325C3 publication Critical patent/DE1795325C3/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C07D241/40—Benzopyrazines
    • C07D241/42—Benzopyrazines with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/50—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with hetero atoms directly attached to ring nitrogen atoms
    • C07D241/52—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3462—Six-membered rings
    • C08K5/3465—Six-membered rings condensed with carbocyclic rings

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Description

in derin the

Ri für Wasserstoff oder einen gegebenenfalls substituierten Alkylrest, einen Methoxy- oder Äthoxy-rest, R2 und Rj für Wasserstoff oder Alkylreste, Ri für einen Alkyl- oder Cycloalkylrest, wobei R 3 und R4 gegebenenfalls ringförmig miteinander verbunden sein können und wobei dieser Ring ein weiteres Heteroatom wie N, S oder O enthalten kann und worin R5 und Rb für Alkylreste stehen, wobei R5 und Rb miteinander zu einem carbocyclischen Ring verbunden sein können, der gegebenenfalls noch Methylgruppen tragen und der noch eine Doppelbindung enthalten kann, bei —20 bis 40° C hydriert und anschließend bei 60 bis 200° C durch weitere Hydrierung den Aminrest reduktiv auspaltet. Ri for hydrogen or an optionally substituted alkyl radical, a methoxy or ethoxy radical, R2 and Rj for hydrogen or alkyl radicals, Ri for an alkyl or cycloalkyl radical, where R 3 and R4 can optionally be connected to one another in a ring and this ring is another may contain heteroatom such as N, S or O, and wherein R 5 and Rb are alkyl groups, it being possible for R 5 and R b together to form a carbocyclic ring connected, which optionally bear methyl groups and which can contain a double bond, at -20 to Hydrogenated 40 ° C and then at 60 to 200 ° C by further hydrogenation reductively cleaving the amine residue.

2. Verfahren nach Anspruch I, dadurch gekennzeichnet, daß man die erste Hydrierung bei - 10 bis 300C und die reduktive Aminabspaltung bei Temperaturen von 70 bis 1500C durchführt.2. The method according to claim I, characterized in that the first hydrogenation at -10 to 30 0 C and the reductive amine cleavage at temperatures of 70 to 150 0 C is carried out.

3. 3,3-Dialkyl-tetrahydro-chinoxaline der allgemeinen Formel3. 3,3-Dialkyl-tetrahydroquinoxaline of the general formula

Ri-Ri-

in derin the

Ri' Wusserstoff, eine Ci -CirAlkylgruppc, die gegebenenfalls durch Ci -Cj-Alkoxyreste oder Halogen substiluieit ist oder Ci — Cj-Alkoxyrcste, R2' Wasserstoff oder Ci -CYAIkylrcstc, R^' und R6' jeweils Methylgruppen oder miteinander einen carbocyclischen 6-Ring bilden, der gegebenenfalls durch eine Methylgruppe substituiert ist, darstellen.Ri 'Wussstoff, a Ci -CirAlkylgruppc, which is optionally substiluieit by Ci -Cj -alkoxy radicals or halogen or Ci - Cj-Alkoxyrcste, R 2 ' hydrogen or Ci -CYAIkylrcstc, R ^ 'and R 6 ' each methyl groups or each other a carbocyclic Form 6-ring, which is optionally substituted by a methyl group.

Es wurde gefunden, daß man gegebenenfalls substituierte 3,3-Dialkyl-tetrahydro-chinoxaline erhält, wenn man gegebenenfalls substituierte 2-Alkylaniino-3,3-dialkyl-di-hydro-chinoxalin-di-N-oxide zuerst bei -20 bis 40°C hydriert und anschließend bei 60 bis 200"C durchIt has been found that optionally substituted 3,3-dialkyl-tetrahydroquinoxalines are obtained if optionally substituted 2-alkylaniino-3,3-dialkyl-di-hydro-quinoxaline-di-N-oxides first hydrogenated at -20 to 40 ° C and then at 60 to 200 "C through

(I)(I)

R1.
R. .»R 1 .
R. "

112/kai.11 2 / kai.

weitere Hydrierung den Aminrest reduktiv abspaltet. Es bilden sich die sonst nicht oder nur sehr schwierig zugänglichen 3,3-Dialkyl-tetrahydro-chinoxaline.further hydrogenation eliminates the amine radical reductively. Otherwise they do not develop, or only with great difficulty accessible 3,3-dialkyl-tetrahydroquinoxaline.

Das Formclbild soll den Rcaktionsablauf veranschaulichen: The form picture should illustrate the reaction process:

NIlNile

NlI7XNlI 7 X

(2)(2)

R,R,

R,R,

R4R4

f- NII + 2H2Of- NII + 2H 2 O

R.IR.I

In den obigen Formeln steht Ri für Wasserstoff oder einen gegebenenfalls substituierten Alkylrest oder einen Methoxy oder Äthoxyrest, R2 und R) für Wasserstoff oder Alkylreste, R1 für Alkyl- oder Cycloalkyirestc, wobei Rj und R4 gegebenenfalls ringförmig miteinander verbunden sein können und wobei dieser Ring einIn the above formulas, Ri stands for hydrogen or an optionally substituted alkyl radical or a methoxy or ethoxy radical, R 2 and R) for hydrogen or alkyl radicals, R 1 for alkyl or cycloalkyl radicals, where Rj and R4 can optionally be connected to one another in a ring and this Ring a

weiteres Heteroatom wie N, S oder O enthalten kann und worin R5 und Ra für einen Alkylrest stehen, wobei R5 und Rb miteinander zu einem carbocyclischen Ring verbunden sein können, der gegebenenfalls noch Methylgruppen tragen kann, der im Ausgangsmaterial noch eine Doppelbindung enthalten kann. Die Reste Rj und R4 können z.B. 1 bis 12 C-Atome enthalten, während es sich bei dem Rest R2 vorzugsweise um einen niederen Alkylrest mit bis zu 4 C-Atomen handelt.may contain further heteroatom such as N, S or O and in which R5 and Ra stand for an alkyl radical, where R5 and Rb can be connected to one another to form a carbocyclic ring which can optionally also carry methyl groups which can also contain a double bond in the starting material. The radicals Rj and R4 can contain, for example, 1 to 12 carbon atoms, while the radical R 2 is preferably a lower alkyl radical with up to 4 carbon atoms.

Der Rest Ri kann sich in der 6- oder 7-Ste!lung befinden. Dieser Alkylrest kann z. B. 1 bis 12 C-Atome enthalten und durch weitere Reste substituiert sein, z. B. durch niedere Alkoxyreste, wie Methoxy-, Äthoxy oder Propoxyreste oder Halogen, wie Chlor. Die Reduktion kann in üblicher Weise in Lösungsmitteln wie Alkoholen und Äthern, insbesondere Methanol und Tetrahydrofuran durchgeführt werden.The rest of Ri can be in the 6- or 7-position. This alkyl radical can, for. B. 1 to 12 carbon atoms contain and be substituted by other radicals, e.g. B. by lower alkoxy such as methoxy, ethoxy or Propoxy radicals or halogen, such as chlorine. The reduction can be carried out in a customary manner in solvents such as alcohols and ethers, in particular methanol and tetrahydrofuran, can be carried out.

Gegenstand der Erfindung ist daher ein Verfahrtn zur Herstellung der genannten 3,3-Dialkyl-tetrahydrochinoxaline der vorstehenden allgemeinen Formel (2), das dadurch gekennzeichnet ist, daß man 2-Alkylamino-3,3-dialkyl-dihydro-chinoxalin-di-N-oxide der vorstehenden allgemeinen Formel (1) bei -20 bis 40° C hydriert und anschließend bei 60 bis 2000C durch weitere Hydrierung den Aminrest reduktiv abspaltet.The invention therefore relates to a process for the preparation of said 3,3-dialkyl-tetrahydroquinoxalines of the above general formula (2), which is characterized in that 2-alkylamino-3,3-dialkyl-dihydro-quinoxaline-di-N oxides of the above general formula (1) is hydrogenated at -20 to 40 ° C, and then cleaving off at 60 to 200 0 C by further hydrogenation of the amine radical reductively.

In der ersten Reduktionsstufe wc.den die Sauerstoffatome der N-oxid-Gruppen bei vorzugsweise -10 bis -30°C abreduziert, anschließend wird vorzugsweise bei 70 bis 1500C die Umsetzung unter Abreduktion des Aminrestcs zu Ende geführt.In the first reduction stage, the oxygen atoms of the wc.den N-oxide groups of preferably -10 to -30 ° C abreduziert, then the reaction is preferably conducted under the Abreduktion Aminrestcs to an end at 70 to 150 0 C.

Die Aufarbeitung kann durch Ausfällen mit Wasser oder durch Destillation der entstehenden Verbindungen erfolgen.Working up can be carried out by precipitation with water or by distillation of the compounds formed take place.

Beispiele der Reduklionskatalysatoren für das Verfahren sind sowohl Edelmetalle wie Platin und Palladium als auch Raney-Nickcl, Rancy-Cobalt und Nickel auf Trägcrmaterialien.Examples of the reduction catalysts for the process are precious metals such as platinum and palladium as well as Raney-Nickcl, Rancy-Cobalt and Nickel on carrier materials.

Ein weiterer Gegenstand der Erfindung sind 3,3-Dialkyl-tctrahydro-chinazolinc der allgemeinen Formel (2')The invention also relates to 3,3-dialkyl-tetrahydro-quinazoline of the general formula (2 ')

in derin the

Ri' Wasserstoff, eine Ci — Ci^-Alkylgruppe, die gegebenenfalls durch Ci-Ci-Alkoxyreste oder Halogen substituiert ist oder Ci — CVAIkoxyreste, R/ Wasserstoff oder Ci — Q-Alkylreste, Rs und Rt' jeweils Methylgruppen oder miteinander einen carbocyclischen 6-Ring bilden, der gegebenenfalls durch eine Methylgnippe substituiert ist, darstellen.Ri 'hydrogen, a Ci - Ci ^ alkyl group, optionally by Ci-Ci-alkoxy radicals or halogen is substituted or Ci - CVAIkoxyeste, R / hydrogen or Ci - Q-alkyl radicals, Rs and Rt 'each Methyl groups or with each other form a carbocyclic 6-membered ring, which is optionally replaced by a methyl group is substituted represent.

Als Ausgangsmaterialicn für das Verfahren seien beispielhaft folgende 2-Alkylamino-2, 3-Dihydro-3, 3- Dialkyl-chinoxalin-di-N-oxide genannt:The following 2-alkylamino-2, 3-dihydro-3, 3- Dialkyl-quinoxaline-di-N-oxide called:

2-Methylamino-3,3-dimethyl-,
2-Äthylamino-3,3-dimethyl-,
2-Cyclohexylamino-3,3-dimethyl-,
2-Cyclohexylamino-3,3-dimethyl-6- bzw.2-methylamino-3,3-dimethyl-,
2-ethylamino-3,3-dimethyl-,
2-cyclohexylamino-3,3-dimethyl-,
2-Cyclohexylamino-3,3-dimethyl-6- or

7-rnethyl-,
2-Cyclohexylamino-3,3-dimethyl-6- bzw.7-methyl-,
2-Cyclohexylamino-3,3-dimethyl-6- or

7-methoxy,
2-Cyclohexylamin-3,3-dimethyl-b-bzw.7-methoxy,
2-cyclohexylamine-3,3-dimethyl-b- or.

7-äthoxv-,7-ethoxv-,

2-Cyclohexylaminc-3,3-dimethyl-6-bzw.2-Cyclohexylamine-3,3-dimethyl-6- or.

7-chlor-,7-chlorine,

2-Morpho!ino-3,3-dimethyl-,
2-Piperidino-3,3-dimethyl-,
2- Py rrolidino-SJ-dimethyl-,
2-Cγclohexylamiπo-3,3-dimethyl-,
2-CycIohexylamino-3,3-dimethyl-6-bzw.2-morpho! Ino-3,3-dimethyl-,
2-piperidino-3,3-dimethyl-,
2- Pyrrolidino-SJ-dimethyl-,
2-Cγclohexylamiπo-3,3-dimethyl-,
2-CycIohexylamino-3,3-dimethyl-6- or.

7-methyl-,
2-Cyclohexylamino-3,3-dimethyl-6-bzw.7-methyl-,
2-Cyclohexylamino-3,3-dimethyl-6- or.

7-methoxy-,
2-Cyclohexylamino-33-dimethyl-6-bzw.7-methoxy,
2-Cyclohexylamino-33-dimethyl-6- or.

7-äthoxy-,7-ethoxy,

2-Cyclohexylamino-3,3-spiro-(cyclohexenyl)-,
2-Cyclohexylamino-33-spiro-(methylcyclo-2-cyclohexylamino-3,3-spiro- (cyclohexenyl) -,
2-cyclohexylamino-33-spiro- (methylcyclo-

hexenyl)-6- bzw. 7-methyl-,
2-Morpholino-3,3-dimethyI-6- bzw. 7-methyl-,
2-Cyclohexylamino-2-methyl-3,3-dimethyl-,
2-Piperidino-2-methyl-3T3-dimethyl-6-bzw.hexenyl) -6- or 7-methyl-,
2-morpholino-3,3-dimethyl-6- or 7-methyl-,
2-cyclohexylamino-2-methyl-3,3-dimethyl-,
2-piperidino-2-methyl-3 T 3-dimethyl-6 or.

7-methoxy-2,3-dihydro-chinoxalin-di-N-oxid.7-methoxy-2,3-dihydro-quinoxaline-di-N-oxide.

Als nach dem Verfahren herstellbare Verbindungen seien beispielhaft genannt:Examples of compounds that can be produced by the process are:

3,3-Dimeliiyl-l,2,3,4-tetrahydro-chinoxalin;
3,3-Dimethyl-6 bzw. 7-methyl-l,2,3,4-tetra-3,3-dimellyl-1,2,3,4-tetrahydroquinoxaline;
3,3-dimethyl-6 or 7-methyl-1,2,3,4-tetra-

hydro-chinoxalin;
3,3-Dimethyl-6 bzw. 7-methoxy-l,2,3,4-tetr2 ·hydro-quinoxaline;
3,3-dimethyl-6 or 7-methoxy-1,2,3,4-tetr2

hydro-chinoxa.in.hydro-chinoxa.in.

Die erfincningsgemäßen bzw. erfindungsgemäß herstellbaren Verbindungen sind wertvolle Zwischenprodukte z. B. für die Herstellung von Farbstoffen. Weiterhin dienen sie als Zusatzstoffe bei der Herstellung von ozonbeständigen Gummi-Artikeln. Über die Wirkung der erfindungsgemäßen Verbindungen bei der letzteren Anwendung gibt die DE-OS 17 95 326 Aufschluß.Those according to the invention or which can be produced according to the invention Compounds are valuable intermediates e.g. B. for the production of dyes. They also serve as additives in the manufacture of ozone-resistant rubber articles. About the The action of the compounds according to the invention in the latter application is given in DE-OS 17 95 326 Exposure.

Beispielexample

3,3-Dimethyl-6- bzw. 7-methyl-tetrahydrochinoxalin(l) 3,3-dimethyl-6- or 7-methyl-tetrahydroquinoxaline (l)

630 g = 2,08 Mol eines Gemisches aus 2-Cyclohexylaniino-3,3-dimethyl-6· und 7-methyl-dihydro-chinoxalindi-N-oxid werden mit 120 g Raney-Nickel in 2,5 Litern Methanol gegeben und bei 25°C in einem Autoklav hydriert. Nach beendeter Wasserstoffaufnahme erhöht man die Temperatur auf IO0°C und führt die Hydrierung bei 1500C zu Ende. Nach Abfiltrieren des Katalysators und Abziehen des Lösungsmittels und des entstandenen Cyclohexylamine destilliert man den Rückstand. Man erhält 270 g Kp04 mbar 115-125°C. Das Destillat erstarrt und schmilzt nach dem Umlösen aus Benzin von 59-60°C.630 g = 2.08 mol of a mixture of 2-cyclohexylaniino-3,3-dimethyl-6 and 7-methyl-dihydro-quinoxalinedi-N-oxide are added with 120 g of Raney nickel in 2.5 liters of methanol and at Hydrogenated at 25 ° C in an autoclave. After completion of hydrogen uptake, the temperature on IO0 ° C is increased and the hydrogenation at 150 0 C to an end. After filtering off the catalyst and stripping off the solvent and the resulting cyclohexylamine, the residue is distilled. 270 g of boiling point 04 mbar 115-125 ° C. are obtained. The distillate solidifies and melts after dissolving from gasoline at 59-60 ° C.

C,,H,bN2(176)C ,, H, bN 2 (176)

N ber. 15,92
N gef. 15,9N calc. 15.92
N found. 15.9

Das erhaltene Produkt ist ein Gemisch bestehend aus i^-dimethyl-o-methyl-tetrahydro-chinoxalin und 3,3-dimethyl-7-methyl-tetrahydrochinoxalin. Das Gemisch wird durch Chromatographie in seine beiden Bestandteile aufgetrennt. In analoger Weise werden die in der Tal Ic zusammengestellten Verbindungen aus den entsprechenden Ausgangsmaterialien gewonnen:The product obtained is a mixture consisting of i ^ -dimethyl-o-methyl-tetrahydroquinoxaline and 3,3-dimethyl-7-methyl-tetrahydroquinoxaline. The mixture is separated into its two components by chromatography. In an analogous way, the Tal Ic compiled compounds obtained from the corresponding starting materials:

Formelformula CHCH II. HH CH,CH, ff 20",,20 ",, CH,CH, I
jI.
j CH,CH, 55 !! 17 95 32517 95 325 130 133
bei 0.533 mbar
(0.4 mm Hg)130 133
at 0.533 mbar
(0.4 mm Hg) 58 6058 60 66th 74,0. H
17.2674.0. H
17.26 = 8,64= 8.64 Ausbeute
% d. Th.yield
% d. Th. Nr.No. HH CH2 CH 2 33 Kp ("Cl Fp CC|Kp ("Cl Fp CC | Analyseanalysis 73,9. H
17.173.9. H
17.1 = 8.7= 8.7 68.7. H
14.5668.7. H
14.56 = 8.33= 8.33 49,049.0 HH 80"/,,80 "/ ,, 44 4544 45 Ber.Ber. CH3-O--J-CH 3 -O - J- H
N
r ^ H
N
r ^ H fH
N >"-'
I CH,
HH fH
N>"-'
I,
H 37 3837 38 N =N = 68.7. Il
14.468.7. Il
14.4 = 8.8= 8.8 .A,.A, C =
N =C =
N = 64.564.5 IIIIII Bcr.
C
N =Bcr.
C.
N = H
NH
N Gcr.Gcr. 74.9. H
15.974.9. H
15.9 = 9.1= 9.1 H
Ii H
Ii C ^
N =C ^
N = V/\N- V / \ N- 75.1. H
15.975.1. H
15.9 = 9.2= 9.2 IVIV v H v H Bcr.Bcr. 4343 C =
N =C =
N = 75.8. H
14.7375.8. H
14.73 = 9.48= 9.48 CH,
/CH,CH,
/ CH, Gci.Gci. CH,CH, C =
N =C =
N = 76.0. H
15.076.0. H
15.0 = 9.5= 9.5 70.570.5 VV Bcr.Bcr. C =
N =C =
N = CH,
7CH,CH,
7 CH, Gcr.Gcr. \H \ H c =
N = c =
N = CU,CU,

l-ortNct/uMül-ortNct / uMü

Nr. l'iirmolNo. l'iirmol

KpI C-IKpI C - I l'p (Cll'p (Cl

Analyseanalysis

AusheuleHowl

CH, CH,CH, CH,

(H,(H,

I32I32

bei (1.0)67 mharat (1.0) 67 mhar

(0.5 mm HyI Bor.(0.5 mm HyI Bor.

C - 7II.S. Il r-.C - 7II.S. Il r-.

N ■= 12.73N ■ = 12.73

Ger.Ger.

C = 7i.O. ii =C = 7 ok ii =

N = 12.5N = 12.5

CW,CW,

IlIl

N
IlN
Il

CW,CW,

155155

bei (!.533 niharat (! .533 nihar

(0.4 mm Hu) Her.(0.4 mm Hu) Her.

C = 77.4. Il = 9.67C = 77.4. Il = 9.67

N = 12.91N = 12.91

Cier.Cier.

C ■ 77.4. 11 = 9."C ■ 77.4. 11 = 9. "

N - 13.4N - 13.4

7070

Das für die Herstellung von IV benötigte Ausgangsmatcrial wird wie folgt gewonnen:The starting material required for the production of IV is obtained as follows:

85.5 g Bcn/ofuroxan werden zusammen mit 105 g N-Cyclohcxyl-1 -methyl^-dimethyl-Kctimin (Schiffsche Base aus Cyclohexylamin und Methylisopropylketon) unter Rühren in 400 ml Methanol gegeben. Die Temperatur steigt auf 25'C und gleichzeitig erfolgt Lösung. Nach 12 Stunden sind 100 g 2-Cyclohcxylamino^-methyl-S.S-dimethyldihydro-chinoxalin-di-N-oxid auskristallisiert. Die roten Kristalle schmelzen nach dem Umlösen aus Methanol bei 129 bis 13TC85.5 g of Bcn / ofuroxan together with 105 g of N-Cyclohxyl-1 -methyl ^ -dimethyl-Kctimin (Schiffsche Base of cyclohexylamine and methyl isopropyl ketone) added to 400 ml of methanol with stirring. the The temperature rises to 25'C and solution takes place at the same time. After 12 hours there are 100 g of 2-cyclohexylamino ^ -methyl-S.S-dimethyldihydro-quinoxaline-di-N-oxide crystallized out. The red crystals melt at 129 to 13TC after redissolving from methanol

C1-IUN1O, (301)C 1 -IUN 1 O, (301)

CH,
CH,CH,
CH,

CW,
NH CW,
NH

Ber. C' = 67.2 H = 8.31 N =
Gel'. C = 67.2 H = 8.6 N =Ber. C '= 67.2 H = 8.31 N =
Gel'. C = 67.2 H = 8.6 N =

3.95 3.95.3.95 3.95.

Analog weiden mit den entsprechend substituierten Ben/ofuroxanen die Ausgangsmaterialien für V und Vl gewonnen:Analogously, the starting materials for V and Vl are found with the appropriately substituted ben / ofuroxanes won:

CH,CH,

Ip: 147 14S
Rote KristalleIp: 147 14S
Red crystals

(Ml. O(Ml. O

Ip: 128 130
Rote KristalleIp: 128 130
Red crystals

OO ff C II,C II, NN ii
N ■N ■ CH,CH, (H,(H, OO NHNH

ΐ N ΐ N

C\ τ C \ τ

1X 1 X

(Ή, CH,(Ή, CH,

CH, NHCH, NH

IlIl

Claims (1)

Patentansprüche:Patent claims: 1. Verfahren zur Herstellung von 3,3-Dialkyl-tetrahydrochinoxalinen der allgemeinen Formel1. Process for the preparation of 3,3-dialkyl-tetrahydroquinoxalines the general formula in derin the Ri für Wasserstoff oder einen gegebenenfalls substituierten Alkylrest, einen Methoxy- oder Äthoxy-rest, R2 für Wasserstoff oder einen Alkylrest, und R5 und R0 für Alkylreste stehen, wobei R5 und Re miteinander zu einem carbocyclischen Ring verbunden sein können, der gegebenenfalls noch Methylgruppen tragen kann, dadurch gekennzeichnet, daß man 2-Alkylamino-3,3-dialkyldihydro-chinoxalin-di-N-oxide der allgemeinen Formel Ri stands for hydrogen or an optionally substituted alkyl radical, a methoxy or ethoxy radical, R2 for hydrogen or an alkyl radical, and R5 and R 0 for alkyl radicals, where R5 and Re can be connected to one another to form a carbocyclic ring which may also contain methyl groups can carry, characterized in that 2-alkylamino-3,3-dialkyldihydroquinoxaline di-N-oxides of the general formula
DE19681795325 1968-09-13 1968-09-13 3,3-dialkyl-tetrahydroquinoxaline and a process for their preparation Expired DE1795325C3 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
DE19681795325 DE1795325C3 (en) 1968-09-13 1968-09-13 3,3-dialkyl-tetrahydroquinoxaline and a process for their preparation
ES371364A ES371364A1 (en) 1968-09-13 1969-09-10 Tetrahydroquinoxaline derivatives
US856796A US3661905A (en) 1968-09-13 1969-09-10 Tetrahydroquinoxaline derivatives
CS6200A CS161093B2 (en) 1968-09-13 1969-09-11
FR6931088A FR2018055A1 (en) 1968-09-13 1969-09-12
BR21242169A BR6912421D0 (en) 1968-09-13 1969-09-12 ELASTOMERIC COMPOSITIONS BASED ON NATURAL RUBBER AND / OR MIXED SYNTHETIC STABILIZED AGAINST OZONE ACTION AND PROCESS FOR ITS PRODUCTION
NL6913937.A NL156694B (en) 1968-09-13 1969-09-12 PROCESS FOR PREPARING TETRAHYDROQUINOXALINS FOR PROTECTING RUBBER AGAINST OZONE, PROCESS FOR PROTECTING RUBBER AGAINST OZONE, AND FORMED PREPARATION, WHOLLY OR PARTIALLY PROTECTED FROM RUBBER.
GB41353/69A GB1285060A (en) 1968-09-13 1969-09-15 Tetrahydroquinoxalines and their use as anti-ozonants

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19681795325 DE1795325C3 (en) 1968-09-13 1968-09-13 3,3-dialkyl-tetrahydroquinoxaline and a process for their preparation

Publications (3)

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DE1795325A1 DE1795325A1 (en) 1972-01-05
DE1795325B2 DE1795325B2 (en) 1979-11-29
DE1795325C3 true DE1795325C3 (en) 1981-05-14

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DE19681795325 Expired DE1795325C3 (en) 1968-09-13 1968-09-13 3,3-dialkyl-tetrahydroquinoxaline and a process for their preparation

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BR (1) BR6912421D0 (en)
DE (1) DE1795325C3 (en)

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3291757A (en) * 1963-12-26 1966-12-13 Goodyear Tire & Rubber Tetrahydroquinoxalines as antiozonants for rubber

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DE1795325B2 (en) 1979-11-29
BR6912421D0 (en) 1973-01-25
DE1795325A1 (en) 1972-01-05

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