DK150847B - PROCEDURE FOR PREPARING 2-AMINO-BENZYLAMINES - Google Patents
PROCEDURE FOR PREPARING 2-AMINO-BENZYLAMINES Download PDFInfo
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- DK150847B DK150847B DK261873AA DK261873A DK150847B DK 150847 B DK150847 B DK 150847B DK 261873A A DK261873A A DK 261873AA DK 261873 A DK261873 A DK 261873A DK 150847 B DK150847 B DK 150847B
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- amino
- general formula
- hal
- dibromo
- benzylamines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/04—Preparation of carboxylic acid amides from ketenes by reaction with ammonia or amines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
- C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P11/00—Drugs for disorders of the respiratory system
- A61P11/14—Antitussive agents
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P11/00—Drugs for disorders of the respiratory system
- A61P11/16—Central respiratory analeptics
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyridine Compounds (AREA)
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- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
150847 ^ \150847
Den foreliggende opfindelse angår en særlig fremgangsmåde til fremstilling af 2-amino-benzylaminer med den almene formel I (se kravet), hvori Hal betegner 1 2 et chlor- eller bromatom, R betegner et hydrogen-, chlor- eller bromatom, R be- 3 tegner en cyclohexyl- eller hydroxycyclohexylgruppe, og R betegner et hydrogenatom eller en methylgruppe.The present invention relates to a particular process for the preparation of 2-amino-benzylamines of the general formula I (see claim) wherein Hal represents 1 2 a chlorine or bromine atom, R represents a hydrogen, chlorine or bromine atom, R 3 represents a cyclohexyl or hydroxycyclohexyl group and R represents a hydrogen atom or a methyl group.
I den organiske kemi er det en almindelig anerkendt læresætning, at amino-benzaldehyder er meget ustabile og tilbøjelige til selvkondensation. De udgør følgelig yderst ugunstige udgangsforbindelser for videre omsætninger (se f.eks. Fie-ser & Fieser, Organic Chemistry, 3. oplag 1956, side 688, Reinhold Publishing Corporation, New York, og Houben-Weyl, Methoden der organischen Chemie, 4. oplag, bind VII/1, side 408). Således er der heller ikke hidtil i litteraturen beskrevet den reduktive aminering af amino-benzaldehyder med myresyre og aminer, især da 2 150847 det er kendt fra litteraturen, at der ved reduktiv aminering med myresyre eller det tilsvarende formamid opnås et desto ringere udbytte, jo større substitutions-graden er for det anvendte aromatiske aldehyd (se f.eks. Org. Reactions Vol. _5, 309 (1949)).In organic chemistry, it is a widely accepted doctrine that amino-benzaldehydes are highly unstable and prone to self-condensation. Accordingly, they constitute highly unfavorable starting compounds for further turnover (see, e.g., Fieser & Fieser, Organic Chemistry, 3rd Edition 1956, page 688, Reinhold Publishing Corporation, New York, and Houben-Weyl, The Method of Organic Chemistry, 4 Edition, Volume VII / 1, page 408). Thus, the reductive amination of amino-benzaldehydes with formic acid and amines has not been described so far in the literature, especially since it is known from the literature that the lower the yield of formic acid or the corresponding formamide, the greater the yield. the degree of substitution is for the aromatic aldehyde used (see, e.g., Org. Reactions Vol. 5, 309 (1949)).
Det er derfor yderst overraskende, at man kan fremstille forbindelser med den almene formel I i gode udbytter ved fremgangsmåden ifølge opfindelsen, der er ejendommelig ved, at man omsætter et aldehyd med den almene formel II (se kravet), hvori Hal og R^ har den ovenfor anførte betydning, med en amin med den almene formel III (se kravet), hvori R og R har den ovenfor anførte betydning, i nærværelse af myresyre eller det tilsvarende formamid ved temperaturer mellem 150 og 250°C og, såfremt R^ i en forbindelse med den almene formel III betegner et hydrogenatom, derefter opvarmer den opnåede reaktionsblanding med en fortyndet syre, såsom 2N saltsyre, under tilbagesvaling.It is therefore extremely surprising that compounds of general formula I can be prepared in good yields by the process of the invention, characterized by reacting an aldehyde of general formula II (see claim) wherein Hal and R the meaning given above, with an amine of the general formula III (see claim) wherein R and R have the meaning given above, in the presence of formic acid or the corresponding formamide at temperatures between 150 and 250 ° C and, if R a compound of general formula III represents a hydrogen atom, then the reaction mixture obtained is heated with reflux acid, such as 2N hydrochloric acid.
Fra beskrivelsen til dansk patentansøgning nr. 2124/73 kendes der ganske vist en fremgangsmåde til fremstilling af en forbindelse med formlen I, nemlig den sekundære amin N-(trans-4-hydroxycyclohexyl)-(2-amino-3,5-dibrombenzyl)-amin, som fremstilles ved reduktion af den Schiff'ske base N-(2-amino-3,5-dibrombenzy-liden)-trans-4-aminocyclohexanol, især med et komplekst metalhydrid ved lav temperatur. Den nævnte Schiff'ske base fremstilles ved omsætning af 2-amino-3,5-dibrombenzaldehyd med trans-4-aminocyclohexanol, dvs. forbindelser, der falder ind under henholdsvis ovennævnte formel II og III. I forhold til denne kendte fremgangsmåde er der imidlertid med fremgangsmåden ifølge opfindelsen for første gang beskrevet en alment anvendelig fremgangsmåde til fremstilling af benzylami-ner, nemlig både sekundære og tertiære benzylaminer, ud fra et amino-benzaldehyd, hvorved der i hvert fald for de tertiære aminers vedkommende ikke kan være tale om, at der intermediært er dannet en Schiff'sk base.Of course, from the specification of Danish Patent Application No. 2124/73, there is known a process for the preparation of a compound of formula I, namely the secondary amine N- (trans-4-hydroxycyclohexyl) - (2-amino-3,5-dibromobenzyl) -amine which is produced by reduction of the Schiff base N- (2-amino-3,5-dibromobenzylidene) -trans-4-aminocyclohexanol, especially with a complex metal hydride at low temperature. Said Schiff base is prepared by reacting 2-amino-3,5-dibromobenzaldehyde with trans-4-aminocyclohexanol, i.e. compounds which fall under the above formulas II and III respectively. In relation to this known process, however, for the first time, a process of generating benzylamines, namely both secondary and tertiary benzylamines, from a amino-benzaldehyde is disclosed for the first time, whereby at least for the tertiary in the case of amines, there may be no intermediate formation of a Schiff's base.
Den reduktive aminering udføres eventuelt i et opløsningsmiddel og hensigtsmæssigt under samtidig afdestillering af det dannede vand. Særlig fordelagtigt er det dog, når den anvendte amin med den almene formel III og/eller myresyre samtidig tjener som opløsningsmiddel ved omsætningen.The reductive amination is optionally carried out in a solvent and conveniently while simultaneously distilling off the formed water. However, it is particularly advantageous when the amine of general formula III and / or formic acid used simultaneously acts as a solvent in the reaction.
De opnåede forbindelser med den almene formel I kan, som allerede beskrevet i litteraturen, med fysiologisk acceptable uorganiske eller organiske syrer overføres i deres salte. Som syrer har f.eks. saltsyre, hydrogenbromidsyre, svovlsyre, phosphorsyre, mælkesyre, citronsyre, vinsyre eller maleinsyre vist sig egnet.The compounds of general formula I obtained, as already described in the literature, can be transferred into their salts with physiologically acceptable inorganic or organic acids. As acids, e.g. hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, lactic acid, citric acid, tartaric or maleic acid proved to be suitable.
De som udgangsstoffer anvendte aldehyder med den almene formel II kan fremstilles ved fra litteraturen kendte fremgangsmåder, f.eks. ved oxidation af de tilsvarende benzylalkoholer med brunsten.The aldehydes of general formula II used as starting materials can be prepared by methods known in the literature, e.g. by oxidation of the corresponding benzyl alcohols with brownstone.
Opfindelsen angår således en ny fremgangsmåde til fremstilling af forbindelser med den almene formel I, hvilke forbindelser har værdifulde farmakologiske egenskaber, navnlig sekretolytiske og/eller hostestillende egenskaber.Thus, the invention relates to a novel process for the preparation of compounds of general formula I which have valuable pharmacological properties, in particular secretolytic and / or cough-releasing properties.
3 1508473 150847
Fremgangsmåden ifølge opfindelsen belyses nærmere ved hjælp af de efterfølgende eksempler.The process according to the invention is further elucidated by the following examples.
Eksempe1 1 N-(2-Amino-3,5-dibrom-benzyl)-N-methyl-trans-4-amino-cyclohexanol-hydrochlorid.Example 1 N- (2-Amino-3,5-dibromo-benzyl) -N-methyl-trans-4-amino-cyclohexanol-hydrochloride.
5 g 2-Amino-3,5-dibrom-benzaldehyd, 5,75 g trans-4-methylamino-cyclohexanol og 2 ml myresyre opvarmes i 30 minutter til 200°C, idet det dannede vand afdestil-leres. Derefter tilsætter man den samme mængde amin og myresyre og opvarmer i yderligere 1,5 timer. Reaktionsproduktet opløses ved rystning med 0,5 liter fortyndet ammoniak og 50 ml chloroform. Chloroformfasen fraskilles, og den vandige fase ud-rystes med 50 ml chloroform. De samlede chloroformfaser inddampes til tørhed. Remanensen opløses i 30 ml ethanol og syrnes med ethanolisk saltsyre. Efter tilsætning af en vis mængde ether udkrystalliserer hydrochloridet.5 g of 2-Amino-3,5-dibromo-benzaldehyde, 5.75 g of trans-4-methylamino-cyclohexanol and 2 ml of formic acid are heated to 200 ° C for 30 minutes, distilling off the resulting water. Then add the same amount of amine and formic acid and heat for an additional 1.5 hours. The reaction product is dissolved by shaking with 0.5 liters of dilute ammonia and 50 ml of chloroform. The chloroform phase is separated and the aqueous phase is equipped with 50 ml of chloroform. The combined chloroform phases are evaporated to dryness. The residue is dissolved in 30 ml of ethanol and acidified with ethanolic hydrochloric acid. After adding a certain amount of ether, the hydrochloride crystallizes.
Udbytte: 6,3 g (82% af det teoretiske).Yield: 6.3 g (82% of theory).
Smp.: 216,5-217,5°C (sønderdeling).Mp: 216.5-217.5 ° C (dec.).
Eksempe1 2 N-(2-Amino-3,5-dibrom-benzy1)-trans-4-amino-cyclohexano1-hydrochlorid.Example 2 N- (2-Amino-3,5-dibromo-benzyl) -trans-4-amino-cyclohexano1-hydrochloride.
5 g 2-Amino-3,5-dibrom-benzaldehyd, 5,75 g trans-4-amino-cyclohexanol og 2 ml myresyre opvarmes i 30 minutter ved 200°C, idet det dannede vand afdestilieres. Derefter tilsætter man de samme mængder amin og myresyre og opvarmer i yderligere 1,5 timer. Reaktionsproduktet opløses ved rystning med 0,5 liter fortyndet ammoniak og 50 ml chloroform. Chloroformf asen fraskilles, og den vandige fase ud-rystes med 50 ml chloroform. De samlede chloroformf aser inddampes til tørhed. Remanensen opløses i 200 ml 2N saltsyre, koges i nogen tid under tilbagesvaling, affarves med aktivt kul, gøres alkalisk med koncentreret ammoniak og udrystes 2 gange med 50 ml chloroform pr. gang. De samlede chloroformfaser inddampes til tørhed. Remanensen opløses i 30 ml ethanol og syrnes med ethanolisk saltsyre. Efter tilsætning af en vis mængde ether udkrystalliserer hydrochloridet.5 g of 2-Amino-3,5-dibromo-benzaldehyde, 5.75 g of trans-4-amino-cyclohexanol and 2 ml of formic acid are heated for 30 minutes at 200 ° C, distilling off the resulting water. Then add the same amounts of amine and formic acid and heat for an additional 1.5 hours. The reaction product is dissolved by shaking with 0.5 liters of dilute ammonia and 50 ml of chloroform. The chloroform phase is separated and the aqueous phase is equipped with 50 ml of chloroform. The combined chloroforms are evaporated to dryness. The residue is dissolved in 200 ml of 2N hydrochloric acid, boiled under reflux for some time, decolorized with activated charcoal, made alkaline with concentrated ammonia and shaken twice with 50 ml of chloroform per ml. walk. The combined chloroform phases are evaporated to dryness. The residue is dissolved in 30 ml of ethanol and acidified with ethanolic hydrochloric acid. After adding a certain amount of ether, the hydrochloride crystallizes.
Udbytte: 4,5 g (60,6 % af det teoretiske).Yield: 4.5 g (60.6% of theory).
Smp.: 233-234°C (sønderdeling).Mp: 233-234 ° C (dec.).
Eksempel 3 N- ( 2-Amino-3,5-dibrom-benzyl)-N-me thy1-cyclohexylamin.Example 3 N- (2-Amino-3,5-dibromo-benzyl) -N-methyl-cyclohexylamine.
Denne forbindelse fremstilles ud fra 2-amino-3,5-dibrom-benzaldehyd og N-methyl-cyclohexylamin på analog måde som i eksempel 1.This compound is prepared from 2-amino-3,5-dibromo-benzaldehyde and N-methyl-cyclohexylamine in an analogous manner as in Example 1.
Smp. af hydrochloridet: 232-235°C (sønderdeling).Mp. of the hydrochloride: 232-235 ° C (dec.).
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DK500177A DK500177A (en) | 1972-05-12 | 1977-11-10 | PROCEDURE FOR THE PREPARATION OF 2-BENZOYLAMINO-BENZYLAMINE [ |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2223193A DE2223193C3 (en) | 1972-05-12 | 1972-05-12 | Process for the preparation of 2-amino-benzylamines |
DE2223193 | 1972-05-12 |
Publications (2)
Publication Number | Publication Date |
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DK150847B true DK150847B (en) | 1987-07-06 |
DK150847C DK150847C (en) | 1988-01-04 |
Family
ID=5844732
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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DK261873A DK150847C (en) | 1972-05-12 | 1973-05-11 | PROCEDURE FOR PREPARING 2-AMINO-BENZYLAMINES |
Country Status (20)
Country | Link |
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JP (3) | JPS5517020B2 (en) |
KR (1) | KR780000152B1 (en) |
AT (1) | AT321885B (en) |
BG (1) | BG22382A3 (en) |
CA (1) | CA996109A (en) |
CH (1) | CH579019A5 (en) |
CS (1) | CS179415B2 (en) |
DD (1) | DD108278A5 (en) |
DE (1) | DE2223193C3 (en) |
DK (1) | DK150847C (en) |
ES (1) | ES414671A1 (en) |
FI (1) | FI56672C (en) |
HU (1) | HU165627B (en) |
NL (1) | NL158167B (en) |
NO (1) | NO135707C (en) |
PL (1) | PL89241B1 (en) |
RO (1) | RO70464A (en) |
SE (2) | SE396594B (en) |
SU (1) | SU501668A3 (en) |
YU (1) | YU35572B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2423483A2 (en) * | 1978-04-20 | 1979-11-16 | Boehringer Sohn Ingelheim | PROCESS FOR PREPARING SULFUR N-BENZYL-AMINOACIDS |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DK139515B (en) * | 1972-04-18 | 1979-03-05 | Thomae Gmbh Dr K | PROCEDURE FOR THE PREPARATION OF N- (TRANS-4-HYDROXYCYCKYHEXYL) - (2-AMINO-3,5-DIBROMBENZYL) -AMINE OR ACID ADDITION SALTS THEREOF |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
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DE1518375A1 (en) * | 1965-06-08 | 1969-08-14 | Thomae Gmbh Dr K | Process for the preparation of new 2-amino-halobenzylamines |
-
1972
- 1972-05-12 DE DE2223193A patent/DE2223193C3/en not_active Expired
-
1973
- 1973-04-24 KR KR7300654A patent/KR780000152B1/en active
- 1973-05-02 AT AT384973A patent/AT321885B/en not_active IP Right Cessation
- 1973-05-07 RO RO7374699A patent/RO70464A/en unknown
- 1973-05-09 DD DD170733A patent/DD108278A5/xx unknown
- 1973-05-10 BG BG23564A patent/BG22382A3/xx unknown
- 1973-05-10 HU HUTO907A patent/HU165627B/hu unknown
- 1973-05-10 CS CS7300003325A patent/CS179415B2/en unknown
- 1973-05-10 SE SE7306631A patent/SE396594B/en unknown
- 1973-05-10 YU YU1232/73A patent/YU35572B/en unknown
- 1973-05-10 CH CH666173A patent/CH579019A5/xx not_active IP Right Cessation
- 1973-05-10 JP JP5202873A patent/JPS5517020B2/ja not_active Expired
- 1973-05-10 NL NL7306513.A patent/NL158167B/en not_active IP Right Cessation
- 1973-05-11 NO NO1957/73A patent/NO135707C/no unknown
- 1973-05-11 SU SU1919018A patent/SU501668A3/en active
- 1973-05-11 FI FI1520/73A patent/FI56672C/en active
- 1973-05-11 DK DK261873A patent/DK150847C/en not_active IP Right Cessation
- 1973-05-11 ES ES414671A patent/ES414671A1/en not_active Expired
- 1973-05-11 PL PL1973162473A patent/PL89241B1/pl unknown
- 1973-05-11 CA CA171,045A patent/CA996109A/en not_active Expired
-
1976
- 1976-02-25 SE SE7602405A patent/SE421791B/en unknown
-
1977
- 1977-06-29 JP JP7769177A patent/JPS53116339A/en active Pending
- 1977-12-20 JP JP15347577A patent/JPS53149944A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DK139515B (en) * | 1972-04-18 | 1979-03-05 | Thomae Gmbh Dr K | PROCEDURE FOR THE PREPARATION OF N- (TRANS-4-HYDROXYCYCKYHEXYL) - (2-AMINO-3,5-DIBROMBENZYL) -AMINE OR ACID ADDITION SALTS THEREOF |
Also Published As
Publication number | Publication date |
---|---|
ES414671A1 (en) | 1976-02-01 |
FI56672C (en) | 1980-03-10 |
DD108278A5 (en) | 1974-09-12 |
AT321885B (en) | 1975-04-25 |
KR780000152B1 (en) | 1978-05-02 |
NL7306513A (en) | 1973-11-14 |
NL158167B (en) | 1978-10-16 |
JPS53149944A (en) | 1978-12-27 |
DE2223193A1 (en) | 1973-12-13 |
NO135707C (en) | 1977-05-16 |
HU165627B (en) | 1974-09-28 |
JPS4948624A (en) | 1974-05-11 |
FI56672B (en) | 1979-11-30 |
DE2223193B2 (en) | 1974-09-12 |
SE7602405L (en) | 1976-02-25 |
PL89241B1 (en) | 1976-11-30 |
SU501668A3 (en) | 1976-01-30 |
SE421791B (en) | 1982-02-01 |
DE2223193C3 (en) | 1975-05-28 |
NO135707B (en) | 1977-02-07 |
CA996109A (en) | 1976-08-31 |
CH579019A5 (en) | 1976-08-31 |
YU123273A (en) | 1980-10-31 |
YU35572B (en) | 1981-04-30 |
JPS5726667B2 (en) | 1982-06-05 |
SE396594B (en) | 1977-09-26 |
CS179415B2 (en) | 1977-10-31 |
DK150847C (en) | 1988-01-04 |
BG22382A3 (en) | 1977-02-20 |
JPS53116339A (en) | 1978-10-11 |
RO70464A (en) | 1981-06-30 |
JPS5517020B2 (en) | 1980-05-08 |
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