DK149105B - PROCEDURE FOR PREPARING 2-ARYLOXYALKYL MORPHOLINE DERIVATIVES - Google Patents
PROCEDURE FOR PREPARING 2-ARYLOXYALKYL MORPHOLINE DERIVATIVES Download PDFInfo
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- DK149105B DK149105B DK242571A DK242571A DK149105B DK 149105 B DK149105 B DK 149105B DK 242571 A DK242571 A DK 242571A DK 242571 A DK242571 A DK 242571A DK 149105 B DK149105 B DK 149105B
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- carbon atoms
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- alkyl
- morpholine
- aryloxyalkylmorpholine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
- C07D265/30—1,4-Oxazines; Hydrogenated 1,4-oxazines not condensed with other rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Description
i 149105in 149105
Opfindelsen angår en særlig fremgangsmåde til fremstilling af 5 2-aryloxyalkylmorpholinderivater, som er i besiddelse af værdifulde terapeutiske egenskaber, f.eks. central nervedæmpende og thymoleptiske egenskaber.The invention relates to a particular process for the preparation of 5-aryloxyalkylmorpholine derivatives which possess valuable therapeutic properties, e.g. central nerve suppressive and thymoleptic properties.
I de britiske patentskrifter nr. 1.138.405, 1.260.886 og 10 1.295.447 er der beskrevet visse hidtil ukendte aryloxyalkyl- morpholinderivater, som er i besiddelse af de ovennævnte værdifulde terapeutiske egenskaber, og der er ligeledes beskrevet kemiske fremgangsmåder til fremstillingen af disse aryloxyal-kylmorpholinderivater. Disse kendte fremgangsmåder tilveje-15 bringer en fremgangsmåde til fremstilling af aryloxyalkylmorp- holinderivater, hvor nitrogenatomet i morpholinringen er usub-stitueret, ved at fjerne en beskyttende gruppe fra nitrogenatomet i løbet af det sidste trin af syntesen. Det har nu vist sig, at sådanne N-substituerede aryloxyalkylmorpholinderivater 20 kan fremstilles ved omsætning af den passende arylalkohol med et forud dannet morpholinderivat. Man skulle vente, at en sådan reaktion ville føre til polymerisation af morpholi nderivatet ved selvkondensation. Det har imidlertid overraskende vist sig, at der kan opnås et acceptabelt udbytte af det ønskede 25 2-aryloxyalkylmorpholinderivat.British Patent Nos. 1,138,405, 1,260,886 and 10,295,447 disclose certain novel aryloxyalkylmorpholine derivatives which possess the above-mentioned valuable therapeutic properties and also describe chemical processes for their preparation. aryloxyal-kylmorpholinderivater. These known methods provide a process for preparing aryloxyalkylmorpholine derivatives wherein the nitrogen atom of the morpholine ring is unsubstituted by removing a protecting group from the nitrogen atom during the final step of the synthesis. It has now been found that such N-substituted aryloxyalkylmorpholine derivatives 20 can be prepared by reacting the appropriate aryl alcohol with a preformed morpholine derivative. One would expect that such a reaction would lead to polymerization of the morpholine derivative by self-condensation. However, it has surprisingly been found that an acceptable yield of the desired 2-aryloxyalkylmorpholine derivative can be obtained.
I henhold til opfindelsen tilvejebringes en fremgangsmåde til fremstilling af 2-aryloxyalkylmorpholinderivater med den almene formel: 30 R3According to the invention, there is provided a process for the preparation of 2-aryloxyalkylmorpholine derivatives of the general formula:
x-o-cr4r5v^ ^0^^· r6 Xx-o-cr4r5v ^ ^ 0 ^^ · r6 X
R2 HR2 H
35 2 149105 hvori R2, R3, R4, R5 og R6, der kan være ens eller forskellige, betegner hydrogen eller alkylgrupper med indtil 3 carbonato-mer, og hvori X betegner en phenyl- eller naphthylgruppe, som er usubstitueret el ler substitueret med én eller to substituen-5 ter valgt blandt halogenatomer, alkyl-, alkoxy- og alkylthio-grupper, hver med indtil 10 carbonatomer, halogenalkyl- og ha-logenalkoxygrupper, hver med indtil 5 carbonatomer og med indtil 4 halogenatomer, alkenyl-, alkenyloxy-, alkynyloxy-, cyk-loalkyl- og cykloalkyloxygrupper, hver med indtil 6 carbonato-10 mer, aryl-, aryloxy-, alkylaryloxy-, aralkyl- og aralkoxygrup-per, hver med indtil 10 carbonatomer, alkylgrupper med indtil 5 carbonatomer, der er substitueret med alkoxygrupper med indtil 5 carbonatomer, alkanoylgrupper med indtil 6 carbonatomer, hydroxy- og methylendioxygrupper samt alkylengrupper med 3 15 eller 4 carbonatomer, hvilke alkylengrupper sammen med phenyl-eller naphthylgruppen danner en indanyl- eller tetrahydronaph-thylgruppe, eller syreadditionssålte deraf. Fremgangsmåden er ejendommelig ved, at en arylalkohol med formlen X-OH, hvori X har denί ovenfor anførte betydning, omsættes med et morpholinde-20 rivat med formlen: R3 2— CR4 R5v^ 11 25 R2 H 30 hvori R2, R3, R4, R^ og R6 har de ovenfor anførte betydninger, X betegner et halogenatom eller en methansulfonyloxy- eller toluen-p-sulfonyloxygruppe, hvorefter om ønsket et opnået aryloxyalkylmorpholinderivat i form af den frie base omsættes 35 med en syre til dannelse af et syreadditionssalt deraf.Wherein R 2, R 3, R 4, R 5 and R 6, which may be the same or different, represent hydrogen or alkyl groups of up to 3 carbon atoms and wherein X represents a phenyl or naphthyl group which is unsubstituted or substituted by one or two substituents selected from halogen atoms, alkyl, alkoxy and alkylthio groups, each having up to 10 carbon atoms, haloalkyl and halogen alkoxy groups, each having up to 5 carbon atoms and having up to 4 halogen atoms, alkenyl, alkenyloxy, alkynyloxy, cycloalkyl and cycloalkyloxy groups, each having up to 6 carbon atoms, aryl, aryloxy, alkylaryloxy, aralkyl and aralkoxy groups, each having up to 10 carbon atoms, alkyl groups having up to 5 carbon atoms substituted with alkoxy groups of up to 5 carbon atoms, alkanoyl groups of up to 6 carbon atoms, hydroxy and methylenedioxy groups, and alkylene groups of 3 or 4 carbon atoms which together with the phenyl or naphthyl group form an indanyl or tetrahydric group dronaphthyl group, or acid addition salts thereof. The process is characterized in that an aryl alcohol of formula X-OH, wherein X is as defined above, is reacted with a morpholine derivative of formula: R3 2 - CR4 R5v ^ 11 R 2 H 30 wherein R 2, R 3, R 4, R 1 and R 6 have the meanings given above, X represents a halogen atom or a methanesulfonyloxy or toluene-p-sulfonyloxy group, and if desired, an obtained aryloxyalkylmorpholine derivative in the form of the free base is reacted with an acid to form an acid addition salt thereof.
Det må forstås, at den ovennævnte definition af morpholinderi-vater omfatter alle mulige stereoisomerer deraf og blandinger deraf.It is to be understood that the above definition of morpholine derivatives includes all possible stereoisomers thereof and mixtures thereof.
3 1491053 149105
En egnet betydning af R2, R3, R4, r5 eller R6, når de betegner en alkylgruppe, er f.eks. methylgruppen.A suitable meaning of R 2, R 3, R 4, R 5 or R 6 when they denote an alkyl group is e.g. methyl group.
En egnet betydning af z, når det er halogen, er et chlor-, 5 brom- eller jodatom.A suitable meaning of z when halogen is a chlorine, bromine or iodine atom.
En egnet betydning af X er f.eks. en phenyl- eller naphthyl-gruppe eller en phenyl- eller naphthylgruppe, der er substitueret med én eller to substituenter valgt blandt fluor-, 10 chlor- og bromatomer, methyl-, ethyl-, isopropyl-, n-butyl-, t-butyl-, t-amyl-, methoxy-, ethoxy-, n-propoxy- og isopropoxygrupper.A suitable meaning of X is e.g. a phenyl or naphthyl group or a phenyl or naphthyl group substituted with one or two substituents selected from fluoro, chloro and bromo atoms, methyl, ethyl, isopropyl, n-butyl, t-butyl -, t-amyl, methoxy, ethoxy, n-propoxy and isopropoxy groups.
Egnede syreadditionssalte af aryloxyalkylmorpholinderivaterne, 15 der kan fremstilles ved hjælp af fremgangsmåden ifølge opfindelsen, er f.eks. syreadditionssaltene afledt af uorganiske eller organiske syrer, f.eks. hydrochlorider, hydrobromider, phosphater, sulfater, oxalater, lactater, tartrater, acetater, gluconater, salicylater, citrater, ascorbater, benzoater, β-20 naphthoater, adipater eller l,l-methylen-bis-(2-hydroxy-3-naphthoater) eller syreadditionssalte afledt af sure syntetiske harpikser, f.eks. sulfonerede polystyrenharpikser, f.eks. "Zeo-Karb" 225 ("Zeo-Karb" er et varemærke).Suitable acid addition salts of the aryloxyalkylmorpholine derivatives which can be prepared by the process of the invention are e.g. the acid addition salts derived from inorganic or organic acids, e.g. hydrochlorides, hydrobromides, phosphates, sulfates, oxalates, lactates, tartrates, acetates, gluconates, salicylates, citrates, ascorbates, benzoates, β-naphthoates, adipates or 1,1-methylene bis- (2-hydroxy-3-naphthoates) or acid addition salts derived from acidic synthetic resins, e.g. sulfonated polystyrene resins, e.g. "Zeo-Karb" 225 ("Zeo-Karb" is a trademark).
25 Specifikke aryloxyalkylmorpholinderivater, der kan fremstilles ved hjælp af fremgangsmåden ifølge opfindelsen, er dem der især er beskrevet i de britiske patentskrifter nr. 1.138.405, 1.260.886 og 1.295.447.Specific aryloxyalkylmorpholine derivatives which can be prepared by the process of the invention are those described in particular in British Patent Nos. 1,138,405, 1,260,886 and 1,295,447.
30 Af disse er særligt værdifulde forbindelser 2-(o-ethoxyphenoxy-methyl)morpholin og 2-{m-methoxyphenoxymethyl)morpho1in og syreadditionssaltene deraf.Of these, particularly valuable compounds are 2- (o-ethoxyphenoxy-methyl) morpholine and 2- (m-methoxyphenoxymethyl) morpholine and its acid addition salts.
Fremgangsmåden til fremstilling af aryloxyalkylmorpholinderi-35 vater kan f.eks. gennemføres i et fortyndingsmiddel eller opløsningsmiddel, f.eks. dimethylformamid, dimethylsulfoxid, dioxan eller dimethoxyethan. Den kan f.eks. gennemføres ved en forhøjet temperatur, f.eks. ved en temperatur på indtil 4 149105 150eC, og den kan gennemføres i nærværelse af en stærk base, f.eks. et alkalimetal eller et amid eller hydrid deraf, f.eks. natriumhydrid.The process for preparing aryloxyalkylmorpholine derivatives can e.g. carried out in a diluent or solvent, e.g. dimethylformamide, dimethylsulfoxide, dioxane or dimethoxyethane. It can e.g. carried out at an elevated temperature, e.g. at a temperature of up to 4 149105 150 ° C and can be carried out in the presence of a strong base, e.g. an alkali metal or an amide or hydride thereof, e.g. sodium hydride.
5 Opfindelsen belyses ved hjælp af de efterfølgende eksempler.The invention is illustrated by the following examples.
Eksempe 1 1^Example 1 1 ^
En opløsning af kaliumhydroxid (1,12 g) og 2-ethoxyphenol (2,0 10 g) i vand (50 ml) sættes til 2-(toluen-p-sulfonyloxymethy1) . morpholin (0,5 g) i en nitrogenatomsfære. Den resulterende blanding opvarmes til 95°C under nitrogen i 2 timer, afkøles og ekstraheres med toluen (50 ml). Toluenopløsningen ekstrahe-res igen med en opløsning 36% vægt/vægt saltsyre (0,1 ml) i 15 vand (30 ml), og denne sure ekstrakt gøres basisk til pH-værdi 10 med natriumhydroxidopløsning og ekstraheres med toluen (50 ml). Toluenopløsningen inddampes ved et tryk på 18 mm Hg og en temperatur på 45eC til opnåelse af en olie, som destilleres ved et tryk på 0,03 mm Hg. Fraktionen, der koger ved 135-20 145°C, opsamles og opløses i chloroform (2 ml), hvorefter der til denne opløsning sættes 1,0 ml 3 M HC1 i isopropanol. Opløsningsmidlet.fjernes fra opløsningen ved et tryk på 0,1 mm 'Hg og -en temperatur på 22°C, indtil man får et fast. stof. Dette faste stof filtreres fra-og''tørres til 25 opnåelse af 2-(2-ethoxyphenoxymethyl)morpholin-hydrochlorid, smeltepunkt 185,7-186éC.A solution of potassium hydroxide (1.12 g) and 2-ethoxyphenol (2.0 10 g) in water (50 ml) is added to 2- (toluene-p-sulfonyloxymethyl). morpholine (0.5 g) in a nitrogen atom sphere. The resulting mixture is heated to 95 ° C under nitrogen for 2 hours, cooled and extracted with toluene (50 ml). The toluene solution is again extracted with a solution of 36% w / w hydrochloric acid (0.1 ml) in 15 water (30 ml), and this acidic extract is basified to pH 10 with sodium hydroxide solution and extracted with toluene (50 ml). The toluene solution is evaporated at a pressure of 18 mm Hg and a temperature of 45 ° C to give an oil which is distilled at a pressure of 0.03 mm Hg. The fraction boiling at 135-20 145 ° C is collected and dissolved in chloroform (2 ml), then 1.0 ml of 3 M HCl in isopropanol is added to this solution. The solvent is removed from the solution at a pressure of 0.1 mm Hg and a temperature of 22 ° C until solid. fabric. This solid is filtered off and dried to give 2- (2-ethoxyphenoxymethyl) morpholine hydrochloride, mp 185.7-186 ° C.
2-(toluen-p.sulfonyloxymethyl)morpholin, der anvendtes som udgangsmateriale, kan fremstilles på følgende måde: 30 . En opløsning af 3-(2-hydroxyethylamino)-1,2-propandiol (13,3 g) og tol uen-p-sul fonsyremonohydrat (42 g) i xylen (250 ml) opvarmes til 140°C i 19 timer med azeotropisk fjernelse af vand. Det vandige lag skilles fra og ekstraheres med ethylace-35 tat (250 ml), hvorefter natriumhydroxid tilsættes ved en temperatur under 20eC til det vandige lag, indtil pH-værdien heraf er 7. Den neutraliserede blanding ekstraheres tre gang med ethylacetat (100 ml, 100 ml og 50 ml), og de forenede ekstrak- 5 149105 ter tørres (MgSOj), og opløsningsmidlet afdampes ved 45°C og et tryk på 18 mm Hg til opnåelse af 2-(toluen-p-sulfonyloxymethyl) morpholin som en olie. Acetatsaltene, smeltepunkt 131,5-132eC, kan dannes ved at sætte eddikesyre til en opløsning af den 5 frie base i ether.2- (toluene-p.sulfonyloxymethyl) morpholine used as starting material can be prepared as follows: 30. A solution of 3- (2-hydroxyethylamino) -1,2-propanediol (13.3 g) and toluene-β-sulphonic acid monohydrate (42 g) in xylene (250 ml) is heated to 140 ° C for 19 hours with azeotropic water removal. The aqueous layer is separated and extracted with ethyl acetate (250 mL), then sodium hydroxide is added to the aqueous layer at a temperature below 20 ° C until its pH is 7. The neutralized mixture is extracted three times with ethyl acetate (100 mL, 100 ml and 50 ml) and the combined extracts are dried (MgSO 2) and the solvent is evaporated at 45 ° C and a pressure of 18 mm Hg to give 2- (toluene-p-sulfonyloxymethyl) morpholine as an oil . The acetate salts, mp 131.5-132 ° C, can be formed by adding acetic acid to a solution of the 5 free base in ether.
Eksempel 2Example 2
Den i eksempel 1 beskrevne fremgangsmåde gentages under anven-10 delse af en ækvivalent mængde af den passende phenol i stedet for 2-ethoxyphenol som udgangsmateriale og oxalsyre til isolering af den frie base. På denne måde opnås følgende forbindelser:The procedure described in Example 1 is repeated using an equivalent amount of the appropriate phenol instead of 2-ethoxyphenol as the starting material and oxalic acid to isolate the free base. In this way, the following compounds are obtained:
HH
149105 6149105 6
Smeltepunkt Omkrystallisa- R Salt (eC) tionsmiddel 5 H hydrogenoxalat 132-134 methanol/ethyl- acetat 10 2-Me hydrogenoxalat 117-120 methanol/ethyl - acetat 15 2-MeS hydrogenoxalat 136-137 methanol/ether 2-CH3CH=CH oxalat 198-199 methanol/ethyl- acetat 20 2- Ph hydrogenoxalat | 95-96 methanol/ethyl- ! ; acetat | i 25 3- M0e hydrogenoxalat 159-161 methanol/ethyl - acetatMelting point Recrystallization R Salt (eC) 5 H hydrogen oxalate 132-134 methanol / ethyl acetate 10 2-Me hydrogen oxalate 117-120 methanol / ethyl acetate 2-MeS hydrogen oxalate 136-137 methanol / ether 2-CH 3 CH = CH oxalate 198-199 methanol / ethyl acetate 20 2- Ph hydrogen oxalate | 95-96 methanol / ethyl! ; acetate | in 3- MOe hydrogen oxalate 159-161 methanol / ethyl acetate
EE
iin
30__1__I30__1__I
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GB2466870 | 1970-05-21 | ||
GB2466870 | 1970-05-21 |
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DK149105B true DK149105B (en) | 1986-01-27 |
DK149105C DK149105C (en) | 1986-07-21 |
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DK242571A DK149105C (en) | 1970-05-21 | 1971-05-19 | PROCEDURE FOR PREPARING 2-ARYLOXYALKYL MORPHOLINE DERIVATIVES |
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Country | Link |
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CH (1) | CH564000A5 (en) |
CS (1) | CS163254B2 (en) |
DD (1) | DD97207A5 (en) |
DK (1) | DK149105C (en) |
GB (1) | GB1310236A (en) |
HU (1) | HU163286B (en) |
NO (1) | NO136409C (en) |
PL (1) | PL83865B1 (en) |
SE (1) | SE387118B (en) |
SU (1) | SU472506A3 (en) |
YU (1) | YU35247B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US4547584A (en) * | 1983-12-29 | 1985-10-15 | General Foods Corporation | 3-Hydroxy-4-methoxyphenyl benzoates |
WO1998007710A1 (en) * | 1996-08-23 | 1998-02-26 | Neurosearch A/S | Disubstituted morpholine, oxazepine or thiazepine derivatives, their preparation and their use as dopamine d4 receptor antagonists |
EP4308552A2 (en) * | 2021-03-18 | 2024-01-24 | Supernus Pharmaceuticals, Inc. | Derivatives of substituted morpholines and uses thereof |
EP4317141A1 (en) * | 2022-08-04 | 2024-02-07 | Curia Spain S.A.U. | Process and intermediates for the preparation of viloxazine and other 2-substituted morpholine derivatives |
-
1970
- 1970-05-21 GB GB1310236D patent/GB1310236A/en not_active Expired
-
1971
- 1971-05-18 SE SE644971A patent/SE387118B/en unknown
- 1971-05-19 DK DK242571A patent/DK149105C/en not_active IP Right Cessation
- 1971-05-19 PL PL14825671A patent/PL83865B1/pl unknown
- 1971-05-19 NO NO188871A patent/NO136409C/en unknown
- 1971-05-20 YU YU128671A patent/YU35247B/en unknown
- 1971-05-21 CS CS376771A patent/CS163254B2/cs unknown
- 1971-05-21 SU SU1660729A patent/SU472506A3/en active
- 1971-05-21 HU HUIE000450 patent/HU163286B/hu unknown
- 1971-05-21 DD DD15527671A patent/DD97207A5/xx unknown
- 1971-05-21 CH CH748571A patent/CH564000A5/xx not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
GB1310236A (en) | 1973-03-14 |
DD97207A5 (en) | 1973-04-20 |
NO136409C (en) | 1977-08-31 |
NO136409B (en) | 1977-05-23 |
SU472506A3 (en) | 1975-05-30 |
YU128671A (en) | 1980-04-30 |
HU163286B (en) | 1973-07-28 |
SE387118B (en) | 1976-08-30 |
PL83865B1 (en) | 1976-02-28 |
CS163254B2 (en) | 1975-08-29 |
YU35247B (en) | 1980-10-31 |
DK149105C (en) | 1986-07-21 |
CH564000A5 (en) | 1975-07-15 |
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