NO170578B - Fremgangsmaate for fremstilling n,n-dimetylaminometylarylforbindelser - Google Patents
Fremgangsmaate for fremstilling n,n-dimetylaminometylarylforbindelser Download PDFInfo
- Publication number
- NO170578B NO170578B NO903062A NO903062A NO170578B NO 170578 B NO170578 B NO 170578B NO 903062 A NO903062 A NO 903062A NO 903062 A NO903062 A NO 903062A NO 170578 B NO170578 B NO 170578B
- Authority
- NO
- Norway
- Prior art keywords
- kawain
- methysticin
- resp
- zinc
- reaction mixture
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 11
- 150000001875 compounds Chemical class 0.000 title 1
- XEAQIWGXBXCYFX-GUOLPTJISA-N Kawain Chemical compound C1C(OC)=CC(=O)O[C@H]1\C=C\C1=CC=CC=C1 XEAQIWGXBXCYFX-GUOLPTJISA-N 0.000 claims description 20
- XEAQIWGXBXCYFX-UHFFFAOYSA-N dl-kavain Natural products C1C(OC)=CC(=O)OC1C=CC1=CC=CC=C1 XEAQIWGXBXCYFX-UHFFFAOYSA-N 0.000 claims description 10
- GTEXBOVBADJOQH-FWEMWIAWSA-N Methysticin Chemical compound C1C(OC)=CC(=O)O[C@H]1\C=C\C1=CC=C(OCO2)C2=C1 GTEXBOVBADJOQH-FWEMWIAWSA-N 0.000 claims description 9
- CGGHGWCWEAXPLK-CYBMUJFWSA-N Methysticin Natural products CC(=O)C1=CC(=O)O[C@@H](C1)C=Cc2ccc3OCOc3c2 CGGHGWCWEAXPLK-CYBMUJFWSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011541 reaction mixture Substances 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 claims description 5
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 claims description 5
- 229940117916 cinnamic aldehyde Drugs 0.000 claims description 5
- 238000003776 cleavage reaction Methods 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 230000007017 scission Effects 0.000 claims description 5
- 150000003751 zinc Chemical class 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- AXMVYSVVTMKQSL-UHFFFAOYSA-N UNPD142122 Natural products OC1=CC=C(C=CC=O)C=C1O AXMVYSVVTMKQSL-UHFFFAOYSA-N 0.000 claims 1
- 125000005907 alkyl ester group Chemical group 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- -1 cinnamic acid aldehyde Chemical class 0.000 description 4
- ZPSJGADGUYYRKE-UHFFFAOYSA-N 2H-pyran-2-one Chemical group O=C1C=CC=CO1 ZPSJGADGUYYRKE-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 2
- XHAGTHLWALCIKI-UHFFFAOYSA-N 5-phenyl-1,3-dioxole-4-carbaldehyde Chemical compound O1COC(C=O)=C1C1=CC=CC=C1 XHAGTHLWALCIKI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYYVLZVUVIJVGH-UHFFFAOYSA-N caffeine Chemical compound CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 description 2
- 229930016911 cinnamic acid Natural products 0.000 description 2
- 235000013985 cinnamic acid Nutrition 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- LPHGQDQBBGAPDZ-UHFFFAOYSA-N Isocaffeine Natural products CN1C(=O)N(C)C(=O)C2=C1N(C)C=N2 LPHGQDQBBGAPDZ-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229960001948 caffeine Drugs 0.000 description 1
- VJEONQKOZGKCAK-UHFFFAOYSA-N caffeine Natural products CN1C(=O)N(C)C(=O)C2=C1C=CN2C VJEONQKOZGKCAK-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940008139 methylenedioxycinnamic acid Drugs 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Furan Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Fremgangsmåte til utvinning av kawain resp. metysticin fra reaksjonsblandingen erholdt ved omsetning av Y-brom-B-metoksy-krotonsyrealkylestere med kanelsyrealdehyd resp. metylendioksy-kanelaldehyd i nærvær av sink.
Oppfinnelsen vedrører en fremgangsmåte til utvinning av kawain resp. metysticin fra reaksjonsblandingen erholdt ved omsetning av Y-tirom-$-metoksy-krotonsyrealkylestere med kanelsyrealdehyd, resp. metylendioksykanelsyrealdehyd i nærvær av sink. Slike fremgangsmåter er kjent (for sammenligning med hensyn til syntetisk kawain Kostermanns (Recueil 70 (1951) 79-82) resp. syntetisk metysticin US-patent nr. 2.870.164). Ved disse fremgangsmåter forløper kondensasjonen med sink som en normal addisjon av metallorganiske forbindelser til karbonylgrupper i eter, benzen, toluen, tetrahydrofuran og andre inerte oppløsningsmidler.
Ifølge disse forslag gjøres sink i første rekke oksyd-fritt, med fortynnet saltsyre, vaskes med vann-metanol-aceton-eter, tørkes ved 100°C og aktiveres deretter med jod. Reaksjonskomponentene has deretter til det forrensede og aktiverte sink. Etter avsluttet reaksjon rystes i begge tilfeller kondensasjonsblandingen med mettet ammoniumkloridoppløsning og ekstraheres flere ganger med eter resp. kloroform.
Kawain resp. metysticin samt organiske forurensninger
går over i ekstraksjonsmidlet. Utbyttene ved disse fremgangsmåter er så små - ved fremgangsmåten Kostermans fåes bare l6s7% kawain, referert til anvendt kanelaldehyd - at de ikke er teknisk anvendelige. Disse lave utbytter er å tilbakeføre på at det ved reaksjonen dannede sinkbromid ikke kan fraskilles fullstendig pg virker negativt på utbyttet ved ekstraheringsmidlets inndampning.
Denne ulempe unngås ifølge oppfinnelsen/ved; og det tilveiebringes en fremstillingsfreii^angsmåte med høyé utbytter, (f.eks. 90%, resp. 96,^%) ved at reaksjonsblandingen under omrøring innføres som en tynn stråle i en.5-115?-ig mineralsyre, fbrtrinnsvis en vandig fortynnet saltsyreoppløsning.
Derved.faller kawain.resp. metysticin med én gang ut
og i høy prosentsats og renhetsgrad uten tilsetning av et ekstra-heringsmiddel.
Etter en foretrukket utfØrelsesform ifølge oppfinnelsen avkjøles reaksjonsblandingen før innføringen til 40-45°C.
Mineralsyreoppløsningeirs konsentrasjon skalikke overstige 1155., mens konsentrasjoner på under 5% forsinker reaksjons-produktets utfelling.,
Det er kjent ved reaksjonsprodukter ifølge Reformatzki-reaksjonen å anvende fortynnet mineralsyre istedenfor ammoniumklorid-oppløsning til sinksaltets spaltning. Eksempelvis er en slik fremgangsmåte blitt anvendt ved en 6-ha'iogenkrotonsyreester etter omsetning med kanelaldehyd. Ved anvendelse av denne fremgangsmåte ved et metoksykrotonsyreester-omsetningsprodukt, dvs. et omsetningsprodukt med pyronringdannelse, lå imidlertid anvendelsen av en slik fortynnet mineralsyre ikke nær. Den var tvert imot fjern fordi OCH^-gruppen i en halogen-metoksykrotonsyreester er overordertiLig følsom, og pyronringens spaltning inntrer allerede ved meget små syrekonsentrasjoner ved vanlig temperatur ved henstand.
Overraskende inntrer det ingen forsåpning resp.
spaltning av pyronringen når reaksjonsproduktet innbefattende det organiske oppløsningsmiddel innføres i tynn stråle under omrøring i den fortynnede syreoppløsning.
Oppfinnelsen skal forklares nærmere ved hjelp av
noen eksempler.
Eksempel 1. x-
1000 g kanelaldehyd og 1700 g etyl-Y-brom-8-metoksykrotonat blandes med 2500 ml benzen, toluen, tetrahydrofuran eller et annet inert oppløsningsmiddel og has langsomt på sink. Etter begynnende oppvarmning går reaksjonen videre uten varmetil-førsel. Etter en time holdes blandingen ennå ytterligere 2 timer ved 80°C.
Deretter lar man det avkjøle til 40-45°C og suger under stadig bevegelse hele i tynn stråle inn i en 10/S-ig HCl-oppløsning. Kawainet faller ut spontant.
Etter to gangers utvasking er sinksaltet fullstendig fjernet. Således ble det oppnådd 1120 g råkawain og etter omkrystallisering 900 g renkawain, hvilket tilsvarer et utbytte på 90%, referert til kanelaldehyd.
Eksempel 2.
500 g metylendioksy-kanelaldehyd og 640 g etyl-Y-brom-3-metoksykrotonat blandes med 2000 ml benzen, toluen., tetrahydrofuran eller et annet inert oppløsningsmiddel og has langsomt på sink. Etter begynnende oppvarmning går reaksjonen videre uten varmetilførsel. Etter 1 time holdes blandingen ennå ytterligere 2 timer ved 80°C. Deretter lar man det avkjøle til 40-45°C og suger under stadig bevegelse hele i tynn stråle inn i en 10#-ig vandig HCl-oppløsning. Metylsticinet fallerut med en gang med lysebrun farge. Etter to gangers utvasking er sinksaltet fullstendig fjernet.
Det fåes 604 g råmetysticin og etter omkrystallisering 482 g renmetysticin, hvilket tilsvarer et utbytte på 96,4$, referert til metylendioksykanelaldehyd. Smp. ved 134°C.
Claims (2)
1. ' Fremgangsmåte til utvinning av kawain resp. metysticin fra reaksjonsblandingen erholdt ved omsetning av ybrom-B-metoksy-krotonalkylestere med kanelsyrealdehyd resp. metylendioksykanelaldehyd i nærvær av sink og et inert organisk oppløsningsmiddel og spaltning av sinksaltene for frigjøring av kawain resp. metysticin, karakterisert ved at spaltningen gjennomføres ved inn-føring av reaksjonsblandingen i tynn stråle under omrøring i en 5-ll#-ig mineralsyre, fortrinnsvis saltsyre under utfelling av kawain resp. metysticin.
2. Fremgangsmåte ifølge krav 1, karakterisert ved at reaksjonsblandingen etter avkjøling til mellom 40 og 45°C innføres i en ca. 10%- ig saltsyreoppløsning.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DK340089A DK161513C (da) | 1989-07-10 | 1989-07-10 | Fremgangsmaade til fremstilling af n,n-dimethylaminomethylarylforbindelser |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| NO903062D0 NO903062D0 (no) | 1990-07-09 |
| NO903062L NO903062L (no) | 1991-01-11 |
| NO170578B true NO170578B (no) | 1992-07-27 |
| NO170578C NO170578C (no) | 1992-11-04 |
Family
ID=8122450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO903062A NO170578C (no) | 1989-07-10 | 1990-07-09 | Fremgangsmaate for fremstilling n,n-dimetylaminometylarylforbindelser |
Country Status (8)
| Country | Link |
|---|---|
| AT (1) | AT398565B (no) |
| DD (1) | DD296481A5 (no) |
| DE (1) | DE4020964A1 (no) |
| DK (1) | DK161513C (no) |
| FI (1) | FI102166B1 (no) |
| HU (1) | HU206076B (no) |
| NO (1) | NO170578C (no) |
| SE (1) | SE501162C2 (no) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5757480B2 (ja) * | 2011-05-13 | 2015-07-29 | 国立大学法人広島大学 | イオン液体、イオン液体の製造方法、および同イオン液体を含む蓄電装置 |
-
1989
- 1989-07-10 DK DK340089A patent/DK161513C/da not_active IP Right Cessation
-
1990
- 1990-06-20 AT AT131390A patent/AT398565B/de not_active IP Right Cessation
- 1990-06-30 DE DE19904020964 patent/DE4020964A1/de not_active Withdrawn
- 1990-07-05 SE SE9002363A patent/SE501162C2/sv unknown
- 1990-07-09 DD DD34263490A patent/DD296481A5/de not_active IP Right Cessation
- 1990-07-09 FI FI903457A patent/FI102166B1/fi not_active IP Right Cessation
- 1990-07-09 NO NO903062A patent/NO170578C/no unknown
- 1990-07-09 HU HU414390A patent/HU206076B/hu not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DK340089D0 (da) | 1989-07-10 |
| FI102166B (fi) | 1998-10-30 |
| NO903062L (no) | 1991-01-11 |
| DK340089A (da) | 1991-01-11 |
| FI102166B1 (fi) | 1998-10-30 |
| AT398565B (de) | 1994-12-27 |
| HU904143D0 (en) | 1990-12-28 |
| ATA131390A (de) | 1994-05-15 |
| DK161513B (da) | 1991-07-15 |
| HU206076B (en) | 1992-08-28 |
| SE9002363L (sv) | 1991-01-11 |
| NO170578C (no) | 1992-11-04 |
| SE501162C2 (sv) | 1994-11-28 |
| FI903457A0 (fi) | 1990-07-09 |
| DK161513C (da) | 1991-12-23 |
| DD296481A5 (de) | 1991-12-05 |
| SE9002363D0 (sv) | 1990-07-05 |
| DE4020964A1 (de) | 1991-01-17 |
| NO903062D0 (no) | 1990-07-09 |
| HUT54615A (en) | 1991-03-28 |
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