CS269023B1 - [5-Methoxy-4-oxo-4H-pyrene-2-yl] -ethyl-alaniumabromide and its preparation - Google Patents
[5-Methoxy-4-oxo-4H-pyrene-2-yl] -ethyl-alaniumabromide and its preparation Download PDFInfo
- Publication number
- CS269023B1 CS269023B1 CS883606A CS360688A CS269023B1 CS 269023 B1 CS269023 B1 CS 269023B1 CS 883606 A CS883606 A CS 883606A CS 360688 A CS360688 A CS 360688A CS 269023 B1 CS269023 B1 CS 269023B1
- Authority
- CS
- Czechoslovakia
- Prior art keywords
- oxo
- pyran
- preparation
- ethyl
- methoxy
- Prior art date
Links
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Rieianla ea týká zlúčeniny vzorca 1 a epóeobu pripravy tejto zlučeniny pGeobania plynného broaovodike na roztok 2-azidoaetyl-5-aatoxy-4H-pyrén4-ónu v kyselina octoval v pritoanoetl fenolu při raakčnej teplota 70 až 100 °C a raakčnoa čaae 20 až 120 ain.The invention relates to a compound of formula 1 and a process for preparing this compound by adding hydrogen bromide gas to a solution of 2-azidoethyl-5-ethoxy-4H-pyren4-one in acetic acid in the presence of phenol at a reaction temperature of 70 to 100 °C and a reaction time of 20 to 120 min.
Description
CS 269 023 Bl 1
Vynález ea týká /5-aetoxy-4-oxo-4H-pyrán-2-yl/eetylaa6niuabroaidu vzorce I
o apSaobu přípravy tejto zlúčenlny. Podlá znáaeho apéaobu aa žtrukturálne blízka zlú£e-nina /5-hydroxy-4-oxo-4H-pyrán-2-yl/-aetylaaániuabroaid připravuje pSaobenia broaovodi-ka na 2-azidoaetyl-5-hydroxy-4H-pyrán-4-ún v kyselina octovej®
Autoři Atkineon 3®G®, Glrard Y®, Rokách 3®, Rooney C.S®, Mc Farlane C.S®, RockhaaA®, Shere N.N., O.Med.Chea. 22.99/1979/. ktorl uskutočnili tuto přípravu, chladili ra-akčnú zase ledový· kúpeloa a doelahli výřežok produktu 81 %, dlžka reakčného £aau ni·
Je uvedená®
Predmetoa vynálezu Je /5-Betoxy-4-oxo-4H-pyrán-2-yl/aetylaaóniuabroaid vzorce I aapoeob Jeho přípravy, ktorý epočlva v toa, že aa na roztok 2-azldoaatyl-5-aetoxy-4H-pyrán-4-ónu v kyselina octovej pSsobl plynný· broaovodikoa v čaae 20 až 120 ain priraak£nej teplota 70 až 100°C. S výhodou lze uskutočňovat túto pripravu v čase 90 min zareakčnej teplota 80°C.
Zlatilo ea, že znáayn poatupoa, ktorýe aápřipravuje /5-hydroxy-4-oxo-4H-pyrán-2-yl/aatylaBÓniuabroaid ea tento podařilo připravil iba vo výfažku, ktorý nepřevyšuje8 %, /5-Metoxy-4-oxo-4H-pyrán-2-yl/aetylaBÓniuabromid aa týato poatupoa nepodařilopřipravit® Uvedená nedostatky odstraňuje postup podlá vynálezu, v ktoroa aa nažil vhod-ná reak£ná podalenky, pri ktorých Je aožná /5-metoxy-4-oxo-4H-pyrán-2yl/aetylaaániun-broald připravit vo výtažku 67 Pre porovnanie aa uskutečnili prlpravy tejto látkypri rťíznych reakčných čaeoch a teplote*
Podlá najdenáho spSsobu přípravy je prlebeh reakcle velal dobré a lahko kontrolo-vatelnýs v reakčnej banka aožno prlaoo pozorovat vývoj plynnáho duslka i vylu£ovanietuháho produktu z roztoku*
Najdenýa sp6eoboa Je aožná /5-aetoxy-4-oxo-4H-pyrán-2-yl/-aetylaaóniuabroaid při-pravit a použit ho na pripravu nových organických zlú£enin® Najdený spúsob je aožnápoužit aj na pripravu iných priaárnych alifatických aaínov z prlelužných alifatickýchazidov® IČ epaktrá aú naaeraná v KBr tabletách, vlnopo£et Je uvedený v ca-^. NMR spekt-rá aú naaeraná v roztoku deutarovanáho dlaetylaulfoxidu, eheaický poaun v ppa® čistotalátok ea sledovala na tenkých vrstvách ailikagálu /Silufol UV 254, Kavalier Votice/.
Nasledujuce příklady bližžie oevetlujú spdsob přípravy 5-aetoxy-4-oxo-4H-pyrán-2-yl/aetylaaóniuabroaidu, podlá vynálezu. Přiklad 1 A. 2-Azidoaatyl-5-aetoxy-4H-pyrán-4-on 0,2 aol 2-chlúraetyl-5-aetoxy-4H-pyrán-4-ínu aa rozpust! v 40 ca3 bezvodáho diaa-tylforaaaidu a přidá aa po £astiach roztok 0,2 aol azidu sodného v 110 ca3 bezvodáhodlaotylforaaaidu tak, aby teplota reak£nej zaesl nepreatúpila 30°C. Potoa aa zaee24 h aleža při teplote aleetnostl® Vylúčoný chlorid sodný aa odfiltruje a z roztoku eavolné na hodinových aklácb doaucha odpaří rozpúžtadlo. Získaná tuhá látka sa přečistikryitalizáclou z atylacetátu. 2-Azldoaetyl-5-aetoxy-4H-pyrán-4-on aa ziska vo výtažku55 % a tvoři bezfarabná kryžtály, t.t. 74 - 75 °C,Rp-0,56, Analýza pre C Η N 0 /M.r.- CS 269 023 B1 161,15/ vypočítané! 46,41 % C, 3,90 % H, 23,19 H, zlatěné! 46,58 % C, 4,02 % H, 23,54 %N. Ιδ spektrálné charakteristiky!/C-C/ 1585,«p /0-0/ 1610, 1635, /N3/ 2090, 2150. NMR spektrálné charakteristiky! H - 6 8,17 e, H - 3 6,41 a, CH2-C-C 4,42 a, 0-CH33,66 e. 8. /5-Metoxy-4-oxo-4H-pyrán-2-yl/aetylaajnluabroBld
Do troj hrd love J banky eo spatný· chladičoa, teploaeroa a trubicouna přívodplynného broaovodika ea vnesl· 0,1 sol 2-azldoaetyl-5-Betoxy-4H-pyrén-4-čnu, 0,09 solfenolu a 180 ca3 99 %-eJ kyseliny octovej. Do reakčnej zasel aa vovádza plynný broao-vodik. Po uplynuti 15 ain aa reakčná zaes poaocou olejového kúpela ohřeje na teplotu80 °C a broaovodlk aa do zaeai ailnýa p.rúdoa vovédza Saliich 90 ain tak, aby teplotareakčnej zaesl bole 80 °C. Pozoruje ea vývoj plynného dualka a vylučovanie tuhého pro-duktu z roztoku* Zase ea ochladl na 10 °C, tuhé létka ea na frite odfiltruje, preayjeaa ochládanou kyselinou octovou, vysuSi ea a Sistie kryitalizáciou z bezvodého aetenoluza prldanla aktívneho uhlla a sllikagélu. Zlska ea /5-aetoxy-4-oxo-4H~pyrén-2-yl/aetyla-aániuabroaid vo výtažku 67 %, tvorlaci bezfarebné kryítély, t.t. 218 - 219 °C /v zata-venej kapiláře/, Rp - 0,19. Analýza pre C7HioNO3Br /M.r. - 236,06/ vypočítané! 35,62 % C, 4,27 % H, 5,93 % Ň, zistenét 35,52 % C, 4,59 5,98 % N. IČ epektrélne charakte- ristiky Vg/C-C/ 1585, V /0-0/ 1610, 1637, /ff-H/ 2440, NMR spektrálné charakte-ristiky NH3 8,52 e, H - 6 8,19 a, H - 3 6,53 s, CHg-C-C 4,05 a, O-CHj 3,66 s. Přiklad 2
Za použitia navážek i pracovného postupu ako v přiklad* 1 B počeš reakčného času90 ain aviak prl reakčnej teplota 40 °C je vývoj plynného duslka 1 vylučovanie tuhéhoproduktu nepatrné. Z reakčnej zaeai po pročištěni kryitalizáciou z aetanolu aa zlaka/5-aatoxy-4-oxo-4H-pyrán-2-yl/aetylaaóniuabroaid vo výtažku 9 %. Příklad 3
Za použitia navážek i pracovného postupu ako v přiklad* 1 B aviak při reakčnej tep-lot· 80 °C a reakčnoa čase 1 h aa zlaka /5-aetoxy-4-oxo-4H-pyrán-2-yl/aatyla'aúnluabro-ld po prečlatenl kryitalizáciou z aetanolu vo výtažku 59 %. Přiklad 4
Za použitia navážok i pracovného postupu ako v přiklade 1 B pri reakčnoa čaae 90ain aviak pri reakčnej teploto 95 °C dochádza k čarnaniu reakčnej zaeai. Po pročištěniproduktu kryitalizáciou z aetanolu ea /5-metoxy-4-oxo-4H-pyrán-2-yl/metylaB5niuabroeidzlaka vo výtažku 60 %.
CS 269 023 B1
The invention relates to [5-aethoxy-4-oxo-4H-pyran-2-yl] -ethyl-auabroaid of formula I
and the method for preparing the compound. According to the invention and the structurally close compound (5-hydroxy-4-oxo-4H-pyran-2-yl) -ethylaanababa-amide, the preparation of a hydrobromide is prepared to 2-azido-ethyl-5-hydroxy-4H-pyran-4-one. Feb in Acetic Acid®
Authors Atkineon 3®G®, Glrard Y®, Year 3®, Rooney CS®, Mc Farlane CS®, RockhaaA®, Shere NN, O.Med.Chea. 22.99 (1979). who carried out this preparation, cooled the ice-bath and the product's crops recovered 81%, the reaction £ aau ni ·
It is listed
SUMMARY OF THE INVENTION Is-5-Betoxy-4-oxo-4H-pyran-2-yl / -ethyl-aalaniumaba-aa of Formula (I) and its preparation, which results in a solution of 2-azldoaatyl-5-aethoxy-4H-pyran-4- in acetic acid, the gaseous effluent is mixed at a rate of 20 to 120 and a suitable temperature of 70 to 100 ° C. Preferably, this preparation can be carried out at 90 min at a temperature of 80 ° C.
Gold and that the poatupoa that he prepares / 5-hydroxy-4-oxo-4H-pyran-2-yl / aatylaBoniumababaaa and e have only prepared in a yield of not more than 8%, 5-Methoxy-4-oxo-4H- The above-mentioned drawbacks are eliminated by the process according to the invention in which a suitable reaction lot is found in which the 5-methoxy-4-oxo-4H-pyran-2-yl / 5-methoxy-4-oxo-4H-pyran-2-yl is used. to prepare aetylalanane-broald in yield 67 For comparison aa preparations of this substance were carried out at different reaction temperatures and temperatures *
According to the method of preparation described above, the reaction is good and easily controllable in the reaction flask, and the evolution of gaseous nitrogen and precipitated product from the solution can be observed.
The present invention discloses the use of 5-aethoxy-4-oxo-4H-pyran-2-yl / -aethylalanuabroaid for use in the preparation of new organic compounds. aliphatic azide® IR epactants, which are prepared in KBr tablets; The NMR spectra were taken up in a solution of deuterated paletyl sulphoxide, an ehea poaun in ppa® puretalate and monitored on thin layers of silica (Silufol UV 254, Kavalier Votice).
The following examples illustrate the preparation of 5-aethoxy-4-oxo-4H-pyran-2-yl-ethyl-alaionicabaaid according to the invention. EXAMPLE 1 A. 2-Azidoatyl-5-aethoxy-4H-pyran-4-one 0.2 aol of 2-chloroethyl-5-ethoxy-4H-pyran-4-one and a sol. in 40 [mu] l of anhydrous diastylphosphoramide, and a solution of 0.2 [mu] l of sodium azide in 110 [mu] l of anhydrous alalylphosphoramide is added in such a way that the reaction temperature does not rise to 30 [deg.] C. Potoa aa zae24 h but at a temperature of 0 ° C Sodium chloride is eliminated and the solvent is filtered off and the solvent is evaporated and the solution is freed from the solution. The solid obtained was purified by crystallization from ethyl acetate. 2-Azldoaethyl-5-aethoxy-4H-pyran-4-one and 55% yield and form colorless crystals, mp 74-75 ° C, Rp-0.56, Analysis for CΗN 0O / M Mr-CS 269 023 B1 161.15 / calculated! H, 3.90;% H, 23.19; H, 4.02; N, 23.54. Ιδ spectral characteristics! / CC / 1585, «p / 0-0 / 1610, 1635, / N3 / 2090, 2150. NMR spectral characteristics! H-8.17 e, H-6.41 a, CH2-CC 4.42 and O-CH33.66 e. 8. (5-Methoxy-4-oxo-4H-pyran-2-yl) aetylaajnluabroBld
Into a three-necked flask, the cooler, the heat and the gas supply tube were introduced and 0.1 sol of 2-azoloaethyl-5-Betoxy-4 H -pyrene-4-one, 0.09 solfenol and 180 ca 3 99% -eJ were introduced. acetic acid. Broao-hydrogen gas is introduced into the reaction mixture. After 15 minutes and the reaction mixture was heated to 80 DEG C. and the reaction mixture was heated to 80 DEG C. with a temperature of 80 DEG C. until the reaction mixture was heated to 80 DEG. It observes and develops the gaseous doubles and secretes the solid product from the solution. Again, it was cooled to 10 ° C, the solid and ea filtered on the frit, washed with acetic acid, dried, and Sistie crystallized from anhydrous and acetone to give activated carbon and sllikage. The ea and / or 5-aethoxy-4-oxo-4H-pyrene-2-yl / -ethyl-alanuabroaid in 67% yield, colorless crystals, mp 218-219 ° C (in capillary capillary), Rp = 0.19 . Analysis for C7H10NO3Br / Mr - 236.06 / Calcd! 35.62% C, 4.27% H, 5.93% NO, found 35.52% C, 4.59 5.98% N. IR ID Vg / CC / 1585, V / 0-0 (1610, 1637, [ff-H] 2440, NH3 NMR spectral characteristics 8.52 e, H-6, 8.19 a, H-3 6.53 s, CHg-CC 4.05 a, O-CH3 3.66 s. Example 2
Using batches as well as the working procedure as in Example 1B, the reaction time of 90 DEG C. and the reaction temperature of 40 DEG C., the evolution of gaseous nitrogen 1 is negligible. From the reaction mixture, after purification by crystallization from aethanol and a (5-alkoxy-4-oxo-4H-pyran-2-yl) -ethyl-alabolamide in 9% yield. Example 3
Using batches as well as the working procedure as in Example 1B at a reaction temperature of 80 ° C and a reaction time of 1 h and a low of (5-aethoxy-4-oxo-4 H -pyran-2-yl) aa-alanic acid, 1d after recrystallization from aethanol in 59% yield. Example 4
Using batches as well as the working procedure as in Example 1B, at reaction temperature of 95 ° C, the reaction reaction occurs. After purification by crystallization from aethanol a5 / 5-methoxy-4-oxo-4H-pyran-2-yl / methylbenzoic acid in 60% yield.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS883606A CS269023B1 (en) | 1988-05-27 | 1988-05-27 | [5-Methoxy-4-oxo-4H-pyrene-2-yl] -ethyl-alaniumabromide and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS883606A CS269023B1 (en) | 1988-05-27 | 1988-05-27 | [5-Methoxy-4-oxo-4H-pyrene-2-yl] -ethyl-alaniumabromide and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS360688A1 CS360688A1 (en) | 1989-08-14 |
| CS269023B1 true CS269023B1 (en) | 1990-04-11 |
Family
ID=5376606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS883606A CS269023B1 (en) | 1988-05-27 | 1988-05-27 | [5-Methoxy-4-oxo-4H-pyrene-2-yl] -ethyl-alaniumabromide and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS269023B1 (en) |
-
1988
- 1988-05-27 CS CS883606A patent/CS269023B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS360688A1 (en) | 1989-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| SK153696A3 (en) | Process for producing n-£3-(3-cyanopyrazolo£1,5-a|pyrimidin-7-yl) phenyl|-n-ethylacetamide | |
| Bolhofer | β-Phenylserine | |
| McKay | The Preparation of N-Substituted-N1-nitroguanidines by the Reaction of Primary Amines with N-Alkyl-N-nitroso-N1-nitroguanidines | |
| Angier et al. | Synthesis of pteroylglutamic acid. III | |
| CN110845403A (en) | Preparation method of nicorandil | |
| NO783559L (en) | PROCEDURE FOR PREPARING 2,6-DIAMINONE BULARINES | |
| US5498711A (en) | Synthesis of 4,10-dinitro-2,6,8,12-tetraoxa-4,10-diazatetracyclo[5.5.0.05,903,11]dodecane | |
| NO800868L (en) | PROCEDURE FOR THE PREPARATION OF 2,6-DIAMINONBULARINE COMPOUNDS | |
| DE68920648T2 (en) | Process for the preparation of O2,2'-anhydro-1- (beta-D-arabinofuranosyl) thymine. | |
| US5162584A (en) | Fluorobenzene derivatives | |
| Kuritani et al. | Optically Active Triptycenes, V. Synthesis, Optical Resolution and Absolute Configuration of 2, 7-Disubstituted Triptycenes. | |
| US2549685A (en) | Dioxy substituted 2-aminoindanols | |
| CS269023B1 (en) | [5-Methoxy-4-oxo-4H-pyrene-2-yl] -ethyl-alaniumabromide and its preparation | |
| US2637731A (en) | Imidazopyridines | |
| JPS5824569A (en) | Purification of imidazole derivative | |
| US2744932A (en) | Anhydrotetracycline | |
| Honda et al. | Syntheses of 3-nitro-2, 4, 6-trihydroxybenzamide and thiobenzamide derivatives as highly potent inhibitors of photosynthetic electron transport | |
| US3287396A (en) | Phenyldesoxythyronines | |
| KR102801536B1 (en) | Preparation for Benzoamine derivatives | |
| US3094458A (en) | 2, 2, 3, 3-tetrachloro-1, 4-butanediol cyclic acid phosphate | |
| CURRAN et al. | Pteridine Chemistry. VIII. The Cyanoethylation of Some Hydroxypteridines | |
| US2697095A (en) | Penicillin salts of glycine-diphenylamides | |
| KR810001172B1 (en) | Method for preparing N²-substituted-2,6-diaminonebulin | |
| Ertan et al. | Synthesis of New Annellated Flavonoid Derivatives Possessing Spasmolytic Activity‐VII | |
| US2874181A (en) | Salicylic acid 2, 6-dimethyl-4-n-propoxybenzoate |