PL144105B1 - Method of obtaining cis and trans 2-cyclopenten-1,4-dioles - Google Patents
Method of obtaining cis and trans 2-cyclopenten-1,4-dioles Download PDFInfo
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- PL144105B1 PL144105B1 PL25320085A PL25320085A PL144105B1 PL 144105 B1 PL144105 B1 PL 144105B1 PL 25320085 A PL25320085 A PL 25320085A PL 25320085 A PL25320085 A PL 25320085A PL 144105 B1 PL144105 B1 PL 144105B1
- Authority
- PL
- Poland
- Prior art keywords
- trans
- cis
- cyclopentene
- diol
- mixture
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- IGRLIBJHDBWKNA-RFZPGFLSSA-N (1s,3s)-cyclopent-4-ene-1,3-diol Chemical compound O[C@H]1C[C@H](O)C=C1 IGRLIBJHDBWKNA-RFZPGFLSSA-N 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 3
- UKPIBFMHHUEUQR-RKDXNWHRSA-N [(1s,4s)-4-acetyloxycyclopent-2-en-1-yl] acetate Chemical class CC(=O)O[C@H]1C[C@H](OC(C)=O)C=C1 UKPIBFMHHUEUQR-RKDXNWHRSA-N 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000004587 chromatography analysis Methods 0.000 claims description 3
- IGRLIBJHDBWKNA-UHFFFAOYSA-N cyclopent-4-ene-1,3-diol Chemical class OC1CC(O)C=C1 IGRLIBJHDBWKNA-UHFFFAOYSA-N 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- IGRLIBJHDBWKNA-SYDPRGILSA-N (1r,3s)-cyclopent-4-ene-1,3-diol Chemical compound O[C@H]1C[C@@H](O)C=C1 IGRLIBJHDBWKNA-SYDPRGILSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UKPIBFMHHUEUQR-UHFFFAOYSA-N (4-acetyloxycyclopent-2-en-1-yl) acetate Chemical class CC(=O)OC1CC(OC(C)=O)C=C1 UKPIBFMHHUEUQR-UHFFFAOYSA-N 0.000 description 1
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- -1 aliphatic alcohols Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- JAYCALKQXZVABF-UHFFFAOYSA-N cyclopent-3-ene-1,3-diol Chemical class OC1CC=C(O)C1 JAYCALKQXZVABF-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229940094443 oxytocics prostaglandins Drugs 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 150000003180 prostaglandins Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000027272 reproductive process Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Przedmiotem wynalazku jest sposób wytwarzania cis i trans 2-cyklopenteno-1,4-dioli o wysokiej czystosci. Zwiazki te stanowia substraty do wytwarzania prostaglandyn szeregu F i D, zwiazków stosowanych jako regulatory procesów rozrodczych u bydla oraz leków wywolujacych akcje porodowa.Znany jest sposób wytwarzania cis 2-cyklopenteno-1,4-diolu polegajacy na dzialaniu tlenem na cyklopentadien w warunkach reakcji fotochemicznej oraz mieszaniny cis i trans dioli w reakcji hydrolizy ich estrów za pomoca wodorotlenku barowego. Znany jest takze sposób wy¬ twarzania trans-2-cyklopenteno-1f4-diolu w wieloetapowej syntezie, której ostatni etap polega na hydrolizie jego dibenzoesanu za pomoca wodorotlenku barowego. Jednakze wszystkie opisane w literaturze sposoby dotycza wytwarzania niewielkich próbek dioli i nie maja wiekszego znacze¬ nia praktycznego. Ponadto sposoby te nie zapewniaja otrzymywania zwiazków o duzej czystosci i jednoczesnie wymagaja stosowania ponadstechiometrycznych ilosci silnie toksycznych zwiazków baru. Procedury sa skomplikowane a wydajnosci niewielkie.Sposób wedlug wynalazku polega na tym, ze mieszanine cis i trans 3,5-diacetoksycyklo- pentenów poddaje sie reakcji z alkoholem alifatycznym w obecnosci katalitycznej ilosci soli nieorganicznych lub organicznych, a nastepnie otrzymana mieszanine cis i trans 2-cyklopenteno- -1,4-dioli rozdziela sie chromatograficznie.Jako alkohole alifatyczne stosuje sie metanol, etanol lub 2-propanol. Jako sole nie¬ organiczne lub organiczne stosuje sie weglany lub octany alkalicznych metali, fluorek potasowy lub czwartorzedowe fluorki amoniowe. Rozdzial chromatograficzny mieszaniny prowadzi sie w ko¬ lumnie wypelnionej zelem krzemionkowym.Zaleta sposobu wedlug wynalazku jest prostota wykonania i latwosc wyodrebniania cis~ -2-cyklopenteno-1,4-diolu i trans-2-cyklopenteno-1,4-diolu w postaci czystej. Otrzymane zwiazki nie zawieraja szkodliwych soli baru i sa bezwodne. Czystosc cis-2-cyklopenteno-1,4-diolu jest2 144 105 wieksza niz 99,99% a czystosc trans-2-cyklopenteno-1,4-diolu jest wieksza niz 98,8?6. V.rszystkie stosowane w procesie substancje pomocnicze mozna regenerowac i ponownie wprowadzac do procesu.Sposób wedlug wynalazku jest blizej objasniony w przykladzie wykonania.Przyklad. V7 kolbie okraglodennej o pojemnosci 1,5 dnr umieszczono 186 g miesza¬ niny cis i trans 3,5-diacetoksycyklopentenów o zawartosci 56% izomeru cis i kk% izomeru trans, 1 dur bezwodnego alkoholu metylowego oraz 3 g bezwodnego weglanu potasowego. Zawartosc kolby mieszano mechanicznie przez godzine w temperaturze 4o°C a nastepnie lotne skladniki mieszaniny oddestylowano na wyparce obrotowej. Otrzymana pozostalosc w ilosci 108 g naniesiono na kolumne szklana o srednicy 5 cm i dlugosci 220 cm, wypelniona zelem krzemionkowym (Machery-Nagel, 100-200 mesh ASTM). Rozdzial prowadzono eluujac kolumne mieszanina chloroformu i metanolu o skladzie azeotropowym zbierajac frakcje o objetosci 50 cm kazda. Frakcje 1-12 stanowia czysty eluent* który zawraca sie na kolumne. Frakcje 13-20 zawierajace mieszanine monooctanów zateza sie na wyparce obrotowej otrzymujac 12 g pozostalosci. Frakcje 24-49 zawierajace cis-2-cyklo- penteno-1,4-diol zateza sie na wyparce obrotowej otrzymujac 49 g diolu w postaci bezbarwnej krystalizujacej substancji o czystosci 99»99%» Frakcje 60-92 zawierajace trans-2-cyklopenteno- -1,4-diol zateza sie na wyparce obrotowej otrzymujac 38 g diolu o czystosci 98,8%.Sklad kolejnych frakcji z kolumny badano metoda chromatografii cienkowarstwowej stosujac plytki aluminiowe z naniesionym dwutlenkiem krzemu (Silufol), rozwijane mieszanina chloroforra- -metanol (5:1 )• Kf cis-2-cyklopenteno-1,4-diolu 0,45 R* trans-2-cyklopenteno-1,4-diolu 0,30 Czystosc produktów kontrolowano metoda chromatografii gazowej na kolumnie szklanej o dlugosci 2,5 m i srednicy 3 mm, wypelnionej 0V-225t 10% na WHP stosujac detektor plomieniowo-jonizacyjny.Temperatura kolumny wynosila 120°Cf czasy retencji 1 cis-2-cyklopenteno-1,4-diolu 24 minuty 1 trans-2-cyklopenteno-1,4-diolu 27 minut.Zastrzezenie patentowe Sposób wytwarzania cis i trans 2-cyklopenteno-1,4-diolu, znamienny tym, ze mieszanine cis i trans 3,5-diacetoksycyklopentenów poddaje sie reakcji z alkoholem alifatycz¬ nym w obecnosci katalitycznych ilosci soli nieorganicznych lub organicznych a nastepnie otrzy¬ mana mieszanine cis i trans 2-cyklopenteno-1,4-dioli rozdziela sie chromatograficznie.Pracownia Poligraficzna UP PRL. Naklad 100 egz Cena 220 zl PLThe present invention relates to a process for the preparation of high purity cis and trans 2-cyclopentene-1,4-diols. These compounds are substrates for the production of F and D series prostaglandins, compounds used as regulators of reproductive processes in cattle and drugs inducing labor. There is a known method of producing cis-2-cyclopentene-1,4-diol by treating cyclopentadiene with oxygen under the conditions of a photochemical reaction and mixtures of cis and trans diols by hydrolysis of their esters with barium hydroxide. There is also known a method for the production of trans-2-cyclopentene-1-4-diol in a multi-step synthesis, the last step of which consists in the hydrolysis of its dibenzoate with barium hydroxide. However, all the processes described in the literature concern the preparation of small samples of diols and are of no great practical importance. Moreover, these methods do not provide compounds of high purity and at the same time require the use of over-stoichiometric amounts of highly toxic compounds of barium. The procedures are complicated and the yields are low. The method according to the invention consists in reacting a mixture of cis and trans 3,5-diacetoxycyclopentenes with an aliphatic alcohol in the presence of a catalytic amount of inorganic or organic salts, and then the resulting cis-trans mixture 2 Cyclopentene-1, 4-diols are separated by chromatography. Methanol, ethanol or 2-propanol are used as aliphatic alcohols. The inorganic or organic salts used are alkali metal carbonates or acetates, potassium fluoride or quaternary ammonium fluorides. The chromatographic separation of the mixture is carried out in a column filled with silica gel. The advantage of the process according to the invention is the simplicity of implementation and the ease of isolating the cis -2-cyclopentene-1,4-diol and the pure trans-2-cyclopentene-1,4-diol. . The compounds obtained do not contain harmful barium salts and are anhydrous. The purity of the cis-2-cyclopentene-1,4-diol is greater than 99.99% and the purity of the trans-2-cyclopentene-1,4-diol is greater than 98.86. V. all auxiliary substances used in the process can be regenerated and reintroduced into the process. The method according to the invention is explained in more detail in the embodiment example. In a 1.5 dnr round bottom flask, 186 g of a mixture of cis and trans 3,5-diacetoxycyclopentenes containing 56% of the cis isomer and kk% of the trans isomer, 1 dur of anhydrous methyl alcohol and 3 g of anhydrous potassium carbonate were placed. The contents of the flask were mechanically stirred for an hour at a temperature of 4 ° C, and then the volatile components of the mixture were distilled off on a rotary evaporator. The resulting residue, 108 g, was applied to a glass column 5 cm in diameter and 220 cm long, filled with silica gel (Machery-Nagel, 100-200 mesh ASTM). The separation was carried out by eluting the column with the azeotropic mixture of chloroform and methanol, collecting fractions of 50 cm each. Fractions 1-12 are pure eluent which is recycled to the column. Fractions 13-20, containing the monoacetate mixture, are concentrated on a rotary evaporator to give 12 g of a residue. Fractions 24-49 containing cis-2-cyclopentene-1,4-diol are concentrated on a rotary evaporator to obtain 49 g of diol in the form of a colorless crystallizing substance with a purity of 99 »99%» Fractions 60-92 containing trans-2-cyclopentene The -1,4-diol is concentrated on a rotary evaporator, obtaining 38 g of a diol with a purity of 98.8%. The composition of the subsequent fractions from the column was investigated by thin-layer chromatography using aluminum plates with silicon dioxide (Silufol), developed with a chlorophore-methanol mixture (5 : 1) • Kf cis-2-cyclopentene-1,4-diol 0.45 R * trans-2-cyclopentene-1,4-diol 0.30 The purity of the products was checked by gas chromatography on a 2.5 ml glass column diameter 3 mm, filled with 0V-225t 10% on WHP using a flame ionization detector Column temperature was 120 ° Cf retention times 1 cis-2-cyclopentene-1,4-diol 24 minutes 1 trans-2-cyclopentene-1,4 -diol 27 minutes. Patent claim Process for the preparation of cis and trans 2-cyclopentene-1,4-diol, characterized by in that the cis-trans mixture of 3,5-diacetoxycyclopentenes is reacted with an aliphatic alcohol in the presence of catalytic amounts of inorganic or organic salts and the resulting cis-trans mixture of 2-cyclopentene-1,4-diols is separated by chromatography. Printing workshop of the UP PRL. Mintage 100 copies Price PLN 220 PL
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL25320085A PL144105B1 (en) | 1985-05-03 | 1985-05-03 | Method of obtaining cis and trans 2-cyclopenten-1,4-dioles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL25320085A PL144105B1 (en) | 1985-05-03 | 1985-05-03 | Method of obtaining cis and trans 2-cyclopenten-1,4-dioles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| PL253200A1 PL253200A1 (en) | 1986-11-18 |
| PL144105B1 true PL144105B1 (en) | 1988-04-30 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PL25320085A PL144105B1 (en) | 1985-05-03 | 1985-05-03 | Method of obtaining cis and trans 2-cyclopenten-1,4-dioles |
Country Status (1)
| Country | Link |
|---|---|
| PL (1) | PL144105B1 (en) |
-
1985
- 1985-05-03 PL PL25320085A patent/PL144105B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| PL253200A1 (en) | 1986-11-18 |
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