CS233420B1 - Production method of pentacyclic dilactam - Google Patents
Production method of pentacyclic dilactam Download PDFInfo
- Publication number
- CS233420B1 CS233420B1 CS167183A CS167183A CS233420B1 CS 233420 B1 CS233420 B1 CS 233420B1 CS 167183 A CS167183 A CS 167183A CS 167183 A CS167183 A CS 167183A CS 233420 B1 CS233420 B1 CS 233420B1
- Authority
- CS
- Czechoslovakia
- Prior art keywords
- dilactam
- pentacyclic
- formula
- trifluoroacetic acid
- production method
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract 2
- 239000001257 hydrogen Substances 0.000 claims abstract 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 150000003951 lactams Chemical class 0.000 abstract description 7
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
Vynález se týká způsobu výroby pentacyklickáho dilaktamu vzorce I z tetracyklických laktamů obecného vzorce II, kde R značí atom vodíku nebo alkyl s 1 až 4 atomy uhlíku, působením kyseliny trifluoroctové, případné v přítomnosti dioxanThe present invention relates to a process for the preparation of a pentacyclic dilactam of formula I from tetracyclic lactams of formula II wherein R is hydrogen or alkyl of 1 to 4 carbon atoms with trifluoroacetic acid, optionally in the presence of dioxane
Description
Vynález se týká způsobu výroby pentecykllckáho dílekternu vzorce IThe invention relates to a process for the preparation of a pentecyclic compartment of formula I
0’0 ’
O (I)O (I)
Sloučenina vzorce I je známá a představuje důležitý meziprodukt při výrobě látek s biologickou účinností. Podle známého způsobu (čs. autorská osvědčení č. 230 345) se vyrábí cyklizací tetracyklických laktamů obecného vzorce IIThe compound of formula I is known and represents an important intermediate in the production of substances with biological activity. According to the known method (cf. author's certificate no. 230 345) it is produced by cyclization of tetracyclic lactams of the general formula II
JO (II), ve kterém R značí alkyl s 1 až 4 atomy uhlíku, účinkem silné báze, nepř. hydridem sodným nebo T-butoxidem sodným. Nevýhodou tohoto postupu je práce e nebezpečnými silně bazickými činidly, jejichž použití v průmyslu je spojeno se značným rizikem.JO (II), in which R is C1-C4 alkyl by the action of a strong base, e.g. sodium hydride or sodium t-butoxide. The disadvantage of this procedure is the work with dangerous, strongly basic agents, the use of which in industry is associated with considerable risk.
tt
Uvedenou nevýhodu tohoto postupu odstraňuje způsob výroby podle vynálesu, jehož podstata spočívá v tom, že se tetracykllcké laktamy obecného vzorce II (čs. autorská, osvědčení č.224980, 224981, 830345, ve kterém R značí atom vodíku nebo alkyl s 1 až 4 atomy uhlíku, nechají reagovat s kyselinou trifluoroctovou, případně v přítomnosti organického rozpouětědla, jako např. dioxanu.The disadvantage of this process is to eliminate the process according to the invention which consists in the fact that the tetracyclic lactams of the general formula (II) (cf. Certificate No. 224980, 224981, 830345, in which R represents a hydrogen atom or a C1-C4 alkyl) carbon, may be reacted with trifluoroacetic acid, optionally in the presence of an organic solvent such as dioxane.
Následující příklady ilustrují, avěak nikterak neomezují obecnost způsobu výroby podle vynálezu.The following examples illustrate but do not limit the generality of the inventive process.
PřikladlHe did
Roztok 0,66 g (2,1 mmol) tetracyklického laktamu (II: R CH-j) ve 20 ml kyseliny trifluoroctové se ponechá stát za občasného promíchání při teplotě místnosti. Po 8 dnech, kdy dle TLC již není přítomna výchozí látka, se směs zahustí za sníženého tlaku a ke zbytku se přidá 10 ml 5% vodného amoniaku. Chloroformové výtřepy (30 a ,0 ml) se spojí a po vysušení síranem sodným se odpaří na rotační vakuové odparce. Odparek se krystaluje z etyl-acetátu. Získá se 0,46 g (77,8 %) dilaktamu I s teplotou tání 160 až 162 °C.A solution of 0.66 g (2.1 mmol) of tetracyclic lactam (II: R CH-j) in 20 ml of trifluoroacetic acid was allowed to stand with occasional stirring at room temperature. After 8 days, when no starting material is present by TLC, the mixture is concentrated under reduced pressure and 10 ml of 5% aqueous ammonia are added to the residue. The chloroform shakes (30 [mu], 0 ml) were combined and, after drying with sodium sulfate, evaporated on a rotary evaporator. The residue was crystallized from ethyl acetate. 0.46 g (77.8%) of dilactam I is obtained, m.p. 160-162 ° C.
Příklad 2Example 2
Roztok 1,72 g (5,77 mmol) laktam-kyseliny (II: R = H) v 50 ml kyseliny trifluoroctové se za občasného promíchání ponechá stát při 20 °C 4 h a potom se přebytek činidla oddestiluje. Zbytek poskytne krystalizací z etyl-acetátu 1,43 g, tj. 88,5 % dilaktaau I, t. t. 161 až 162,5 °C.A solution of 1.72 g (5.77 mmol) of lactam acid (II: R = H) in 50 ml of trifluoroacetic acid is allowed to stand at 20 ° C for 4 hours with occasional stirring and then excess reagent is distilled off. The residue was crystallized from ethyl acetate to give 1.43 g, i.e. 88.5% of dilacta I, mp 161-162.5 ° C.
Příklad 3Example 3
Postupem podle příkladu 1 se z 0,36 g (1,0 mmol) tetracyklického laktamu (II: R » CHýJHgCHgCHg) v 10 ml kyseliny trifluoroctové při teplotě 40 °C vyrobí 0,19 g (67,8 %) dilaktamu I.Following the procedure of Example 1, 0.19 g (67.8%) of dilactam I was prepared from 0.36 g (1.0 mmol) of tetracyclic lactam (II: R RCHýHHCHgCHgCHCH) in 10 ml of trifluoroacetic acid at 40 ° C.
Příklad 4Example 4
Směs 0,59 g (1,8 mol) tetracyklického laktamu (II: R CHjCHg), 5 ml kyseliny trifluoroctové a 35 ml dioxanu aa ponechá reagovat pří teplotě 60 °C, dokud dle TLC nevymizí výchozí látka. Reakění směs aa potom zpracuje postupem podle příkladu 1. Získá aa 0,36 g dilaktamu I.A mixture of 0.59 g (1.8 mol) of tetracyclic lactam (II: RCH3CH3), 5 ml of trifluoroacetic acid and 35 ml of dioxane and reacted at 60 DEG C. until the starting material disappeared by TLC. The reaction mixture aa is then worked up as in Example 1. Aa 0.36 g of dilactam I is obtained.
Příklad 5Example 5
Směa 0,27 g (0,9 mmol) laktam-kyaaliny (II: R » H), 3 ml kyseliny trifluoroctové a 25 ml dioxanu aa udržuje při teplotě 55 °C a průběh reakce sa sleduje metodou.TLC. Zpracováním reakění směsi podle příkladu 2 ae vyrobí 0,22 g dilaktamu I.A mixture of 0.27 g (0.9 mmol) of lactam-cyanoaline (II: R @ 1 H), 3 ml of trifluoroacetic acid and 25 ml of dioxane and maintained at 55 DEG C. was monitored by TLC. Working up the reaction of the mixture of Example 2 ae produced 0.22 g of dilactam I.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS167183A CS233420B1 (en) | 1983-03-10 | 1983-03-10 | Production method of pentacyclic dilactam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS167183A CS233420B1 (en) | 1983-03-10 | 1983-03-10 | Production method of pentacyclic dilactam |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS233420B1 true CS233420B1 (en) | 1985-03-14 |
Family
ID=5351662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS167183A CS233420B1 (en) | 1983-03-10 | 1983-03-10 | Production method of pentacyclic dilactam |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS233420B1 (en) |
-
1983
- 1983-03-10 CS CS167183A patent/CS233420B1/en unknown
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