DD135726B1 - PROCESS FOR PREPARING C LOW 19-GIBBERELINALDEHYDE - Google Patents
PROCESS FOR PREPARING C LOW 19-GIBBERELINALDEHYDE Download PDFInfo
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- DD135726B1 DD135726B1 DD20477178A DD20477178A DD135726B1 DD 135726 B1 DD135726 B1 DD 135726B1 DD 20477178 A DD20477178 A DD 20477178A DD 20477178 A DD20477178 A DD 20477178A DD 135726 B1 DD135726 B1 DD 135726B1
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- German Democratic Republic
- Prior art keywords
- gibberellin
- oxidizing agent
- adam
- aldehyde
- hydroxymethyl
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- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000003448 gibberellin Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- -1 chromium peroxide Chemical class 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 2
- 229930191978 Gibberellin Natural products 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- IXORZMNAPKEEDV-UHFFFAOYSA-N gibberellic acid GA3 Natural products OC(=O)C1C2(C3)CC(=C)C3(O)CCC2C2(C=CC3O)C1C3(C)C(=O)O2 IXORZMNAPKEEDV-UHFFFAOYSA-N 0.000 description 9
- ORILYTVJVMAKLC-UHFFFAOYSA-N Adamantane Natural products C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 6
- IXORZMNAPKEEDV-OBDJNFEBSA-N gibberellin A3 Chemical class C([C@@]1(O)C(=C)C[C@@]2(C1)[C@H]1C(O)=O)C[C@H]2[C@]2(C=C[C@@H]3O)[C@H]1[C@]3(C)C(=O)O2 IXORZMNAPKEEDV-OBDJNFEBSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229930195732 phytohormone Natural products 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- YCQANBSROMMIQP-UHFFFAOYSA-N 1-chloropyrrolidine-2,5-dione;methylsulfanylmethane Chemical compound CSC.ClN1C(=O)CCC1=O YCQANBSROMMIQP-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000005557 antagonist Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 238000011138 biotechnological process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229940047545 earoxide Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- ZOWHLBOPCIHIHW-KQBHUUJHSA-N gibberellin A5 Chemical compound C([C@H]12)C[C@@](C3)(O)C(=C)C[C@@]13[C@@H](C(O)=O)[C@@H]1[C@]3(C)C(=O)O[C@@]12CC=C3 ZOWHLBOPCIHIHW-KQBHUUJHSA-N 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- UFONDNJTHOTBBM-UHFFFAOYSA-N iron(2+);tetracyanide Chemical compound [Fe+2].N#[C-].N#[C-].N#[C-].N#[C-] UFONDNJTHOTBBM-UHFFFAOYSA-N 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Description
Erfinder:Inventor:
Dr. M. LISCHEWSKI Dr. habil. G. ADAMDr. M. LISCHWSKI habil. G. ADAM
Verfahren zur Herstellung von Сигг-Gibberellinaldehyden Process for the preparation of С иг г-Gibberellinaldehyden
Die Erfindung betrifft ein Verfahren zur Herstellung von C.Q-Gibberellin-(7)-aldehyden. Darunter sind Gibberellin-Derivate zu verstehen, die in Position 6 des 20-nor-ent-Gibberellan-Grundgerüsts eine Aldehydgruppe besitzen. Dabei ist das 20-nor-ent-Gibberellan-Grundgerüst intakt oder geringfügig (z.B. seco-, homo- oder nor -ent-Gibberellan) verändert und gegebenenfalls in verschiedenster Weise substituiert.The invention relates to a process for the preparation of C.Q gibberellin (7) aldehydes. These are gibberellin derivatives which have an aldehyde group in position 6 of the 20-nor-ent-gibberellan skeleton. The 20-nor-de-gibberellan backbone is intact or slightly modified (e.g., seco-, homo- or nor-pent-gibberellan) and optionally substituted in a variety of ways.
Gibberelline besitzen als Phytohormone multipler 7/irkung große biologische Bedeutung. Es ist bekannt, daß eine Strukturmodifikation solcher natürlich vorkommender Gibberelline zu Verbindungen mit veränderter biologischer Aktivität führt. Beispielsweise zeigen Desoxygibberellin C, Pseudogibberellin Аи sowie bestimmte fluorierte Vertreter gibberellin-antagonistische Eigenschaften. Zahlreiche weitere strukturmodifizierte Gibberelline wurden auf partial- und totalsynthetischem Wege dargestellt und auf ihre biologische Aktivität geprüft. Ferner werden Gibberelline in Form ihrer markierten Vertreter angewandt, so z.B. für biotechnologische Verfahren, für die Untersuchung von Biosynthese, Metabolismus, Transport, Verteilung, Wirkungsweise und Struktur/Wirkungs-Analyse dieser Phytohormone und ihrer partialsynthetischen Strukturanaloga als Grundlage für die Synthese heuer Wirkstoffe.Gibberellins have great biological significance as phytohormones of multiple origin. It is known that structural modification of such naturally occurring gibberellins leads to compounds with altered biological activity. For example, deoxygibberellin C, pseudogibberellin Ai and certain fluorinated species exhibit gibberellin antagonist properties. Numerous other structurally modified gibberellins have been synthesized by partial and total synthetic methods and tested for their biological activity. Furthermore, gibberellins are used in the form of their labeled representatives, e.g. for biotechnological processes, for the investigation of biosynthesis, metabolism, transport, distribution, mode of action and structure / activity analysis of these phytohormones and their partial synthetic structural analogues as a basis for the synthesis of active substances.
Charakteristik der bekannten technischen Lösungen Characteristic of the known technical solu tions
C^g-Gibberellin-Derivate mit 6-ständiser Aldehydfunktion sind bekannt und können nach folgenden Methoden synthetisiert werden:C ^ g-gibberellin derivatives with 6-position aldehyde function are known and can be synthesized by the following methods:
1. Durch Reduktion von C^g~Gibberellinanhydriden mit Dinatriumtetracarbonyl-ferrat (-II) entstehen C^-G-ibberellin-(7)-aldehyde /~LI. LISCHEV/SKI und G. ADAM, DDE-Pat ent schrift 112 753 vom 22.5.197^; ІЛ. LISCHEtfSKI und G. ADAM, Tetrahedron Letters 2835 (1974)_7.1. Reduction of C ^ g gibberellin anhydrides with disodium tetracarbonyl-ferrate (-II) produces C ^ -G-ibberellin- (7) -aldehydes / ~ LI. LISCHEV / SKI and G. ADAM, DDE patent specification 112 753 of 22.5.197 ^; ІЛ. LICHERTSKI and G. ADAM, Tetrahedron Letters 2835 (1974) _7.
2. Durch Oxydation von CL^-Gibberellin-Derivaten mit in 6-Stellung befindlicher Hydroxymethylgruppe durch bestimmte SuIfoniumsalze, insbesondere durch den N-Chlorsuccinimid-Dimethylsulfid-Komplex, entstehen C,,g-Gibberellin-(7)-aldehyde /"M. LISCHE77SKI und G. ADAM, DDR-Patentschrift 120 875 vom 29.4.1975» M. LISCHEWSKI und G. ADAI,!, Tetrahedron Letters 2569 (1975)? M. LISCHEWSKI und G. ADAM, Z. Chem. 16, 486 (1976)_7.2. By oxidation of CL ^ gibberellin derivatives with 6-position hydroxymethyl group by certain sulfonium salts, in particular by the N-chlorosuccinimide-dimethyl sulfide complex, arise C ,, g-gibberellin (7) -aldehydes / "M. LISCHE 77SKI and G. ADAM, GDR Patent 120,875, 29.4.1975 M. LISCHEWSKI and G. ADAI, I, Tetrahedron Letters 2569 (1975), M. LISCHEWSKI and G. ADAM, Z. Chem., 16, 486 (1976 ) _7.
Die beschriebenen Verfahren besitzen folgende Nachteile:The described methods have the following disadvantages:
Zu 1: Die hierbei gebildeten C^g-Gibberellin~(7)-aldehyde entstehen in nur niedriger Ausbeute und sind außerdem schwierig isolierbar, so daß die Aldehyde bei diesem Verfahren sofort zu C,.Q-Gibberellin-(7)-alkoholen reduziert werden.To 1: The C ^ g-gibberellin ~ (7) -aldehydes formed in this way are produced in low yield and are also difficult to isolate, so that the aldehydes in this process immediately reduced to C, .Q-gibberellin (7) -alcohols become.
Zu 2: Bei diesem Verfahren entsteht als Nebenprodukt ein 6ß-/~ivlet hy It hi o-met hy 1 oxy-met hyl_7- ( 7 ) -nor -g ibb er e 11 in-Derivat.To 2: A by-product of this process is a 6β- / ω-tetrahydroxy-methoxy-1-hydroxy-7-yl-7-ylbigene 11 in derivative.
Es ist das Ziel der Erfindung, ein allgemein anwendbares Verfahren zu entwickeln, das die Herstellung von G.q-GibbereilinDerivat en mit 6-stendiger Aldehydgruppe in hoher Ausbeute und ohne Nebenprodukte ermöglicht.It is the object of the invention to develop a generally applicable process which enables the production of G.q. Gibbereilin derivatives with 6-stage aldehyde group in high yield and without by-products.
Darlegung des V/esens der ErfindungLoan of the invention
Die Aufgabe der Erfindung besteht darin, G^Q-Gibberellin-Derivate mit 6-ständiger Hydroxymethylgruppe spezifisch zu CnQ-Gibberellin-(7)-aldehyden zu oxydieren.The object of the invention is to oxidize G ^ Q-gibberellin derivatives with 6-position hydroxymethyl group specifically to CnQ gibberellin (7) aldehydes.
Erfindungsgemäß wird ein C.q-Gibberellin-Derivat mit 6-ständiger Hydroxymethylgruppe mit einem chromhaltigen Oxydationsmittel zum C^Q-Gibberellin-(7)-aldehyd umgesetzt.According to the invention, a C.q. gibberellin derivative having a 6-membered hydroxymethyl group is reacted with a chromium-containing oxidizing agent to give C, Q-gibberellin (7) -aldehyde.
Die als Ausgangsstoffe eingesetzten C^q-Gibberellin-Derivate mit in 6-Stellung befindlicher Kydroxymethylgruppe werden nach bekannten Verfahren synthetisiert /~M. LISCHEüSKI und G. ADAM, DDE-Pat ent schrift 112 753 vom 22.5.1974; Ы. LISCHE7/SKI und G. ADALI, DDE-Pat ent schrift 121 784 vom 4.7.1975; M. LISCHEV/SKI und G. ADAM, Tetrahedron Letters 2835 (1974); M. LISCHEWSKI und G. ADAM, Tetrahedron Letters 3691 (1975); M. LISCHEV/SKI und G. ADAM, Z. Chem. 16i (1976), 486_7.The C ^ q-gibberellin derivatives with 6-position kydroxymethyl group used as starting materials are synthesized by known methods. LISCHEüSKI and G. ADAM, DDE Pat. No. 112 753 of May 22, 1974; Ы. LISCHE7 / SKI and G. ADALI, DDE Pat. No. 121,784 of July 4, 1975; M. LISCHEV / SKI and G. ADAM, Tetrahedron Letters 2835 (1974); M. LISCHEWSKI and G. ADAM, Tetrahedron Letters 3691 (1975); M. LISCHEV / SKI and G. ADAM, Z. Chem. 16i (1976), 486_7.
Die Oxydation wird in einem unter den angewandten Bedingungen nicht oxydierbaren Lösungsmittel durchgeführt, z.B. Methylenchlorid oder Chloroform. Als Oxydationsmittel werden chromhaltige Mittel eingesetzt, z.B. Chrom(VI)-oxid, Pyridiniumchlorochromat oder der Ohr omper oxid/Pyr idin-Komp lex (CrO1-'Py).The oxidation is carried out in a solvent which is not oxidizable under the conditions used, for example methylene chloride or chloroform. Chromium-containing agents are used as the oxidizing agent, for example chromium (VI) oxide, pyridinium chlorochromate or the ear oxide / pyridine complex (CrO 1 -'Py).
Ferner ist die Beaktionstemperatur in einem weiten Bereich variierbar, wobei am zweckmäßigsten bei Raumtemperatur gearbeitet wird. Beim Einsatz von C^q-Gibberellin-Derivaten mit weiteren oxydationsempfindlichen Hydroxylgruppen ist es vorteilhaft, diese vor der Oxydation mit einer Schutzgruppe zu versehen. Als Schutzgruppen finden z.B. Acylgruppen, wie Acetyl, Propionyl oder Benzoyl, Silylgruppen wie Trimethylsilyl, oder die Tetrahydropyrany!gruppe Anwendung. Beispielsweise muß die am C-3 befindliche Hydroxygruppe in 6іЗ-Нусгoxyme"nnyl-(7)-nor-gibberellin-Ao oder in 6ß-Hydroxymethyl-(7)-nor-gibberellin A^ auf diese 7»Teise geschützt werden.Furthermore, the reaction temperature can be varied within a wide range, with the most expediently being carried out at room temperature. When using C ^ q-gibberellin derivatives with other oxidation-sensitive hydroxyl groups, it is advantageous to provide them with a protective group prior to oxidation. Examples of protective groups are acyl groups, such as acetyl, propionyl or benzoyl, silyl groups, such as trimethylsilyl, or the tetrahydropyranyl group. For example, the hydroxyl group located at the C-3 must in 6іЗ-Нусгoxyme "nnyl- (7) -nor-gibberellin-Ao or in 6ß-hydroxymethyl be protected (7) -nor-gibberellin A ^ to this 7» T else.
Die Aufarbeitung der Reaktionsprodukte erfolgt nach den üblichen Methoden, beispielsweise durch Säulenchromatographie unter Verwendung von organischen Lösungsmitteln.The workup of the reaction products by the usual methods, for example by column chromatography using organic solvents.
Das erfindungsgemäße Verfahren ist allgemein anwendbar und liefert die gewünschten Gx,g-Gibberellin-(7)-aldehyde in hoher Ausbeute und ohne Nebenprodukte.The process according to the invention is generally applicable and gives the desired G x , g-gibberellin (7) aldehydes in high yield and without by-products.
Die dargestellten Verbindungen besitzen als wachstumsregulatorisch v/irksame Substanzen mit zum Teil gibberellin-antagonistischen Eigenschaften biologisches Interesse und praktische Bedeutung zur Steuerung von gibberellin-regulierten 7/achstums- und Entwicklungsprozessen. Sie dienen außerdem als Ausgangsstoffe für die Synthese weiterer strukturmodifizierter Gibberelline sowie radioaktiv markierter Analoga.The compounds shown as growth-regulatory active substances with partly gibberellin-antagonistic properties of biological interest and practical importance for the control of gibberellin-regulated 7 / achstums- and development processes. They also serve as starting materials for the synthesis of other structurally modified gibberellins and radiolabeled analogues.
Nachfolgende Beispiele erläutern die Erfindung, wobei die darin angegebenen speziellen Bedingungen die Erfindung nicht einschränken.The following examples illustrate the invention, wherein the specific conditions specified therein do not limit the invention.
Ausführungsbeispiele Ausführungsbe games
Zu 4-31,2 mg (2 oMol) Pyridiniumchlorochromat in 5 ml trockenem GHpGl^ tropft man unter Rühren und Argonatmosphäre bei Raumtemperatur eine Lösung von 416,5 mg (1 mMol) O(3)jO(13)-Diacetyl-6ß-hydroxymethyl-(7)-nor-gibberellin-Ao (I) in 5 ml trockenem CHpCIg. Nach 2 Stdn. wird die Mischung mit 50 ml Äther versetzt. Nach dem Abtrennen der Ätherphase v/ird der Rückstand mehrfach mit frischem Äther extrahiert. Die vereinigten Äther extrakt e v/erden mehrfach mit "wasser gewaschen, getrocknet und eingeengt. Nachfolgende Chromatographie des Rückstandes an 20 g Kieselgel (Woelm) liefert bei Elution mit n-Hexan/Chloroform 40:60 v/v 338 mg = 87 % d.Th. (Ausbeute berechnet auf umgesetzte Alkoholverbindung) 0(3)»0(13)-Diacetyl gibberellin-A3-(7)-aldehyd (IV) /"Schmp.: 162-164 0G (Äther/n-Hexan); [ρί]ψ +204,8° (c = 0,542, abs. Dioxan)_7 und mit Chloroform 26 mg nichtumgesetztes 0(3),0(13)-Diacetyl-6ßhydroxymethyl-(7)-nor-gibberellin-Ao·A solution of 416.5 mg (1 mmol) of O (3) jO (13) -diacetyl-6ß- is added dropwise with stirring and argon atmosphere to 4-31.2 mg (2 mol) of pyridinium chlorochromate in 5 ml of dry GHpGl ^ hydroxymethyl (7) -nor-gibberellin Ao (I) in 5 ml of dry CHpCIg. After 2 hours, the mixture is mixed with 50 ml of ether. After separating the ether phase, the residue is extracted several times with fresh ether. The combined ether extract is extracted several times with water, dried and concentrated, and subsequent chromatography of the residue on 20 g of silica gel (Woelm) gives, on elution with n-hexane / chloroform, 40:60 v / v 338 mg = 87 % of theory . Th. (Yield calculated on reacted alcohol compound) 0 (3) -Diacetyl gibberellin-A 3 - (7) -aldehyde (IV) / "Mp: 162-164 0 G (ether / n-hexane) ; [ρί] ψ + 204.8 ° (c = 0.542, abs dioxane) _7 and with chloroform 26 mg unreacted O (3), 0 (13) -diacetyl-6β-hydroxymethyl- (7) -nor-gibberellin Ao ·
BeisDiel2BeisDiel2
Zu 660 mg (3 ΐώίοΐ) Chromperoxid/Pyridin-Komplex (CrOn- *Py) in 20 ml GH2Cl2 ^ibt man bei E aurat emp er at иг 940 mg (2,5 irJ.Iol) 6ß-Hydroxymethyl-(7)-nor-gibber IUn-A5 (II) in 50 ml CH2Cl2. Nach 5 Stdn. wird die Mischung mit verd. HCl, ges. NaHCOv-Lösung und V/asser ausgeschüttelt. Anschließende Trocknung über Na2SO. und nachfolgendes Einengen der CH2C12-Phase liefert einen Rückstand, der an 50 S Kieselgel (V/oelm) chromatographiert wird. Slution mit Hexan/CHCl^ 1:9 v/v liefert 78? mg (81 % d.Th.) Gibberellin-A5-(7)-aldehyd (Y) /"amorphes Produkt, [$ψ -36,8° (с = 0,53, Äthanol)_7 ^nd mit CHCl3 48 mg 6ß-Hydroxymethyl-(7)-nor-gibberellin-A5 (II).To 660 mg (3%) of the chromium peroxide / pyridine complex (CrO n - * Py) in 20 ml of GH 2 Cl 2 is added, in ethyl acetate, 940 mg (2.5 mg / l) of 6β-hydroxymethyl- (7) -or-gibber IUn-A 5 (II) in 50 ml CH 2 Cl 2 . After 5 hours, the mixture with dil. HCl, sat. NaHCOv solution and V / asser shaken. Subsequent drying over Na 2 SO. and subsequent concentration of the CH 2 Cl 2 phase yields a residue which is chromatographed on 50 S silica gel (v / oelm). Slution with hexane / CHCl ^ 1: 9 v / v provides 78? mg (81% of theory) gibberellin A 5 - (7) -aldehyde (Y) / "amorphous product, [$ ψ -36.8 ° (с = 0.53, ethanol) with CHCl 3 48 mg of 6β-hydroxymethyl (7) -nor-gibberellin A 5 (II).
30,2 mg (0,1 mlvlol) 6ß-Hydroxymethyl-(7)-nor-gibberellin-Aq (III) werden bei Eaumtemperatur in 3 dl Hexamethylphosphorsäuretriamid mit 30 mg (0,3 mMol) CrO^ umgesetzt. Nach 2stündigem Eühren wird die Mischung an 1 g Kieselgel (V/oelm) chroma"cographiert. Slution mit Hexan/CPICl^ 1:1 v/v liefert 24 mg (80 % d.Th.) Gibberellin-Ao-(7)-aldehyd (YI) /,"amorphes Produkt; \ς§ψ +17,3° (c = 0,42, Äthanol)_7.30.2 mg (0.1 ml) of 6β-hydroxymethyl (7) -nor-gibberellin Aq (III) are reacted at room temperature in 3 dl of hexamethylphosphoric triamide with 30 mg (0.3 mmol) of CrO 2. After stirring for 2 hours, the mixture is chromatographed on 1 g of silica gel (v / oelm). Chromatography with hexane / CPICI ^ 1: 1 v / v gives 24 mg (80 % of theory) of gibberellin ao (7). aldehyde (YI) /, "amorphous product; \ ς§ψ + 17.3 ° (c = 0.42, ethanol) _7.
Claims (4)
CxjQ-Gibberellin~(7)-aldehyd umgesetzt wird.1. A process for the preparation of CLg-Giboerellinaldehyden, characterized in that a (L · g-gibberellin derivative having 6-hydroxyethyl in a solvent with a chromium-containing oxidizing agent for
C x jQ-gibberellin ~ (7) -aldehyde is reacted.
wird.2. "Process according to item 1, characterized in that used as the oxidizing agent pyridinium chlorochromate
becomes.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD20477178A DD135726B1 (en) | 1978-04-13 | 1978-04-13 | PROCESS FOR PREPARING C LOW 19-GIBBERELINALDEHYDE |
| SU797770503A SU1025710A1 (en) | 1978-04-13 | 1979-03-13 | Process for preparing c-19 gibberellin aldehydes |
| CS170279A CS217431B1 (en) | 1978-04-13 | 1979-03-14 | Method of preparing c19-giberelin aldehyde |
| DE2911618A DE2911618A1 (en) | 1978-04-13 | 1979-03-24 | MARKED GIBBERELLINE AND METHOD OF MANUFACTURING IT |
| US06/024,781 US4282154A (en) | 1978-04-13 | 1979-03-28 | Tagged gibberellins |
| GB7912596A GB2022576B (en) | 1978-04-13 | 1979-04-10 | Marked gibberellins and the preparation thereof |
| HU79WI299A HU184706B (en) | 1978-04-13 | 1979-04-11 | Process for preparing labelled gibberellines |
| NL7902888A NL7902888A (en) | 1978-04-13 | 1979-04-12 | MARKED GIBBERLINS OF THEIR DERIVATIVES AND METHOD FOR PREPARING THESE COMPOUNDS. |
| FR7909539A FR2438019A1 (en) | 1978-04-13 | 1979-04-13 | MARKED GIBBERELLINS AND PROCESS FOR THEIR MANUFACTURE |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD20477178A DD135726B1 (en) | 1978-04-13 | 1978-04-13 | PROCESS FOR PREPARING C LOW 19-GIBBERELINALDEHYDE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DD135726A1 DD135726A1 (en) | 1979-05-23 |
| DD135726B1 true DD135726B1 (en) | 1980-08-27 |
Family
ID=5512208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DD20477178A DD135726B1 (en) | 1978-04-13 | 1978-04-13 | PROCESS FOR PREPARING C LOW 19-GIBBERELINALDEHYDE |
Country Status (3)
| Country | Link |
|---|---|
| CS (1) | CS217431B1 (en) |
| DD (1) | DD135726B1 (en) |
| SU (1) | SU1025710A1 (en) |
-
1978
- 1978-04-13 DD DD20477178A patent/DD135726B1/en not_active IP Right Cessation
-
1979
- 1979-03-13 SU SU797770503A patent/SU1025710A1/en active
- 1979-03-14 CS CS170279A patent/CS217431B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS217431B1 (en) | 1983-01-28 |
| SU1025710A1 (en) | 1983-06-30 |
| DD135726A1 (en) | 1979-05-23 |
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| Date | Code | Title | Description |
|---|---|---|---|
| ENJ | Ceased due to non-payment of renewal fee |