CS224972B1 - The production of ghiberele acid from the glucosilesters of the latter - Google Patents

The production of ghiberele acid from the glucosilesters of the latter Download PDF

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CS224972B1
CS224972B1 CS554382A CS554382A CS224972B1 CS 224972 B1 CS224972 B1 CS 224972B1 CS 554382 A CS554382 A CS 554382A CS 554382 A CS554382 A CS 554382A CS 224972 B1 CS224972 B1 CS 224972B1
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gibberellic
solution
acids
methanol
acid
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Anton Ing Ondrejkovic
Gabriela Rndr Csc Vizarova
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Anton Ing Ondrejkovic
Gabriela Rndr Csc Vizarova
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Vynález sa týká spósobu přípravy kyselin giberelových z glukozylesterov kyselin giberelových.The present invention relates to a process for preparing gibberellic acids from glucose esters of gibberellic acids.

Rastové Regulátory typu giberelínov získali Curtis a Croos /?· J. Curtis, B.E. Croos: Chem. Ind. /Lond./ 1066 /LS54//extrakciou z rastlinného materiálu studeným metanolom alebo acetónom obsahujúcim až 50 % vody. Kyseliny giberelové extrahovali do octanu etylového pri pH 2,5 a 3,0, reextrahovali do pufru o pH 8,0 alebo pH 6,5 a znova extrahovali do octanu etylového po úpravě na pH 2,5 až 3,0. Takmer vset ky volné kyseliny giberelové obdržali v kyslej frakcii octanu etylového. Časť glukozylesterov kyselin giberelových sa móže extrahovat’ z okyÉ0Lenej vodnej fázy 1-butanolom /fr.Takahashi: Plant Growth Substances 1973, Hírokawa, Tokyo, 228 /1974/Vysoká koncentrácia fosfátového pufru móže viesť k neúplnému získaniu nepolárných glukozylesterov kyselin giberelových pri pH 8,0 /k.C. Durley, R.P. Pharis: Phytochemistry 11,317/1972/^resp. 6,5. Extrémně hodnoty pH spósobujú degradáciu giberelínov. Lipidy, ktoré by překázali pri separácii a biologických metodách sa odstraňujú petroléterom alebo dietyléterom pri neutrálnora alebo slabo alkalickom pH před extrakciou giberelínov. Zatial čo petroléter neextrahuje giberelíny z pufrovej .fázy pri pH 8,0, dietylóter extrahuje značnú časť málo polárných giberelípov /fc.C. Durley, R.P. Pharis: Phytochemistry 11, 317 /1972/ J, Polovičně množstvo giberelínov sú glukozylestery kyselin giberelových, ktoré sa móžu rozrušit’ hydrolýzou anorganickými kyselinami alebo zásadami a potom extrahovat’ octanom etylovým. Oproti kyslej a alkalickéj hydrolýze je preferovaná enzymatická hydrolýza, pretože vzniká menej deštrukčnýchGibberellin type growth regulators were obtained by Curtis and Croos. J. Curtis, B.E. Croos. Chem. Ind. (Lond./ 1066 (LS54)) by extraction of plant material with cold methanol or acetone containing up to 50% water. Gibberellic acids were extracted into ethyl acetate at pH 2.5 and 3.0, re-extracted into buffer at pH 8.0 or pH 6.5, and re-extracted into ethyl acetate after adjusting to pH 2.5 to 3.0. Almost all of the free Gibberellic acid was obtained in the acid fraction of ethyl acetate. A portion of the gibberellic acid glucosyl esters can be extracted from the acidified aqueous phase with 1-butanol (T. Sakahashi: Plant Growth Substances 1973, Hirokawa, Tokyo, 228/1974). High concentrations of phosphate buffer can lead to incomplete recovery of nonpolar glucose esters at 8 gibberellic acids. 0 / kC Durley, R.P. Pharis: Phytochemistry 11,317 (1972), respectively. 6.5. Extreme pH values cause degradation of gibberellins. Lipids that would interfere with separation and biological methods are removed with light petroleum or diethyl ether at neutral or slightly alkaline pH prior to extraction of the gibberellins. While petroleum ether does not extract gibberellins from the buffer phase at pH 8.0, diethyl ether extracts a significant portion of the low-polar gibberellins (fc.C). Durley, R.P. Pharis: Phytochemistry 11, 317/1972 / J, Half the amount of gibberellins are glucose esters of gibberellic acids which can be destroyed by hydrolysis with inorganic acids or bases and then extracted with ethyl acetate. Compared to acidic and alkaline hydrolysis, enzymatic hydrolysis is preferred because less destructive is formed

224 972 produktov fi· Yokota, N. Murofushi, N. Takahashi, S. Tamura: Agr·'Biol. Chem. 35,583 /1871/; K.Higara, T. Yokota, N. Murofushi, N. Takahashi: Agr. Biol. Chem· 38, 2511 /1974/ }· Ovšem i enzymatická hydrolýza okrem vyšších nákladov na přípravu znečisťuje produkt. Hydrolýzu pomocou $-glukozidázy, celulázy a iných enzýmov skúmali ďalší autoři /H. - D·224,972 products fi Yokota, N. Murofushi, N. Takahashi, S. Tamura: Agr · Biol. Chem. 35,583 (1871); K. Higara, T. Yokota, N. Murofushi, N. Takahashi: Agr. Biol. Chem., 38, 2511 (1974)} However, in addition to the higher preparation costs, enzymatic hydrolysis also pollutes the product. Hydrolysis with $ -glucosidase, cellulase and other enzymes has been investigated by other authors / H. - D ·

Knofel, P. Muller, G. Sembdner: Biochemistry and Chemistry of Plant Growth Regulators, Eds.: K.Schreiber, H. R· Schutte, G. Sembdner, Acad. Soi· G.D.R., Halle /Saale/ 121 /1974//· Pre extrakciu giberelínov z rastlinného materiálu v menšej miere sa používajú neutrálně alebo slabo alkalické pufre.Knofel, P. Muller, G. Sembdner: Biochemistry and Chemistry of Plant Growth Regulators, Eds .: K. Schreiber, H. R. Schutte, G. Sembdner, Acad. Neutral or weakly alkaline buffers are used to extract gibberellins from plant material to a lesser extent.

/λ· J. McComb: Nature/Lond·/ 192, 575 /1961//· Nitka reprodukovatelnosť delenia je u metod, kde sa giberelíny adsorbuji! na aktivně uhlie a potom eluujú s acetónom /Č. A· West,/ λ · J. McComb: Nature / Lond · / 192, 575/1961 // · The thread reproducibility of splitting is in methods where Gibberellins adsorb! on activated carbon and then eluting with acetone. A · West,

B. 0. Phinney: J.Amer. Chem· Soc. 81, 2424 /1959/; J.MacMillan, J. C. Seaton, P. J. Suter: Tetrahedron 11, 60 /1960// Pri izoláoii na chemicky modifikovaných dextranoch ostává časť giberelínov irreverzibilne neadsorbovaná.B. Phinney, J.Amer. Chem., Soc. 81, 2424 (1959); MacMillan, J.C. Seaton, P.J. Suter: Tetrahedron 11, 60/1960 // In isolation on chemically modified dextrans, a portion of the gibberellins remains irreversibly unadsorbed.

Uvedené nevýhody v podstatnej miere odstraňuje spósob přípravy kyselin giberelových z glukozylesterov kyselin giberelových podlá vynálezu, ktorého podstata spočívá v tom, že sa 1,6 až 2,0 % roztok glukozylesterov kyselin giberelových v 80 % metanole deionizuje na ionomeničoch s funkčnými sulfoskupinami a ionomeničoch s funkčnými skupinami trimetylamoniumhydroxidovými a potom sa zahustí pri tlaku 3 kPa na 30 až 90 % roztok, ktorý sa zriedí s 80 % metanolom ha 3 až 5 % roztok, ktorý sa hydrolyzuje ionomeničom s funkčnými sulfoskupinami za miešania pri teplote 20 až 25 °C po dobu 2 až 3 h a hydrolyzát po odfiltrovaní ionomeniča sa zahustí pri tlaku 3 kPa na 90 % sirup·The above-mentioned disadvantages are substantially eliminated by the process for the preparation of gibberellic acids from the glucose esters of gibberellic acids according to the invention, which is characterized in that a 1.6 to 2.0% solution of gibberellic acid glucose esters in 80% methanol is deionized on sulfonated and ion exchangers. trimethylammonium hydroxide and then concentrated at 3 kPa to a 30-90% solution, which is diluted with 80% methanol and a 3-5% solution that is hydrolyzed with a sulfo-functional ion exchanger under stirring at 20-25 ° C for 2 to 3 ha of the hydrolyzate after filtering the ion exchanger is concentrated to 90% syrup at 3 kPa ·

Výhodou navrhovaného spósobu přípravy kyselin giberelovýchzglukozylesterov kyselin giberelových oproti doterajším postupom přípravy je, že předmětný spósob je jednoduchší a ekonomicky nenáročný. Vzniká menej deštrukčných produktov a kyseliny giberelové sú zbavené anorganických solí·An advantage of the proposed method of preparing gibberellic acids from glucose esters of gibberellic acids over the prior art processes is that the present process is simpler and economically unpretentious. Less destructive products are formed and gibberellic acid is free of inorganic salts ·

Příklad 1Example 1

224 972224 972

400 g suchéj fazule Phaseolus vulgaris sa zvlhčí 600 ml vody a nechá sa napučiavat? v tme pri teplote 8 °C po dobu 18 h. Po napučaní sa fazula extrahuje s 3 000 ml 80 % metanolů v tme pri 8 °C po dobu 48 h. Extrakt sa sfiltruje a nechá sa stát? v trne pri teplote 8 °C po dobu 72 h. Pevný zvyšok sa reextrahuje s 3 000 ml 80 % metanolu v tme pri teplote 8 °C po dobu 72 h. Filtráciou sa získá ďalší extrakt, ktorý sa spojí s predošlým a spolu sa zahustia pri tlaku 3 kPa na 200 ml roztoku· Lipidy sa odstránia trojnásobnou extrakciou s 200 ml dietyléteru po úpravě na pH 8,0 s pevným hydrogenuhličitanom sodným· Vodná fáza /260 g/. sa po úpravě na pH 2,5 s 37 % kyselinou chlorovodíkovou trojnásobné extrahuje s 200 ml octanu etylového a získá sa extrakt obsahujúci kyseliny giberelové. Vodná fáza po extrakci! octanom stylovým sa pát?násobne extrahuje so 100 ml 1-butanolu a 1-butanolický extrakt sa zahustí pri tlaku 3 kPa na 43 g sirupu obsahujúceho glukozylestery kyselin giberelových, ktorý sa zriedi s 200 ml 80 % metanolu. Roztok · glukozylesterov kyselin giberelových sa zbaví anorganických solí, organiekýoh kyselin a zásad deíonizáciou na kolono naplněněj ionomeničom s funkčnými Sulfoskupinami /Wofatit KPS 200 0,3 až 0,85 mm/ s dížkou 50 cm a priemerom 4 cm a na koloně naplněněj ionomeničom s funkčnými skupinami trimetylaraoniumhydroxidovými /Dowex 1 X 8 0,3 až 0,85 mm/ s dížkou 50 cm a s priemerom 4 cm. Ako elučné činidlo sa použije 2 000 ml 80 % metanolu. Deionizováný roztok a eluát sa spol očně zahustia pri tlaku 3 kPa na 3,2 g 90 % sirupu, ktorý sa rozpustí v 100 ml 80 % metanolu. Me táno lOJ.c Rozvodný roztok glukozylesterov kyselin giberelových sa hydrolyzuje s 50 g ionomeniča s funkčnými sulfoskupinami /Dowex 50 W X 4 0,040 až 0,075 mm/ za miešania pri teplote 20 °C po dobu 3 h. Iono.raenič sa odfiltruje a premyje s 20 ml 80 % metanolu· Sfiltrovaný roztok sa odfarbí a 1 kg aktívneho uhlía a sfiltruje po doba 16 h. Odfarbený roztok sa zahustí400 g of dry Phaseolus vulgaris beans are moistened with 600 ml of water and allowed to swell? in the dark at 8 ° C for 18 h. After swelling, the bean is extracted with 3000 ml of 80% methanol in the dark at 8 ° C for 48 h. The extract is filtered and allowed to stand? in a mandrel at 8 ° C for 72 h. The solid residue was re-extracted with 3000 mL of 80% methanol in the dark at 8 ° C for 72 h. Filtration yields another extract which is combined with the previous and concentrated together at 3 kPa to 200 mL of solution. Lipids are removed by extraction three times with 200 mL of diethyl ether after adjustment to pH 8.0 with solid sodium bicarbonate. · Aqueous phase / 260 g /. After adjusting to pH 2.5 with 37% hydrochloric acid, it is extracted three times with 200 ml of ethyl acetate to give an extract containing Gibberellic acid. The aqueous phase after extraction! It is extracted five times with 100 ml of 1-butanol and the 1-butanol extract is concentrated at 3 kPa to 43 g of a syrup containing glucose esters of gibberellic acid, which is diluted with 200 ml of 80% methanol. The gibberellic acid glucosyl ester solution is freed from inorganic salts, organic acids and bases by deionization to a sulfonic-functional ion exchange column (Wofatit KPS 200 0.3 to 0.85 mm) with a length of 50 cm and a diameter of 4 cm and to a column with functional ion exchanger trimethylaraonium hydroxide groups (Dowex 1 X 8 0.3 to 0.85 mm) with a length of 50 cm and a diameter of 4 cm. 2000 ml of 80% methanol are used as eluent. The deionized solution and the eluate are concentrated together at 3 kPa to 3.2 g of a 90% syrup which is dissolved in 100 ml of 80% methanol. The aqueous solution of glucose esters of gibberellic acids was hydrolyzed with 50 g of sulfonic acid ion exchanger (Dowex 50 W X 4 0.040-0.075 mm) with stirring at 20 ° C for 3 h. The filter was filtered and washed with 20 ml of 80% methanol. The filtered solution was decolorized and 1 kg of activated carbon and filtered for 16 h. The discolored solution is concentrated

224 972 pri tlaku 3 kPa na 2,6 g 90 % sirupu obsahujúceho 60 % kyselin giberolových a 30 % O-glukózy, ktorý sa zriedi s 80 % Kiet ano lom na 6 % roztok kyselin giberelových. Biologická aktivita kyselin giberelových sa stanoví biotestom /G. V. Krylova: Rošt rostenij i prirodnyje regulátory, Akademia nauk ZSSR, Moskva, 175 /1978/.7-na principe rastu klíčiaceho trpasličieho hrachu^’ 0,05 ml 6 % kyselin giberelových sposobihrl50 % prírastok oproti kontrole a 0,075 ml 6 % kyselin giberelových spóiíobi3zv2OO % prírastok oproti kontrole^ 50^g kyseliny giberelovej GA^ sposobil^200 % prírastok oproti kontrole.224 972 at a pressure of 3 kPa to 2.6 g of a 90% syrup containing 60% gibberolic acids and 30% O-glucose, which is diluted with 80% ketone to a 6% gibberellic acid solution. The biological activity of gibberellic acids is determined by bioassay / G. V. Krylova: Grate growing and natural regulators, Academy of Sciences of the USSR, Moscow, 175 /1978/.7- on the principle of growth of germinating dwarf peas ^ '0,05 ml 6% gibberellic acids sposobihrl50% increase over control and 0,075 ml 6% acids gibberellus spores of 300% 200% gain over control 5050 µg of gibberellic acid GA os caused a 200 200% gain over control.

Příklad 2Example 2

000 g suchej fazule Phaseolus vulgaris sa zvlhčí 1 000 ml vody a nechá sa napuéiavať v tme pri teplote 8 °C po dobu 17 h. Po napučaní sa fazula extrahuje s 4 000 ml 80 % metanolu v tme a pri 8 °C po dobu 48 h. Extrakt sa efiltruje a nechá sa stát? v tme pri teplote 8 °C po dobu 72 Ji. Pevný zvyšok sa reextrahuje s 4 000 ml 80 % metanolu v tme pri teplote 8 °C po dobu 72 h. Filtráciou sa získá ďalší extrakt, ktorý sa spojí s predošlým a spolu sa zahustia pri tlaku 3 kPa na 300 ml roztoku. Lipidy sa odstránia štyrnásobnou extrakciou so 150 ml diatyléteru po úpravě na pH 8,0 s pevným hydrogenuhličitanom sodným. Vodná fáza /440 g/ sa po úpravo na pH 2,5 s 37 % kyselinou chlorovodíkovou trojnásobné extrahuje s 500 ml octanu etylového a získá sa extrakt obsahujúci kyseliny giberelové. Vodná fáza po extrakcii octanom etylovým sa dvojnásobné extrahuje s 500 ml l-butanolom a 1-butanolicky extrakt sa zahustí pri tlaku kPa na 56 g sirupu obsahujúceho glukozylestery kyselin giberelových, ktorý sa zriedi s 250 ml 80 % metanolu. Roztok glukozylesterov kyselin giberelových sa zbaví anorganických solí, organických kyselin a zásad deionizáciou na koloně naplněněj ionoraeničom s funkčnými sulfoskupinami /Dowox 50 W X 8 0,3 až 0,85 mm/ s dížkou 50 cm a priemerom cm a na koloně naplnenej ionomeničom s funkčnými skupinami trimetylamoniumhydroxidovými /Ostion AT 0809 0,315 až000 g dry Phaseolus vulgaris beans are moistened with 1000 ml of water and allowed to swell in the dark at 8 ° C for 17 h. After swelling, the bean is extracted with 4000 ml of 80% methanol in the dark at 8 ° C for 48 h. The extract is filtered and allowed to stand? in the dark at 8 ° C for 72 µl. The solid residue was re-extracted with 4000 mL of 80% methanol in the dark at 8 ° C for 72 h. Filtration gave another extract which was combined with the previous and concentrated together at 300 psi to 300 mL of solution. The lipids are removed four times by extraction with 150 ml of diethyl ether after adjustment to pH 8.0 with solid sodium bicarbonate. The aqueous phase / 440 g / was modified to pH 2.5 with 37% HCl three times extracted with 500 ml of ethyl acetate, and the obtained extract containing gibberellic acid much lazy. The aqueous phase, extracted with ethyl acetate, is extracted twice with 500 ml of 1-butanol, and the 1-butanol extract is concentrated under a pressure of 10 mbar to 56 g of syrup containing glucose esters of gibberellic acid, which is diluted with 250 ml of 80% methanol. The gibberellic acid glucose ester solution is freed from inorganic salts, organic acids and bases by deionization on a column packed with a sulfonic-functional ion exchange (Dowox 50 WX 8 0.3-0.85 mm) 50 cm long and cm in diameter and on a column packed with a functional group trimethylammonium hydroxide / Ostion AT 0809 0.315 to

224 972224 972

0,8 mm/ s dížkou 50 cm a priemerom 4 cm. Ako elučné činidlo sa použije 2 000 ml 80 % metanolu. Neionizovaný roztok a eluát sa spoločne zahustia pri tlaku 3 kPa na 10 ml roztoku, ktorý sa rozpustí v 100 ml 80 % metanolu. Metanolicko-vodný roztok glukózylesterov kyselin giberelových sa hydrolyzuje s 50 g ionomeniča s funkčnými sulfoskupinami /Dowex 50 W X 4 0,040 až 0,075 mm/ za miešania pri teplote 25 °C po dobu 2 h. lonomenič sa odfiltruje a premyje s 20 ml 80 % metanolu. Sfiltrovaný roztok sa odfárbí s 1,5 g aktívneho uhlia a sfiltruje po době 17 h. Odfarboný roztok sa zahustí pri tlaku 3 kPa na 3,6 g 90 % sirupu obsahujúceho 60 % kyselin giberelových a 30 % D-glukózy, ktorý sa' zriedí s 80 % metanolom na 6 % roztok kyselin giberelových; Biologická aktivita: 0,05 ml 6 % kyselin giberelových sposobilo’17O % prírastok oproti kontrole a 0,075 ml 6 % kyselin giberelových spósobilť210 % prírastok oproti kontrole^ 50 /ig kyseliny giberelovej spósobifc^OO % prírastok oproti kontrole.0.8 mm / with a length of 50 cm and a diameter of 4 cm. 2000 ml of 80% methanol are used as eluent. The non-ionized solution and the eluate are concentrated together at 10 mbar to 10 ml of a solution which is dissolved in 100 ml of 80% methanol. The methanolic-aqueous solution of glucose esters of gibberellic acids is hydrolyzed with 50 g of sulfonated ion exchanger (Dowex 50 W X 4 0.040-0.075 mm) with stirring at 25 ° C for 2 h. The ion exchanger is filtered off and washed with 20 ml of 80% methanol. The filtered solution is decolorized with 1.5 g of activated carbon and filtered after 17 h. The decarbonate solution is concentrated at 3 kPa to 3.6 g of a 90% syrup containing 60% gibberellic acid and 30% D-glucose, which is diluted with 80% methanol to a 6% gibberellic acid solution; Biological activity: 0.05 ml of 6% gibberellic acid produced a 170% increase over the control and 0.075 ml of 6% gibberellic acid caused a 210% increase over the control of ≥50 µg of gibberellic acid to give a 50% increase over the control.

Vynález móže nájsť široké použitie v polnohospodárstve a při štúdiu biochemických procesov v rastlinách· Kyselinami giberelovými sa móže rušit4 dormancia semien a spiacich pupoňov rastlín· U niektorých rastlín sa móže indukovat’ kvitnutie. Ďalej sa může kyselinami giberelovými zváčšiť velkost’ plodov.The invention can find widespread use in agriculture and in the study of biochemical processes in plants. 4 Dormancy of seeds and sleeping buds of plants can be abolished by gibberelic acids. Furthermore, the size of the fruits can be increased by gibberellic acids.

Claims (1)

PREDMET VYNÁLEZUOBJECT OF THE INVENTION 224 972224 972 Spósob přípravy kyselin giberelových z glukozylesterov kyselin giberelových obsiahnutých vo vodnej fáze extraktu po extrakcii volných kyselin giberelových etylacetátom s použitím hydrolýzy uvedených glukozylesterovyyyznačujúci sa tým, že sa 1,6 až 2,0 % roztok glukozylestercv kyselin giberelových v 80 % metanole deionizuje na ionomeničoch s funkčnými sulfoskupinami a ionomeničoch s funkčnými skupinami trimetylamoniumhydroxidovýiai a potom sa zahusti pri tlaku 3 kPa na 30 až 90 % roztok, ktorý sa zriedí s 80 % nie táno lom na 3 až 5 % roztok, ktorý sa hydrolyzuje ionomeničom s funkčnými sulfoskupinami za miešania pri teplote 20 až 25 °C po dobu 2 až 3 h a hydrolyzát po odfiltrovaní ionomeniča sa zahustí pri tlaku 3 kPa na 90 % sirup·A process for the preparation of gibberellic acids from glucose esters of gibberellic acids contained in the aqueous phase of the extract after extraction of the free gibberellic acids with ethyl acetate using the hydrolysis of said glucose esters, characterized in that a 1.6-2.0% solution of gibberellic glucose esters in 80% methanol is deionized and then concentrated at 3 kPa to a 30-90% solution, which is diluted with 80% non-tan to a 3-5% solution which is hydrolyzed with a sulfonated ion exchanger under stirring at 20 ° C. to 25 ° C for 2 to 3 h and the hydrolyzate after filtering the ion exchanger is concentrated to 90% syrup at 3 kPa
CS554382A 1982-07-20 1982-07-20 The production of ghiberele acid from the glucosilesters of the latter CS224972B1 (en)

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