CS231555B1

CS231555B1 - Method of epimerization of giberellin-7-aldehydes

Info

Publication number: CS231555B1
Application number: CS566479A
Authority: CS
Inventors: Manfred Lischewski; Guenter Adam
Original assignee: Manfred Lischewski; Guenter Adam
Priority date: 1978-09-12
Filing date: 1979-08-17
Publication date: 1984-12-14
Also published as: DD138663A1; SU1109399A1; DD138663B1

Abstract

Cíiem vynálezu je poprvé připravit giberellin-7-aldehydy s aldehydovou skupinou v 6X -poloze a tak poskytnout novou skupinu biologický aktivních látek. Dále se giberellin-7-aldehydy značí deuteriem nebo tritiem. Podle vynálezu se giberellin-7-aldebyd s aldehydovou skupinou v poloze 6<j4 nebo 6/3 - enolizují alkalií a přídavkem sloučenin s vlastnostmi donorů vodíku, deůterie nebo tritia zreagují na epimerní směs, sestávající z giberellin-7-aldehydu s aldehydovou skupinou v W- poloze a giberellin-7-aldehydu s aldehydovou skupinou v 6^-poloze, přičemž při použití donorů deuteria nebo tritia jsou oba získané epimary značeny na šestém atomu uhlíku. Způsob podle vynálezu je obecně přijatelný pro všechny giberellin-7-aldehydy, přičemž se nemění jejich části citlivé k alkáliím. Podle vynálezu získané značené giberellin-7-aldehydy slouží jako výchozí látky pro přípravu značených přírodních giberellinů a jejich derivátů.The aim of the invention is to prepare for the first time gibberellin-7-aldehydes with an aldehyde group in the 6X-position and thus provide a new group of biologically active substances. Furthermore, gibberellin-7-aldehydes are labeled with deuterium or tritium. According to the invention, gibberellin-7-aldehydes with an aldehyde group in the 6<j4 or 6/3-position are enolized with alkali and, by adding compounds with the properties of hydrogen, deuterium or tritium donors, they react to form an epimeric mixture consisting of gibberellin-7-aldehyde with an aldehyde group in the W-position and gibberellin-7-aldehyde with an aldehyde group in the 6^-position, whereby when deuterium or tritium donors are used, both epimers obtained are labeled at the sixth carbon atom. The method according to the invention is generally acceptable for all gibberellin-7-aldehydes, while their alkali-sensitive parts are not changed. The labeled gibberellin-7-aldehydes obtained according to the invention serve as starting materials for the preparation of labeled natural gibberellins and their derivatives.

Description

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Tax, HanpHMep, Η3βθοτηη raddepejL7iHH“7ajiBjierHjm, κοτορυθ i-msioTb θοτθοτβθηηομ β^β-noJioseHHH οοηοβηογο cxejieTa sHT-ruddepejDia-Ha aJIBíerHflHyiO rpynny M. Lischewski und G. Adam, ΟΠΗΟΒΗΗΘΗ300ρθΤθΗΗΗ K naTeHTy TEP 112 753; M.Lischewski unďG. Adam,Tetrahedron Letters 2835 (1974); 15. Lischewski und G. Adam,oimcamie H3odpeTeHHH κ naTeHTy ΓΕΡ 120975; m. Lischewski undG. Adam, Tetrahedron Letters 2569 (1975); M. Lischewski undG. Adam, Z. Chem 16, 486 (1976); J. R. Hanson and J. Hawker, J. Chem.Soc.Chem.Comm. 1971, 208 und Phytochemistry 12, 1o73 (1973); B. E. Cross, K. Horton und J. C. Steward, J. Chem.Soc. (C) 1968, 1054; B. E. Cross und I.L. Gatfield, ibid.-1971,1539 .Tax, HanpHMep, Η3βθοτηη raddepejL7iHH '7ajiBjierHjm, κοτορυθ i-msioTb θοτθοτβθηηομ ββ-noJioseHHH οοηοβηογο cxejIBTi ny i ny ny ny ny ny ny ny ny ny ny ny ny ny ny ny ny ny ny M.Lischewski unďG. Adam, Tetrahedron Letters 2835 (1974); 15. Lischewski and G. Adam, Oimcamie H3odpeTeHHH na naTeHTy ΓΕΡ 120975; m. Lischewski undG. Adam, Tetrahedron Letters 2569 (1975); M. Lischewski und G. Adam, Z. Chem. 16, 486 (1976); J.R. Hanson and J. Hawker, J.Chem.Soc.Chem.Comm. 1971, 208 and Phytochemistry 12, 1973 (1973); Cross Cross, B. E., Horton, K., and Steward, J.C., J. Chem. (C) 1968, 1054; B. E. Cross and I.L. Gatfield, ibid.-1971, 1539.

OjmaKO, Ao, chx nop He dtuio cicíTesiipoBaHo rnddepejuixH-7-aJibpe-ΓΗΑΟΒ,ΚΟΤΟρΗβ ΗΜθΛΗ ÓH B 3ΠΗΜθρΗ0Μ ^^-ΠΟΛΟΣίθΗΗΜ ΘΛΒΛΘΓΗΛΗγίΟrpynny. Tarase HMeeTCH CBe^eraie onoJiyneHUH Ηθκοτορυχ μθηθηηχnióóepejiJiHH-7-aJiLjierajíOB c ajibíernjmofí rpgimoií b 6^-noJiozeHnn.OjmaKO, Ao, chx nop He dtuio ticiiTesiipoBaHo rnddepejuixH-7-aJibpe-ΓΗΑΟΒ, ΚΟΤΟρΗβ ΗΜθΛΗ OH B 3ΠΗΜθρΗ0Μ ^^ - ΠΟΛΟΣίθΗΗΜ ΘΛΒΛΘΓΗΛΗγίΟrpynny. Tarase HMeeTCH CBe ie ie on on ne ne ne ne ne ne Η κ κ κ κ κ μ μ μ μ μ H H H H H H H H

TaK duno oiracano nojiyneHHe 6-¾ - hjih 6- H -rnddepejuniH-Aj2“ajih^ern^a n -raddepeJumH-A^-anbflerw £i. R. Bearder, J. MacMil-lan und B. 0. Phinney, Phytochemistry 12, 2173,2615 (19737; J. H. Graebe, P. Hedden und J. MacLíillan, J. chem. Soc.Chem.Comm. 1975» 161; P. Hedden, J, MacMillan und B. 0. Phinney, J.chem.Soc.,Perkin I, 1974, 587^ 0.,TaK duno oiracano nojiyneHHe 6-¾ - hjih 6- H -nddepejuniH-22 aj ih ^ ^ n n n n n n n an an an R. Bearder, J. MacMillan and B. 0. Phinney, Phytochemistry 12, 2173, 2615 (19737; JH Graebe, P. Hedden and J. MacLillan, J. Chem. Soc.Chem.Comm. 1975 »161; P. Hedden, J, MacMillan and B. 0. Phinney, J. Chem. Soc., Perkin I, 1974, 587-4,

OjmaKo, H3-3a scecTKHx ycjroBHií (jyniTejiLHoe BpeMH pearaniíi, óojil-Uioft H3ÓHT0K meJIOHH, ΠΟΒΗΙΠβΗΗΗβ TeMnepaTypa) 3T0T cnocoó npxMe-HHM JDIIHb K raÓÓepejLTDIHaM, KOTOptie £0B0Jn>H0 CTOta no OTHOineHHIOκ mejionaM h £aeT jduiib Hedojibmoft bkxq#.OjmaKo, H3-3a scecTKHx ycjroBHií (jyniTejiLHoe BpeMH pearaniíi, óojil-Uioft H3ÓHT0K meJIOHH, ΠΟΒΗΙΠβΗΗΗβ TeMnepaTypa) 3T0T cnocoó npxMe HHM-K JDIIHb raÓÓepejLTDIHaM, KOTOptie £ 0B0Jn> H0 CTOT well OTHOineHHIOκ mejionaM h £ AET jduiib Hedojibmoft bkxq #.

Jlajiee, ηββθοτθη οηητθ3rnjía B. Dockerill ,[r.Comm. 1977, 919^]. T/t 7-°H, 17- C -radtíepejuniH-Aj2“a^W“Evans und J* R. Hanson, J.chem. Soc .Shem,Jlajiee, οββθοτθη οηητθ3rnjía B. Dockerill, [r.Comm. 1977, 9194]. T.l.c. -7 ° H, 17-C-radiiepejuniH-A12 'and ^ W' Evans and J * R. Hanson, J.chem. Soc .Shem,

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CoiyiacHo H3oópeTeHiw raóóepejuniH-7-ajiBjíerHjí c ajiLHenajíHoS rpyn-ΠΟΐί B Scxf-nOJIOSeHKH HJIH 6 —IIOJIOSGHEH 3HOJIH3HpyiOT ΙΙίθΠΟΗΒΚ) H nyTCM XOÓaBJíeHHH ΟΟΘΗΗΗΟΗΗβ CO CBOÍÍCTBaMH SOHOpa TBHTKH, Heíí-TepnH hjbí soHopojia npeBpamasT b sídMepHyio CMecs, cocToamyio H3rHóóepejinHH-7-ajiBAerH£a c awerHnHoíí rpyrmo^ b 6^-ποηοζθηηηh raóóepejuiHH-7-ajiBnerHna c anBjzerHXHoS rpyímoíi b 6/2-ποποηθηηη,. ΠρΗΗΘΜ ΠρΠ ΤφΗΜΘΗβΗΗΗ ΟΟβχΗΗΘΗΗβ CO ΌΒΟβΟΤΒΗΜΕ £OHOpa ΛθβΤΘ-'ρππ hjih τρκτππ otía nonyHeHime 3ΠΗΜερκ μθηθηη y mecToro aTOMayrneposa. IIpHweHeHHue κηκ iicxojyíHe Eemecrsa rKddepemoK-7-ajiB£erHfíK no- *. jiynaiOT H3BecTHHMH cnocodaMH χημηηθοκημ πγτθΜ m. Lischev/skiu. G.AdamtormcaHRH n3OÓpeTemiS κ πβτθηθλ PUP 120 875; C 07 d , 307/77; | II2753, 0 07 , 5/06; M. lischewski n. G. Adam, Tetrahedron Letters j 1974, 2835? ibid. 1975, 2569? ibid. 1975, 3691? Z.Chem, 16, 486(1976l· HO MHKpoÓHHM nyTeM j. r. Bearder, J. MacMillan u. B. 0. Phinney, ΐCoiyiacHo H3oópeTeHiw raóóepejuniH 7-c ajiBjíerHjí ajiLHenajíHoS rpyn ΠΟΐί-B-Scxf nOJIOSeHKH HJIH 6 -IIOJIOSGHEH 3HOJIH3HpyiOT ΙΙίθΠΟΗΒΚ) H nyTCM XOÓaBJíeHHH ΟΟΘΗΗΗΟΗΗβ CO CBOÍÍCTBaMH SOHOpa TBHTKH, Heiii-TepnH hjbí soHopojia npeBpamasT b sídMepHyio CMecs, cocToamyio H3rHóóepejinHH 7-ajiBAerH £ c a 6H-7H-7H-7H-7H-7H-7H-7H-7H-7H-7H-7H-7H-7H-7H-7H-7H-7H-7H-7H-7H-7H-7H-7H. OHOpa COθβΤΘ-'ρππ hjih τρκτππ otía nonyHeHime ΠρΗΗΘΜ ΠφΗΜΘΗβΗΗΗ ΟΟβχΗΗΘΗΗβ CO ΌΒΟβΟΤΒΗΜΕ £ OHOpa ΗΜθβΤΘ-'ρππ hïih nonyHime 3ΠΗΜερκ μθηθηη y mecToro aTOMayrneposa. IIpHweHeHHue κηκ iicxojyHe Eemecrsa rKddepemoK-7-ajiBerHfíK no- *. jiynaiOT H3BecTHHMH cnocodaMH χημηηθοκημ πγτθΜ m. Lischev / skiu. G.AdamtormcaHRH n3OOPeTemiS and PUP 120 875; OJ C 07, 307/77; | II2753, 0 07, 5/06; M. lischewski n. G. Adam, Tetrahedron Letters j 1974, 2835? ibid. 1975, 2569? ibid. 1975, 3691 Z.Chem, 16, 486 (1976) · HO MHKpoOHHM by Bearder, J. MacMillan and B. 0. Phinney, ΐ

Phytochemistry 12, 2173 (1973)? J· R. Hanson u. J. Hawker, J.chem. ?Phytochemistry 12, 2173 (1973). J. Hanson and J. Hawker, J.chem. ?

Soc.Chem.Comm. 1971t 208 u. Phytochemistry 12, 1073 (1973). íSoc.Chem.Comm. 1971 t 208 u. Phytochemistry 12, 1073 (1973). and

IAND

Cnocotí, COrJiaCHO Η300ρθΤβΗΗΚ, npOBOJOITCH 0Θ3 B03JQOCa, Hanpn-Mep b aiMocftepe aproHa ho a30Ta, b opramraecKOM pacTBopHTejie,npejinoHTHTejihHo b adc. TeTparajipoáypaHe ho adc. ooKcaHe. lípu cnocode, corJiacHo H3oópeTeimio, b xanecTBe mejionen HcnojiL3y-kt npesqje Bcero CHJiBHue, ho Mano ητκλθοΦηοηηθ mejioo. Πρπ stom IocoóeHHo βηγοον inenooHe θμηλη, npezne Bcero Taime c opraone- | ckhmh ocTaTKaMH, 3anojiHJwmm.® npocTpaHCTBo, HanpHMep, oH3onpo- ) πηομηη othh on 2,2,6,6-TeTpaMeTHJinHnepmm3 othh ηλη γηηρη- ·|OT,OCOÓeHHO ΓΗίφΗβ KaJIHH. TaKHM 0Ópa30M, C ΠρΗΜθΗΘΗΗΘΜ 3THX j CHJIBHHX, HO MaJIO HyKJieOffiHOHHX ΠίθΛΟΗθβ ΒΠθρΒΗθ B03M0KH0 3ΗΟΟ·-3HpoBaTB Cj-g-raddepeJiOH-7-ajiBnerHO c I9->I0 oktohhhm kojib-HOM. OcoóeHHoe npeHMymecTBO θτογο cnocoda samnonaeTCH b tom,Night, COrJiaCHO Η300ρθΤβΗΗΚ, nPOBOJOITCH 0Θ3 B03JQOCa, Hanpn-Mep b aiMocftepe aproHa ho a30Ta, b pacTBopHTejie, npejinoHTHTejihHo b adc. TeTparajipoáypaHe ho adc. ooKcaHe. lime tree cnocode, corJiacHo H3oópeTeimio, b xanecTBe mejionen HcnojiL3y-kt npesqje Bcero CHJiBHue, ho Mano ητκλθοΦηοηηθ mejioo. Πρπ stom IocoóeHHo βηγοον inenooHe θμηλη, not known Bcero Taime c opraone- | ckhmh ocTaTKaMH, 3anojiHJwmm.® npocTpaHCTBo, HanpHMep, oH3onpo-) π otομηη othh on 2,2,6,6-TeTpaMeTHJinHnepmm3 othh ηλη γηηρη- · | OT, OCOOHH. TaKHM 0Opa30M, C ΠρΗΜθΗΘΗΗΘΜ 3THX CH CHJIBHHX, HO MaJIO HyKJOOffiHOHHX ΠίθΛΟΗθβ ΒΠθρΒΗθ B03M0KH0 3ΗΟΟ · -3HpoBaTB C--g-raddepeJiOH-7-ajiHo0h ihh> hh> hh> hh> hh> hh> hh> h. OcoóeHHoe npeHMymecTBO θτογο cnocoda samnonaeTCH

ΨΓ0 ftJlH 0Ópa30BaHHH 3H0JiaTa AOCTaTOHHO ftOÓaBOTL meJIOHB B 3KBHB3JieHTH0M ΚΟΟΉθΟΤΒΘ HO JIHIHL· B HeÓOJIBmOM H3ÓHTKe (HanpH-Mep, 1,1 3KBHB3JieHT). Oto ΛθϋοτΒΗΤθΟΗΟ w rHddepeoHH-7-ajiB-,nerH£OB de3 khcjihx aTOMOB Bonopona (HanpHMep, oddepenoH-Ag- ’ -7-οβλθγηλ) . Πρπ HcnojiL3OBaHHH rHddepejioH-7-anBneranoB ckhcjihmh' aTOMSMH sonopona (HanpHMep, rHddepenoH-7-ajiBjTerHnH,conepKaoe ropoKCHJiLHtie ho KapdoKCHJiBHue rpymm) nenecoodpaB-ho 3aMemaTb sth ητομη Bonopona. B KanecTBe θβιιϊητκνχ rpyrni noΓΗίρΟΚΟΙΙΛΒΗΒΚ rpyíM MOBHO ΙΤρΗΜΘΗΗΤΒ, HanpHMep, TpHMeTHJICHOJIB—ΨΓ0 ftJ1H 0Opa30BaHHH 3H0JiaTa AOCTaTOHHO ftOÓaBOTL meJIOHB B 3KBHB3JieHTH0M ΚΟΟΉθΟΤΒΘ HO SOUTH · B HeOOJIBM H3ÓHTKe (HanpH-Mep, 1,1 3KBHB3JieHT). Oto depθϋοτΒΗΤθΟΗΟ w rHddepeoHH-7-iiB-, nerH OB OB de3 khcjihx andTOMOB Bonopon (HanpHMep, decoupledH-Ag- '-7-οβλθγηλ). Πρπ HcnojiL3OBaHHH rHddepejioH-7-anBneranoB ckhcjihmh 'aTOMSMH sonophone (HanpHMep, rHddepenoH-7-ajiBjTerHnH, conepKaoe ropoKCHJiLHtie ho KapdoKCHJoBoHoHoBoHoPoHoPoHoPoHoPoHoPoHoPoHoPoHoPoHoPoHoPoHoNoPoHoPoHoNoHoPoHoBoHoBoHoHoI B KanecTBe θβιιϊητκνχ rpyrni noΓΗίρΟΚΟΙΙΛΒΗΒΚ rpyiM MOBHO ΙΤρΗΜΘΗΗΤΒ, HanpHMep, TpHMeTHJICHOJIB—

Hyw rpynny, TpeTHHHyio dyTHnoMeTrnicHOJiBHyio rpynny ho TeTpa-wpomipaHmiLHyio rpynny. Πομκμο θτογο KapdoKCHJiLHEe rpynrm 3Te-pHfžHHHpyKT ho HeiíTpao3yioT H3dHTK0M menoo. 0H0O3aimH rndde-peOHH-7-aJILnerHnOB B npHCyTCTBHH KHCJIHX aTOMOB Bonopona TOSeB03M0SHa.· OnHaKO, 3£ecB TpedyeTcn οοοτΒβτοτΒθΗΗΟ doorne skbh- i iHyw rpynny, TpeTHHHyio dyTHnoMeTrnicHOJiBHyio rpynny ho TeTpa-wpomipaHmiLHyio rpynny. Πομκμο θτογο KapdoKCHJiLHEe rpynrm 3Te-pHfžHHHpyKT ho HeiiTpao3yioT H3dHTK0M name. 0H0O3aimH rndde-peOHH-7-aJILnerHnOB B npHCyTCTBHH KHCJIHX aTOMOB Bonopona TOSeB03M0SHa · OnHaKO, 3 £ ecB TpedyeTcn οοοτΒβτοτΒθΗΗΟ doorne skbh- i i

BaneHTOB menoo, HTodu npoH3onwo odpa3OBaHHe SHOJiaTa. - 5 -BaneHTOB name, HTodu npoH3onwo odpa3OBaHHe SHOJiaTa. - 5 -

KaK coeaHHeHHH co cBoftcTBaMH noHopa Bonopona-, nefiTepna mτρητηζ (b jiaJiLHefiiueM oóo3HaaeHH KaK noHopa Boaopona, nefíTepnaXJttl TpJÍTIlH) ΠρΚΜΘΗΚΜΚ CaMHe pa3HHe COe>IHeHKH C BCWpOflOM,nefíTepnew njm τρητηθμ, ciiocoóhhmh k otíMeHy, Hanpnwep, HgO, ^HgO, ^HgO, H-Or , ^H-Or, npiraeM r ctoht jyia 3aMemeHH0# mmHe3aMeuícHHo0 ajiKHJiBHoíi, apmiBHofí njm amuiLHoft rpynnnpOBKH,a Tanze opraHHnecxnx m HeopraHHnecKHx khcjiot. řípu πρημθηθηηηkkcjiot oópa3ynwca mtítíepejumH—7—ajiLnomaa ne noasepraioTcaIHeJIOHHHM HJm HyKJieOČÓHJIBHHM yCJIOBHHM, HTO OCOtíeHHO. BaZKO JUIHnoJiyaeHna HeycTowHJíBHX κ mejionaM rHtítíepeJumH-7-ajiBnerHnoB. . He3aBiiciiM0 ot toto, hcxouht jih íjih μθηθηηη rHóóepejuniH-7--, ajiLnerH^ax ajiMerHAHOíí rpynnoit b S^-noaozemm mm ze c ajit- aerHUHoíí rpynnof: b 6^-πολοζθηηη, BcernanojiyaaiOT kbk MěněnaerHóóepejLTHH-7-aJiBjíerHHH c sjiwphhho@ rpynnofi b 6^-πο,ίοζθηηη?thk K.LíeHeKLie nitítíepejmHH-7-arBaermiH c ajiLnermmoi* rpynnoií b6</7-nojiozeHHH.KaK coeaHHeHHH what cBoftcTBaMH noHopa Bonopona-, nefiTepna mτρητηζ (b jiaJiLHefiiueM oóo3HaaeHH KaK noHopa Boaopona, nefíTepnaXJttl TpJÍTIlH) ΠρΚΜΘΗΚΜΚ Camhi pa3HHe coe> C IHeHKH BCWpOflOM, nefíTepnew NJM τρητηθμ, ciiocoóhhmh to otíMeHy, Hanpnwep, HgO ^ HgO ^ HgO, H Or, HH-Or, npiraeM r ctoht jyia 3aMemeHH0 # mmHe3aMeuicHHo0 aiKHJiBHoi, apmiBHofi n am am lHoft rpynnnpOBKH, and Tanze opraHHnecxnx m HeopraHHnecKHx khcji. pu pu ρ ρ ρ 7 — yn yn — — — — — — — — — — — 7 7 7 7 7 7 7 — 7 — 7 — — 7 — — HT HT HT HT HT HT HT HT HT HT HT HT HT HT HT HT. BAZKO JUIHnoJiyaeHna HeycTowHJíBHX m mejionaM rHtítepeJumH-7-ajiBnerHnoB. . He3aBiiciiM0 ot this, hcxouht south and south of the rhóepejuniH-7--, aiNerHe and aiMerHAHOi rpynnoit b S n -noaozemm mm of c ait-aerHUHoi rpynniHeNeHeHeHeHeHeHeHeHeHeHeHeHeHeHeHeHeHeHeHeHeHeHeHeHeHeHeHeHeHeHeHeHeHeHeHeHeHe 6, 6, 7, 8, 9, 9, 9, 9, 9, 9, 9, 9 and 9 and 16, respectively.

KaK bo BpewH otípa3OBaHHH snoaaTa, tbk ή npn npespamemm c no-Hopai-.m sonopona, nefiTepna mm τρητκΗ TewnepaTypa μοζθτ KoaetíaTB·ca b imipoKi-ix npeaejiax. Uejiecootípa3Ko patíoTaTB b npeneaax msz-ny -78° C h KOMHaTHOíí TewnepaTypoft.KaK bo BpewH otípa3OBaHHH snoaaTa, tbk or npn npespamem c no-Hopai-.m sonopon, nefiTepna mm τρητκΗ TewnepaTypa μοζθτ KoaetíaTB · c and b imipoKi-ix npeaejia. Uejiecooti3Ko patáoTaTB b npeneaax msz -78 ° C h KOMHaTHOí TewnepaTypoft.

OtípatíoTKy -npoayKTOB peaKmm npoH33oaHT no ο<5ηηηημ Μβτοηοη, Ha-npHMep, nyTew xpoMaTorpaácm na KCJioHKe c npHMeneHHeM opramme-ckhx pacTBopHTeJiež. Em.ienaTeaBHo to, hto otía otípa3OBaBizixca nocnocotíy, corjiacHo H3otípeTeHHio, ii3cuepa xapaKTepimyiOTca JieraonxpozaTorpažnaecKon pa3nejnn.iocTBio.OtípatíoTKy -npoayKTOB peaKmm npoH33oHT no ο <5ηηηημ Μβτοηοη, Ha-npHMep, nyTew xpoMaTorpaac on KCJioHKe c npHMeneHHeM opramme-ckhx pacTBopHTe. Em.ienaTeaBHo to hto otípa3OBaBizixca nocnocotie, corjiacHo H3otippeTeHHio, ii3cuepa xapaKTepimyiOTca JieraonxpozaTorpažnaecKon pa3nejnn.iocTBio.

Cnocotí, comacHo H3otípeTeicw, otíqenpHT.ieHHM κ rntítíepejumH-7-aJiB-Cnocotí, comacHo H3otípeTeicw, otíqenpHT.ieHHM κ rntítepejumH-7-aJiB-

CTQ-mtítíepejumH-7ajiLírerHaoB c 19 —> 10 JiaKTOHHHM· kojibhom, Ha-CTQ-mtítepejumH-7ajiLírerHaoB c 19-> 10 JiaKTOHHHM · kojibhom, Ha-

.Henu, -raóÓepejLTHH-Ag^-ajiLneran, -ΐΉ0όδρωυιηΗ--Α4-7-3ΛΕηθΓΗΗ,-raótíepeJuiHH-A5-7-anB£era#, -rHÓóepejuniH-A7->7-ajiBneraz,-raóóepeJUHH-Ag-7-aTiBJíerHa η rHÓóepejuniH-Ag-7-aJiBnerHn, κο- ΤΟρΗΧ £0 CHX ΠΟρ Ηθ ÓLUIO ΒΟ3ΜΟ3ΚΗΟ ÍIOJipiaTL· ,ΣφγΠϊΜ ΠγΤΘΜ. ΚρΟΜΘ ΤΟΓΟ, CHHTe3IípyiOT 3ΤΧΜ CHOCOÓOM, COrJiaCHO H30ÓpeTeHHIO,Henu, -raoóepejLTHH-Ag Ag -ajiLneran, -ΐΉ0όδρωυιηΗ - Α4-7-3ΛΕηθΓΗΗ, -raoóepeJuiHH-A5-7-anB £ era #, -rHoóepejuniH-77-> 7-ajiBneraz, -raoHepe aTiBJierHa η rHÓóepejuniH-Ag-7-aJiBnerHn, κο- ΤΟρΗΧ £ 0 CHX ΠΟρ Ηθ ÓLUIO ΒΟ3ΜΟ3ΚΗΟIIOJipiaTL ·, ΣφγΠϊΜ ΠγΤΘΜ. ΚρΟΜΘΟΜΘ, CHHTe3IípyiOT 3ΤΧΜ CHOCOÓOM, COrJiaCHO H30ÓpeTeHHIO,

Taiz&e nojiyneirae jcboShhx MeHemx raóóepejumH-^-ajiEnernnoBB03M0JKH0 c πομοιιιβιο cnoco^a, coiviacHo H3odpeTeHHio, HanpiiMep,Taiz & nojiyneirae jcboShhx MeHemx raóóepejumH - ^ - ajiEnernnoBB03M0JKH0 c πομοιιιβιο cnoco ^ a, coiviacHo H3odpeTeHHio, HanpiiMep,

IIojiyqeHiiHe no cnocoóy, cornacHO H3oópeTeHjno, rnóóepejuniH-7-anE-neriiAH· c ajiBnernnHoíí rpynnoS b β^-ποηο^θΗκη noKa3HBaiOT H3Me-HeHHyio ónojionraecKyio βκτηβηοοτβ no. ορββηθηηιο c hcxoehhmii Beme-CTBar.ra.IIojiyqeHiiHe no cnocoóy, cornacHO H3ooppeTeHjno, rnóepejuniH-7-anE-neriiAH · c ajiBnernnHoíí rpynnoS b β ^ -ποηο ^ θΗκη noKa3HBaiOT H3Mo-HeHHoy. Y io β β. ορββηθηηιο c hcxoehhmii Beme-CTBar.ra.

XapaxTepHo jyin nonyneHHHX no cnocoóy, cornacHO Η3θόρθτβΗκιο,weneHHX rnóóepejLmíH-7-ajrLnernnoB to, hto MeneHne ycTOíímiBoe n£OCTnraeTCfl c όοηκποκ ynenLHon pannoaKTnBHocTEio, Tax xax Meray, C OflHOÍí CTOpOHH, Π9ΓΚ0 ΜΟΗΉΟ OÓHapyXÍITB ra X0XaT230BaTL II OHa,c Apyroií CTopoHH, HaxoniiTCH na Taxofí'ηο3ΐίΐζκη, na κοτοροκ nocxx nop H-e tíwio odnapyzeHO 0ηοχημπηθοκηχ H3MeHeHnS, sth coenn-ηθηηη, HanpxMep, οττπΐΗΉΟ ποηχοηητ ηχΗ nccnenoBaffiiH ónocnHTe3aHJIH MeTaÓ0JIH3Ma.XapaxTepHo jyin nonyneHHHX well cnocoóy, cornacHO Η3θόρθτβΗκιο, weneHHX rnóóepejLmíH 7-ajrLnernnoB it HTO MeneHne ycTOíímiBoe n £ OCTnraeTCfl c όοηκποκ ynenLHon pannoaKTnBHocTEio, Tax XAX Mera C OflHOÍí CTOpOHH, Π9ΓΚ0 ΜΟΗΉΟ OÓHapyXÍITB ra X0XaT230BaTL II OH and c Apyroií CTopoHH, HaxoniiTCH on Taxofí'ηο3ΐίΐζκη, on κοτοροκ nocxx nop He tíwio odnapyzeHO 0ηοχημπηθοκηχ H3MeHeHnS, sth coenn-ηθηηη, HanpxMep, οττπο ποηHHINaaNaaNo3e ccΗeeeeeeeccee

KpoMe Toro, nonyneHKae no cnocoóy, cornacHo Η3θόρθΤθΗΧΚ, μθήθηηθ níóóepejuniH-7-aj[BnernnH cjiysaT HcxonHHMH BemccTB.ar.m nnn nony- neHHH MeneHHX npnponimx raóóepejumHOB n nx npoH3BO£HHX. - 7 - nocJiejiywie npUMepu odBacmror H3odpeTeinie, npiraeM aaHKHe cne-HnajiBHHe ycJioBKH He orpamraiBaioT H3odpeTeHHe h ycJioBHH peaKipifinpHMeHiM Taicse jyiH noJiyqeHHH npyrax coejmHeHHií. ΠΡΚΜΕΡΒ1 OCWCTBJímH Κ3ΟΕΡΕΤΈΗΗΗKpoMe Toro, nonyneHKae no cnocooy, cornacHo θ3θόρθΤθΗΧΚ, μθήθηηθ óóóepejuniH-7-α [BnernnH γysaT HcxonHHMH BemccTB.ar.m nnn nony- nHHóH ene np ej n p ej ej ej ej n p ep p p ej p - 7 - nocJiejiywie npUMepu from Bacmror H3odpeTeinie, npiraeM aaHKHe cne-HnajiBHHe ycJioBKH He orpamraiBaioT H3odpeTeHHe h ycJioBHH peaKipifinpHMeHiM coicseHyeHiM coicseHiHeHiM coic. ΠΡΚΜΕΡΒ1 OCWCTBJímH Κ3ΟΕΡΕΤΈΗΗΗ

ΠρίϊΜθΡ I K 330,4 μγ (I mmoji) raóóepejuiHH-Ag-V-ajrBflerjijia (Ia), pacTBopeHHO—ro b 15 Mjr.aóc, impHOTHa, nodaBJíinoT 2 wi reKcaMewijCíCHJiasaHa h2 wi TpHMeTJLwiopcoaHa. OcTaBJímoT Ha 3 naca npn .KOMHaTHog τθμ-nepaType h nocjie stopo BHnapHBaioT b BanyyMe. Ilocjie jjodaBJíeHHHHacLimeHHoro pacTBopa afíCOgiicHepnuBaioine βοτρηχηββκτ c θφκροΜ.OdBejB-iHenHLie soíipHtie φΗ3Η BHCTynaioT 0θ3βοήηημ í.fe.sO4 h Btmapn-Baior b BaKyywe. Οοτετοκ octobjisot Ha hohb no# BaKyyi;:oM Han; P4 010ílocjie 3Toro CHJiHJiHpoBaHHHÉ rHddepeJuiEH-7-ajiBneriiB; pacTBopmoT baTMOcmepe aproHa b 8 mji cBodosHoro ot KHCJiopojia adc. TP5-e z ·AodaBJUWT lípu KOMHaTHOK TeMnepaType 44 mt (1,1 bioji) nmpimaKam-iH. ITocjie onHoro aaca nepeMemHBaHHH npii κομηβτηοιι Tei.mepaTy-pe íod2B.JLHK3T I i.ui JieíHHOfr yKcycHOH khcjioth h 2 mji boalí. PacTBopocTaBJíHioT na hohl hjlh ynajiemiH 3ainHTHHx rpynn, ποτομ BunapíiBasTh nocjie AodaBJíeHHH HaciffiieHHoro pacTBopa NaPCOg ηθοκολβκο pa3BCTpHXHBaiOT C 3THJI0BHM δφκρΟΜ yKCyCHOÍt KKOJIOTK. ΒηουέιηββηηθopraHHHecKHx $a3 c homoiubio I^SO^ h BunapiiBaHiie b BaKyywe naeTocTaTOK, κοτορκβ xpoMaTorpamiipyiOT Ha 20 r cnJEiKarejiH (Woelm ).Βημκβηηηθ c ΧΛοροφορΜΟΜ (mpaKinm 1-35), XJIOpOfflOpMOM/sTKJIOBHM3φιιροΜ yncycHoč KHCJiOTH 9:1 od/od (rapaKipiH 36-60), χτοροφορι.·ιοι.ι/stiuiobhm θφιιροΐΛ yncycHofi kiicjioth 8:2 od/od (φρεκι#ΐΗ 61-90) nxjiopooopmom/sthjiobhm sňiipoM yncycHOK khcjioth 7:3 od/od (φρεκπΗχ91-150) naeT npn odBejBíHeHO φρεκιχκκ 68-89 96 μγ ηοχοβηογο a;iB#e-rapa Ia. Π3 φρεκιχιΐΗ 94-141 H30JiHpyK>T 143 μγ = 61 % TeopeTiinecKoro 3Haae-ffiiH^-smirHddepej^íH-Ag-O-ajTBjíenuza (Id) (pacneT Buxojia othoch-T6JILH0 npeBpameHHOMy ajiB£ernjry Ia): Tonna iuiasjíeKnn: 185-187 0 C(h3 aneTOHa/H-reKoana), 0° 0 (c - 0,35 - STaHOJi), MC : w/e330ρ,4,4,4,4,4,4,4,4) ra,4,4,4,4,4,4 330,4,4,4 330,4 330 330 330,4 330 330 330 330 330 330 330 330 330 330 330 330 330 330 330 330 330 330 330 330 330 330 330HHH bH b bH w b w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w .222222222222222222222222222. OcTaBJímoT Ha 3 naca npn .KOMHaTHog τθμ-nepaType h night track BHnapHBaioT b BanyyMe. Ilocjie jjodaBJíeHHHHacLimeHHoro pacTBopa afíCOgiicHepnuBaioine βοτρηχηββκτ c θφκροΜ.OdBejB-iHenHLie soíHHie φΗ3Η BHCTynaioT 0θ3βοfeηημ4. Hοτετοκ octobjisot Ha hohb no # BaKyyi; P4 010i 3-toro CH3iHiHpoBaHHH rHddepeJuiEH-7-ajiBneriiB; pacTBopmoT baTMOcmepe aproHa b 8 mji cBodosHoro ot KHCJiopojia adc. TP5-e from AodaBJUWT lime tree KOMHaTHOK TeMnepaType 44 mt (1.1 bioji) nmpimaKam-iH. ITocjie onHoro aaca nepeMemHBaHHH npii κομηβτηοιι Tei.mepaTypepod2B.JLHK3T I i.ui JieíHHOfr yKcycHOH khcjioth h 2 mji boalí. PacTBopocTaBJíHioT on hohl hjlh ynajiemiH 3ainHTHHx rpynn, ποτομ BunapíiBasTh nocjie AodaBJeeHHH pacTBopa NaPCOg ηθοκολβκο pa3OTCTHHHHHHHHHHHHHH ΒηουέιηββηηθopraHHHecKHx a3 $ c homoiubio I ^ SO ^ h BunapiiBaHiie b BaKyywe naeTocTaTOK, κοτορκβ xpoMaTorpamiipyiOT Ha 20 r cnJEiKarejiH (Woelm) .Βημκβηηηθ c ΧΛοροφορΜΟΜ (mpaKinm 1-35) XJIOpOfflOpMOM / sTKJIOBHM3φιιροΜ yncycHoč KHCJiOTH 9: 1 to / from (rapaKipiH 36- 60), χτοροφορι. · Ιοι.ι / stiuiobhm θφιιροΐΛ yncycHofi kiicjioth 8: 2 from / from (φρεκι # ΐΗ 61-90) nxjiopooopmom / sthjiobhm sňiipoM yncycHOK khcjioth kee 7e / 7e / 7eφ 7e / 7e / 7e / 7e / /e / 7e / /e -89 96 μγ ηοχοβηογο a; iB # e-rapa Ia. Π3 φρεκιχιΐΗ 94-141 H30JiHpyK> T 143 μγ = 61% TeopeTiinecKoro 3Haae-phiH ^ -smirHddepej ^H-Ag-O-ajTBieenuza (Id) (pacneT Buxojia othoch-T6JILHomnneiNaynnjunnjunnaiNaynneiNeBiameNeBryme) 0 ° C (h3 aneTOHa / H-reKoana), 0 ° 0 (c - 0.35 - STaHOJi), MC: w / e

1775 ( ^-jiaKTQH-CO) z 1665 cm “Σ ( = CH^ 100 MIH - ΣΗ-ΗΜΡ: ó ggT0H ”% 1,19 ( s , I8-H), 2,75 ( dd , J = ΙΟ Γΐχ Z J* = .2,5 Ιϊχ, 6-fí), 2,97 ( d , J = ΙΟ Ιϊχ 5-H), 4,32 (m , 3-H), 4,89 z 5,21 ( , 17 Ιϊχ) 5,84 ( dd , J = 9 Γιχ z J’ = 2,5 Ιϊχ, 2-H), 6,28 ( dd , J = 9 Ιϊιη J* = 2-Γϊχ, I-H) z 9,80 ppm (zacTZ na mho. nacTefí) ( d , j» = 2,5 Ιϊχ, 7-H). AHajioruHHo nojiyqaiDT Z3 I mmoji rzóóepejuizH-7-ajiLBerHfla c 3βϊ>ββΓΖβ-hoíí rpyznoíi b 6 -ποζοκθηζζ 'z 1,1 mmoji rzzpzza Kajizz czeflyiomzerHóóepejuiHH-7ajii>nerHHH c θβΒβθΓΖβΗΟδ rpyrmoíí b 6 -ποζοζθηζζ:6-PHzrzctóepejuiXH-Aj-7-ajiwraa (lid): bhxou: 153 μγ = 64 % TeopeTznecKoro 3HaHeHZH (93 μγ II a noJiy-HZJIZ Ha3an) , BHMHBaHHe C XJI0p0$0pM0M/9WI0BHM θφΖρΟΜ yKCyCHOH KZ-cjioth 7:3 oó/oó, tohk^ iuiaBJíeHZH: 182-186 0 C (z3 aixeTOHa/H-reK-caHa), MC: M/e 332 (Μ ), HK (HyžoJi): p" Maze 3410 (br· , OH),1755 ( p-JiaKTOH-C0) z 1720 CM^tajii^erzz). 6-3ΠΖΓΖόόθΡ6χπζΗ-Α^-7-8βΒβ6ΓΖβ (III ó): ΒΗΧΟβ: 152 ΜΓ = 66 / ΤβΟρθΤΖΉΘΟΚΟΓΟ 3HazeHZH (86 ΜΓ III a πο-1775 (β-iKTQH-CO) from 1665 cm Σ (= CH ^ 100 MIH - ΣΗ-ΗΜΡ: δ ggT0H "% 1.19 (s, 18-H), 2.75 (dd, J = ΙΟ Γΐχ ZJ) * = .2.5 cm, 6-phi), 2.97 (d, J = cm 5-H), 4.32 (m, 3-H), 4.89 out of 5.21 (, 17 cm) ) 5.84 (dd, J = 9 zιχ from J '= 2.5 Ιϊχ, 2-H), 6.28 (dd, J = 9 Ιϊιη J * = 2-χ, IH) from 9.80 ppm ( zacTZ on m (nacTefi) (d, j = 2.5 Ιϊχ, 7-H). Kajizz czeflyiomzerHóepejuiHH-7ajii> nerHHH c ββΒβθΓΖβΗΟδ rpyrmoí b 6-πζζctζζηηζζ: 6-PHzrzctóepejuiXH-Aj-7-ajiwraa (lid): bhxou: 153 µHaHeHeHeHeHeHeHeHeHeHeHeHeO $ 0pM0M / 9WI0BHM θφΖρΟΜ yKCyCHOH KZ-cjioth 7: 3 o / o, this time: 182-186 0 C (z3 aixeTOHa / H-reK-caHa), MC: M / e 332 (Μ), HK (HyzaoJ) : p "Maze 3410 (br ·, OH), 1755 (β-JiaKTOH-CO) of 1720 CM ^ tajii ^ 6-3ΠΖΓΖόόθΡ6χπζΗ-Α ^ -7-8βΒβ6ΓΖβ (III δ): ΒΗΧΟβ: 152 ΜΓ = 66 / ΤβΟρθΤΖΉΘΟΚΟΓΟ 3HazeHZH (86 ΜΓ III and πο-

Jiywni ΗΒ33β) ΒΗΜΗΒΒΗΗβ C XJIOPOČOPOMOM, 3Μ0ρφΗΗΚ, MC: M/e316 (M+), HK (CHCL 3):$~ . 3610 (OH), 2725, 2820 z 1725 (ΒΖΒββΓΖβ) z 1775 cm^ ( ^-zaKTOH-CO). 6-3nzrzóóepezjizH-A3-7-ajiLzerzz (Ikó): ΒΗΧΟβ: 152 μγ *= 70 $ TeopeTZzeczoro 3ΗΒΉΘΗΖβ: (97 μγ IVaIIOJiyHXJIZ ΗΒ3θβ) , BHMHBaHZe C ΧβΟροφόρΜΟΜ,Jiywni ΗΒ33β) ΒΗΜΗΒΒΗΗβ C XJIOPOCOPOMOM, 3Μ0ρφΗΗΚ, MC: M / e316 (M +), HK (CHCL 3): $ ~. 3610 (OH), 2725, 2820 out of 1725 (ββββ) out of 1775 cm @ 2 (? -ZaKTOH-CO). 6-3nzrzóóepezjizH-A3-7-ajiLzerzz (Ikó): ΒΗΧΟβ: 152 µg * = 70 $ TeopeTZzeczoro 3ΗΒΉΘΗΖβ: (97 µg IVaIIOJiyHXJIZ θ3θβ), BHMHBaHZe C ΧβΟροφόρΜΟΜ,

Tozza imaBJíeHza: 195-197 0 C (z3 xzopoaopMa/H-reKcaHa), MC M/e 314 (M+), HK (Hyta): r MaKC< 3400 (br., OH) , 1755 ( ^-zazTOH-CO) z 1720 cm (ββΒβθΓΗβ). - 9 - 6-3ΠΙΤΓΗ006Ρ0·7υΐπΗ-Αο-7-5.τΐΕπ6π^ ( V d) : MC: M/e 348 (M+), \O — jL· 1750 ( ^-JiaKTOH-CO) h 1720 cm^ blkoa: 150 μγ = 60 % TeoperanecKoro 3Ηηήθηηη (98 mt \/a nony-HHJK HS3a^) , BHMHBaHHe C ΧΛΟροφορΜΟΜ/θΤΟΟΒΗΜ SffiHpOM yKCyCHOSkhcjioth 2:8 od/od, εΜορφΗυδ, MK (Hyta): f mskc. 3400 (br OH),(aJiL^enií). 6-3rEirHóóepeAOH-Ag-7-3JihjTgmji ( l/I d):Tozza imaBJíeHza: 195-197 ° C (z3 xzopoaopMa / H-recaCa), MC M / e 314 (M +), HK (Hyta): r MaKC < 3400 (br., OH), 1755 (? -ZazTOH-CO) of 1720 cm (ββΒβθΓΗβ). - 9 - 6-3ΠΙΤΓΗ006Ρ0 · 7ΐΐπΗ-Αο-7-5.τΐΕπ6π ^ (V d): MC: M / e 348 (M +),) - · · 1750 (-- KTKTKT-CO) h 1720 cm ^ blkoa : 150 μγ = 60% TheoperanecKoro 3Ηηήθηηη (98 mt \ / a nony-HHJK HS3a ^), BHMHBaHHe C ΧΛΟροφορΜΟΜ / θΤΟΟΒΗΜ SffiHpOM yKCyCHOSkhcjioth 2: 8 from / from, εΜορφΗυδ: MK (msk): 3400 (br OH), (α). 6-3rEirHoepeAOH-Ag-7-3JihjTgmji (l / ld):

EepeTcn 30 μγ (0,1 mmoji) l/I a n 9 mt ranpnna Kajmn. 3necbEepeTcn 30 μγ (0.1 mmoji) l / l and n 9 mt ranpnna Kajmn. 3necb

He Hano cujnumpoBaTB. Bnxon: 14,2 mt = 69% H 6 (9,7 mt l/I a nojiywra Ha3an), βημηβθήιιθ c Η-ΓθκοβΗΟΜ/χζιοροφορΜΟΜ 4:6 od/od, SMOpČHLIÍí, MC: M/e 300 (M+), HK (CHCI 3):γ —0. 2725 η 1725 (am^ero) ,1775 cm"·®· ( f^-JiaKTOH-CO). ΠΡΗΜΕΡ 2 330,4 μγ -(Ι mm oji) raddepeJUBíH-A^^-ajiLseníjía (Ia) aunumpyioT ana-jioranHo npHMepy I. Hotom GMeuniBaiDT no KaiuiHM pacTsop H3 0(3),0(l3)-dnc-Tpm^eTMcnjnur-raddepejuiHH-A2-7-anLnernna b 5 mji adc. ij ΊΤΦ b aTMOcóepe apoHa npn -78°C c pacTBopoM ÁHH30nponiíJiaMiina jj jdithh (n3roTOBJieHHoro n 3 2 mji adc. ΊΊΦ, III μγ Mn3onpormjiaMHHa !! h 70 μγ dyrajumTHH).He Hano cujnumpoBaTB. Bnxon: 14.2 mt = 69% H 6 (9.7 mt l / l and nojiywra Ha3an), βημηβθήιιθ c Η-ΓθκοβΗΟΜ / χζιοροφορΜΟΜ 4: 6 from / from, SMOpČHLIíí, MC: M / e 300 (M +), HK (CHCl 3): γ —0. 2725 η 1725 (am ^ ero), 1775 cm "· · · (^ J KT KT KT OH OH CO CO.). Π ΕΡ 2 330.4 μγ - (Ι mm ji mm) raddepeJUBíH-A ^^ - iiLsjíjíjí I I I I (Ia) aunumpyioT ana-jioranHo npHMepy I. Hotom GMeuniBaiDT no KaiuiHM pacTsop H3 0 (3), 0 (13) -dnc-Tpm ^ eTMcnjnur-raddepejuiHH-A2-7-annernna b 5 mji adc. jj jdithh (n3roTOBJieHHoro n 3 2 mji adc. ΊΊΦ, III μγ Mn3onpormjiaMHHa! h 70 μγ dyrajumTHH).

OcTaBJLmoT Ha 10 MHHyT npn -78°C, 10 mhhvt npn 0°C h 30 MKHyr npn ! +20°C η ποτοΜ AodaBJímoT 2 mji bojhi η I mji Jiejymofí yncycnoS kh- j cjioth. TenepL οοτββληκτ Ha 12 nacoB η ποτομ odpadaTHBaJOT anajio- | ιήηηo npHMepy. I n xpoMaTorpaánpyioT. 5OcTaBJLmoT Ha 10 MHHyT npn -78 ° C, 10 mhwt npn 0 ° C h 30 MKHyr npn! + 20 ° C η ποτοΜ AodaBJímoT 3 mji bojhi η I mji Jiejymofí yncycnoS kh- j cjioth. TenepL οοτββληκτ Ha 12 nacoB η ποτομ odpadaTHBaJOT anajio- | ιήηηo npHMepy. I n xpoMaTorpaanpyioT. 5

Bnxon: 104 μγ = 50 % TeopemnecKoro δΗΗΗβΗΗΗ 6-3nHraddepejumH- ? A3-7-aJiLflern.ua (Id.) (122 mt Ia nojiymuin Ha3an), BHMHBaHne c zno- |ροφορΜΟΜ/θΤΙϋΙΟΒΗΜ ΒφηρΟΜ yKCyCHOŽ KHCJIOTH 7:3 od/od, φΗ3ΗΗΘ0ΚΗΘ | n cneKTpocKOfflmecKne naHHHe, cm. npzMep I. |Bnxon: 104 µg = 50% TeopemnecKoro δΗΗΗβΗΗΗ 6-3nHraddepejumH-? A3-7-aJiLflern.ua (Id.) (122 mt Ia nojiymuin Ha3an), BHMHBaHne c zno- | ροφορΜΟΜ / θΤΙϋΙΟΒΗΜ ΒφηρΟΜ yKCyCHOŽ KHCJIOTH 7: 3 from / from, φΗ3ΗΗΘ0ΚΗΘ | n cKTKTocKOfflmecKne naHHHe, cm. npzMep I. |

HH

Z v f - ΙΟ - IIpaMep 3 1' (-, * i Κ 330 μγ (I mmoji) raddepejumH-Ag-^ajiBEeraaa (Ia), κοτορυβ aHa- |Z in f - ΙΟ - IIpaMep 3 1 '(-, * i Κ 330 μγ (I mmoji) raddepejumH-Ag- ajiBEeraaa (Ia), κοτορυβ aHa- |

JIOmHHO npHMepy I CHJnumpOBaJIH, «HOÓaBJIÍTOT ΠΟ KaUJLHM B ΒΤΜΟΟφβρβ IJIOmHHO npHMepy I CHJnumpOBaJIH, «HOÓaBJIÍTOT ΠΟ KaUJLHM B ΒΤΜΟΟφβρβ I

aprOHa npa —78°C 5 mji adc. ΤΓΦ 0 pacTBop 2,2, 6,6-TeTpaMeTaJmnne- FaprOHa npa -78 ° C 5 mji adc. ΤΓΦ 0 pacTBop 2,2,6,6-TeTpaMeTaNm-F

pajuma (asroTOBJíeHHoro H3 2 mji adc. ΤΓΦ, 160 mt 2,2,6,6-TeTpa- Epajuma (asroTOBJeHHoro H3 2 mji adc. ΤΓΦ, 160 mt 2,2,6,6-TeTpa- E

MeTHJiminepHOTHa a 70,4 μγ. dyTajumTaa). OcTaBJunoT Ha 10 Manýr npn [ -78°C, 10 ΜΗΗγτ npaO°C- a 30 MHHyr npa +20°C a nodaBJDWT I mji fMeTHJiminepHOTHa and 70.4 μγ. dyTajumTaa). OcTaBJunoT Ha 10 Manner npn [-78 ° C, 10 ΜΗΗγτ npa 0 ° C- and 30 MHHyr npa + 20 ° C and nodaBJDWT I mji f

MeTaHOJia a I mji Jiejamož yncycHOft khcjioth. OcTasjuroT Tenept Ha12 nacoB a odpadaTimaiDT aHajioranHo no npaMepy I a octbtok xpo-MaTorpa^apyET. < Βηχολ: 99 μγ = 47,% τθορθτζπβοκοΓο 3ηβή6ΗΗΗ S-anaraóčepeJUiHH-Ag-7-ajiLnerKna (Id) (120 μγ Ia nojiynajm Ha3a£), βημηβηηηθ c XJiopo- ; $opmom/3Thjioblim θφηροΜ yncycHoii KHCJiOTH 7:3 od/od,$a3anecKae a ř cneKTpocKOnaHecKae Easmie cm. npaMep I. > ΠΡΗΜΒΡ 4 i- Αηβλογηηηο npaMepy I 03 I mmoji raddepejuiHH-T-ajiBjíerajia c anLne- ‘ ΓΗβΗοίί rpyímoíí b 6oC-nojioseHaa a I, I mmoji raj^pajca najma nojiy- l naioT cjiejornnae raddepejumH-TajiBnerHnH c ajisjíerajcHO^ rpyímoíí b í 6 p -nojioJKeimn: |MeTaHOJia and I mji Jiejamož yncycHOft khcjioth. OcTasjuroT Tenept Ha12 nacoB and WasteTimaiDT and HaiioranHo no npaMepy I and octbtok xpo-MaTorpa ^ apyET. <:Ηχολ: 99 μγ = 47,% of 3-β6-β-S-anareacepeJUiHH-Ag-7-αInerner (Id) (120 μγ Ia nojiynajm Ha3a £), βημηβηηηθ c c XJiopo-; $ opmom / 3Thjioblim θφηροΜ yncycHoii KHCJiOTH 7: 3 from / from, $ a3anecKae a rcKTKTocKnaHecKae Easmie cm. npaMep I.> ΠΡΗΜΒΡ 4 α- Αηβλογηηηο npaMepy I 03 I mmoji raddepejuiHH-T-iBΗerajaj cΓΗpy anΗίpypypypyΗ b b a a a Inernernernernernernernernernernernerna lnana l l l l l l l l l l b 6 6 p -nojioJKeimn: |

PaddepejiJiaH-Ag^-aJiBjíeraa (Ia): fPaddisHiH-Agb-aJiBjeeraa (Ia): f

Buxon: 99 mt = 54 % TeopeTanecKoro 3κβήθηηη (146 μγ Id nojiymr- í- jia ηβ33λ) , βημηβηκηβ c xjiopotpopMOM/STajioBHM θφηροΜ yncycHoft na- £ cjioth 8:2 od/od, Toana iuiasjíeHaa: I72-I75°C (h3 aneTOHa)^(.7^$ . p + 118,8° (c=0,6I, 3TaH0Ji), MC: M/e 330 (M4" ajia M“), £ HK (CHC& 3): fMaKC>36I0 (OH), 2723,2820 a 1725 (aJiLneran),Buxon: 99 mt = 54% TeopeDanceKoro 3 ββήθηηη (146 μγ Id nojiymr- ia ββ33λ), βημηβηκηβ c xjiopotpopMOM / STajioBHM θφnρHΜnnycHoft at £ cjioth 8: 2aaeanaaae ana ee ana ee ana ana ana ana ana ana ana ana ana ana ^ ((. 7 ^) p + 118.8 ° (c = 0.6I, 3TaH0J), MC: M / e 330 (M4 "and M M), HK HK (CHC & 3): fMaKC> 3610 ( OH), 2723, 2820, and 1725 (αInerner),

1775 (y^-JianTOH-CO) a 1635 cm“^ (-CH=CH-), I 100 ΜΓη - ΣΗ-γΗΜΒ: o ^T°H”^6 1,14( s , 18-¾), [ 2,79 (dd J = 10 Γρ aJ1’ = 2,5 Γη, 6-H), Γ í‘ Ϊ ř t J· i’ t - II - 3,29 (d , J = 10,5 Πξ, 5-H), F. 4,06 (d , J = 3,5 Γρ, 3-H), 4,93 H 5,24( m, 17-¾), , p 5,90 (dd ,J - . 9,5 Γϊζ h j’ = 3,5 Γρ, 2-H), 6,39 (d,.J = 9,5 Γρ, I-H) x 9,84 nmm( d, J - 2,5 Pp, 7-H), - í·,' . - · riióóepejumH-Aj-7~ajiwrHj3; (Ila): r Βηχολ: 90 mt = 52 % TeoperanecKoro 3HaHeHPH (158 mt IIó nojiy-HHJDÍ ΗΗ33Λ)ΐ-ΒϋΜΗΒ3ΗΗβ^Ο·-ΧΛθρθφθρΜΟΜ/3ΤΗΛΟΒΙ2Μ-3φΐΐρθΜ JHCyCHOŽ—khcjioth 8:2 oó/oó, aMopčpHHft, MG: M/e 332 (M+ M M“) , HK ( CHCt3): <MaKCt 3610 (OH), 2725, 2820 x 1725 (aJiLperap) x1770 cm*"^ (j^-^aKTOH-C0).raóóepejuniH-Ag-7-aji£aerna (IV a): Βηχοή: 94 μγ=59 $ TeopeTircecKoro 3HaHSHHH (155 μγ IVó nwiywiH.1775 (γ ^ -JianTOH-CO) and 1635 cm ^ ^ (-CH = CH-), I 100 ΜΓη - ΣΗ-γΗΜΒ: δ T ° H "δ 6 1.14 (s, 18-¾), [ 2.79 (dd J = 10 Γρ and J1 '= 2.5 Γη, 6-H), Γ' t t J · i 't - II - 3.29 (d, J = 10.5 Πξ, 5 -H), F. 4.06 (d, J = 3.5, 3-H), 4.93 H, 5.24 (m, 17-β), δ 5.90 (dd, J -. 9.5 Γϊζ h j '= 3.5 Γρ, 2-H), 6.39 (d, J = 9.5 Γρ, IH) x 9.84 nmm (d, J - 2.5 Pp, 7 -H). Hepoepejum H-A-7-aiwrH3; (IIIa): r Βηχολ: 90 mt = 52% TeoperanecKoro 3HaHeHPH (158 mt IIó nojiy-HHJDÍ ΗΗ33Λ) ΐ-ΒϋΜΗΒ3ΗΗβ ^ Ο · -ΧΛθρθφθρΜΟΜ / 3ΤΗΛΟΒΙ2Μ-3φΐΐρθΜ JHCoCHoŽ: khcji [α] 332 (M + MM +), HK (CHCl 3): δ MaKClt 3610 (OH), 2725, 2820 x 1725 (α i per ap 17)) j 1770 cm * "(^ - a aKTOH-CO). aji £ aerna (IVa): 94 μγ = 59 $ TeopeTircecKoro 3HaHSHHH (155 μγ IVo nwiywiH.

Ha3ají), BHMHBaHHe c H-reKcaHOM/χριοροφορΜθΜ 1:9 oó/oó, TOHKa ........ iwaBJíeHHH: ~I52-I53°C (H3 9$npa), MC: M/e 314 (M+), HK (CHCQ: 3605 (OH), 2725 x 1725 (araperra) h 1775 cm -¾ φ-jmxioH-CO).raóóepejij3iH-Ag-7-ajn>fferHfl (V a):Ha3aj), BHMHBaHHe c H-recaHOM / χριοροφορΜθΜ 1: 9 o / o, TOHKa ........ iwaBJeHHH: -152-153 ° C (H3 9 $ npa), MC: M / e 314 (M +) , HK (CHCQ: 3605 (OH), 2725 x 1725 (araperra) h 1775 cm -1 φ-mmaxioH-CO).

Bhxoí: 95 mt = 49 % TeopeTircecKoro 3HaHeHHH (154 mtVó nojiyqiuniHa3a£) , BNMKBaiGie C ΧΛΟροφορΜΟΜ/3ΤΗΛ03ΗΜ 3φκρ0Μ yKCyCHOfi KHCJIOTH4:6 oó/oó, aMopČHLiS, MC: M/e 348 -(M+),, HK (Hyta): ^MaKC 3400 (br OH), 1750 (J^-jraKTOH-CO) x1720 cm -1 (aJiLperap).Bhxoi: 95 mt = 49% TeopeTircecKoro 3HaHeHHH (154 mtVo nojiyqiuniHa3a £), BNMKBaiGie C ΧΛΟροφορΜΟΜ / 3ΤΗΛ03ΗΜ 3φκρ0Μ yKCyCHOfi KHCJIOTH4: HC o / o8, mOo / o8, mOo / oO, aOo / oO, MaKC 3400 (br OH), 1750 (.gamma.-hexane-OH) x1720 cm @ -1 (.alpha.).

i>:l P ’·: iK·: í Ěii>: l P i: iK · i i

v"<·i r-in "<· i r-

- 12 - ruddepeJiJiHH—Αθ-7—aJiBnerHU ( Ia): πρΗΜβΗΗΐοτ tojibko 30 μγ (0,1 mm oji ) 6-3mirHddepejuiHH-Ag-7-ajiLjierHji.CHjmjHípOB&HHH 3fleCL He HajIO.- 12 - reddish-A-7-aJiBnerHU (Ia): 30 to 30 µg (0.1 mm draw) 6-3mirHddepejuiH-Ag-7-aiLjierHji.CHjmjHipOB & HHH 3fleCL He HajIO.

Bhxou: 9,3 mt = 62 $ y Ia (15 μγ Xld nojiywm Ha3aji), ΒΗΜΗΒΒΗΗβ C Η-ΓβΚΟβΗΟΜ/χΗΟροφορΜΟΜ IíI OÓ/otí, ΗΜΟρφΗΗ®, MC: m/e 300(M*). ΠρΗΜβρ 5: K 330,4 μγ (I mmoji) rHÓÓepejuraH-Ag^-aHBBerHJia (Ia), κοτορπϋ ana· jionnHo npzMepy I cnjoumpoBajiz, b aTMOcčbepe ^oroHa nodasjímoT 8 mjiadc. ΤΙΦ h 44 mt (I,’( mmoji) rHBpHna.KajrHH. Ilocjie nacoBoro nepe-MeiuHBaHHH κ siiOTHiy noóaBJíHioT npn KOMHaTHOii TeMnepaType 0,1 mji^HgO (5,55 mmoji) (ysejiLHaa pajmoaKTHBHocTB 3 mkkph/mmoji) .Bhxou: 9.3 mt = 62 $ y Ia (15 μγ Xld nojiywm Ha3aji), ΒΗΜΗΒΒΗΗβ C Η-ΓβΚΟβΗΟΜ / χΗΟροφορΜΟΜ I I O / í, ΗΜΟρφΗΗ®, MC: m / e 300 (M *). ΠρΗΜβρ 5: K 330,4 μγ (1 mmoji) rHÓOepejuraH-Ag ^-aHBBerHJia (Ia), κοτορπϋ ana · jionnHo npzMepy I cnjoumpoBajiz, b aTMOcèbepe ^ oroHa nodasjím. 44 h 44 mt (I, ´ (mmoji) rHBpHna.KajrHH. Ilocjie nacoBoro nepe-MeiuHBaHHH κ siiOTHiy noóaBJíHioT npn KOMHaTHOii TeMnepaType 0.1 mj ^ HgO (5.55 mmoji) mkeji / mkeji / mkeji / mkeji / mkeji

TenepB nepeMemHBaíOT τρπ MHHyTH h cMeniHBaDT hotom c I mji jieXHHOíiyKcycHoft khcjioth.. IlyTeM μηογοκρβτηογο aunapHBaHHH b BanyyMe hμηογοκρητηογο aodaBJíeHHH MeTanoJia bo3mosho yjcajEHTB HecTadHJiBHHÍiTpHTHfi-i .ta ysajieHHH 3aimiTHnx rpynn κ ocTaray sodaBJL®oT 8 mji ΊΤΦ, r-TenepB nepeMemHBaíOT τρπ MHHyTH h cMeniHBaDT Hoto C np jieXHHOíiyKcycHoft khcjioth .. IlyTeM μηογοκρβτηογο aunapHBaHHH b BanyyMe hμηογοκρητηογο aodaBJíeHHH MeTanoJia bo3mosho yjcajEHTB HecTadHJiBHHÍiTpHTHfi-i .ta ysajieHHH 3aimiTHnx rpynn κ ocTaray sodaBJL®oT 8 ΊΤΦ ay, R

2 mji HgO h I mji Jiejpnioíí yKcycHofl khcjioth η oct8bjihiot Ha hohb.Ilocjie BHnapHBaHHH b BaKyyMe HajiHBajoT HacHmeHHHií pacTBop N. aHCOgH HeCKOJIBKO pa3 BCTpHXHBaDT C 9THJI0BHM θφπρΟΜ yKCyCHOÍÍ KHCJIOTH.BucywHBaHHe opramraecKOft <$a3H c πομοπιβιο N a^O^ h BHnapuBaHHeb BaxyyMe naeT ocTaTOK, κοτορκϋ βηθηογηηηο npHMepy I xpoMaTorpa-$HpyiOT. ΠρΗ BHMHBaHHH C XJIOpO$OpMOM/3THJIOBHM θφπρΟΜ yKCyCHO# KH—cjioth 8:2 od/od noJiynaiDT 99 mt = 30 $ TeoperanecKoro 3HaneHHH rHddepejuiHH-Ao-7-ajiBnerHna (Ib), HMeioigero yneJiBHyio panHO- aKTHBHocTL 1,37 mkkph/mmoji. nocJiejxoBaTejiBHoe βημηββηηθ c xjiopo-(Jopmom/sthjiobhm 9φπροΜ yKcycHoíí khcjioth 7:3 od/od uaeT 145 mt == 44 % TeopeTHHecKoro 3HaneHHH /7 S-^Hj-é-aimrHddepejLTiHH-A^-?-ajiBJíerHna (Ir) c ynejiBHoŽ ρβηηοβκτηβηοοτβε 1,47 mkkph/mmoji . Φη-3HHecKHe h cneKTpocKonHHecKHe raHHne 9thx coejBíHeHHÉ cm. b npz-Mepax I h 4. ÁHajiorHHHO nojiynaioT H3l mmoji iHddepejLOH-TanAiierHjia c ajiLnernn-2 np np HgO h I Jiejpnioíí yKcycHofl khcjioth η oct8bjihiot Ha hohb.Ilocjie BHnapHBaHHH b BaKyyMe HajiHBajoT HacHmeHHHií pacTBop N. aHCOgH HeCKOJIBKO PA3 BCTpHXHBaDT C 9THJI0BHM θφπρΟΜ yKCyCHOÍÍ KHCJIOTH.BucywHBaHHe opramraecKOft <$ πομοπιβιο 3 H C N ^ O ^ and h BHnapuBaHHeb BaxyyMe NAET ocTaTOK , κοτορκϋ βηθηογηηηο npHMepy I xpoMaTorpa- $ HpyiOT. ΠρΗ BHMHBaHHH C XJIOpO $ OpMOM / 3THJIOBHM θφπρΟΜ yKCyCHO # KH — cjioth 8: 2 from / by noJiynaiDT 99 mt = 30 $ . nocJiejxoBaTejiBHoe βημηββηηθ c xjiopo- (Jopmom / sthjiobhm 9φπροΜ yKcycHoí khcjioth 7: 3 from / from uaeT 145 mt == 44% TeopeTHHecKoro 3HaneHHH / SβLTi aim aim aim aim? aim???? é é é é é é é é é é é é é é é é é é é é é é é é é é é é é é é? 1.47 mkkph / mmoji Φη-3HHecKHe h cNKTpocKonHHecKHe raHHne 9thx ejeHeHeHHÉ cm b npz-Mepax I h 4. aj aj ior n oj 3 3 3 3 oj oj oj oj oj oj oj aj aj aj aj aj aj

hoS rpynnoft b 6p-nojiozeHHH, 1,1 mmoji ranpHna K3jihh h 0,1 mji ^O k t-HoS rpynnoft b 6p-nojiozeHHH, 1.1 mmoji ranpHna K3jihh h 0.1 mji ^ 0 k t-

I r*· r ť. t; r - 13 - (y^ejiLHaH pajmoaKTZBHocTi 3 mkx>ph/mmoji) cjiejxyioníHe raóóe- pejuiHH-7-aJii,jierHjm c ajisjíerHjmoíi rpymioft b 6c<-nojioseHHH h/?6-3h7- raóóepejiJMH-7-oL£erH£H c ajiwrwoft rpynnoÉ b 6^-noJioseHira (φιι~ 3HHecKHe h cneKTpocKomrcecKHe jiaHHHe nojiyqeHHHx coejBffleHxfi cm. b npHMepax I h 4): /~6-3Hj-rHgdepeJUMH-Aj-7-ajii>j:ermi: (IIb) h_________ Λ6-3Η7-6-3ΐΐΗΓΗ0ά6ϋωυΓΗΗ-Α^-7-&Μ6Πί£ (Ur): BHMHBaHne c XJiopaJopMOM/sTíuioBHM θφπροΜ yiccycHOft khcjioth 8:2 oó/oó;bhxojí 93 mt =-28% TeopeTiraecKoro 3HanenHH II b (yxejiBHaa pajmo-aKTHBHOCTB -I, -32 -MKEPh/mMOJI, ΒΗΜΗΒ3ΗΗθ -C -ΧΗΟροφορΜΟΜ/θΤΐυΐΟΒΗΜ 'θφπροΜ yKcycHoS. khcjioth 7:3 oó/oó,~βηχολ~Ι50 mt = 45 %~τβορβΤΗ—ήθοκογο 3ΗΗΉβΗΚΗ lir (ysejiiHan pajmoaKTHBHOcTB: 1,48 mksdph/mmoji) . L&^l^-v^óóe^QJiJW-k^-ajii^QTZR (IIIb) h Γβ~38?^3ΙΏΙΓΗ006Ρ6Χ?ΠΙΗ~Αίί~7--3^ΒΖ[6ΓΗ^ (ΙΙΙγ) : - βημηββηηθ c H-reKcaHOM/x^opoóopMOM 2:8 oó/oó, bhxo#9I,5 mt29 % TeopeTmecKoro 3HaneHHH IIIb (yseJiLKan pajmoaKTHBHOcTB: 1,35 MKlOpn/MMOJl) , βΜΟρφΗΗ#, ' MC: M/e 316 (M+), HK (CHCEg): ^MaKC 3610 (OH), 2725 H 1725 (aJiBJíerHs) H 1775 cm' ( -;iaKTOH-C0), BHMUBaHHe c χζτοροφορΜΟΜ,bhxos: 149 mt = 47 % TeoperanecKoro 3HaneHHH ΙΙΙγ (yrejiBHan pa- -OToaKTKBHocTL: 1,49 mkbph/mmoji) . f~6- ^HJ - rHÓÓepeJumH-Ac-7-ajiBiierHji (IYb)h____ f 6- 3H7-6-3iiHrHóóepejun:H-A^-7-aJLjergTT (X£r): ; BHMHBaHze c H-reKcaHOM/xJiopo$opMOM 1:9 oó/oó, bhxozi;: 101 mt = 32TeopeTinecKoro 3HaHeHHH I b (y^eJiLHan pajuioaKTHBHOCTB: :1,39 mkd-Ph/mMOJI) , ΒΗΜΗΒΒΗΗΘ c ΧΛΟροφορΜΟΜ, . bhxojz: 1,53 μγ = 49 % TeopeTimecKoro .3Ha^eHHH XFr (y^eJiLHaa pa-ΛΗΟβκτηβηοοτβ: 1,5 mkioph/mmoji) . Ě; l·-I r * · r ť. t; r-13- (γ-ω-ω-ω-ω-ω-ω-ω-ω-ω-ω-ω-ω-ω-ω-ω-ω-ω-ω-ω-ω-ω-ω-ω-ω-ω-ω-ω-ω) aj i h ((e e e e e e e e e e e e e -3 e e e e -3 -3 e e e -3 e e e -3 -3 -3 3 Ur7-6-3ΐΐΗΓΗ0ά6ϋωυ c-^ ^ -7- & Π6Πί £ (Ur): BHMHBaHne c XJiopaJopMOM / sTíuioBHM 8: 2 o 6 / o 6; -I, -32 -MKEPh / mMOJI, ΒΗΜΗΒ3ΗΗθ -C -ΧΗΟροφορΜΟΜ / θΤΐυΐΟΒΗΜ 'θφπροΜ yKcycHoS. Khcjioth 7: 3 o / o, ~ βηχολ Ι50 mt = 45% &; l l l l T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T : - βημηββηηθ c Hr eKcaHOM / x ^ opoopMOM 2: 8 o / o, bhxo # 9I, 5 mt29% TeopeTmecKoro 3HaneHHH IIIb (yseJiLKan pajmoaKTHBHOcTB: 1.35 MKlOpn / MMOJl), βΜΟρφΗΗ #, (MC: M / e), (MC: M / e) CHCEg): MaMKC 3610 (OH), 2725 H 1725 (aJiBíerHs) H 1775 cm -1 (-; iaKTOH-C0), BHMUBaHHe c χζτοροφορΜΟΜ, bhxos: 149 mt = 47% 49 mkbph / mmoji). f-6-H-6-H-6-E-H-Ac-7-ai-BierHi (Ib) h ____ f 6-H-6-H-6-H-6-epichloride: BHMHBaHze c H-recaHOM / xJiopo $ opMOM 1: 9 oO / oO, bhxozi; 101 mt = 32TeopeTinecKoro 3HaHeHHH I b (y ^ eJiLHan pajuioaKTHBHOCTB:: 1.39 mkd-Ph / cMOJφ, φφο, φοο, φΜΟΜΜΟΜ, φΜΟΜ). bhxojz: 1.53 μγ = 49% TeopeTimecKoro .3Ha ^ eHHH XFr (y ^ eJiLHaa pa-ΛΗΟβκτηβηοοτβ: 1.5 microns / mmoji). E; l · -

-I - 14 - 3J-raóóepeJumH-AA-7-a^wraa (yB) H | /^6--¾ J-e-9nHrHgóepejL7DiH-Ag~7-eiJii>flerHfl Q?r): BHMHBaHHC C ΧΛΟρΟφορΜΟΜ/ρΤΟΟΒΗΜ θφζρΟΜ yKCyCHOfi KHCJIOTH fc 4:6 od/od, bhxoa: 100 mt = 29 % TeoperanecKoro 3HaneHHH 7" b | (yflejiBHan paflHoaKTHBHocTB: 1,10 mkioph/mmoji) , | ΒΗΜΗΒ3ΗΗ6 C OOpO^pMOM/STHJIOBHM . δφζρΟΜ JKCyCHOS KHCJIOTH 2:8 od/od, |bhxoa: 147 mt = 42 % TeopeTznecKoro 3ηηηθηηηΪγ (ysejiLHaa pauzo- FaXTHBHOCTB: 1,21 MKJOpz/MMOJl) . J. Í6- 3ď —mddepsjuiHH—Ag—7—ajiLnerzu U?Ib) z ' f~6- -6-3iiHniddepejijMH-Ag-7-ajiLflerzfl (Klr): ΠρΗΜβΗΗΒΤ 30 ΜΓ (0,1 MMOJl) 7la H 9 ΜΓ rHflpHfla KaJIHfl. 3fleci> He Haflo czjizjizpoBamifl, BHMHBaHze c H-reKcaHOM/xJiopo$op-mom 1:1 od/od, bhxoa: 9,9 μγ = 33 % TeopeTHHHCKoro 3ηβήθηηη2Ιβ(yflejiLHafl paflHoaKTHBHocTL: 1,42 mkioph/mmoji), j BHMHBaHze c H-reKcaHOM/xjiopo$opMOM 4:6 od/otí, bhxoa: 13,8 mt = = 46 % TeopeTinecKoro 3ηβήθηηη Zlr (yfleJiBHaa paflHoaKTHBHOcTL: 1,5 mkioph/mmoji) . &- %]-rzddepejumH-Ajg-7-anLflerzfl (7lII) z C6- ^Hj-6-3HzrzddepejiJiHH-Aj2-7-aflLflerzfl (IX) K pacTBopy, cocTonmeMy Z3 3,16 mt (0,01 mmoji) rzddepejuiHH-Ajg-?-aJiLflerzfla (?II) b 0,5 mji atíc.TI$ flodasjunoT npz κομηβτηοη TeMne-paType b amoc$epe ajrona I μγ γηαρηαβ κβαζη. IlocJie nacoBoro ne-peMeipiBaHZH flod£3flHE)T 0,1 mji ^HgO (yflejiLHafl pafliioaKTZBHOCTL : 3 MKiopz/MMOJi) h iiocjie Tpex MHHyT HajizBaiOT 0,5 mji Jieumíofí yncyc-Hofl kzcjioth. Ποτομ BHnapzBaioT b BaKyywe. z c nejiLio yflajieHHH τρζτζΗ,cnocodHoro κ odweHy, octhtok pacTBopmoT b othjiobom ažzpe yncycHoSKHCJIOTH H HeCKOJIBKO pa3 BCTpHXHBaDT C 2 $-HM BOflHHM HC£. IlOCJie .BHcyniHBaHHH c noMOflBio N a^O^ h BHnapHBaHHH b BaKyyMe nOJiynaiDTnocJie TOHKOCJio&íoro xpoMaTorpa|z^ecKoro pa3flejieHza sa CHJiHKarejle( Merck). f ř-I-14-3J-6-chloro-6H-AA-7-α (wB) H | (^ 6 - JeHnHrHgóepejL7DiH-Ag ~ 7-eiJi> flerHfl Q? R): BHMHBaHHC C ΧΛΟρΟφορΜΟΜ / ρΤΟΟΒΗΜ θφζρΟΜ yKCyCHOfi KHCJIOTH fc 4: 6 from / from: m / m / min " | (yflejiBHan paflHoaKTHBHocTB: 1.10 mkioph / mmoji), | ΗΗ3ΗΗ6 C OOpO ^ pMOM / STHJIOBHM. δφζρΟΜ JKCyCHOS KHCJIOTH 2: 8 from / from, | 21 (MJ / PJ / MMJJ) J 1-6-3d -ddepsjuiHH-Ag-7-αlnerz U-Ib) f f-6- -6-3iiHniddepejijMH-Ag-7-γl-lerllerler (Klr): ΠρΗΜβΗΗΒΤ 30 ΜΓ (0.1 MMHI) 7la H 9 ΜΓ rHflpHfla KaJIHfl.3fleci> He Haflo czjizjizpoBamifl, BHMHBaHze c H-reKaHOM / xJiopo $ op-mom 1: 1 od / od, bhxoa: 9,9 μγ = 33% TeopeHHlCoThHlCoTHHoCoHoCoHhCo 42 microns / mmoji), BHMHBaHze c H-recaHi / xjiopo $ opMOM 4: 6 from / rpm, bhxoa: 13.8 mt = = 46% TeopeTinecKoro 3% ή θ η Zl Zl Zlr (yfleJiBHaa paflHoaKTHBHOcTL: 1.5); -%] - rzddepejumH- Ajg-7-anlflerzfl (7lII) from C 6 H 11-6-3 H 2 O-H 2 -H 2 -7-aflLflerzfl (IX) K pacTBopy, cocTonme Z3 3.16 mt (0.01 mm 3) rzddepejuiH-Ajg? 2? II) b 0,5 mji atíc.TI $ flodasjunoT npz ομηβτηοη TeMne-paType b amoc $ epe ajrona I μγ γηαρηαβ κβαζη. It is a 0.15 µg / ml (0.1 µg / ml) 2 µg / ml (0.5 µg / ml) 3 µg / ml H 3 O 2 H 3 O 2 H 3 O 2 H 2 O 3. Ποτομ BHnapzBaioT b BaKyywe. z c nejiLio yflajieHHH τρζτζΗ, cnocodHoro κ odweHy, octhtok pacTBopmoT b othjiobom upzp yncycHoSKHCJIOTH H HeCKOJIBKO pa3 BCTpHXHBaDT C 2 $ -HM BOflHHM HC £. BALKYYMe nOJiynaiDTNocJie TOHKOCJio & xorMaTorpa | zCzech PaPleaeHza with CHJiHKarejle (Merck). f ř

b*. £ i- ΐ K- r - 15 1,27 μγ. = 40 % TeopeTzzecKoro 3HazeHza [δ- ^Hj-rzóÓepejDiZH-Ajg-?-ajiLzerzza (Vlil): Tozza iuiaBJíeHZH: I60-I62°C (z3 aixeTOHa/-:H'- τβκ-cana), MC: μ/θ 316 (M+), HK (CHCZ3): YMaKC< 2730 (aJiizerzji) z .1710 cm“1 (Jbr., C=0), z-Ι,Ι μγ = .35 % TeopeTinecKoro SHazenza [6-¾]-O-smirzóóepejuizH-Aj2“^-a^wrajia (Π), βΜορφιαώ, MC: μ/θ 316 (M+), MK (CHCČ3): f"MaKC 2730 (ajiznerzji) z 1705 cm~^( br?C = 0), AříajiorzzHO noJiyaaiOT Z3 I mmoji rzóóepejiJizH--7--ajiLrn;erz£a c ajitzerz#»·ho$-rpynnoí! b 6{A-nojioseHZZ, 1,1 mmoji rzapzaa Kaaza z 0,1 wi %2θ(yflejn>HaH-pajuioaBKTZBHocTB :--3-mkkph/mmoji) cjiezywie [6- -%]-rzó-óepe^7iHH~7-ajiLjierzOT -c-ajiwrzjmoS ^rpyímož b 64-nojioseHzz z[6-^H]-rzóóepejuizH-7aJiLae-rzjiH c azLzerzzHoft rpynnoft b 6/-nojiose-hzz (mz3zzěcKze z cneKTpocKonzaecKze zazme bhzbjiozhhx coezHzezztzanzcaHH b npZMepax I z4): r6A]-rzgóepejuizH-A3-7-aJiLzerz.z (Ib.) z Γδ- ^lj-6-3iizrzóóepejuniH^ -A3-7-ajiL,gerzfl Ir: BHMHBazze -c xJiopočopMPM/sTz^oBHM θφζροι,ι yKcyczoft KZCJIOTH 8:2 oó/oó,BHXPfl: 103 μγ = 31 % Ib (y^ejuzaa pa^zoaKTZBHOCTB: 1,5 mkopz/mmoji) ,BHMHBaHze c xjiopo$opmom/3TZjiobhm θφζροΜ yzcycHoS kzcjioth 7:3 oó/oóřbhxoji: 148,3 μγ = 45 % τθορθτζήθοκογο 3HaaeHza Ir (yaejiLHaa pa-ffiioaKTZBHocTL: 1,38 mkepz/mmoji) : r6ATrzddepeJUizH-Aj-7-azBzerzj (IIb) z /^6-¾)-6-9zzrzóóepejuizH-A-p7-ajiBflerzz (Ur): SHMHBaHZe C ΧποροφορΜΟΜ/θΤΖΛΟΒΗΜ θφζροΜ yKCyCHOÍÍ kzcjioth 8:2 oó/oó,βηχολ: 86,5 μγ = 26 % τθορθτζζθοκογο zaazezza IIb (yzeaLHaa pa-BZoaKTZBHOCTB: 1,43 mkiopk/mmoji) . BHMHBaKze c xJIopoφopMOM/^τzJIOBHM εφζροΜ yzcycao# kzcjioth 7:3 oó/oó, bhxoa: 163 μγ = 49 % TeopeTHzecKoro 3Hazezza Ur (ysejizHaa pazzo- aKTZBHOCTB: 1,33 μκ&ρζ/μμoji) . r-y i>·*,1 r* s · r· ři; L‘-·.b *. £ i- ΐ K- r - 15 1.27 μγ. = 40% TeopeTzzecKoro 3HazeHza [δ- ^ Hj-rzóÓepejDiZH-Ajg -? - ajLzerzza (Vlil): Tozza iuiaBJíeHZH: I60-I62 ° C (z3 aixeTOHa / -: H'- τβκ-cana), MC: (M +), HK (CHCZ3): YMaKC <2730 (aJiizerzji) of .1710 cm -1 (Jbr., C = 0), z-Ι, Ι μγ = .35% TeopeTinecKoro SHazenza [6-¾] -O- smirzóepejuizH-Aj2 '^ - a ^ wrajia (Π), βΜορφιαώ, MC: μ / θ 316 (M +), MK (CHCl 3): f "MaKC 2730 (ajiznerzji) of 1705 cm-1 (br? C = 0), Z3 I mmoji rzóepejiJizH - 7 - ajiLrn; erz £ ac ajitzerz # 6 · A-nojioseHZZ, 1,1 mmoji rzapzaa Kaaza z 0,1 wi% 2θ (yflejn> HaH- [0000] 3-mkkph / mmoji) cis [6- -%] - rzo-oepe-7HH-7-aiLjierzOT-c-ajiwrzjmoSrpyimoz b 64-nojioseHzz from [6-H] -zo-hzejuu c azLzerzzHoft rpynnoft b6 / -nojiose-hzz (mz3zzěcKze z cneKTpocKonzaecKze zzme bhzbjiozhhx coezHzezztzanzcaHH bnpZMepax I z4): r6A] -rzgóepejuizH-A3-7z-zi (H-A3-7-a). A3-7-ajiL, gerzfl Ir: BHMHBazze-c x Jiopo opMPM / sTz ^ oBHM θφζροι, γ yCcyczoft KZCJIOTH 8: 2 σ / σ, BHXPfl: 103 μγ = 31% Ib (γ u u pa pa Z Z Z Z Z Z Z Z Z Z Z Z Z Z) kzcjioth 7: 3 ø / øøbhxoji: 148,3 μγ = 45% of 3HaaeHza Ir (yaejiLHaa pa-ffiioaKTZBHocTL: 1,38 mkepz / mmoji): r6ATrzddepeJUizH-σ (σ-σ-σ-σ-σ-σ-σ-σ-σ-σ) 6-9zzrzóepejuizH-A-p7-ajiBflerzz (Ur): SHMHBaHZe C ΧποροφορΜΟΜ / θΤΖΛΟΒΗΜ θφζροΜ yKCyCHO Í kzcjioth 8: 2 oó / oó, βηχολ: 86.5 μZoZoZoZaZoZaZaZoZaZaZoZaZaZoZaZa = 26% / mmoji). BHMHBaKze c xJIopoφopMOM / ^ τzJIOBHM εφζροΜ yzcycao # kzcjioth 7: 3 oo / oo, bhxoa: 163 µg = 49% TeopeTHzecKoro 3Hazezza Ur (ysejizHaa pazzo-µZ3βζζζ / ZZ3OCTB); r-y i> · *, 1 r * s · r · i; L‘- ·.

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L k . k - 16 - Γβ- ^Hj-riid6epe7JiiiH-A^-7-ajiLgeriíji (IIIb) η [ 6- ^H?e-3iixrxdgepejuixH-A^^-ajiBjOrHj; (Illr): BHMHBaHHS C H-reKCaHOM/xJIOpO$OpMOM 2:8 Oó/θό, BHXOJU 82 ΜΓ = 26 %TeopeTHHecKoro 3ηηήθηηη IIIb (yjieJiBHaa pajwoaKTHBHOCTB: 1,5 mkdph/MMOJl) , BHMUBamie C ΧΠΟροφορΜΟΜ, βηχο,ιι: 161 μγ = 51 % TeopeTiraecKoro 3HaH6HHH Illr (ynejiBHaH pa-jmoaKTHBHOCTB: 1,31 mkkph/mmoji) . f6~^H?-THÓgepeJUPiH-Ag-7-ajiBjerHii (IVb) η Γθ- ^H~|-6-3roiriidÓepejuixH-A5-7~aJi£jgrHj (IÚr): BHMHBaHHe c H-reKcaHOM/xjiopo$opMOM 1:9 oó/oó, bhxou: 94 mt = 30 $TeopeTinecKoro 3ηβηθηηη ifó (ynejiBHaa pajmoaKTXBHoc.TB: 1,5 MKiopa/MMOJl) , BHMHBaHHe C XJIOpoáJODMOM, BHXO#: 157 ΜΓ = 50 % TeopeTH-βθοκογο 3ηβήθηηη iPr (ynejiBHaa panHoaKTHBHOCTB: 1,36 mmdph/mmoji) . Γ 6- ^rHÓÓepejiOH-Ag-7-ajiBJierHa (VIb) η f6- ^-6-9imrBódepejijmH-Ag-7-3Jiwrna (Pír):.L k. k-16-β-β-β-β-β-β 6 -α-β-β-β-β-β-β-γ (IIIb) η - (Illr): BHMHBaHHS C H-reKCaHOM / xJIOpO $ OpMOM 2: 8 O / O, BHXOJU 82 26 = 26% TeopeTHHecKoro 3-stroke IIIb (yjieJiBHaa pajwoaKTHBHOCTB: 1,5 mkdph Χ ΜΟΜ Χ ie ie ie / ie ie UB ie ie ie) μγ = 51% TeopeTiraecKoro 3HaH6HHH Illr (ynejiBHaH pa-jmoaKTHBHOCTB: 1.31 mkkph / mmoji). (6b) -HÓ-THÓgepeJUPiH-Ag-7-γiBjerHii (IVb) η Γ-----6 -6 -6 -6 -3 -3 -3 -3 -3 -3 -3 -3 -3 -3 -3 -3 A5 A5 A5 A5 A5 A5 A5 A5 A5 A5 9 oo / oo, bhxou: 94 mt = 30 $ TeopeTinecKoro 3ηβηθηηη ifo (ynejiBHaa pajmoaKTXBHoc.TB: 1.5 MKiopa / MMOJ1), BHMHBaHHe C XJIOpoaJODMOM, BHXOHoBoHoPo eop e 50 50 50 50 50 50 50 1.36 mmdph / mmoji). Γ 6 -R 6 -PhoepeeOH-Ag-7-iBiierHa (VIb);

Eepyr 30 μγ (0,1 mmoji) ýló h 9 mt rajcpoa Kamm. CmnumpoBainifl3necB He Hano. Βημηββηηθ c H-reKcaHOM/xjiopo$opMOM 1:1 oó/oó,blkos: 9,6 μγ = 32 % TeoperanecKoro 3HaHeHHH Pis (ynejiLHaa paw-θκίήβηοοτβ: 1,5 mk»ph/mmoji) , βημηββηιιθ c H-reKcaHOM/xJiopoóopMOM 4:6 oó/oó, bhxou: 15,9 mt = 53 % TeoperanecKoro 3ηβηθηηη Pír (ynejiBHaa pa-JWaKTHBHOCTL: 1,40 mkk>ph/mmoji) . ΠριίΜβρ 6 AHajioruHHO npHMepy 5 SHOJiaT noJiynaioT H3 330,4 μγ (I mmoji) raóóe- pejumH-A3-7-aJiLAernna (Ia) h 44 μγ (1,1 mmoji) rajčíma Kaním, ko-Eepyr 30 μγ (0,1 mmoji) öh h 9 mt rajcpoa Kamm. CmnumpoBainifl3necB He Hano. Cημηββηηθ c H-reKcaHOM / xjiopo $ opMOM 1: 1 o / o, blkos: 9,6 μγ = 32% TeoperanecKoro 3HaHeHHH Pis x JiopoopMOM 4: 6 o / o, bhxou: 15.9 mt = 53% TeoperanecKoro 3ηβηθηηη Feather (ynejiBHaa pa-JWaKTHBHOCTL: 1.40 mkk> ph / mmoji). ΠριίΜβρ 6 AHajioruHHO nPHMepy 5 SHOJIAT noJiynaioT H3 330,4 μγ (I mmoji) raóóe-pejumH-A3-7-aJiLAernna (Ia) h 44 μγ (1,1 mmoji) tomato Kaní, ko-

Topae npespama-or c homcicbio 0,1 .mji ^HgO (5,55 mmoji, 99,9 ^-aaTopae npespama-or c homcicbio 0.1 .mu.l HgO (5.55 mmoji, 99.9 .mu.-aa)

HHCTOTa). AHanorinHaH oópaÓOTKa rt xpoMaTorpa$appBaHHe zaeT ^6-^Hj-rHdóepejuniH-A2-7-aJiLnerHH (X): 4* - 17 - βηχολ: 102,5 μγ = 31 % TeopeTzaecKoro 3HaHeHza,HHCTOTa). AHanorinHaH oópaÓOTKa rt xpoMaTorpa $ appBaHHe zaeT ^ 6- ^ Hj-rHdóepejuniH-A2-7-aJiLnerHH (X): 4 * - 17 - βηχολ: 102.5 μγ = 31% TeopeTzaecKoro 3HaHeH

Tomca ruiaBJíeroiH I72-I74°C (z3 aneTOHa/H-rencaiía), MC: μ/θ 331 (M+ zjth M") b ^H-HMP-cneKTpe προτοΗΗ (5—Η) z (7-H) ποηβληκτοη khk czHryjieT,cjie^oBaTeJiBHo, (6- H) He bhzho, z [C-^Hj-e-snxrzóóepejuizH-Ag-?-ajiB^ero (XI): buxoa: 142,3 mt = 43 % TeopemaecKoro sHaneHna,TOHKa iuiaBJíeHH^: I84-I87°C (23 aiíeTOHa/H-rencaHa), MC: M/e 331 (M zan M~), b ^H-HMP-cnenTpe Tanze προτοΗΗ (5-H) z (7-H) noaBJLfWTca-KaK czh-ryjieT, (6-¾) oTcyTCTByeT.Tomc has a temperature of 72 ° -174 ° C (from 3 aneOH / H), MC: μ / θ 331 (M + from M ") b ^ H-HMP-5 (—) from (7-H) from kHk , (6H) He bhzho, from [C-H H--e-snxrzóepejuizH-Ag-- aj aj ^ (XI): buxoa: 142.3 mt = 43% TeopemaecKoro sHaneHna, TOHKa iuiaBJíeHH] Mp: M-e 331 (M + M +), m / z H-HMP-cnenTpe Tanze προτοΗΗ (5-H) z (7-H) noaBJLfWTca- KaK czh-ryjieT, (6-¾) oTcyTCTByeT.

OO

HpzMep 7 Αηθλογζήηο npzMepy 5 3H0JiaT nojiynaioT 23 3,3 mt (0,01 mmoji) £17-14cJ-rzóóepea3iHH-A3-7-ajiBaer2aa' (yaeaBHaH paazoaxTZBHocTB:0,23 mkmpz/mmoji) z 4 μγ rz^pzaa narza, κοτορΗζ nocae SToro 3a-MemaioT τρζτζθΜ c noMomtio 0,1 mji ^HgO (yaejiBHaz pajmoanTZBHOcTB: 3 mkwh/mmoji) . AHaJiorz^Haa oópaóoTKa z TOHKPCJio&íaa xpoMaTorpa^zaHpzMep 7 NpzMepy 5 3H0JiaT nojiynaioT 23 3.3 mt (0.01 mmoji) 1717-14cJ-rzóoepea3iHH-A3-7-ajiBaer2aa '(yaeaBHaH paazoaxTZBHocTz): 0.23 mkzz / 0.23 mkzz / 0.23 mk (0.23 mk) The SToro 3a-MemaioT is no more than 0.1 mji HgO (yaejiBHaz pajmoanTZBHOcTB: 3 mkwh / mmoji). AHaJiorz ^ Haa oópaóoTKa from TOHKPCJio & xpoMaTorpa ^ za

18 ΦΟΡηίΠΙΑ Κ30ΕΡΕΤΕΗΪΕΊ 1. Cnocoó snHMepnsainn: móóepejL7mH-7-ajiBnern7íOB, OTjmsio- wnzcn Ter.i, ητο rnóóepejMim-7-awiera£ c ajiB^eiwíoÉ rpynnofi b6 oZ - nojioseHHK se 6/3 - nojiosemm 3E0Jin3npyBT c πομοπεκ) me- JIOEE Η ΠγΤΘΜ SOÓaBJíeHHH EOHOpOB BOAOpOJía, ^eHTepiIH ΕΠΕ TPHTHHnpeBpajiíaror b DmiepHyft cwecL, cocTonmyTo h3 móóepejuniH-7. -aoiL-nernna c aJiBjzeriifíHofi rpynnon b 6^ -ποεοκθηεη h mÓóepexzmH-7-ajn>nernna c ajrb.nernnHofi rpynnofi b 6/3 -nojloseHnn, npiner.Tπρπ ΠρίΠ.ΊΘΗΘΗΕΗ £OHOpOB ΕΘΕΤΟρΚΗ KJffi ΤρΚΤΙΚ OÓa ΠΟ^ΕΘΗΗΗθ 3ΠΖ-LiepE μθεθηη y mecToro aTOLia yrnepona. . 2. Cnocoó no nyHKTy I, OTjnrnawScH τθϊ.ι, eto npeBpantenneπροΒο^Ητ óe3 B03,nyxa, HanpEMep, b aTMocoepe aprona ra a30Ta,b opraHznecKOM pacTOBpETejre. 3. Cnocoó no nyHKTau I n 2, OTJmnaEEmncn τθε, eto b nane-ctbs iqejionefi πρβπποητητθ^ίΒΗΟ κοποηΒ3νκτ γεερηε najma srn mejioE-HHe aMro, npew Bcero Tanne c opramnecnm^ ocTaTKaME, 3anoji-Hiwffl npocTpancTBo, Hanp., ffEE3onponnjiaiOT JD-teh eje 2,2,6,6-TeTpaMeTnEmmepEOTí jhiteh . 4. Cnocoó no nynKTan 1-3, oTJiHHaKEmfica tcli, eto nncjmeaTOMK Bonopo^a b hcxoahhx coennHennax 3aí/emaE3T nepen 3H0jm3aim-en 3aimíTHHMH rpynnaim. 5. Cnocoó no nyHKTaM 1-4, OTjmEawslca τβι.:, eto nojiyna-ιοτ nBanimfi izeweHHtie rnóóepejnmK-7-aTBnerE.nH, npircei.í nanpniviep,ojek 1 ~C - n/njm %- %-rnóóepexEffi-7-aEwiw npespamaiorB- nonojmETCELEo 3θωβΕριηΞΗΒτρητΕΒΕ nw,.neííTepneE. na mecTonπο3πεπϊ móóepejL7mn-7-ajiLnarnn. 1918. ΤΘΜ Π ΤΘΜ Ó Ó Ó OB OB OH p OB OB,,,,, b b b b b b b b b b b b b b b b b b b b---- -aoiL-nernna c aJiBjzeriifíHofi rpynnon b 6 - οπεεοκθηεη h móóepexzmH-7-ajn> nernna c ajrb.nernnHofi rpynnofi b 6/3 -nojloseHnn, npiner. μθεθηη y mecToro aTOLia yrnepona. . 2. Cnocoon noHKTy I, OTjnrnawScH τθϊ.ι, eto npeBpantenneπροΒο ^ Ητ e3 B03, nyxa, HanpEMep, b aTMocoepe aprona ra a30Ta, b opraHznecKOM pacTOBpETejre. Third Cnocoó no nyHKTau I n 2 OTJmnaEEmncn τθε, ethoxy b nane-TBS iqejionefi πρβπποητητθ ^ ίΒΗΟ κοποηΒ3νκτ γεερηε Najma germany mejioE-HHE Amro npew Bcero Tanne opramnecnm c ^ ocTaTKaME, 3anoji-Hiwffl npocTpancTBo, hANP., Teh-JD ffEE3onponnjiaiOT It is 2,2,6,6-TeTpaMeTnEmmepEOTi jhiteh. 4. Cocoa no nynktan 1-3, oTJiHHaKEmfica tcli, eto nncjmeaTOMK Bonopo ^ a b hcxoahhx coennHennax 3a / emaE3T nepen 3H0jm3aim-en 3aimíTHHMH rpynnaim. 5. npespamaiorB- nonojmETCELEo 3θωβΕριηΞΗΒτρητΕΒΕ nw, .neííTepneE. to mecTonπο3πεπϊ móóepejL7mn-7-ajiLnarnn. 19 Dec

AfíHOTAIW υ,βΧΒ H3OÓpeTeHHH COCTOZT B TOM, ZTOdhl ΒΠΘρΒΗβ CfíezaTL ΤξΟΟΤ^ΊΙΞΗΜrzddepejuiSH-7-awierH>i c aw;erx£HOz rpynnoz b 6<jí -ποαοηθηζζz tom csmhm npeAOCTaBHTt b paczopAHezze Hosyio rpymry dZOJIOPK-zeczz aktzbhux BeiqecTB. Jtajiee rzddepejiAZH-7-ajiBz:erz(nří motatββΐίΤθρί'ΙΘΜ ÍUBI ΤρΖΤΖΘΜ.AfíHOTAIW υ, βΧΒ H3OÓpeTeHHH COCTOZT B TOM ZTOdhl ΒΠΘρΒΗβ CfíezaTL ΤξΟΟΤ ΊΙΞΗΜrzddepejuiSH-7-awierH> i c w; ERX Hoz rpynnoz b £ 6 <her -ποαοηθηζζz the CSMA npeAOCTaBHTt b paczopAHezze Hosyio rpymry dZOJIOPK-zeczz aktzbhux BeiqecTB. Jtajiee rzddepejiAZH-7-ajiBz: erz (low motatββΐίΤθρί'ΙΘΜ ÍUBI ΤρΖΤΖΘΜ.

CorzacHo Z3odpeTeHHio rzddepejL7izH-7-ajiLzePz1iT c aAL£erx£HofirpyUHOZ B 6 oL - ZJIH B 6 β - ΠΟΑΟΗδΗΚΗΧ 3HOJIH3ZpyíOT ΜβΑΟΖΒΏ Z CHOMOIULK JXOdaBJISHKA ΟΟββΗΗΘΗΗίϊ CO CBOZCTEaME ΖζΟΗΟΌΟΒ BO£OpO£a,ΉθκτβρΕΗ zjzi τρζτζΗ npeBpw^r b szzMepHyio cMecb, coctoazotoH3 rzddepejMZH-7-ajiL^erzza c MerwoS rpyímofi b Q°í - nozo-κθηζζ z rzddepejMiZH-7-ajn>zerzza c aJH>£erz£Hofi rpyímofi b 6/i- ΠΟΖΟΜδΗΖΖ, ΠΌΖΖΘΜ Oda ZOJiyzeHKHe ΘΠΗΜβρΗ ΜΘΖβΗΗ y 6-ΓΟyrJiepo^a. npz npzMeHezzz hohobob ^θζτθόζη zjih τρζτζπ. coraacHO zsodpeTemzoCorzacHo Z3odpeTeHHio rzddepejL7izH 7-Aal ajiLzePz1iT c £ £ ERX HofirpyUHOZ oL 6 B - B 6 ZJIH β - ΠΟΑΟΗδΗΚΗΧ 3HOJIH3ZpyíOT ΜβΑΟΖΒΏ Z CHOMOIULK JXOdaBJISHKA ΟΟββΗΗΘΗΗίϊ CBOZCTEaME ΖζΟΗΟΌΟΒ BO CO £ £ OPO and, ΉθκτβρΕΗ zjzi τρζτζΗ npeBpw ^ rb szzMepHyio cMecb, coctoazotoH3 rzddepejMZH- 7-ajiL ^ erzza c MerwoS rpyimofi b Q ° - - noso-κθηζζ z rzddepejMiZH-7-ajn> zerzza c aJH> £ erz £ Hofi rpyimofi b 6 / i-ΠΟΖΟΜδΗΖΖ, ΠΌΖΖΘΜ Oda ZOJiyzeHKHe ΜΘΖΠΗΜβρ ^ ΜΘΖΠΘβρΗ . npz npzMeHezzz hohobob ^ θζτθόζη zjih τρζτζπ. coraacHO zsodpeTemzo

Cnocod/odrqenpzMeHW ko Bcew rzddepejirnm-7-&TLnerK.zaM, zpzzeMzyBCTBHTeJiBHHe κ G^ejiozaM-GTpyKTypHHe πρζ3Η&κκ ne η3μθηηιοτοα:.CorjiacHo Z3odpeTeHZio zojiyzeHHze iezeHHEie rzddepeJUizH-7-ajiLserz- cjiysaT hcxo#hhmz BemecTBarm rjiz nojiyzeHW^eHHHx npzpojmHXrzddepejLTZHOB z zx IipOZ33O>mX.Cnocod / odrqenpzMeHW Bcew rzddepejirnm co-7- & TLnerK.zaM, zpzzeMzyBCTBHTeJiBHHe κ ^ G-ejiozaM GTpyKTypHHe πρζ3Η & κκ not η3μθηηιοτοα: .CorjiacHo Z3odpeTeHZio zojiyzeHHze iezeHHEie rzddepeJUizH 7-ajiLserz- cjiysaT hcxo # hhmz BemecTBarm rjiz nojiyzeHW ^ eHHHx of npzpojmHXrzddepejLTZHOB zx IipOZ33O> mX.

Claims

Object of the Invention

A process for the epimerization of giberellin-7-aldehydes, characterized in that giberellin-7-aldehyde with an aldehyde group in the 6-position or 6-position is enolized in the presence of a base with the addition of hydrogen donors, deuterium or tritium to the epimeric mixture consisting of from giberellin-7-aldehyde with an aldehyde group of 6-position and gibberellin-7-aldehyde with an aldehyde group at 6-position, wherein when using deuterium or tritium donors the epimers obtained are labeled at the sixth carbon atom.

2. A process as claimed in claim 1, wherein the reaction is carried out in the absence of air, for example under an argon or nitrogen atmosphere in an organic solvent.

3. A process according to claim 1 or claim 2, wherein the base is preferably a potassium hybrid or a basic amide, in particular amides having organic spatial residues, for example lithium diisopropylamide or lithium 2,2,6,6-tetramethylpiperidide.

4. A process according to any one of claims 1 to 3, wherein the hydrogen acid atoms of the starting compounds are replaced by enol-protecting groups.

5. A process according to any one of claims 1 to 4, wherein two-labeled giberellin-7-aldehydes are prepared, for example, C- and / or -H- or E-giberellin-7-aldehyde is converted into tritium. or deuterium at position six labeled with giberellin-7-aldehyde. 2 drawings Recognized by the invention on the basis of the results of the expert review by the Inventory and Patent Office, Berlin, DD