Purines. LXII. Both Enantiomers of
N^6‑(1,3‑Dimetyl‑2‑butenyl)adenine and Their 9‑β‑D‑Ribofuranosides : Synthesis and
Cytokinin Activity
著者 Fujii Tozo, Ohba Masashi, Kawamura Hitoshi, Nakashio Yoshiyuki, Honda Kei, Matsubara Satoshi
journal or
publication title
Chemical & pharmaceutical bulletin
volume 42
number 5
page range 1045‑1049
year 1994‑05‑15
URL http://hdl.handle.net/2297/7617
’
Ｍａｙｌ９９４ C/ｉｅｍＰＡｑ'、ＢⅢ"４２(5)1045-1049(1994） 1045
Purines､LXn1)Botl1EmntiOmersofⅣ6-(1,S-Dimethyl-z-mtenyl)adenine mdTlneir9-β-D-RilDOmmosides:SyntllesiMndCytokininActivity
TozoFuJn,*，aMasashiOHBA,qHitoshiKAwAMuRA,qYoshiyukiNAKAsHIo,aKeiHoNDA,q
andSatoshiMATsuBARAbHJc"ノリｑ/Ｐﾉﾘα""ace"がαzﾉＳｃだ"ces,肋"αｚａｗａＵ>jivelTj(〕ﾉ,ｑＴＭａｒａ－ｍａｃﾉｉｉ,Knlzazawa920,ノヒＷ〃α"‘Ｌａｂｏｒα/川 c小！〃ﾉＭＢｉｏﾉog〕ﾉ,ﾊｳﾉojoBe/bcZz"．αﾉ伽veMy,６s/i〃oga,"ｏＨＺＪ,Zgfcﾉto,SZME〕'o-k",ＫＯ′oro606,ノヒ柳凪
ReceivedNovemberl8，1993；acceptedDecember27，１９９３
Bothenantiomers[(1'R)-6and(1'S)-6]ｏｆⅣ6-(1,3-dimethyl-2-butenyl)adenineandtheirM-D-ribofUIranosides [(1"R)-16ａｎｄ(1''８)-16］havebeensynthesizedfOrthefirsttimefrombothenantiomersofalamine(15)innine steps､Theseaglyconesandnucleosides,togetherwithⅣ6-(3-methyl-Z-butenyl)adenine(5)andits9-β-D-ribofmranoside (18)asweUasM-D-ribofUranosyl-c応-zeatin(20)ａｎｄＤ－(Z-deoxy-ﾉｰD-ribofnranosyl)-cjS-zeatin（19),weretested hrcytokininactivityinthetobaccocaUusbioassay・Theorderoftheiractivitywas5＞(1'R)-6＞(1"R)-16-18＞
(1'８)-6＞(1''８)-16＞20＞19.ThebioassayresultsarecomparedwiththoseobtainedpreviouslyfDrthederivatives modifiedanalogousｌｙｉｎｔｈｅⅣ6-substituentintheciS-and〃α"酷zeatinseries･
KeywordsN6-isopentenyladenine’'一mcthyl；chiralsynthesis；cytokininactivityiⅣ6-isopentenyladenosinel''－，ethyl；
cな‐zeatin9-(2-deoxyribofUranosyl）
Cytokininsconstituteaclassofphytohormoneschar‐andoftheir9-β-D-ribofnranosides［(1''R)-16ａｎｄ(1''８)‐
acterizedprimarilybytheabilitytopromotecelldivisionl6]inthepresentstudy・
inplanttissueculturesorsecondarilybytheabilitytoThesynthesisｏｆ(1'R)－６ａｎｄ(1"R)-16startedwiththe promoteseedgerminatio､,leafandcotyledongrowth,orbrominationoftheallylicalcohCl(R)-12,preparedfrom lateralbuddevelopment,toinhibitchlorophylldegrada‐D-alanine［(R)-15]through(R)-10ａｎｄ(R)-11according tion，ortoinducebudsonmossprotonema､2）Ｂｅｓｉｄｅｓｔｏｔｈｅｐreviouslyreportedprocedures､5b’7c’'2i)Treatment alargenumberofsyntheticcytokinins,whoseactivityof(R)-12withIVbromosuccinimide(NBS)inbenzenein variesfromhighlyactivetoalmostinactive,morethan30thepresenceoftriphenylphosphineatroomtemperature naturallyoccurringcytokininshavesofarbeenisolatｅｄｆｂｒ５０ｍｉｎ，anapplicationoftheknownbromination fmmplantsandmicroorganisms，andtheirchemicalmethod,'3)affbrdedtheallylicbromide（R)-13ｉｎ８３％
structuresestablished2c'3-7）Interestingly，alltheseyieldForconversionof（R)-13ｉｎｔｏｔｈｅγ,γ-dimethyl- naturalcytokininsaｒｅ/V6-substitutedadenineswithorallylaminederivative[(R)-Ｍ],expenmentsusingtriethyl- withoutsubstituent(s)onthepunnenucleus,8)andtheysilane［Et3SiH/2,2'一azobisisobutyronitrile（AIBN)/川一 maybestructuraUyclassifiedintotwogroupsaccordingdodecanethiol,boilinghexaneunderargon,５h]'4)and totheirN6-substituents:(1)thezeatin[jV6-(4-hydroxy-3‐tributyltinhydride（Bu3SnH/AIBN，boilingbenzene，
methyl-2-butenyl)adenine］family(e､９，ｔｙｐｅｌｏｒ３)ａｎｄ４５ｈ)'5)asthereducingagentsweretried,butwithout (2)theIPA［/V6-(42-isopentenyl)adenine;jV6-(3-methyl‐satisfactoryresultsHowever，Super-Hydridereduction 2-butenyl)adenine;lV6-(γ,γ-dimethylallyl)adenine］family［LiBEt3H/tetrahydrohlran（THF)，２５°Ｃ，３０ｍin]'6)ｏｆ
(e､9.,type５).9） （R)-13wasfbundtoproceedsmoothly,giving(R)-Min
Thezeatinfamilyincludes(1'R)-1'一methyl-〃"s-zeatin80q'６yieldThecarbamate(R)-14wasthenhydrolyzed [(l'R)-2]4'5）andits9-riboside［(1"R)-1''一methyl-〃"s‐withhydrochloricacidin50％aqueousEtOHatroom zeatin9-β-D-ribofilranoside］［(1"R)-7],3,5)bothisolatedtemperaturefbr7h,andthebasicproductwasisolatedin fiPomtheculturefiltrateofthegall-fbnningphytopatho‐thefbrmoftheoxalate(R)-17ｉｎ59％yield・Purinylation genicbacteriumAe汕加o"ａｓ〃Ｍｇａｅｐｖｓａｖａｓ/α"oi,3,4）ｏｆ(R)-17with6-chloropurineinboilingl-butanolcon- and2-hydroxy-1'一methyl-"α"s-zeatin(9)７．１０)frommetha‐tainingEt3Nfbr3haffbrded(R)-1'一methyl-IPA[(1'R)_句
､olicextractsofamarinegreenalga(codeNo.NIO-143)7｡）ｉｎ９２％yieldAsimilarcondensationof(R)-17with6- orfiFomAcOEtextractsoftheculturebrothofthefimguschloro-9-β‐D-ribofilranosylpurine17)gavethetargetribo＿
肌er"αria6rassicae・'1)Theselatestmembersareuniqueside(l''R)-16ｉｎ９８％yield・
inthattheirⅣ6-substituentspossessanasymmetriccenterAparallelsequenceofreactionsstartingfrom(8)-12 adjacenttotheN6atom,ａｎｄtheirnaturaloccurrenceprovided(8)-13(73％yield),(S)-14(80％),(S)-17(56％)，
suggcststhatanalogouslymethylatedderivativesinthe（S)-1'一methyl-IPA［(1'８)-6］（86％)，andthenucleoside IPAfamilymayalsoexistinnature・Ifsyntheticreference（1''８)-16(74％).Thecorrectnessofthestructuresofthese sampleswereavailable，ｔｈｅｓｅａｒｃｈｆｂｒｓｕｃｈｌ'一methylorcompoundswasconfirmedbyspectralcomparisonwith l''一methylanaloguesasnaturalproductswouldbegreatlythecOrrespondingcompoundsinthe(Dseriesdescribed facilitated・Forthisreason,ｔｏgetherwithourcontinuingabove・
interestinthepreparationandstructur←activityrela‐Theabovefbur-steproutefipom(R)-or(8)-10to(R)_or tionshipsofcytokinins,5,76,c''2)wehaveinvestigatedthe（８）MwouldbeshortenedbyapplicationofaWittig-type synthesisandcytokimnactivityofbothenantiomersofisopropenylationto(R)-ｏｒ(8)-101napilotexperiment，
Ⅳ6-(1,3-dimethyl-2-butenyl)adenine（1'一methyl-IPA）（６）（±)-105c)wasallowedtoreactwithisopropyltriphenyl-
o1994PharmaceuticalSocietyofJapan
1046
Vol､42,Ｎｏ．５
5゜ Ｈ 5０ ５面 Ｈ
ＭｅＭｅ
ＯＨ ＯＨ
Ｍｅ
４．
ｅ ｅ
1
HＯ ＨＯ
ｌ:Ｒ１＝Ｒ２＝Ｈ (1'R)-2:Ｒ'＝ＭｅＲ２＝Ｈ (1,s)-2:Ｒ'＝ＨＲ２＝Ｍｅ
ａＲ１＝Ｒ２＝Ｈ (11R)-4:Ｒ'＝Ｍｅ,Ｒ２＝Ｈ (1s)-4:Ｒ'＝Ｈ,Ｒ２＝Ｍｅ
５:Ｒ’＝Ｒ２＝Ｈ (1'Ｒ)６:Ｒ'＝ＭａＲ２＝Ｈ (１１ｓ)-6:Ｒ'＝Ｈ,Ｒ２＝Ｍｅ
９ ＨＯＯＨ
(1Ｍ月)-7:Ｒ'＝Ｍｅ,Ｒ２＝Ｈ (f'S)-7:Ｒ'＝Ｈ,Ｒ２＝Ｍｅ
ＨＯＯＨ
(10`Ｒ)-8:Ｒ'＝ＭａＲ２＝Ｈ (1`0ｓ)８:Ｒ'＝Ｈ,Ｒ２＝Ｍｅ
＋
Ｍｅ ＭｅＭｅ
>｣しLMe
HIV瓢Ｃ
ＣＯ２ＣＭｅ（R)-10
（S)-10
。ＰＩＦ ＤＨｍｏｕ
ｏ２ＣＭｅ３
（R)-14
１１ １１ 一⑤ｍｑ ｌＩ
(月)-12 (S)-12
(R)-13
’
(ref5b） (ref7c） (refl2O ５画ｗｉ〕qll》
Ｃｌ ＲｉｂlMIjU:J」
州鵬
釧叩〆
２０ＭＨ溝帖眺
２５５ ＨイイＲｓEt3N HＯ
(R)-17
(S)-17 (11R)GR1＝Ｍｅ,Ｒ２＝Ｈ
(1s)-6:Ｒ'＝Ｈ,Ｒ２＝Ｍｅ
ＨＯＯＨ
(1m、)-16:Ｒ'＝Ｍｅ,Ｒ２＝Ｈ (110ｓ)-16:Ｒ'＝Ｈ,Ｒ２＝Ｍｅ
Chart
phosphoniumiodide18)（3molarequiv.）inTHFinthe presenceofbutyUithiu、（3molarequiv.）atroomtem- peraturefbr3h,producing(±)-14ｉｎ３６％yieldReplace‐
mentOfthephosphoniumidodidebythecorresponding bromide19)inthisolefinationdidnotimprovetheyield lgf(±)-14,andmeUseofanequimolaraniountofylidor TH低hexamethylphosphoramide(ＨMPA)asthesolvent reducedtheyieldPreviously,（±)-10hadbeenprepared ffom(±)-(ﾉWerZ-butoxycarbonyl)alaninemethylesterby LiBH4reductiontothecorrespondinga]aninol,fbllowed byMe2SOoxidationusingSO3-pyridinecomplexinthe presencｅｏｆＥｔ３Ｎ､5c）Inthepresentwork，thistwo-step sequencewasreplacedbydiisobutylaluminumhydride reduction（CH2Cl2-hexane，-78°Ｃ,７５ｍin）tofnrnish (±)-10inonestepin76％yield,parallelingthepreviously reportedresultsinboththe(R)-12i)ａｎｄ(8)-series九)In thehopeofiindingashort-cuttothechiralcarbamatel4，
(8)-1056,7c)wastreatedwith1.5molaramountsofiso‐，
prOpyltriphenylphosphoniumiodide18)ａｎｄｂｕｔｙｌｌｉｔｈｉｕｍ ｉｎＴＨＦａｔ－７８ｏＣｆｂｒ４ｈａｎｄｔｈｅｎａｔＯｏＣｆｂｒ２ｈＨｏw- ever,theyieldandopticalpurityoftheproduct[(S)-14］’
ｗｅｒｅsolowthatthisapproachwasabandoned
WiththecompletionoftheabovesynthesesofbothI enantiomers［(1Ｒ)－６ａｎｄ（''８)-6］ｏｆ''一methyl-IPAandl oftheirribosides[(l"R)-16and('''８)-16],itwaspossibleI
ＨＮ－、ｸﾞLl
Ｍｅ Ｍｅ ｅHＯ ＨＯ
HＯＯＨ １８
ＨＯＺ １９:Ｚ＝Ｈ ２０Ｚ＝ＯＨ
灘i灘i灘
those5h7c''2i)reportedpreviouslyfbrthecorresponding
1047
Mayl994
TABLEICytokininActivityofN5-(3-Methyl-2-butenyl)adenineAnaloguesandZeatinAnalogucsintheTobaccoCaUusBioassay AveragehFcshweightoftobaccocallus(ｍg）
ｃｏｎｃｎ.α） ＯｐＬ Concentrationoftestcompound(川） 仏M）
Compound
４１０４０１００ ００．００１０．０１０．０４0.10.4
0.04 0.04 1444
６２２ １０２５ １３８７ １５３ ２１ ７９７ １２８４ 354 1665 1301 ３７ ２３ １０５９ １０４ １２３８ ５２ ４４９ ID）
(rR)-26）
(rs)-26）
3c）
(1'R)-4c）
(1's)-4`）
５ (1'R)－６ (1'S)－６ (1"R)-7b）
(1"s)-7b）
(1"R)-8c）
(1"s)-8`）
(1"R)-16 (1"S)-16
18 19 20
９０２０２２０７－３９８９０１７５４９ ４４２６３２１６２１２２３３２１２３ ４１９１ １５４６ ２８１ １ｌｌ ｌ ｌ
1053 1065 ６２ １５３ １９
1770 1490 ４３０ ７１４ ２６
７７３４６４０６１０６８６９０９０２ １１２２１２３２２３２２２２２２２２
1５３
１２０ 557
1512 1503 ８３５ ２３ 623 1395 1480 1576 1426 ８４ ２７ １５５１ １０８１ １２９９ １８９ ７２８
1006
１ ４ ４０
0.04-0.1 0.4-1
１－４ ０．４ 0.4-1 100e）
1205 1252 ８７５ 3７
５６７ １４３８ 1869
９４ 1６１
641 116 ２４ １６５ １０５
1５１１ ２８１ ２４ ４３６ ２７０ 8９
５６２ １３３１ ７２２ ８２９ １８６ ２１ 824 1446 1102 674 1124
４７５ ８５０ ４８１ ７９１ ２１９ １６ ４６３ ６４９ 638 1152 1368
657 １８
1067 １７
1 ４ １ ４０
４－１０ ５９
２１ ２３８
1１８ ２１ ５０３ 2９
1778１３０９ 8４ ６３２
α)Optimumconcentration．b)Takenhomref56．ｃ)Takenhomrefl2j．。）Takennomref7c．ｅ)ｏｒ＞lOMvL
sides[(1''R)-16and(l"S)-16]havenowbecomeavailable bysynthesisinninestepsstartingfiombothenantiomers ofalanine(15)andproceedingthroughtheintermediates showninChartLTheknowledgeobtainedwiththe
syntheticcytokininsamplesshouldaidthesearchfbr
thesesubstancesinplantsandmicroorganisms､Itisalsohopedthatthestructure-activityrelationshipsfbund
inthepresentandpreviousstudiesfbrthenaturaland unnaturalcytokininｓｗｉｔｈａｎａｓｙｍｍｅｔｒｉｃｃｅｎｔｅｒｉｎｔｈｅﾉV6-substituentwillbeusefmfbrdevelopingastereo- chemicalmodel2o)thatexplainsthedifferenceincytokinin activitybetweencJs-and伽"s-zeatins．
configurationatthelノーｏｒ’''一positionｉｎｔｈｅｌＰＡｆｌａｍｉｌｙ
ｓｃｅｍｓｔｏｂｅｍｏｒｅｉｍportantthantheSconfigurationin detenniningcytokininactivity・AlthoughintheZrα"s- zcatinseriesthel'一methylderivative(1'R)－２isasactiveas thel'一unsubstitutedcytokinin(1),theintroductionofamethylgroupintoIPA(5)ａｔｔｈｅｌ'一positionwiththeR configurationlowersthecytokininactivitybyafactor oflO・Thisparallelsthestructure-activityrelationship observedinthecな‐zeatinseries12i）（Tableｌ)．Ａｓｅｘ‐
pected,２６．`'５６，７｡，'2i)thenucleosides(l"R)-16ａｎｄ（1''８)-16
werelessactivethanthecorrespondingaglycones(l'R)－６and（1'S)-6,respectivelyHowever，thisdifferencein cytokininactivitybetweenthenucleosideandtheaglycone isonlyslight，resemblingthat5b)between（'''８)－７ａｎｄ (''８)-2．Itisinterestingtonotcthat9-(2-deoxy-β-,‐
ribofilranosyl)-伽-zeatin(19)inducedthemaximalyield ofthecalｌｕｓａｔ４０似Mconcentration；ｉｔｉｓｌｅｓｓａｃｔｉｖｅ ｔｈａｎ９－β-D-ribofiuranosyMs-zeatin（20）byafactorof 4--lO・Thedeoxyribosidel9hasbeenreportedtolack
cytokininactivityat45似Mconcentrationinthecucum‐bercotyledonbioassay.'ＺｌＯＴｈｕｓ，thecytokininactivity
ofthecompoundslistedinTableIfbllowstheorder：〃"s-zeatin(1)－(1'R)-1'一methyl-jrα"s-zeatin［(l'R)-2]＞
IPA(5)＞(1"R)-1'ｲｰmethyl-"α"s-zeatin9-riboside［(1"R)－
７]＞(1'R)-1'一methyl-IPA［(1'R)-6]－(1''８)-1''一methyl‐
rlα"s-zeatin9-riboside［(1''８)-7]＞(1'８)-1'一methyl-Zrα"s‐
zeatin［(1'８)-2]－cな-zeatin(3)－(1"R)-1''一methyl-IPA9‐
riboside[(1"R)-16]－IPA9-riboside(18)＞(1'８)-1'一meth‐
yl-IPA［(1'S)-6]＞(1'R)-1'一methyMs-zeatin［(l'R)-4]－
(1"S)-1''一methyl-IPA9-riboside［(1''８)-16]＞cな-zeatin 9-riboside（20)＞(1'８)‐''－，ethyl-cな‐zeatin［(1'８)-4]－９‐
(Z-deoxy-β-D-ribofUranosyl)-cな-zeatin（19)＞(1"R)-1"‐
methyl-cな-zeatin9-riboside［(1"R)-8]＝(1''S)-1''一meth‐
yl-c応‐zeatin9-riboside[('''８)-8](inactive)．
Inconclusion,bothenantiomersofN6-(1,3-dimethyl-
Z-butenyl)adenine（''一methyl-IPA）（６）andtheir9-ribo‐Experimental
GeneraINotesAllmeltingpointsweredeterminedbyusingaYamato MP-1capillarymeltingpointapparatusandarecorrectedSeercfl21c fordetailsofchromatographies,instrumentation,andmeasurements､In addition,the1HNMRspectraofthenucleosides(l''R)-16and(1"S)-16 wereｒｅｃｏｒｄｅｄｏｎａＪＥＯＬＪＮＭ－ＧＳＸ－５００（ｌＨ５００ＭＨｚ)instrument、
ElementalanalyseswereperfbrmedｍａｉｎｌｙｂｙＭｒ、YItataniandhis associatesatKanazawaUniversityandpartlybythestafTofthe MicroanalyticalLaboratoryofHokurikuUniversity,Thefbllowingab‐
breviationsareusedbr＝ｂroad,。＝doublet,。。＝doublet-ofLdoublets，
ｍ＝、ultiplet,ｓ＝singlet・
MaterialsTheknowncompoundstestedfbrcytokininactivityinthe tobaccocaUusbioassayweretakenftomstocksofconmercialoriginor whichhadbeenpreparedinourlaboratoriesaccordingtopublished procedures:IV6-(3-methyl-2-butenyl)adenine(IPA)(5)(purchasedfrom SigmaChemicalCo.)；Ⅳ6-(3-methyl-2-butenyl)adenosine（18）（Sigma ChemicalCoj;９－(2-deoxy-β-D-ribofUranosyl)-cjS-zeatin(19)'2k);9-β-,‐
ribofilranosyl-cな-zeatin(20)(SigmaChemicalCo.).Othercompounds wcresynthesizedasdescribedbelow．
［R-(E)]-(4-Bromo-1,3-dimethyl-2-butenyl)carbamicAcidZerr-ButylEs‐
ter［(R)-13］Astirredsolutionof［R-(E)]-(4-hydroxy-L3-dimethyl‐
2-butenyl)carbamicacid1erﾉｰbutylester［(R)-12]5bo7c）（2519,11.7 ,mol)andtriphenylphosphine(6.149,23.4,mol)inbenzene(120ｍl）
wascooledto5゜Cinanicebath,andNBS(4169,23.4,mol)wasadded Afterthemixturehadbeenstirredatroomtemperaturefbr50min,the reactionwasqucnchedbyadding１０％aqueousNa2S203(120ｍl).The aqueouslayerwasseparatedfromthebenzenelayerandextractedwith ether(3x50ml).Theetherealextractsandtheabovebenzenelayerwere
ＶＯＬ42,Ｎｏ．５ 1048
Combined，washedsuccessivelywithsaturatedaqueousNaHCO3and saturatedaqueousNaCLdriedoveranhydrousMgSO4,andconcen- tratedmwJcⅢQTheresiduewastrituratedwithether(50ｍl),ｔｈｅin‐
solublesolidthatresultedwasremovedbyfiltration,andthefiltratewas concentrated〃ｌｗＪａｌｏｔｏｌｅａｖｅａｂｒｏｗｎｓｅｍisolid(6.939).Purification ofthesemisolidbyflashchromatography21)［silicageLCH2Cl2-hexane (5:1,Ｖ/v)］afIbrded(R)-13(2709,83％）asslightlyyellowishneedles，
mｐ38.5-39.5°Ｃ；［α]８３＋13.6°（c＝1.00,McOH)；［α]莞５＋501°
(c＝LOqMeOH);ＭＳｍ/z:280,278[(Ｍ＋1)+];IRv認Ｆ１3cm~':３４５０ (ＮＨ)，１７０６（carbamateCO)；’Ｈ－ＮＭＲ（CDCl3）６：１．１８［3Ｈ，ｄ，
ノー6.5Ｈｚ，Ｃ(1)-Ｍe]，１．４４（9Ｈ，ｓ，ＣＭｅ３)，1.84［3Ｈ，。，ノーＬ５Ｈｚ，
C(3)-Ｍe],3.92[2Ｈ,ｄ,ノー1Ｈｚ,Ｃ(3)-CH2Br],4.2-4.5[2Ｈ,ｍ,Ｃ(1)‐Ｈ ａｎｄＮＨ],５．４３［1Ｈ,ｍ,Ｃ(2)‐H]．
［＆(E)]-(4-Bromo-1,3-dimethyl-2-butenyl)carbamicAcidrerr-ButylEs‐
ter［(S)-13］Brominationof（S)-1256,7c）（950ｍｇ，4.41,mol）ｗｉｔｈ ＮＢＳ(1.589,8.88,mol)inbenzene(50ｍl)inthepresenceoftriphenyl‐
phosphine(2.349,8.92,mol)atroomtemperaturefbr2handwork- upofthereactionmixturewereeflbctedinamannersimilartothat describedabovefbr（R)-13,giving（S)-13（900ｍｇ，７３％）asslightly ycllowishneedles,ｍｐ35.5-37.5°Ｃ;［０dB6-12.2｡(c＝049,MeOH)；
[00鑑-500｡(c＝0.49,MeOH）TheIRand1H-NMRspectraand TLCmobilityofthissamplewereidenticalwiththoseof(R)-13．
（R)-(1,3-Dimethyl-2~butenyl)carbamCAcidrerr-ButylEster［(R)-14］
Asolutionof(R)-1３(495ｍｇ,1.78,mol)indryTHF(20ｍl)wasstirred atroomtemperatureinanatmosphereofargon，ａｎｄａｌＭｓｏｌｕｔｉｏｎ (3.6ｍ1,3.6,mol)ofLiBEt3HinTHFwasaddeddropwiseover5min Afterthemixturehadbeenstirredatroomtemperaturefbr30min,the reactionwasquenchedbyaddingsaturatedaqueousNH4Cl（20ｍl)．
TheaqueouslayerwasseparatedfiPomtheorganiclayerandextracted withether(3x30ml).Theetherealcxtractsandtheaboveorganiclayer werecombined，washedsuccessivelywithsaturatedaqueousNH4Cl andsaturatedaqueoｕｓＮａＣｌ,driedoveranhydrousMgSO4，andcon- centratedmvaczｲotoleaveacolorlesssemisolid(560ｍｇ)Purificationof thesemisolidbyHashchromatography21）［silicageLhexane-AcOEt (10:１，Ｖ/v)］yielded（R)-14（285ｍｇ，８０％）ascolorlessneedles，mp 40-41oC;［α];:5-13.1.(c＝LOqMeOH);ＭＳｍ/z:１９９(Ｍ+);ＩＲ ｖ鵲fl3cm-1:３４６０(NH),１７０６(carbamateCO);lH-NMR(CDCl3M：
1.15［3Ｈ,。,ノー6.5Ｈｚ,Ｃ(1)-Ｍe]，1.43（9Ｈ,ｓ,ＣＭｅ３)，Ｌ６９［6Ｈ,。，
ノー1Ｈｚ,Ｃ(3)-Ｍe,s],4.2-4.5［2Ｈ,ｍ,Ｃ(1)-ＨａｎｄＮＨ],５．００［ｌＨｍ，
Ｃ(2)-H］
（S)-(1,3-Dimethyl-2-butenyl)carbamicAcidrerr-ButylEster［(S)-14］
i)BySuper-HydrideReductionof(S)-13:Reductionｏｆ(S)-13(2.509, 8.99,mol)withLiBEt3H（l8mmol)inTHFatroomtemperaturelbr 40minａｎｄwork-upofthereactionmixturewereconductedasdcscribed abovelbr(R)-14,filrnishing(S)-14(Ｍ49,80％)ascolorlessneedles，
mp40-435oC;[α]霊5＋lL8｡(c＝LOO,MeOH)ThelRand1H-NMR spectraandTLCmobilityofthissamplewereidenticalwiththoseｏｆ (R)-14
ｉｉ)ByWittigReactionof(S)-10:Astirredsuspensionofisopropyl- triphenylphosphoniumiodide'8）（648ｍｇ，1.50,mol）ｉｎｄｒｙＴＨＦ (15ｍl)wascooledto-78oCinanatmosphereofN2,andaLl8Mso- Iution（1.27ｍ1,L50mmol)ofbutyllithiuminhexanewasaddeddrop- wiseoverlOmin,Afterthemixturehadbeenstirredaｔ－７８ｏＣｆｂｒ２ｈ，
(S)-(l-methyl-2-oxoethyl)carbamicacid／err-butylester［(S)-10]56,7c）
(173ｍｇ,１，mol)wasadded,ａｎｄtheresultingmixturewasstirredfiｒｓｔ ａｔ－７８ｏＣｆｂｒ４ｈａｎｄｔｈｅｎａｔＯoCfbr2hThereactionmixturewas hlteredinordcrtOremovetheinsolublematerial，whichwaswashed withether・Thefiltrateandwashingswerecombinedandconcentrated J〃ｖａｃ"ｏｔｏｌｅａｖｅａｙｅｌｌｏｗ，viscousoiLTheoilwasthenpartitioned betweenCHCl3andH20(thepHoftheaqueouslayerwasadjustedto 6-7byadditionoflO％aqucousHCl)TheCHCl3extractswerewashed withsaturatedaqueousNaCl，driedoveranhydrousNa2SO4，and concentratedmwzc"otoleaveayellowoil(295ｍｇ)Purificationofthis oilbyHashchromatography21)［silicageLhexane-AcOEt(8:１，Ｖ/v)］
provide｡(S)-14(38ｍｇ,19％)asacolorlesssolid,ｍp37.5-40°Ｃ;[α]::５
＋8.3。（c＝0.313,McOH).ＴｈｅＩＲａｎｄ１ＨＮＭＲｓｐｅｃｔｒａａｎｄＴＬＣ ｍｏｂilityofthissamplewereidenticalwiththoseoftheproductobtained bymethod(i)．
（±)-(1-Methyl-2-oxoethyl)carbamicAcidrerr-ButylEster［(±)-10］
Astirredsolutionof（±)-1Vと[(1,1-dimethylethoxy)carbonyl]alanine methylester5c)(2.039,10.0,mol)indryCH2Cl2(50ｍl)wascooledto
-78゜Cinanatmosphereofargon,andaLOMsolution(20ｍ1,20,mol）
ofdiisobutylaluminumhydrideinhexanewasaddeddropwiseover 20min・Afterthemixturehadbeenstirredaｔ－７８ｏＣｆｂｒ７５ｍｉｎ，ｔｈｅ
reactionwasquCnchedbyadding2NaqueOusHCl(10ｍl)Theresulting mixturewasbroughtｔｏｐＨ４－５ｂｙａｄｄｉｔｉｏｎｏｆｓａｔｕｒａｔｅｄａｑueous NaHCO31turningintoageLThegelwasthenfilteredwiththeaidof Celite535(NacalaiTesque,Inc.)ｔｏobtainacleartwo-layerfiltrate､The aqueouslayerwasseparatedfi･omtheorganiclayerandextractedwｉｔｈ ＣＨＣｌ３ＴｈｅＣＨＣｌ３ｅｘｔｒａｃｔｓａｎｄｔｈｅaboveorganiclayerwerecombined，
washedwithsaturatedaqueousNaCl，driedoveranhydrousNa2SO4，
andconcentratedml'ααｲotoleaveacolorlesssolid・Recrystallizationof thesolidfTomhexaneyielded（±)-10(L329,76％)ascolorlessplates，
ｍｐ77.5-79°Ｃ(lit､Sc)ｍｐ83.5-84.5°Ｃ).Thissamplewasidentical(by comparisonoftheIRspectrum)withauthentic(±)-10.Ｓｃ）
（±)-(1,3-Dimethyl-2-butenyl)carbamicAcidrerr-ButylEster[(±)-14］
Astirredsuspensionofisopropyltriphenylphosphoniumiodide18)(１３０ ９，３０１，mol)ｉｎｄｒｙＴＨＦ(13ｍl)wascooledtoOoCinanatmospheｒｅ ｏｆＮ２，andaL38Msolution（2.2ｍ1,3.05,mol）ofbutyllithiumin hexanewasaddeddropwiseover5minAfterthemixturehadbeen stirredatO･CfbrL5h,asolutionof(±)-10（173ｍｇ,１，mol)ｉｎｄｒｙ ＴＨＦ(2ｍl)wasaddeddropwiseover5min,andtheresultingmixture wasstirredatroomtemperaturefbr3h・Thereactionwasthenquenched byaddingsaturatedaqueousNH4C1(lOml)Theaqueousmixturewas filteredinordertoremOvetheinsolublematerial，whichwaswashed withether､Thefiltrateandwashingswerecombinedandconcentrated z〃yaczJo，andtheresiduewaspartitionedbetｗｅｅｎＣＨ２ＣｌｚａｎｄＨ２０，
TheCH2Cl2extractswerewashedwithsaturatedaqueousNaCI,dried overanhydrousNa2SO4,andconcentratedj〃ｖαcHotoleaveayellowish jelly(210ｍｇ)ThejellyWaspurifiedbymeansofflashchromatogra‐
phy21)[silicageLCH2Clz-hexane(5:1,Ｖ/Ｖ)]toafYbrd（±)-14(72ｍｇ，
36％)asacolorlessoiLTheIRand1H-NMRspectraofthissamplewere supenmposableonthoseof(R)-ｏｒ(S)-14
Replacementofisopropyltriphenylphosphoniumiodidebythecor‐
respondingbromidesalt19）ｉｎｔｈｅａｂｏｖｅｒｅａｃｔｉｏｎｗａｓｌｂｕｎｄｔｏｂｅ possible,ｂｕｔｔｈｃｙｉｅｌｄｏｆ（±)-14ｗａｓｏｎｌｙ３１％、Replacementofthe solventTHFbyTHF-HMPA（１２:３ｏｒｌ３:8,Ｖ/v)wasalsoinefIective．
（R)-1,3-Dimethyl-2-buten-1-amineEthanedioate(2:1）（Salt)［(R)-17］
Asolutionof(R)-14(900ｍｇ,４５２，mol)ｉｎ５０％(v/v)aqueousEtOH (6ｍl)wasstirredatroomtemperature,ａｎｄ２０％aqueousHCl(5ｍl）
ｗａｓａｄｄｅｄｄｒｏｐｗｉｓｅｏｖｅｒ５ｍｉｎＴｈｅｒｅｓultingmixturewasstirredat roomtemperaturefbr7h,madealkalineandsaturatedwithKZCO3by addinganhydrousK2CO3underice-cooling,andextractedwithether，
TheetherealextractsweredriedoveranhydrousK2CO3andconcentrated atatmosphericpressuretoleave(R)-1,3-dimethyl-2-buten-1-amineasa slightlyyellowishoiLTheoilwasdissolvedin99％(v/v)aqueousEtOH (3ｍl),andtheethanolicsolutionwasexactlyneutralizedbyadditionof asolutionofoxalicacid(203.5ｍｇ,２２６，mol)ｉｎ９９％(v/v)aqueous EtOH（5ｍl)and,ifnecessary,withEt3NThemixturewascooledin anicebath,andtheprecipitatethatresultedwasfilteredofl;washed withalittle99％(v/v)aqueousEtOHanddriedtogive(R)-17(381ｍｇ，
59％）asacolorlesssolid,mp219-221oC(dec.)RecrystaUizationof thcsolidfrom９２％（v/v)aqueousEtOHyieldedananalyticalsample of(R)-17ascolorlessneedles,mp220-221°Ｃ(dec.);[α]汗-9.7｡(c＝
0123,MeOH);[α]巽5-33.6｡(c＝0123,MeOH);IRvH:lPl1580cm~’
(COO-andNH］);ｌＨ－ＮＭＲ(MezSO-姥)６:Ｌ１４[3H,。,ノー6.5Ｈｚ，
C(1)-Ｍe]，Ｌ６５ａｎｄＬ６９［6Ｈ,。each,ノー1Ｈｚ,Ｃ(3)-Ｍe，s],３．８５［1Ｈ，
ｍ,Ｃ(1)-Ｈ],５．０５［1Ｈ,ｍ,Ｃ(2)-ＨＪＡ"αﾉ.CalcdlbrC14H28N204:Ｃ，
58.31；Ｈ,9.79;Ｎ，９．７１．Found:Ｃ,58.22;Ｈ，10.14;Ｎ,9.61．
（S)-1,3-Dimethyl-2-buten-1-amineEthanedioate(2:1)(Salt)［(S)-17］
Hydrolysisof(S)-14(1.4959,7.50,mol)ｉｎ５０％(v/v)aqueousEtOH (10ｍl)containing20％aqueousHCl（10ｍl)atroomtemperaturefbr ３handwork-upofthereactionmixturewerecarriedoutinamanner
similartothatdescribedabovefbr(R)-17,giving(S)-17(608ｍｇ,56％)as acolorlesssolid,mpZO5-208oC(dec.).RecrystaUizationofthesolid from92％(v/v)aqueousEtOHyieldedananalyticalsampleascolorless ncedles,mp219-221oC(dec.);[α]83＋7.1゜(c＝0.069,McOH);[α]竈ｓ
＋35.7｡(c＝0.069,ＭｅＯＨ).肋α/､CalcMorC14H28N204:Ｃ,58.31;Ｈ，
9.79;Ｎ,9.71.Found:Ｃ,５８１５;Ｈ,9.51;Ｎ,9.81.ThelRand1H-NMR spectraofthissampleweresupenmposableonthoseFof(R)-17．
（R)-/V6-(1,3-Dimethyl-2-butenyl)adenineI(1'R)-6］Astirredmixmre of(R)-17(86.5ｍｇ’０．３，mol),６－chloropurine(773ｍｇ,0.5,mol),ａｎｄ Ｅｔ３Ｎ(0.5ｍl)inl-butanol(5ｍl)washeatedunderrenuxlbr3hThe reactionmixturewasconcentrated加川Jα/oandtheresiduewasparti‐
ｔｉｏｎｅｄｂｅｔｗｅｅｎＣＨＣｌ３ａｎｄＨｚＯ・ＴｈｅＣＨＣｌ３ｅｘｔｒａｃｔｓｗｅｒｅｄｒｉｅｄｏｖｅｒ ａnhydrousMgSO4andConcentratedj〃ＷＩＣ"otoleaveayellowsolid・
PurificationofthesolidbyHashchromatography21)[silicagel,ＣＨＣｌ３－
ＭｅＯＨ（１５：１，Ｖ/v)］ｇａｖｅ（l'R)-６（100ｍｇ９２％）asayellowishsolid，
’
1049
Mayl994
mpl95-l97oCRecrystallizationfromMeCNfilmishedananalytical sampleascolorlessminuteneedles,ｍｐｌ９５-197.5°Ｃ;［α]80-886゜
(c＝0128,MeOH);ＣＤ(c＝726×10~5Ｍ,ＭｅＯＨ)[O]25(nｍ):-16400 (273)(negmax.)，-5920(252)(pos・max.),-6610(245)(negmax.)，
＋58900(215)(pos・max.);ＭＳｍ/z:217(Ｍ+);ＵⅦ悪li6…(oH271nm (618800);几臘(ｐＨ1)275(17000);几齪(ｐＨ7)270(18600);几鵬(ｐＨ13）
275（18300);ｌＨ－ＮＭＲ(CDCl3)５:１．３８［3Ｈ,ｄ,ノー6.5Ｈｚ,Ｃ(1')-Ｍe]，
Ｌ７３ａｎｄＬ７６［3Heach,ｓ,Ｃ(3')-Ｍe，s１５．２２［2Ｈ，ｍ,Ｃ(1')-Ｈａｎｄ C(2')‐H],５９３(ｌＨ,br,ＮＨ),7.96and8.44(1Heach,s,purineprotons)，
13.7（1Ｈ,ｂｒ,ＮＨ)』"α/､CalcdfbrC11H1sN5:Ｃ,6081；Ｈ,6.96;Ｎ，
32.23．Found：Ｃ,60.78；Ｈ,７０３；Ｎ１３２．１１．
（S)-Ⅳ6-(1,3-Dimethyl-2-butenyl)adenine［(1'S)-6］Condensationof (S)-17with6-chloropurineandwork-upofthereactionmixturewere conductedasdescribedabovefbr（l'R)-6,afTbrding（1'S)－６ｉｎ８６％
yieldasacolorlesssolid，ｍｐｌ８８－ｌ９０ｏＣ、Recrystallizationfrom MeCNprovidedananalyticalsampleascolorlessminuteneedles，mp l96-198oC;[α]８７＋940゜(c＝0152,MeOH);ＣＤ(c＝692x10-sM，
MeOH)[O]25(nm):＋16800(274)(posmax.),＋6360(252)(negmax)，
＋7080(246)(posmax.),-55900(216)(neg・max.);ＭＳ"z/z:２１７(Ｍ+）
A"αﾉ.CalcdfbrC11H15Ns:Ｃ60.81;H,6.96;N,32.23.Found:C,60.52;
Ｈ，7.08；Ｎ，32.16．ＴｈｅＵＶ，ＩＲ，ａｎｄ１Ｈ－ＮＭＲｓｐｅｃｔｒａｏｆｔｈｉｓｓａｍｐｌc weresupenmposableonthoseof(l'R)-6．
（R)-/Ｗ1,3-Dimethyl-2-butemyl)adenosine［(1"R)-16］Astirredmix‐
tureof(R)-17(86.5ｍｇ,0.3,mol),6-chloro-M-D-ribofUranosylpurine'7）
(143.3ｍｇ,Ｏ５ｍｍｏｌ),ａｎｄＥｔ３Ｎ(０５ｍl)inl-butanol(5ｍl)washeated underrefluxfbr7hThereactionmixturewasconcentratedj〃ｖααｨoto leaveaslightlyyellowishoil，whichwaspartitionedbetweenCHCl3 andH２０．TheCHCl3extractswerewashedwithsaturatedaqueous NaCl,driedoveranhydrousMgSO4,andconcentratedmwJmotoleavc ayellowoiLPurificatidnoftheoilbyHashchromatography2')［silica gel,CHCl3-MeOH(8:1,Ｖ/v)]gave(l"R)-16(172ｍｇ,９８％)asafaintly yellowishglass;[α]87-949｡(c＝0.474,McOH);ＣＤ(c＝6.66×10~３Ｍ，
MeOH)[O]25(nｍ):-19200(276)(negmax.),-3750(255)(posmax.)，
-4650(244)(negmax.),＋53900(217)(posmax);ＭＳｍ/z:349(Ｍ+)；
UVﾉl勝aqEIoH270nm(817600);ﾉ１Ｍ霊(ｐＨl)266(18100);几柵(ｐＨ7）
270(18200);入患?(ｐＨ13)270(Iβ300);'Ｈ－ＮＭＲ(CDCl3)6:１３１[3H，
｡,ノー７Ｈｚ,Ｃ(l'')-Ｍe]，1.73ａｎｄＬ７５［3Heach,ｓ,Ｃ(3")-Ｍe，s]，333, 455,5.87,ａｎｄ６．６（lHeach,ｂｒ,threeOH，ｓａｎｄＮＨ),３．７２（ｌＨｄ，
ノー13Ｈｚ)ａｎｄ３．９３（ｌＨ,．｡,ノー13,1.5Ｈｚ)［C(5')-Ｈ，s],４３２［1Ｈ,ｓ，
C(4')‐H)],444[1Ｈ,。,ノー5.5Ｈｚ,Ｃ(3')-Ｈ],４９９[1Ｈ,．｡,ノー7,5.5Ｈｚ，
C(2')-H],5.09[1Ｈ,ｂｒ,Ｃ(1'')-H],５．１８[1Ｈ,ｄ,ノー8.5Ｈｚ,Ｃ(2'')Ｈ],５．７７ [1Ｈ,。,Ｊ＝７Ｈｚ,Ｃ(l')-Ｈ],７．７１ａｎｄ８．２２(lHeach,s,punneprotons）
（S)-ﾉＷ1,3-Dimethyl-2-butenyl)adenosine［(1''S)-1qAstirredmix- tureof(S)-17(86.5ｍｇ,0.3,mol),6-chloro-9-β-D-ribofUranosylpurine17）
(143.3ｍｇ,０．５，mol),ａｎｄＥｔ３Ｎ(0.5ｍl)inl-butanol(5ｍl)washeated underreHuxfbr5h・Thereactionmixturewasworkedupasdescribed abovefbr(1"R)-16,yielding(l"S)-16(130ｍｇ,74％)asafaintlyyellowish glass,[α];7-8.4゜(c＝0.500,MeOH);[α]認5＋771｡(c＝0.500,MeOH)；
ＣＤ(c＝6.4ｌｘ10-5Ｍ,MeOH）［0]2ｓ(nｍ)：＋12800(277)(posmax.)，
＋3120(257)(negmax.),＋5310(242)(pos・max),-45300(217)(neg・
max.);ＭＭ/z:349(Ｍ+);ＵＶ几綴…loH270nm(cl7500);几髭?(ｐＨ l)２６６(18200);ﾉl鵠？(ｐＨ７)２７０(18100ＭM霊(ｐＨ１３)２７０(18200)；
ｌＨ－ＮＭＲ(CDCl3)５:１３１［3Ｈ,ｄ,Ｊ＝6.5Ｈｚ,Ｃ(l'')-Ｍe],１．６８ａｎｄＬ７０ [3Heach,ｓ,Ｃ(3")-Ｍe,s],３．６９ａｎｄ３．８９［IHeach,brd,ノー12.5Ｈｚ，
C(5')-H，s],4.14,5.5,601,ａｎｄ６９(lHeach,ｂｒ,threeOH,ｓａｎｄＮＨ)，
4.28［1Ｈ,ｓ,Ｃ(4')‐H],４４２［1Ｈ,。,ノー5Ｈｚ,Ｃ(3')-Ｈｌ４９８［1Ｈ,．｡，
ノー7,5Ｈｚ,Ｃ(2')-H]，５．０５［1Ｈ,ｂｒ,Ｃ(1")-H]，５．１２［1Ｈ,。,ノー８Ｈｚ，
Ｃ(2")-H],５．７７［1Ｈ,ｄ,Ｊ＝7Ｈｚ,Ｃ(1')Ｈ],７．７４ａｎｄ８．１５（lHeach,ｓ，
punneprotons)．
BioassayProcedureThecytokininactivitiesof5,（1'R)-6,（1'S)-6, (1''R)-16,（1"S)-16,18,19,and20weretestedinthetobaccocallus bioassayinamannersimilartothat5b)describedpreviously､Ｔｈｅｒｅｓｕｌｔｓ
ａｒｅｓｈｏｗｎｉｎＴａｂｌｅＩ．
２）Forreviewsoncytokinins,ｓｅｅα）KKOshimizu,HIwamura，
MPPolzノVDgejhZga肋KmMli,５２，Ｒ4９（1978);ｂ）SMatsubara，
Ｐ"川cAemm〃,19,2239(1980);c)ＤＳＬｅｔｈａｍ,ＬＭＳＰａｌｎｉ，
」""Ⅸ.ｈv・Ｐｂ"/PAysjoﾉ.,３４，１６３（1983);ｄ)SMatsubara,Ｃｒｊｒ・
ＲｅｖＰｂ"/Scj.,９，１７（1990)．
３）Ｇ､Surico，AEvidente,Ｎ・Slacobellis，GRandazzo,Ｐﾉﾘﾉﾉｏ－
ｃｈｅ"１Ｍ〕'’24,1499(1985)．
４）AEvidente,OSurico,Ｎ、Ｓ・Iacobellis,Ｇ・Randazzo,PAWo- chemMy,２５，５２５(1986)．
５）α)Ｔ・Itaya,TFUjii,AEvidente,GRandazzo,Ｇ・Surico,NS Iacobellis,T1e1ra比〃o"Ｌｅ".,27,6349(1986);6)TFUjii,Ｔ､Itaya，
Ｓ､Matsubara,Ｃｈｅ､､ＰＡｑｒ"ｚＢ"".,37,1758(1989);c)Ｔ・FUjii,Ｔ・
Itaya,Ｓ・Yoshida,SMatsubara,肋虹,37,3119(1989Ｍ)MOhba，
Ｔ・FUjii,Ａ・Evidente,GSurico,ＮＳ・Iacobellis,ＨｾZeroC〕ﾉc上s,３１，
５９９(1990)．
６）α)AEvidente,NSIacobellis;RVellone,ASisto,GSurico，
Ｐﾉ1WochemiD〃28,2603(1989);6)LDeNapoli,Ａ・Evidente;G Piccialli,CSantacroce,RVellone,必".,２９，７０１（1990)．
７）α)AHAFarooqi,Ｙ・NShukla,AShukla,DSBhakuni，
Ｐ/1WOCﾉle腕jSZ〃,29,2061(1990);6)Ｔ・FUjii,MOhba,Ｔ・Haneishi，
Ｓ・Matsubara,Ａ､Ｈ・AFarooqi,Ｙ､Ｎ・Shukla,HbZeroG〕ﾉc伽,３４，
２１（1992);ｃ)Ｔ・FUjii,Ｍ・Ohba,HKawamura,Ｔ・Haneishi,S Matsubara,ＣｈｅｍＰ〃αr腕Ｂ"".,41,1362(1993)．
８）AnexceptiontothisstatementmaybeL3-diphenylurca,whichwas isolatedfi｢omcoconutmilkasagrowthstimulatorfbrcarrotroot tissuejmWraEMShantz，ＦＣ・Steward,Ｊ､１，．Che、、SOC.，
77,6351（1955）However,itscytokininactivityisweak､2）
，）Anexceptiontothisclassificationmaybe2-hydroxy-Ⅳ6-methyl- adenine,whichwasisolatedfiPommethanolicextractsofbluecoral
（codeNo.NIO-156)ﾌﾞ)However,itscytokininactivityhasbeen lbuｎｄｔｏｂｅｖｅｒｙｗｅａｋ７ｃ）
10）TheabsoluteconfigurationatC(1'）ｉｓunknown,ｂｕｔｈａｓｂｅｅｎ ａｓｓｕｍｃｄｔｏｂｅＲ,7b，c）
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Ｔ､FUjii,Ｃ/1ｃｍ.〃αr腕ＢⅢ".,40,1937(1992)．
13）α)ＲＴＤｅａｎ,HRapoport,ノ.Ｏ'9.Ｃ/1ｃｍ.,43,2115(1978);b)Ｋ、
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15）α)Ｓ・Takano,YIwabuchi,KOgasawara,Ｊ、Ｃ/1ｃｍβoc.,Ｃ/i２，．
Col"腕Ⅲ".,1988,1204;６)Ｊ・ELeibner,Ｊ､Jacobus,ノ０埴.Ｃｈｅ腕.Ｊ ４４Ｍ４９(1979)．
16）α)HCBrown,Ｓ・Krishnamurthy,』.』、､ｄｌｅｍ.ＳＤＣ.,95,1669
（1973);6)Ｒ､OHutchins,Ｋ・Ｌｅａｍ,』.Ｏ'9..,.,47,4380(1982)．
17）Ｊ・Zemli6ka,ＦＳｏｒｍ,ＣＯ比α・Czech.Ｃﾉiem.Ｃｏｍｍｍ.,30,1880
（1965)．
18）GWittig,DWittenberg,九F/"sLie6jgM""・ｄｉｅ､.,606,1(1957)．
19）Ｕ,Ｈ､MFagerlund,，.Ｒ・Idler,Ｊ・Ａｍ・Ｃｈｅ、､ＳＯＣ.,79,6473
（1957)．
20）See,fbrexample,ZRKorszun,CKnight,Ｃ､-Ｍ.Chen,ＦＥＢＳ Ｌｅ".,２４３，５３（1989）
21）Ｗ､CStill,MKahn,Ａ・Mitra,』.Ｏ'9..z2,.,43,2923(1978)．
AcknowledgmentThisworkwassupportedbyaGrant-in-Aidfor ScientiiicResearch(B)(No.04453152)fromtheMinistryofEducation，
ScienceandCulture,Japan．
RefereuBcesandNotes
l）PaperLXIinthisseries,Ｔ､FUjii,Ｔ・Saito,Ｋ・Iguchi,Ｃ/1ｃｍ､ＰＡａｍｚ．
〃".,４２，４９５(1994)．
