Synthesis and crystal structure of meso-R(Ph)Sb-Sb(Ph)R [R = (Me 3Si)2CH]

Article abstract of DOI:10.1515/znb-2005-1218

R(Ph)Sb-Sb(Ph)R (1) [R = (Me₃Si)₂CH] is formed by reduction of Ph(R)SbCl with Mg. The meso-diastereomer of 1 has been characterised by X-ray crystallography. It adopts an antiperiplanar conformation in the solid state.

Full text of DOI:10.1515/znb-2005-1218

Notiz
1321
Ergebnisse und Diskussion
Synthese und Kristallstruktur von meso-
R(Ph)Sb-Sb(Ph)R [R = (Me3Si)2CH]
Die Synthese von 1 erfolgte entsprechend dem Re-
aktionsschema (1) durch Umsetzung von PhSbCl2 mit
RMgCl [R = (Me3Si)2CH] im Molverha¨ltnis 1:1 und
Reduktion des so gebildeten asymmetrischen Chlo-
rids Ph(R)SbCl mit Mg in Tetrahydrofuran. Die Aus-
beuten der beiden Reaktionsschritte betragen 72 bzw.
64 %. Alternativ wurde auch die Reduktion von
Ph(R)SbCl mit LiAlH4 untersucht. Dabei entstand das
thermisch stabile Stiban Ph(R)SbH [7]. Ph(R)SbH ist
eine farblose, bei Raumtemperatur stabile, lichtemp-
findliche Verbindung, die sich in organischen Solven-
tien gut lo¨st und sich durch Destillation reinigen la¨sst.
Erst ku¨rzlich wurde erstmals u¨ber analoge asymme-
trische Verbindungen, wie R’[(Me3Si)2CH]SbCl und
R’[(Me3Si)2CH]SbH [R’ = 2–(Me2NCH2)C6H4] be-
richtet [11].
Synthesis and Crystal Structure of meso-
R(Ph)Sb-Sb(Ph)R [R = (Me3Si)2CH]
Lucia Bala´zsa, Hans Joachim Breuniga,
Cristian Silvestrub, and Richard Vargab
a Institut fu¨r Anorganische und Physikalische Chemie,
Universita¨t Bremen, D-28334 Bremen, Germany
b
Facultatea de Chimie si Inginiere Chimica, Universitatea
Babes-Bolyai, RO-400028 Cluj-Napoca, Romania
Sonderdruckanforderungen an Prof. Dr. H. J. Breunig.
Fax: 0049-421-218-4042.
E-mail: breunig@chemie.uni-bremen.de
Z. Naturforsch. 60b, 1321 – 1323 (2005);
eingegangen am 16. September 2005
R(Ph)Sb-Sb(Ph)R (1) [R = (Me3Si)2CH] is formed by re-
duction of Ph(R)SbCl with Mg. The meso-diastereomer of 1
has been characterised by X-ray crystallography. It adopts an
antiperiplanar conformation in the solid state.
Key words: Antimony, Group 15 Element, Sb-Sb Bond,
Organoantimony Compound
(1)
Einleitung
Das Distiban 1 ist eine luftempfindliche Verbin-
dung, die sich in Kohlenwasserstoffen gut lo¨st und
durch Umkristallisation aus Petrolether in Form gelber
Asymmetrische Distibane des Typs RR’Sb-SbR’R
ko¨nnen als meso- und d,l-Diastereomere vorliegen
[1, 2]. Im Fall des disekunda¨ren Distibans R(H)Sb-
Sb(H)R [R = (Me3Si)2CH] wurden in Lo¨sung die
meso- und die d,l-Form im Molverha¨ltnis 1:1, im Kris-
tall nur die meso-Form gefunden [1]. In Lo¨sung rea-
◦
Kristalle (Fp. = 86 – 88 C) erhalten la¨sst. 1 kristalli-
siert im monoklinen Kristallsystem in der Raumgrup-
pe P21/c. Die Moleku¨lstruktur im Kristall ist in Abb. 1
dargestellt.
Es liegt ein Distiban in der antiperiplanaren (trans)
giert R(H)Sb-Sb(H)R mit MeI zu R(Me)Sb-Sb(Me)R, Konformation vor. Der Diederwinkel φ =lp-Sb-Sb-
einem asymmetrischen Tetraalkyldistiban, das eben- lp (lp = angenommene Orientierung des einsamen
falls als Isomerengemisch (meso-Form/d,l-Form = Elektronenpaars am Antimon) weicht mit 137.42(2)◦
1/1.4) erhalten wurde [2]. Die Trennung der Diastereo- erheblich vom idealen Wert von 180◦ ab, der bei
meren gelang im Fall der Distibankomplexe [R(H)Sb- Ph4Sb2 [8], Me4Sb2 [9, 10] und meso-R(H)Sb-Sb(H)R
Sb(H)R][W(CO)5]2 durch fraktionierte Kristallisati- [R = (Me3Si)2CH] [1, 2] gefunden wurde. Die Sb-Sb
˚
on [2]. Wir berichten hier u¨ber Untersuchungen zu Bindungsla¨nge von 1 ist mit 2.844(1) A kaum la¨nger
˚
Synthese und Struktur von R(Ph)Sb-Sb(Ph)R (1) [R als bei Ph4Sb2 [2.837(1) A], meso-R(H)Sb-Sb(H)R
˚
˚
= (Me3Si)2CH], einer Verbindung bei der im Kristall [2.830(1) A] oder Mes4Sb2 [2.849(1) A]. Die SbC2
und in Lo¨sung die meso-Form dominiert. meso-1 ist und SbSbC Bindungswinkel variieren im Bereich 90 –
das erste asymmetrische Tetraorganodistiban, das kris- 102◦. Wie Abb. 2 zeigt, sind die Moleku¨le im Kristall
tallographisch charakterisiert wurde. Analoge Diphos- stapelfo¨rmig angeordnet. Es liegen keine besonders en-
phane und Diarsane sind schon la¨nger bekannt [3 – 6].
gen zwischenmolekularen Kontakte vor.
c
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1322
Notiz
¨
Ahnliche Verha¨ltnisse wie bei 1 liegen auch beim
Diphosphan R(Ar)P-P(Ar) [R = (Me3Si)2CH, Ar = 2-
Me2NCH2C6H4] vor. In Lo¨sung u¨berwiegt das meso-
Isomere und im Kristall wurde die meso-Form charak-
terisiert [3].
Experimenteller Teil
Alle Arbeiten wurden in einer Argonatmospha¨re durch-
gefu¨hrt.
Ph(R)SbCl [R = (Me3Si)2CH]
Zu einer eisgeku¨hlten Lo¨sung von 3,70 g (13,7 mmol)
PhSbCl2 in 20 ml THF (THF = Tetrahydrofuran) wird ei-
ne aus 2,67 g (13.7 mmol) (Me3Si)2CHCl und 0,33 g
(13,7 mmol) Mg in 50 ml THF bereitete Grignard-Lo¨sung
zugetropft. Danach wird das Reaktionsgemisch 1 h unter
Ru¨ckfluss erwa¨rmt und 20 h bei R.T. geru¨hrt. Nach Entfer-
nen des Lo¨sungsmittels bei vermindertem Druck wird der
Ru¨ckstand mit 100 ml Diethylether aufgenommen und auf
Abb. 1. Moleku¨lstruktur von meso-1. Die Schwingungs-
ellipsoide sind mit 30 % Wahrscheinlichkeit dargeste◦llt.
˚
Ausgewa¨hlte Bindungsla¨ngen (A) und Bindungswinkel ( ):
Sb(1)-Sb(2) 2.854(1), Sb(1)-C(5) 2.166(14), Sb(1)-C(7)
2.201(12), Sb(2)-C(10) 2.126(16), Sb(2)-C(8) 2.183(11);
C(5)-Sb(1)-C(7) 101.1(5), C(5)-Sb(1)-Sb(2) 101.2(4), C(7)- einem Eisbad mit 35 ml mit Argon gesa¨ttigtem Wasser ver-
Sb(1)-Sb(2) 101.6(3), C(10)-Sb(2)-C(8) 97.5(5), C(10)-
Sb(2)-Sb(1) 89.8(3), C(8)-Sb(2)-Sb(1) 97.7(3).
setzt. Die Etherphase wird abgetrennt und die wa¨sserige Pha-
se mit weiteren 2 × 20 ml Et2O extrahiert. Die Etherex-
trakte werden vereinigt und u¨ber Na2SO4 getrocknet. Die
Lo¨sung wird u¨ber Kieselgur filtriert. Das Entfernen des
Lo¨sungsmittels ergibt 6,5 g (71,7 %) Ph(R)SbCl als farb-
◦
lose o¨lige Flu¨ssigkeit (Sdp. 53 C / 10−3 mbar). -1H-NMR
(200 MHz, C6D6): δ = −0,08 (s, 9 H; CH3), 0,26 (s, 9 H;
CH3), 1,04 (s, 1 H; CH3); 7,00 – 7,18 (m, 3 H), 7,60 – 7,65
(m, 2 H C6H5). -13C-NMR (50 MHz, C6D6): δ = 2,39
(CH3Si), 3,52 (CH3Si), 21,31 (CH), 129,19 129,81, 134,38,
145,5 (C6H5). MS (EI, 70 eV): m/z (%) 394 (15) [M+], 379
(100) [M+–Me], 207 (35), 129 (45), 73 (90).
R(Ph)Sb-Sb(Ph)R [R = (Me3Si)2CH] (1)
Zu 0,34 g (14,1 mmol) mit 0.25 ml 1,2-Dibromethan ak-
tivierten und mit 20 ml THF bedeckten Mg-Spa¨nen wird bei
◦
−10 C unter Ru¨hren eine Lo¨sung von 6,5 g (16,5 mmol)
Abb. 2. Orientierung der Moleku¨le von meso-1 entlang der
x-Achse.
Ph(R)SbCl in 70 ml THF gegeben. Das Ka¨ltebad wird ent-
fernt und die entstandene Reaktionsmischung u¨ber Nacht
bei R.T. geru¨hrt. Das THF wird im Vakuum entfernt und
der Ru¨ckstand mit 100 ml Petrolether aufgenommen. Die
Petrolether-Lo¨sung wird auf 20 ml konzentriert. Bei −28 ◦C
kristallisiert 3,75 g (64 %) 1 in Form gelber Nadeln (Schmp.
86 – 88 ◦C). -1H-NMR (200 MHz, C6D6): δ = 0,02 (s, 18 H;
CH3), 0,18 (s, 18 H; CH3), 0,37 (s, 2 H; CH), 6,91 – 7,08 (m,
6 H; m-,p-C6H5), 7.83 – 7.87 (m, 4 H; o-C6H5). -13C-NMR
(50 MHz, C6D6): δ = 3,43 (s, (CH3)3Si), 3,38 (s, (CH3)3Si),
2,06 (s, CH), 129,18, 136,65, 139,18, 134,30 (C6H5).
Das 1H-NMR Spektrum von 1 in C6D6 entha¨lt
zwei intensive Signale fu¨r die diastereotopen Me3Si-
Gruppen, ein Singulett fu¨r die CH-Gruppen und zwei
Multiplett-Signale fu¨r die Protonen der Phenylgrup-
pen. Daneben sind noch Signale geringer Intensita¨t im
Bereich der Methyl- und Methin-Protonen zu erken-
nen. Entsprechend dem kristallographischen Befund
ordnen wir die intensiven Signale der meso-Form von 1
zu. Die kleinen Signale ko¨nnten von der d,l-Form von 1
stammen. Der Intensita¨tsvergleich fu¨hrt in diesem Fall
zu einem Molverha¨ltnis von meso-1/d,l-1 von 12/1.
Ein Einkristall von 1 wurde mit einem Bruker Smart Dif-
fraktometer vermessen. Kristalldaten: C26H48Sb2Si4, Mr =
716,50, Kristallgro¨ße 0,26×0,37×0,18 mm3, monoklin, a =
Unauthenticated
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Notiz
1323
◦
˚
9,374(3), b = 29,243(8), c = 13,748(4) A, β = 109,377(6) , zelheiten zu der Kristallstrukturuntersuchung ko¨nnen als
Raumgruppe P21/c, Z = 4, V = 3,555(2) nm3, berechnete CIF-File beim Cambridge Crystallographic Data Centre
Dichte 1,339 g/cm3, F(000) = 1448, T = 297(2) K. An- (CCDC, 12 Union Road, Cambridge CB2 1EZ (Fax: int. Co-
zahl der gemessenen Reflexe 26861, unabha¨ngige Refle- de +(1223)336-003; e-mail: deposit@ccdc.cam.ac.uk)) unter
xe 6681 [R(int) = 0,1889]. Eine Absorptionskorrektur wur- Angabe der Hinterlegungsnumer CCDC-279554 angefordert
de mit dem Programm DIFABS durchgefu¨hrt. Absorpti- werden.
onskoeffizient 1,666 mm−1, Tmin = 0,566, Tmax = 0,738,
Dank
endgu¨ltige R-Werte [I > 2σ(I)] R1 = 0,0836, wR2 = 0,1427,
R-Werte (alle Daten) R1 = 0,2184, wR2 = 0,1835, Gro¨ßtes
Wir danken der Deutschen Forschungsgemeinschaft fu¨r
die finanzielle Unterstu¨tzung.
Max. und Min. 0,612 bzw. −0,902 e·A−3. Weitere Ein-
˚
[6] F. Knoch, R. Appel, B. Bruck, Z. Kristallogr. 210, 314
(1995).
[1] G. Bala´zs, H. J. Breunig, E. Lork, W. Offermann, Orga-
nometallics 20, 2666 (2001).
[7] L. Bala´zs, Dissertation, Bremen (2003).
[8] K. von Deuten, D. Rehder, Cryst. Struct. Comm. 9, 167
(1980).
[9] A. J. Ashe III, E. G. Ludwig, J. Oleksyszyn, J. C. Huff-
man, Organometallics 3, 337 (1984).
[10] O. Mundt, H. Riffel, G. Becker, A. Simon, Z. Natur-
forsch. 39b, 317 (1984).
[2] G. Bala´zs, H. J. Breunig, E. Lork, S. Mason, Organo-
metallics 22, 576 (2003).
[3] S. Blair, K. Izod, R. Taylor, W. Clegg, J. Organomet.
Chem. 656, 43 (2002).
[4] X.-W. Li, J. Lorberth, K. Harms, J. Organomet. Chem.
483, 229 (1994).
[5] S. Loss, C. Widauer, H. Gru¨tzmacher, Angew. Chem.
111, 3546 (1999), Angew. Chem. Int. Ed. 38, 3329
(1999).
[11] H. J. Breunig, I. Ghesner, M. E. Ghesner, E. Lork, In-
org. Chem. 42, 1751 (2003).
Unauthenticated
Download Date | 1/25/18 11:54 AM

1324
Note
in associated lichens [10]. From our interests in the
metabolic capability of the mycobionts isolated from
lichens of the genus Lecanora, we cultivated the spore-
derived mycobionts of Lecanora nipponica H. Miyaw.
and isolated two new acidic compounds 3 and 4 from
their cultures. We report here the isolation and charac-
terization of these compounds.
Two Aliphatic Acid Derivatives from
the Cultured Mycobionts of Lecanora
nipponica
Yukiko Takenakaa, Nobuo Hamadab, and
Takao Tanahashia
a Kobe Pharmaceutical University, 4-19-1, Motoyamakita-
machi, Higashinada-ku, Kobe 658-8558, Japan
The polyspore-derived mycobionts of L. nippon-
ica were cultivated on conventional malt-yeast extract
b
Osaka City Institute of Public Health and
◦
Environmental Sciences, 8-34, Tojo-cho, Tennouji-ku,
Osaka 543-0026, Japan
medium supplemented with 10% sucrose at 18 C in
the dark. After cultivation over 15 months, the colonies
were harvested and extracted with acetone. The extract
was separated by a combination of preparative TLC to
afford two new compounds 3 and 4.
Reprint requests to Prof. T. Tanahashi. Fax: +81-78-441-
7546. E-mail: tanahash@kobepharma-u.ac.jp
Z. Naturforsch. 60b, 1324 – 1326 (2005);
Compound 3 was obtained as colourless oil. Its
HR-EIMS spectrum indicated a molecular formula of
C13H20O4. Its 1H NMR spectrum exhibited signals
for two methyl groups at δ = 0.90 (t, J = 7.0 Hz)
and 2.00 (s), three sets of methylene protons at δ =
1.32, 1.42 and 2.21, a pair of trans olefinic protons
at δ = 5.95 (dt, J = 16.0, 7.0 Hz) and 6.34 (dt,
J = 16.0, 1.5 Hz) and two carbomethoxyl groups at
δ = 3.75 and 3.86 (each s). The 13C NMR spec-
trum of 3 showed two methyls, two methoxyls, three
methylenes, two sp2 CH carbons and four sp2 qua-
ternary carbons, of which two were carbonyl carbons.
1H-1H COSY sequences starting from the methyl sig-
received February 15, 2005
Spore-derived mycobionts of the lichen Lecanora nippon-
ica were cultivated on a malt-yeast extract medium supple-
mented with 10% sucrose and their metabolites were in-
vestigated. Two new metabolites, methyl (2Z, 4E)-3-meth-
oxycarbonyl-2-methyl-2,4-nonadienoate and (4E)-3-meth-
oxycarbonyl-2-methyl-4-nonenoic acid were isolated. Their
structures were determined by spectroscopic methods.
Key words: Lecanora nipponica, Lichen Mycobiont,
Aliphatic Acid
Thalli of lichens of the genus Lecanora were known nal at δ = 0.90 to the olefinic proton signals formu-
to contain a variety of characteristic lichen substances lated a 1E-hexenyl residue. HMBC correlations from
[1, 2]. Many depsides and depsidones were reported the olefinic proton (H-4) at δ = 6.34 and methyl sig-
from the lichens of this genus such as L. planaica [3]. nal (H3-10) at δ = 2.00 to two sp2 quaternary car-
An aliphatic acidic compound, roccellic acid (1), its bons indicated the hexenyl and methyl groups substi-
related lactonic acid, roccellaric acid (2), and a xan- tuted at the tetra-substituted double bond where two
thone, thiophanic acid as well as depsides and dep- carbomethoxyl groups were also substituted. Further
sidones were isolated from L. rupicola (L.) Zahlbr HMBC cross peaks between H-4 and carbony carbon
[4, 5]. On the other hand, the cultured mycobiont of at δ = 169.6 and between H3-10 and carbony car-
L. rupicola produced neither depside nor depsidone, bon at δ = 167.6 as well as an important NOESY
but novel chromones and roccellic acid [6]. A chemo- correlation between H-4 and H3-10 depicted the sub-
type of the natural lichen L. dispersa contains 2,7- stitution pattern at the double bond as shown. Thus,
dichlorolichexanthone as the major product, but cul- the isolated compound 3 was determined as meth-
tured spore isolates produced two typical lichen depsi- yl (2Z, 4E)-3-methoxycarbonyl-2-methyl-2,4-nonadi-
dones [7]. We have recently cultivated the mycobionts enoate.
of L. cinereocarnea (= L. leprosa) and L. iseana and
The MS spectrum of compound 4 established the
isolated from their cultures diverse novel dibenzofu- composition C12H20O4. The 1H NMR spectral features
rans, which have never been isolated from the natural of 4 were closely similar to those of 3; the signifi-
lichens [8, 9]. These studies demonstrated that cultures cant difference in their spectra being that 4 showed
of mycobionts have an ability to produce lichen sub- only one singlet for carbomethoxyl group and sig-
stances or novel metabolites, which could not be found nals for two methine protons at δ = 2.68 and 3.14,
c
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Note
1325
Fig. 1. Structures of roccellic acid (1), roccellaric acid (2), methyl (2Z, 4E)-3-methoxycarbonyl-2-methyl-2,4-nonadienoate
(3), (4E)-3-methoxycarbonyl-2-methyl-4-nonen oic acid (4) and piliformic acid (5).
pounds might most likely be biosynthesized from a
C8-fatty acid and a C3-unit originated from oxaloac-
etate [11]. Analogous dicarboxylic acids and their re-
lated lactones represented by 1 and 2, which pos-
sess a C14-, C16-, or C18-chain as a fatty acid unit,
have so far been isolated from natural lichens [1].
The dicarboxylic acids and their relatives with a C8-
fatty acid chain such as 3 and 4 had not been iso-
lated from the lichens in nature, but piliformic acid (5)
was reported from xylariaceous fungi Xylaria mali and
X. longipes [12].
Experimental Section
Optical rotation was measured on a Jasco DIP-370 digital
Fig. 2. 1H-1H COSY (bold lines), HMBC (bold arrows) and
polarimeter. HR-EIMS were obtained with a Hitachi M-4100
mass spectrometer. The NMR experiments were performed
with Varian VXR-500 spectrometer with tetramethylsilane as
internal standard. Thin-layer chromatography was performed
on precoated Kieselgel 60F254 plates (Merck) and spots were
visualized under UV light.
NOESY (dotted arrows) correlations observed for 3 and 4.
which were not observed in 3. Two sp2 quaternary car-
bons were replaced by two sp3 methine carbons in the
13C NMR spectrum of 4. These findings indicated 4
to be a demethylated compound of 2,3-dihydro deriva-
tive of 3. The methoxycarbonyl group was placed at
C-3 by its HMBC spectrum, which showed signifi-
cant correlations from the methoxyl at δ = 3.63 and
a doublet at δ = 5.28 to the carbonyl carbon at δ =
176.4 and from the methyl at δ = 1.10 to the car-
bonyl carbon at δ = 178.0. Accordingly, compound
4 was assigned to (4E)-3-methoxycarbonyl-2-methyl-
4-nonenoic acid. The stereochemistry of C-3 and C-4
could not be determined due to a minute amount.
In the present study, we isolated two dicarboxylic
acid derivatives from the cultured mycobionts of
Plant material. Specimens of Lecanora nipponica H.
Miyaw. were collected from the bark of trees in Kimitsu,
Boso Peninsula, Chiba Prefecture, Japan (200 m alt.). The
voucher specimens were identified by Prof. H. Miyawaki,
Saga University, Japan and were deposited at Osaka City
Institute of Public Health and Environmental Sciences with
the registration No. NH9730161. Mycobionts were obtained
from the spores discharged from apothecia of a thallus,
and were cultivated in test tubes containing modified MY10
medium (malt extract 10 g, yeast◦extract 4 g, sucrose 100 g,
agar 15 g, H2O 1 l, pH 7) at 18 C in the dark. After culti-
vation for 15 months, the colonies and slants were harvested
L. nipponica. It can be postulated that these com- and freeze-dried.
Unauthenticated
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1326
Note
Extraction and isolation. The harvested colonies (84 test 1.10 (br d, J = 6.5 Hz, 3H, H3-10), 1.32 (m, 2H, H2-8),
tubes, freeze-dried weight 7.89 g) were extracted with ace- 1.37 (m, 2H, H2-7), 2.05 (br q, J = 7.0 Hz, 2H, H2-6), 2.68
tone at r. t., and the combined extracts were concentrated (m, 1H, H-2), 3.14 (br t, J = 9.0 Hz, 1H, H-3), 3.63 (s, 3H,
under reduced pressure to give a residue (588 mg). The ex- 1-OMe), 5.28 (br dd, J = 15.0, 9.0 Hz, 1H, H-4), 5.65 (br dd,
1
tract was repeatedly subjected to preparative TLC (toluene- J = 15.0, 7.0 Hz, 1H, H-5). – 13C{ H} NMR (125.00 MHz,
acetone, 4:1 or toluene-AcOH, 9:1), giving rise to 3 (3.9 mg) CD3OD): δ = 14.2 (C-9), 16.1 (C-10), 23.2 (C-8), 32.5
and 4 (5.1 mg).
(C-7), 33.2 (C-6), 44.4 (C-2), 52.2 (11-OMe), 54.3 (C-3),
Methyl (2Z, 4E)-3-methoxycarbonyl-2-methyl-2,4-nona- 127.1 (C-4), 137.0 (C-5), 176.4 (C-11), 178.0 (C-1) – HR-
dienoate (3). Colorless oil. — 1H NMR (499.99 MHz, EIMS m/z: calcd. for C12H20O4 [M+]: 228.1362; found
CDCl3): δ = 0.90 (t, J = 7.0 Hz, 3H, H3-9), 1.32 (br sext, 228.1351.
J = 8.0 Hz, 2H, H2-8), 1.42 (m, 2H, H2-7), 2.00 (s, 3H, H3-
10), 2.21 (br q, J = 7.0 Hz, 2H, H2-6), 3.75 (s, 3H, 1-OMe),
Acknowledgements
3.86 (s, 3H, 11-OMe), 5.95 (dt, J = 16.0, 7.0 Hz, 1H, H-5),
1
6.34 (dt, J = 16.0, 1.5 Hz, 1H, H-4). – 13C{ H} NMR
This research was financially supported by Grant-in-Aid
(C)(No.13836009 and 15510186) from the Ministry of Ed-
ucation, Culture, Sports, Sciences and Technology of Japan,
and the Kobe Pharmaceutical University Collaboration Fund.
We are grateful to Dr. H. Miyawaki (Saga University, Japan)
for identification of the voucher specimen. Thanks are also
due to Dr. M. Sugiura (Kobe Pharmaceutical University) for
1H and 13C NMR spectra, and to Dr. K. Saiki (Kobe Phar-
maceutical University) for mass spectra measurements.
(125.00 MHz, CDCl3): δ = 13.5 (C-10), 13.9 (C-9), 22.3
(C-8), 30.8 (C-7), 33.3 (C-6), 52.2 (1-OMe), 52.3 (11-OMe),
123.7 (C-4), 123.9 (C-2), 141.6 (C-5), 141.8 (C-3), 167.6
(C-1), 169.6 (C-11). – HR-EIMS m/z: calcd. for C13H20O4
[M+]: 240.1362; found 240.1354.
(4E)-3-Methoxycarbonyl-2-methyl-4-nonenoic acid (4).
Colorless oil. – [α]2D2 − 102◦ (c=0.5, MeOH). – 1H NMR
(499.99 MHz, CD3OD): δ = 0.90 (t, J = 7.5 Hz, 3H, H3-9),
[7] C. Leuckert, V. Ahmadjian, C. F. Culberson, A. John-
son, Mycologia 82, 370 (1990).
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