The oxidation of partially acylated myoinositols

Article abstract of DOI:10.1515/znb-1996-0114

1,3,4,6-Tetrakis-and 1,3,4,5,6-pentakis-acylmyoinositols are obtained by the controlled catalyzed acylation of myoinositol. The extent of the substitution depends both on the reaction conditions and the structure of the acylating agent, including steric f

Full text of DOI:10.1515/znb-1996-0114

The Oxidation of Partially Acylated Myoinositols
Frederick Kurzer, Dennis Chapman
Royal Free Hospital School of Medicine, University of London, London NW 3, England
Z. Naturforsch. 51b, 68-78 (1996); received May 17, 1995
Tetrakisacylmyoinositols, Pentakisacylmyoinositols, Acylated Myoinososes-2, Mass Spectra,
Myoinositol Esters
1,3,4,6-Tetrakis- and 1,3,4,5,6-pentakis-acylmyoinositols are obtained by the controlled cat-
alyzed acylation of myoinositol. The extent of the substitution depends both on the reaction
conditions and the structure of the acylating agent, including steric factors. Chromic acid
oxidation converts the acylmyoinositols into the corresponding 2-ketones. Under electron
impact, the compounds undergo stepwise deacylation.
Introduction
cleavage [11,12,15] and complete degradation
[11,12,15]. A singular case is the action of hot con-
centrated nitric acid, which converts myoinositol
into DL-epi-inosose in moderate yield [8,16], in-
volving the anomalous preferential oxidation of an
equatorial hydroxy group.
The design of targeted syntheses involving cycli-
tols [1,2] is impeded by difficulties arising from
the full substitution by hydroxy groups of their ali-
cyclic nucleus, necessitating more or less elaborate
procedures for the protection of selected groups.
In the six-membered pattern, conformational dif-
ferences provide a means of steering reactions into
a particular course, based on contrasting reactivi-
ties of axial versus equatorial hydroxyls in the cy-
clohexane ring [3], acylation [4] occurring prefer-
entially at equatorial, and oxidation at axial
hydroxy-groups [la,5].
Myoinositol (1) conforms in both respects to
this general behaviour. Esterification (and hydrol-
ysis) occurs more rapidly at its equatorial hydrox-
yls [la], while dehydrogenation by oxygen in the
presence of a platinum catalyst [6] or suitable
microorganisms (especially Acetobacter suboxi-
dans) [7] is confined to its 2-ax-hydroxy group, af-
fording myoinosose-2 (14, R = H) [8], y-Irradiation
also forms the 2-monoketone as the primary pro-
duct, though not in isolable quantities [9]. Mild
bromine oxidation produces chiefly moderate
amounts of diketones [10]. In contrast to these ste-
reospecific dehydrogenations, the action of other
oxidizing agents (including permanganate [11],
periodate [12], nitric acid [13], dimethyl sulpho-
xide [14] and photolytic oxygen [15]) commonly
effect more deep-seated changes, tending to aro-
matization [13,14], quinone formation [13], ring
Results and Discussion
Our exploratory experiments aimed at re-
stricting the action of conventional oxidizing
agents to the 2-ax-hydroxy group of myoinositol
by employing equimolar (or lower) proportions of
oxidant under restrained conditions, as an effec-
tive approach to the 2-monoketone, were not suc-
cessful. Thus, an equivalent of aqueous chromic
acid, hypobromite, permanganate or hydrogenper-
oxide-ferrous sulphate (Fenton’s reagent) was
rapidly consumed in completely degrading a por-
tion of the total available myoinositol, leaving
most of the remainder unaffected and recoverable
(e.g. as hexaacetate). Attention was therefore di-
rected to the production and oxidation of suitable
partially acylated myoinositols, with the results re-
ported below.
Acylation
Substitution at all six hydroxyl-groups of myo-
inositol occurs readily on treatment with acyl ha-
lides or anhydrides in the presence of zinc chloride
[17] or sulphuric or perchloric acid [lc]. The re-
quired partial acylation, with preservation of the
free 2-ax-hydroxy-group, has now been effected in
pyridine, in the presence of 4-dimethylaminopyri-
dine as catalyst. The latter catalyzes acylations up
* Reprint requests to Dr. F. Kurzer.
N
0932-0776/96/0100-0068 $06.00 © 1996 Verlag der Zeitschrift für Naturforschung. All rights reserved.
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F. Kurzer-D. Chapman • The Oxidation of Partially Acylated Myoinositols
69
OR
to 104 times more effectively than pyridine itself
OH
Me3C.COCI
ZnCI2
[18], thus making the use of milder conditions ac-
RC
RO
HC
OR
cessible. Applied under specified conditions to
acyl halides incorporating sufficiently bulky head
groups, the procedure afforded partially acylated
products retaining their free 2-ax-hydroxy group
in satisfactory and reproducible yields.
OH
( to 1 2 )
Ho
RO
HO
8: R = COOEt
9: R = COMe
10: R = COCH2Me
11: R = COCHM e2
RCOCI -
12:
R
= COCM e3
Py-DMAP
Thus, 1,3,4,6-tetrakispivaloylmyoinositol (3) was
readily obtained by the catalyzed action of piva-
loyl chloride under controlled conditions (temper-
ature, rate of addition). Reaction did not proceed
beyond the tetrasubstitution stage, in spite of the
necessary use of a large excess (12 mol) of the
acylating agent. The remaining free 2- and 5-hy-
droxy groups (of 3) underwent acetylation by ace-
tic anhydride-zinc chloride [17] as expected, re-
sulting in 16. This procedure was also used for
preparing the hexakispivaloyl compound 12 for
comparison. The structure of 3 was confirmed by
the symmetrical distribution of its acyl-substitu-
ents, as shown by its 13C NMR spectrum: The four
pivaloyl groups produce only two low-field car-
bonyl singlets ((3 176.7, 176.3 ppm), while their
(trimethyl)methyl moieties give rise to one pair of
singlets (C of CMe3, at 38.2, 38.1 ppm) and one
pair of quartets (d 26.9, 26.7 ppm), the latter origi-
nating collectively from the triple groups of the
equivalent methyl entities. The four doublets of
the cyclohexane ring carbons, two of them of
double relative intensity, are assigned in accor-
dance with the mapped spectrum of the parent
compound 1 [19].
RCOCI-
Py -DMAP |
t
OH
OH
RCOCI-
Py-DMAP
RC
RC
HO
OR
OR
RO
RO
RO
R = COCH2CHMe2
R = COPh
R = C 0 C 9H«N02 -p
R = COC6H4B r-p
2 : R = CO CHM ej
3 : R = COCM e3
jpOs
14: R = COCH2CHM 62
15: R = COPh
13: R = COMe3
OAc
OAc
RC
AcO
RC
OR
OR
RO
RO
RO
17 : R = C 0C H 2CHMe2
18 : R = COPh
16: R = COCM e3
[21] for preferentially acylating equatorial over
axial hydroxy groups, did not differentiate be-
tween them in the present instance, giving 8 in
low yield.
Isobutyroyl chloride, having comparable mo-
lecular dimensions, similarly produced the 1,3,4,6-
tetrakisacyl derivative (2) as the major product
(35-40%), together with some 1,3,4-tris-acyl com-
In the aromatic series, the catalyzed acylation
pound (15-18%), formulated in accordance with afforded 1,3,4,5,6-pentakisaroylmyoinositols (5-7)
the known [20] descending reactivity towards acy- as sole products consistently in high yield (80-
lation and tosylation of the hydroxyl groups of 1. 90% for 5, 6). The use of smaller proportions of
With isovaleroyl chloride, however, acylation con- acylating agent at lower temperatures still effected
tinued to the 1,3,4,5,6-penta-substituted stage 4; penta-acylation, though in diminished yields. The
here, replacement of all the equatorial hydroxy- structure of the pentakisbenzoyl-compound 5 (and
groups may be promoted by the reduced steric that of its isovaleroyl-analogue 4) was confirmed
hindrance operating between the bulky head
groups of the substituents, due to their increased
by their 13C NMR spectra (see Experimental).
Both compounds underwent further mono-ace-
distance from the central cyclohexane ring. This tylation (to 18 and 17, respectively). Attempts to
apparent steric influence is further emphasized by obtain a monobenzoyl derivative of 1 by the use
the behaviour of linear aliphatic acyl halides, of a large excess of myoinositol at 0-10 °C were
which effected hexa-acylation (to 9-11). Ethyl
chloroformate, described as a reagent of choice
unsuccessful, the benzoyl chloride being recovered
as the anhydride.
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70
F. Kurzer-D. Chapman • The Oxidation of Partially Acylated Myoinositols
Oxidation
the appropriate carboxylic acid, and occasional
loss of water. While the sequence of these events
The remaining free 2-ax-hydroxy-group of the
foregoing acylated myoinositols readily underwent
oxidation. The action of Fieser’s chromic acid rea-
gent [22] converted the reactants (3-5) into the
corresponding 2-ketones (13-15) in good yield,
contrasting with the difficulty of accomplishing
this reaction with the parent compound (see
is clear, there remains some uncertainty concern-
ing the precise position isomerism of the interme-
diate ionic fragments, depending on which of two
or more identical acyl groups is removed preferen-
tially in any fission stage. These uncertainties are
reduced, but not entirely removed, by a compari-
son of the mass spectra of acylmyoinositols with
those of their analogues incorporating a differenti-
ating structural element, such as a keto group (e.g.
in 13-15) or an acyl group distinct from the others
(e.g. in 16-18).
Thus, pentakisisovaleroylmyoinositol (4) and its
corresponding 2-ketone (14) give rise to a match-
ing series of signals consistently 2 mass units apart
(Table I), suggesting a strictly parallel fragmenta-
tion sequence for both structures, and the conse-
quent likely retention of the 2-keto- and hence the
2-hydroxy-group (in 14 and 4 respectively) and
their immediate structural environment during the
fission. The same consistency, though over a nar-
rower range, is seen in the case of the pentakisben-
above). The 2-ax-5-eq-dihydroxy compound
3
gave the monoketone 13, even though more than
sufficient oxidant was employed to produce the
2,5-diketone, thus illustrating again the greater
susceptibility to oxidation of axial over equatorial
hydroxy groups in cyclohexane. The pentakisiso-
valeroyl-2-ketone 14 was converted into the parent
inosose-2 (14, R = H) by alkaline hydrolysis, but
the well-documented difficulty [6,8] of isolating
this compound as its phenylhydrazone, especially
on the small scale, impaired the yields (35%).
Mass Spectra
Under electron impact, cyclohexanol [23] and
cyclohexanone [24] as well as the inositols [25] are zoyl pair of compounds (5,15).
ring-cleaved, with the production of such fragments
The initial fragmentation stage of mixed acetyl-
as CH2=CH -CH =O H + [23] of CH2= C H -C = 0+ acylmyoinositols (16,17) provides the following
[24] from the former, and of HOCH=CH-CH=OH+ information (Scheme 1): The ion radical 17a of the
(m/z 73) from the latter [25]. In contrast, the pre- 2-acetyl-l,3,4,5,6-pentakisisovaleroyl derivative 17
sent myoinositol esters underwent a multi-stage undergoes simultaneous loss of an isovaleroyloxy-
fission, with prevailing retention of their alicyclic or acetoxy-moiety, yielding 17b and 17c respec-
ring structure: their base peaks correspond almost tively. The former is the greatly predominating fis-
invariably to the intact molecular ion, while subse- sion, 17b producing the base peak (compared with
quent prominent signals indicate the sequential re- a 15% abundance of 17c). In the 2,5-diacetyl-
moval of their peripheral substituents as acyl-or
acyloxy entities, or elimination of the elements of
1,3,4,6-tetrakispivaloyl compound 16, the acetyl
groups are again preferentially retained, favouring
n +
R9 ------ P R
- • CO M e
RO ____D R
RQ------ P R
M e C O O \ > +
-.O C O M e
----------------- M e C O O (
•O R
+*H
M eC O O <
RO
>OCOM e
O R
)0 C 0 M e
«— X----
hooO*R
RO
O R
RO
O R
R O
16h 499.2543 [53]
16a 600
16d 499.2909
16c 541 [37]
N a + 16a 623 [100]
O R“' 1+
R'O____
R'O ^
R'O
*
y O C O M e
OR'
R 'Q ------ P R ' - .O C O M e
- • O R
R = •C 0 C M e3
R' = . C O C H 2CHM e2
CO M e
RR'’°O v v
OR'
17a 642
Na + 17a 665 [17]
17c 583 [15]
Scheme 1.
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F. Kurzer-D. Chapman • The Oxidation of Partially Acylated Myoinositols
71
Table I. Correspondence
of ion fragments of acyl-
myoinositols (4,5) and
their 2-ketones (14,15).
4
14
5
15
Abundance
Abundance
Abundance
Abundance
m/z
m/z
m/z
m/z
623
607
539
521
499
483
415
397
313
211
100
7
621
605
537
519
497
481
413
395
311
209
70
4
723
619
601
579
481
100
3
721
617
599
577
479
45
9
18
12
20
22
13
58
7
22
7
2
8
6
13
6
100
5
14
38
34
38
4
11
the formation of 16 b. Its possible formulation as
16 d (C26H43O9, m/z 499.2909), which would arise specimen fragmentation scheme is tentatively pro-
from 16 a by loss of an acetoxy and acetyl frag-
ment, is excluded by high-resolution measurement representative pattern (Scheme 2). The spectrum
is dominated by the molecular ion 4 a, which pro-
On the basis of the foregoing considerations, a
posed for the pentakisisovaleroyl derivative 4 as a
of its exact mass (C25H 39O 10, found: m/z
499.2543). Provided that these observed effects are duces the base peak, and by species arising there-
not due to differences in the bulk of the acyl from by loss of an acyloxy or acyl radical, forming
groups concerned, they suggest a tendency for the
4d and 4 b, respectively. Subsequent comparable
preferred, though not exclusive, removal of the steps account for all the significant signals, finally
substituents from the sides rather than the apexes yielding Cn H 150 4+ formulated as the dihydroxy-
of the chair conformations.
isovaleroyl species 4 k. The molecular formulae of
-
OH
OX~| +
“ 1+
~]
XO-----
xo,— ox
XO,------,OX
Vo
xo— ox
•
+• H
xo
xo/
\oH
x o — OX
4a 600
Na +4a 623 [100]
X = COCH2CHMe2
Xo/
o
x o '— 'OX
4e 584 [32]
14a 598
Na +4e 607 [ 7]
Na + 14a 671 [70]
-
X
+• H
“ I+
XO/---> ' *
- OH
+•H
P t
OH
XO,
XO.---
--x o / \oH
xo,—+
xo^
xo---ox
,OH
-H20
XO
xo/
\oH -X
o
XO
OX
x o — OX
x o — OX
4C 498
4d 499.2907 [58]
4b 516
4f 483 [ 7]
Na +4b 539 [22]
Na + 4c 521 [13]
-X
H
■rf-
xo,
-X
+•H
XOn—t
*°/7—t
-HzO
,
-XOH
( / \ o h
OH
HO
1 3
OX
o;
Ö -
u
HO'——^
HO-----OX
4i 313 [4]
xo
xo
ox
4h 397 [8]
4g 415.2333 [22]
4k 211 [11]
xo^_^(-
XO„__ ,+
;=o
HÖ-----'OX
o
- oox
O »
HO'——^
XO ox
XO----
14i 311 [34]
14k 209 [38]
14h 395 [38]
14g 313 [ 4]
Scheme 2.
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F. Kurzer-D. Chapman • The Oxidation of Partially Acylated Myoinositols
72
The numerical data recorded refer to the proton
noise decoupled chemical shifts and first order
multiplicities of the individual signals. Chemical
shifts are given in d (ppm) downfield from SiMe4
as internal standard.
the key-intermediates 4d and 4 g (which feature
also significantly in the mass spectra of 3, 12 and
17) were confirmed by measurement of their accu-
rate masses. The ketone 14 corresponding to 4 un-
dergoes a precisely parallel degradation, the last
four stages of which (14g-14k, formed inciden-
tally in greater abundance than 4g-4k ), are in-
cluded in Scheme 2 for comparison.
1,3,4,6-Tetrakispivaloylmyoinositol (3)
A stirred solution of myoinositol (3.6 g, 0.02
mol) and 4-dimethylaminopyridine (0.3 g) in pyri-
dine (80 ml), preheated to 90 °C, was treated drop-
wise during 1 h with pivaloyl chloride (28.9 g, 0.24
mol; ca. 20 drops/min), the mixture being kept at
90-95 °C by heating as necessary. Stirring at this
temperature was continued for 1 h, and the reac-
tion mixture containing crystalline solid added to
The proposed scheme accounts satisfactorily for
the salient features of the fragmentation process.
With the reservation that the adopted position iso-
merism of the structures may be subject to minor
modification, it may serve as model for con-
structing analogous schemes for the other com-
pounds of the series, from the numerical data and
assignments recorded in the Experimental Part.
It is noteworthy that the proposed fragmenta-
tion schemes for the acylmyoinositols share their
essential characteristics with those of monosaccha-
ride esters [26]. In particular, the degradation of
peracetylpyranoses [27, 28] and analogues [29] is
characterized by the rapid loss of acetyl and ace-
toxy moieties, as well as acetic acid, with marked
initial retention of the cyclic structure [27]; how-
ever, the pyranose nucleus appears to undergo sig-
nificant parallel and subsequent ring fission
[27, 28] that is not prominent in the homocyclic
acylmyoinositol structure.
ice (350 g)
-
concentrated hydrochloric acid
(80 ml). The precipitated oil was extracted with
ether, the ethereal extracts washed with M sodium
hydroxide (removal of pivaloic acid) and with
water to neutrality. Removal of the ether gave a
crystalline solid enveloped in a resin. Dissolution
in boiling ethanol (30 + 20 + 10 ml) deposited mi-
crocrystalline 3, m.p. 260-264 °C (sintering from
250 °C, somewhat rate-dependent) (3.8-4.6g,
35-42%).
C26H44O™ (516.6)
Calcd
Found C 60.8
C 60.45 H 8.6%,
H8.7% M 516.
IR: 3500 vs (OH), 3000, 2980 vs, 1490 vs, 1480
ms (CH3, CH2), 1745-1720 vs vbr (C =0 ester),
1405 s, 1375 s (CMe3), 1295-1280 vs, 1180-1135
vs mult (C -O ester), 1235 m, 1040 s, 1010 m cm-1.
m/z: 1056 [7] (Mx2 + 23,Na + l), 539 [100]
(M+ +23), 540 [28] (corresp. to C26), 516 [45] (M),
500 [28] (M-17, OH + 1, H), 438 [17] (M + 23-101,
Me3C.COO), 432 [10] (M-85, Me3C.CO + l);
415.2337 [47] (C21H350 8, M-101), 399 [5] (500-
101 or 415-17 + 1), 348 [6] (M-2x85 + 2 x l), 331
[20] (415-85 + 1), 247 [5] (415-2x85 + 2x1), 211
[4] (331-102, Me3C.COOH - 18,H20 ).
13C NMR: 176.7 s, 176.3 s (CO at C-1,3 and C-
4,6); 71.4 d, 71.2 d (double relative intensity; CH
respectively of C-1,3 and C-4,6, ring); 69.5 d, 66.6
d (CH respectively of C-5 and C-2, ring); 38.2 s,
38.1 s (C of Me3C at C-1,3 and C-4,6 or vice versa);
26.9 q, 26.7 q (Me3 of Me3C at C-1,3 and C-4,6 or
vice versa).
Experimental
Melting points are uncorrected. Light petroleum
had b.p. 60-80 °C. Analysis specimens were desol-
vated at 100-120 °C in a vacuum for 2 -4 h, if
necessary.
Infrared spectra were measured on a Unicam
1000 instrument, using KBr discs. Unassigned
peaks are not recorded except for selected com-
pounds (3, 13, 5, 15).
Mass spectra were determined using a VG-
ZAB-2F instrument operating at 70 eV. Numbers
in square brackets denote the intensity of the
peaks relative to the base peak [100]. Molecular
formulae were confirmed and ion fragments iden-
tified, in appropriate cases, by the determination
of accurate molecular weights by the fast atom
bombardment technique, involving the use of a 3-
methylnitrobenzene-sodium matrix.
13C NMR spectra were determined on a Bruker
WM 250 Fourier transform instrument equipped
with an Aspect 3000 data system, at 62.89 MHz.
The solvent was deuterio-dimethyl sulphoxide.
2,5-Bisacetyl-l,3,4,6-tetrakispivaloylmyoinositol
(16)
A stirred suspension of 3 (0.52 g, 0.001 mol) and
anhydrous zinc chloride (1 g) in acetic anhydride
(12 ml) was kept at 75-80 °C for 45 min, its colour
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73
F. Kurzer-D. Chapman • The Oxidation of Partially Acylated Myoinositols
yellow microneedles, m.p. 208-210 °C (decomp)
changing gradually to dark brown. It was
quenched with water (50 ml) and stirred, when the (from ethanol).
precipitated oil changed to a pale brown solid
C32H46N40 13 (694.75)
(0.52 g, 87%), yielding 16 as microprisms, m.p.
296-300 °C (from acetone - ethanol).
Calcd C 55.3 H 6.7 N8.1%,
Found C 55.6 H 6.6 N 7.8%.
C3oH48O l2 (600.7)
Calcd
C 60.0 H 8.05% M 623.3043 (incldg. Na)
Tetrakis-1,3,4,6- (2) and tris-1,3,4-
isobutyrylmyoinositol
Found C 60.6 H 8.2% M 623.3040
IR: 3460 m blunt (H20 ); 2990 vs, 2950 s sh, 2880
m sh, 1485 vs, 1470 s (CH3,CH 2); 1770-1750 vs
(C=0); 1400 s, 1375 vs (CMe3), 1285 vs, 1240-
1215 vs mult (C -O ), 1175-1140 vvs mult, 1040 vs
cm-1.
m/z: 623 [100] (M+ +23,Na), 624 [33] (C30), 581
[4] (M + 23-43, MeCO + 1,H), 541 [37] (M-59,
MeCOO), 521 [4] (M + 23-102, Me3C.COOH),
499 [52] (M -101, Me3COO), 499.2543 (for
C25H 39O 10), 457 [12] (499-43 + 1), 415 [26] (457-
43 + 1), 415.2333 (for C21H3S0 8), 373 [6] (457-85,
Me3C.CO + l), 289 [18] (373-85 + 1), 211 [9]
(415-2x102).
To a stirred solution of 1 (1.80 g, 0.01 mol) and
4-dimethylaminopyridine (0.2 g) in pyridine (45
ml), isobutyryl chloride (6.4 g, 0.06 mol) was
added dropwise at 80-85 °C over 45 min. The liq-
uid, clearing after a temporary appearance of
resin, was set aside for 1 h, then stirred into ice -
concentrated hydrochloric acid (250 and 45 ml).
The precipitated viscous resin coagulated on stir-
ring, so that the turbid aqueous phase could be
decanted (AP, below). The resin was stirred with
fresh water, and disintegrated to a granular pre-
cipitate (1.4-1.6g, 30-35% ), which gave 2 as
microprisms, m.p. 168-172 °C (from ethanol -
light petroleum). - The turbid aqueous phase AP
deposited a granular precipitate, which was col-
lected within 1-2 h, and identified as 2 (ca. 5%)
(filtrate: F).
l,3,4,6-Tetrakispivaloylmyoinosose-2 (13)
To a stirred solution of 3 (1.63 g, 0.003 mol) in
glacial acetic acid (50 ml) at 90 °C, chromium-
(Vl)oxide (0.60 g, 0.006 mol, equivalent to 0.009
g.atoms available oxygen) was added. The mixture
was stirred at this temperature for 20 mins, the
oxidant dissolving gradually. The deep olivegreen
liquid was added to ice-water (150 ml) containing
sodium metabisulphite (l-2 g ). The resulting
finely divided precipitate gave, on crystallization
from acetone-ethanol (ca. 25 and 10 ml per g, and
partial evaporation), opaque microprisms of 13
(1.05-1.15 g, 70-75% ), m.p. 250-254 °C (sin-
tering and turning brown from 220 °C, decompos-
ing to a dark brown mass).
C22H36O 10 (460.5)
Calcd
C 57.4 H7.9% ,
Found C 57.8 H 8.0%.
IR: 3500-3350 vs with max. at 3480 (OH), 3000
vs, 2950 s sh, 2900 ms sh, 1480 s (CH3,CH2), 1770-
1720 vs (C=0 ester), 1400 s, 1360 s d (CMe2), 1280
vs (C -O ester), 1210-1070 vs vb mult, 980 m
(sharp) (the last the only difference from the IR
spectrum of the tris-compound).
m/z: 942 [7] (2xM + 23, Na-1), 483 [100]
(M+ +23), 484 [24] (C22), 443 [12] (M-17, OH), 413
[4] (M + 23-71, C3H7CO + l,H), 395 [7] (413-18,
H20 ), 373 [14] (443-71 + 1 or M-87, C3H7COO),
303 [2] (373-71 + 1), 285 [2] (377-88, C3H7COOH
or 303-18).
C26H42O 10 (514.6)
Calcd
C 60.7 H8.2% ,
Found C 60.3 H 8.6% M 514.
IR: 3480 ms (OH), 2995 vs, 2980 s sh, 2895 ms sh,
1490 s, 1470 ms (CH3,CH2), 1780 vs sh, 1760-1740
vs br (C=0 ester and ring), 1290-1280 vs, 1170-
1130 vvs mult (C -O ester), 1410 ms, 1375 ms br
(CMe3), 1040 s, 980 s, 900 m, 810 w, 765 m cm"1.
m/z 537 [100] (M+ +23,Na), 538 [29] (C26),
515 [25] (M + l), 497 [21] (M-17, OH), 435 [20]
(M + 23-102, Me3C.COOH), 413 [44] (M-101,
Me3C.COO), 329 [59] (413-85, Me3C.CO +1,H),
311 [20] (329-18, H20, or 413-102), 227 [30]
(329-102), 209 [62] (311-102 or 227-18).
The aqueous filtrate F slowly deposited crystal-
line solid (0.6-0.7 g, 15-18% ), which gave opaque
white 1,3,4-trisisobutyrylmyoinositol, m.p. 200-
202 °C (from a little ethanol).
C18H30O9 (390.4)
Calcd C 55.4 H7.7%,
Found C 55.1 H7.7%.
IR: 3480 vs vbr (OH), 2995 s, 2960 ms sh, 2790
sh, 1480 s (CH3,CH2), 1760 s - 1735 vs (C=0
The 2',4'-dinitrophenylhydrazone of 13, ob- ester), 1390 s, 1360 s (CMe2), 1270 vs, 1225 s, 1205
tained (35%) as described for 14 (below) formed vs (C -O ester), 1170, 1165 vs d cm-1.
Unauthenticated
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74
F. Kurzer-D. Chapman • The Oxidation of Partially Acylated Myoinositols
m/z: 413 [100] (M+ +23, Na), 414 [19] (C18), 395 chloride (1 g) at 80-75 °C for 45 min and the dark
[7] (M + 23-18, H20 ), 373 [22] (M-17, OH), 343
[3] (M + 23-71, C3H7CO + l), 325 [7] (M + 23-88,
C3H7COOH), 303 [12] (373-71 + 1 or M-87,
C3H7COO), 285 [2] (303-18).
In this example, the molar proportion of
R.COC1 had to be kept low, since the usual large
excess (12 moles) under identical conditions pro-
duced the hexakis-derivative 11, m.p. 179-181 °C
(yield 90%). Lit. [17] m.p. 181 °C (For IR, m/z,
see below).
brown liquid added to warm water. The crystalline
precipitate gave prisms (0.41 g, 64%) of 17, m.p.
102-105 °C (from very little ethanol).
C33H540 12 (642.8)
Calcd
C 61.7 H8.5% ,
Found C 61.5 H8.7%.
IR: 3480 m br blunt (HzO), 2980 vs - 2900 s,
1475 s (CH3,CH2), 1775-1750 vs br (C=0, ester),
1375 vs (CMe2), 1230 vs, 1210-1160 vs mult,
1130-1100 vs br (C -O , ester) cm-1.
1,3,4,5,6-Pentakis-isovaleroylmyoinositol (4)
m/z: 665 [17] (M+ +23,Na), 666 [6] (C33), 583
[18] (M-59, MeCOO), 541 [100] (M-101,
C4H9COO), 542 [31] (C28), 499 [11] (541-43,
MeCO + l,H), 457 [25] (541-85, C4H9CO + l), 441
[2] (541-101 + 1), 415 [4] (457-43 + 1 or 499-
85 + 1), 399 [4] (499-101 + 1 or 441-43 +1), 331 [2]
(415-85 + 1), 313 [2] (415-102, C4H9COOH, or
331-18, H20 ), 211 [9] (313-102).
The use of isovaleroyl chloride (16.9 g, 0.14 mol)
in the procedure described for 3 above (temper-
ature kept at 95-90 °C for the first, and 90-85 °C
for the second half hour; stirring at 80 °C contin-
ued for 20 min) gave a pink to brown liquid which
was filled with a crystalline precipitate on cooling.
Its addition to ice-concentrated hydrochloric acid
produced a soft resin, converted on stirring with
fresh water to a buff granular solid (ca. 12 g). Its
solution in ethanol (30 ml) gave opaque micro-
prisms (6-6.5 g, 50-54% ) of 4, m.p. 200-202 °C
(sintering from 196 °C). Spontaneous evaporation
of the motherliquors gave a resin enveloping some
solid; preferential removal of the former with cold
ethanol gave more 4 (10-15%).
1,3,4,5,6-Pentakis-isovaleroylmyoinosose-2 (14)
A solution of 4 (2.4 g, 0.004 mol) in glacial acetic
acid (35 ml) was stirred at 85-80 °C with sus-
pended chromium(VI)oxide (0.67 g, 0.0067 mol;
0.01 g-atom of available oxygen), so as to crush
and gradually dissolve the oxidant. The brown liq-
uid was kept at 70 °C for another 15 min, allowed
to cool and stirred into water containing sodium
metabisulphite (1 g). The precipitated finely di-
vided solid (ca. 2 g) gave silky needles of 14 (yield
60%), m.p. 118-124 °C (from ethanol).
C31H s2O n (600.8)
Calcd
C 62.0 H8.7% ,
Found C 61.9 H 8.7%.
IR: 3520 s vbr (OH), 2980 vs, 2880 ms, 1475 ms
(CH3,CH2), 1765-1740 vs vbr (C=0 ester), 1375
s (CMe2), 1300 vs, 1200, 1190, 1170 vs mult (C -O
ester) cm“1.
C31H50O n (598.7)
Calcd
C 62.2 H8.4% ,
Found C 62.7 H8.4%.
For m/z, see Table I and Scheme 2.
IR: 3450 ms br blunt (H20 ), 2970 vs, 2880 ms,
1475 s (CH3,CH2), 1780-1755 vs mult (C =0 ester
and ketone), 1380 ms (CMe2), 1205-1160 vs mult,
1125-1110 vs mult (C -O ester) cm-1.
13C NMR: 171.3 s, 171.0 s (double relative inten-
sity; CO at C-1,3 and C-4,6); 170.8 s (CO at
C-5); 70.7 d, 68.9 d (double relative intensity; CH
respectively of C-1,3 and C-4,6, ring); 70.1 d, 66.2 d
(CH respectively of C-5 and C-2, ring); 42.5 t, 42.3 t
(double relative intensity, CH2 of CH2CHMe2 at
C-1,3 and C-4,6 or vice versa); 42.2 t (CH2 at
C-5); 25.0 d, 24.9 d (double relative intensity, CH
of CH2CHMe2 at C-1,3 and C-4,6 or vice versa);
24.7 d (CH at C-5); 21.95 q. 21.9 q (double relative
intensity, CH3 of CH2CHMe2 at C-1,3 and C-4,6
or vice versa); 22.0 q (CH3 of CH2CHMe2 at C-5).
For m/z, see Table I and Scheme 2.
To a boiling solution of 14 (0.30 g, 0.0005 mol)
in ethanol (15 ml) 2,4-dinitrophenylhydrazine
(0.12 g, 0.0006 mol) was added, followed by con-
centrated hydrochloric acid (6 drops), and boiling
of the resulting orange solution continued for 5
min. The yellow solid (0.35 g) which separated
slowly gave bright-yellow needles of the 2',4'-dini-
trophenylhydrazone o f 14, m.p. 192-196 °C (de-
comp) (from ethanol).
2-Acetyl-1,3,4,5,6-pentakis-isovaleroylmyoinositol
(17)
C37H 54N40 , 4 (778.8)
Calcd
C 57.05 H 7.0 N 7.2%,
A solution of 4 (0.60 g, 0.001 mol) in acetic an-
Found C 56.9
H7.1 N 6.9%.
hydride (15 ml) was stirred with anhydrous zinc
Unauthenticated
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F. Kurzer-D. Chapman • The Oxidation of Partially Acylated Myoinositols
75
Myoinosose-2 (14, R = H)
m/z 539 [48] (M+ +23,Na), 540 [13] (C24), 465
[5] (M + 23-74, C2H5COOH), 443 [100] (M-73,
C2H5COO), 444 [23] (C21), 387 [18] (M-73-57,
C2H5CO + l,H), 331 [4] (M -73-2x57 + 2), 313 [5]
(387-74 or 331-18, HzO), 257 [4] (313-57 + 1),
239 [14] (313-74), 183 [25] (239-57 + 1).
The foregoing penta-acyl ketone 14 (1.8 g, 0.003
mol), dissolved in ethanol (25 ml), was treated
with a solution of sodium (0.46 g, 0.02 g-atom) in
methanol (20 ml) and boiled under reflux for 1 h.
The solution was distilled to small volume (ca. 10
ml), diluted with water (10 ml), acidified with 5 M
hydrochloric acid, and extracted with ether (re-
moval of isovaleric acid). The aqueous phase was
again concentrated (to 12-15 ml), and gave, on
addition of glacial acetic acid (2 ml) and phenylhy-
drazine (0.75 g) and immediate chilling and stir-
ring, myoinosose-2 phenylhydrazone, m.p. 172-
175 °C (decomp) (0.28 g, 35%). Lit. [6,8] m.p.
174-176 °C.
Hexakis-n-butyrylmyoinositol.
-
(12 moles
RCOCI, 60-70 °C, addition 1.5 h, stirring at ambi-
ent temperature, 1.5 h, yield 17%), m.p. 88-92 °C
(from ethanol-light petroleum). Lit. [17] m.p.
81 °C.
IR: 3500-3420 ms br (H20 ), 2980 vs, 2940 s sh,
2890 s, 1470 s (CH3, CH2), 1770-1745 vs (C=0
ester), 1255 s, 1200-1160 vs mult (C -O ester),
1390-1345 s mult, 1110 vs-1090 s br cm-1.
m/z 623 [20] (M+ +23, Na), 624 [6] (C30), 535 [2]
(M + 23-88, C3H7COOH), 513 [100] (M-87,
C3H 7COO), 514 [28] (C26), 443 [29] (M-87-71,
C3H7CO + l,H), 373 [7] (M -87-2x71 + 2), 355 [5]
(443-88 or 373-18, H20 ), 285 [3] (373-88), 267
[14] (355-88), 215 [2] (285-71 + 1), 197 [21] 267-
71 + 1), 127 [7] (197-71 + 1), 109 [7] (197-88 or
127-18).
C12H 16N20 5 (268.2)
Calcd
N 10.45%,
Found N 10.2 %.
1,2,3,4,5,6-Hexakis-acylmyoinositols
The use, in the foregoing catalyzed procedure,
of acyl chlorides terminating in smaller acyl groups
resulted exclusively in hexakisacyl derivatives in
variably moderate yields. Each of the following
known [17] compounds had the correct percent-
age composition.
Hexakis-isobutyrylmyoinositol (11). For prepa-
ration, see 2, above.
IR: 2990 vs, 2945 s sh, 2890 m sh, 1485 s
(CH3,CH2), 1775-1740 vs (C =0 ester), 1395 s,
1355 s (CMe2), 1260 s, 1200 vs br (C -O ester),
1170-1120 vbr mult cm-1.
m/z 623 [54] (M+ +23,Na), 624 [18] (C30), 553
[12] (M + 23-71, /-C3H7CO + l,H ), 513 [100]
(M-87, /-C3H7COO), 514 [28] (C26), 443 [28] (M-
71-87 + 1), 427 [4] (443-17, OH + 1), 373 [5] (M-
87-2x71+2), 355 [4] (443-88, /-C3H7COOH or
373-18, H20 ), 267 [9] (373-88).
Hexakisacetylmyoinositol (9).
-
(12 moles
RCOCI, 40-50 °C, 1+3 h, yield 40%), m.p. 214-
216 °C (from ethanol), Lit. [17] m.p. 212 °C.
IR: 3480 s (H20 ), 3000, 2980 w d, 1445 m (CH3),
1785-1745 vs br (C=0 ester), 1250-1220 vs mult
(C -O ester), 1380 vs br, 1055 vs cm-1.
m/z: 455 [100] (M+ +23,Na), 456 [20] (C18), 413
[8] (M + 23-43, CH3CO + l,H ), 395 [7] (M + 23-
60, CH3COOH), 373 [8] (M-59, CH3COO), 353 [3]
(413-60), 331 [3] (373-43 + 1), 271 [2] (373-60),
211 [4] (271-60).
13C NMR: 169.7 s, 169.1 s (CO at C-2 and C-5);
169.3 s, 169.2 s (double relative intensity, CO at C-
1.3 and C-4,6); 70.0 d, 67.6 d (CH respectively of
C-5 and C-2, ring); 68.9 d, 68.1 d (double relative
intensity, CH respectively of C-1,3 and C-4,6,
ring); 20.3 q, 20.1 q (CH3 at C-2 and C-5); 20.25 q,
20.2 q (double relative intensity, CH3 at C-1,3 and
C-4,6).
Hexakis-ethoxycarbonylmyoinositol (8 ). - (12
moles EtOOC.Cl, 20-30 °C for 15 min, room tem-
perature 1 h, yield 12%), m.p. 114-116 °C (from
ethanol-light petroleum). Lit. [30] m.p. 131 —
135 °C.
IR: 3450 s br (H20 ), 3000 s, 2960 m sh, 1485 ms,
1455 ms (CH3,CH2), 1785-1730 vs mult
(C=0 ester), 1320-1240 vs mult (C -O ester),
1385 vs cm-1.
Hexakispropionylmyoinositol (10). - (12 moles
RCOCI, 60-65 °C, 1.5 + 1 h, yield 47%), m.p. 112-
113 °C (from ethanol - light petroleum); Lit. [17]
m.p. 100 °C.
m/z 635 [45] (M+ +23,Na), 636 [12] (C24), 563
[100] (635-73, COOEt+ 1,H), 564 [23] (C21), 523
[8] (540, M-73 + l-17,O H ), 491 [4] (563-73 + 1),
473 [8] (491-18, H20 ), 451 [7] (523-73 + 1 or 468,
IR: 3500-3400 s br (H20 ), 3000 vs, 2860 s, 2800 M -2x72-17), 385 [5] (473-89, EtOOC.O + 1), 361
[3] (451-90, EtOOC.OH), 289 [3] (361-73 + 1),
199 [4] (289-90), 109 [26] (199-90).
m sh, 1470 s (CH3,CH2), 1780-1750 vs (C=0
ester), 1210-1160 vs mult (C -O ester), 1090 vs,
1070 s cm-1.
Unauthenticated
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76
F. Kurzer-D. Chapman • The Oxidation of Partially Acylated Myoinositols
1.2.3.4.5.6-Hexakispivaloylmyoinositol (12)
260 °C (sintering from ca. 245, clearing at 270 °C,
somewhat rate-dependent) (total 11.2-11.9 g, 80-
85%, lustrous prisms, disintegrating to a white
opaque powder on drying).
A suspension of 1 (1.80 g, 0.01 mol) and anhy-
drous zinc chloride (2 g) in pivaloyl chloride
(14.5 g, 0.12 mol) was boiled under reflux for 1.5 h.
The resulting suspended sponge-like yellow mass,
nearly solidifying on cooling, was taken up in suc-
cessive portions of ether (with addition of M-hy-
drochloric acid, removal of zinc salt), the ethereal
layer washed with 1.5 M sodium hydroxide (re-
moval of pivaloic acid) and to neutrality with
water. Removal of the solvent gave 12 (3.1 g, 45%)
C4iH32O n (700.7)
Calcd
C 70.3 H4.6%,
Found C 70.4 H4.6%.
The compound is formed as a byproduct in the
production of the hexakis- [31], m.p. 269 °C and
1,3,4,5-tetrakisbenzoylmyoinositol [32], and by re-
as massive prisms, m.p. 228-232 °C (from etha- duction of the corresponding pentabenzoylino-
sose-2 [33], m.p. 260 °C.
nol). - More prolonged boiling (2.5 h) did not im-
prove yields, and caused some resinification.
IR: 3480-3420 s vbr (OH), 3080 w, 2980 w
(CH=), 1750-1730 vs d (C=0 ester), 1320 s sh,
1290-1250 vs vbr (C -O ester), 710 vs, 685 ms
(Ph), 1000 mw, 975 mw, 940 mw, 920 w (diagnostic
quartet), 1610 ms, 1590 m, 1500 mw, 1455 s, 1180
s, 1120-1090 vs mult, 1030 s cm-1.
m/z 723 [100] (M+ +23,Na), 724 [45] (C4i), 701
[2] (M + l), 683 [6] (M -O H ), 619 [3] (M + 23-105,
PhCO + 1,H), 601 [6] (M + 23-122, PhCOOH), 579
[13] (M-121, PhCOO), 560 [2] (M-122-18, H20 ),
481 [6] (601-121 + 1), 457 [7] (579-122), 438 [4]
(560-122), 334 [25] (438-105 + 1), 230 [16] (334-
105 + 1).
C36H60O 12 (684.9)
Calcd
C 63.1 H8.8% ,
Found C 63.6 H8.9% .
IR: 3480 w br (H20 ), 3000 vs, 2960 ms sh, 2890
m sh, 1485 vs, 1470 s sh (CH3,CH2), 1760-1715 vs
mult (C=0 ester), 1410 s, 1375 s d (CMe3), 1290
vs br (C -O ester), 1180-1120 vs mult cm l. The
IR spectra of 12 and 3 are almost identical except,
in the former, of a doublet at 920, 910 cm-1, and
the absence of the sharp hydroxyl absorption at
3500 cm-1.
m/z 707 [47] (M+ +23,Na), 708 [18] (C36), 623
[25] (M + 23-85, Me3C.CO + l,H), 605 [3]
(M + 23-102, Me3C.COOH), 583 [100] (M-101,
Me3C.COO), 584 [32] (C31), 516 [28] (M-
2x85 + 2), 499 [51] (516-17, OH or 583-85 + 1),
415.2333 [20] (C21H3,O s, 516-101), 397 [3] (415-
18, H20 ), 331 [7] (415-85 + 1), 313 [4] (331-18),
295 [12] (313-18), 247 [3] (331-85), 211 [17]
(313-102).
13C NMR: 165.3 s, 165.0 s (double relative inten-
sity, CO at C-1,3 and C-4,6 or vice versa), 164.9 s
(CO at C-5); 72.0 d, 70.6 (double relative intensity,
CH respectively of C-1,3 and 4,6), 71.1 d, 66.8 d
(CH respectively of C-5 and C-2); Aromatic sig-
nals: 133.7 d, 133.6 d (double relative intensity, C-
4' at C-1,3 and C-4,6 or vice versa), 133.8 d (C-4'
at C-5), 129.0 s, 128.6 s (double relative intensity,
C -l' at C-1,3 and C-4,6 or vice versa), 128.4 s (C-
V at C-5), 129.2 d, 128.9 d, 128.8 d, 128.75 d, 128.7
d, 128.6 d (collectively assigned to C-2' and C-3'
of pairs of Ph at C-1,3 and C-2,4 and Ph at C-5).
The use of smaller proportions of benzoyl chlo-
ride under more restrained conditions gave in each
case the same product 5 in diminished yields. - In
experiments employing 1 or 2 moles of benzoyl
chloride at 0-10 °C, the solid product was diben-
zoyl anhydride (80 or 90% on the basis of the ben-
zoyl chloride used), m.p. 38-40 °C (from ben-
zene - light petroleum).
Aromatic Series
1.3.4.5.6-Pentakisbenzoy[myoinositol (5)
To a stirred solution of 1 (3.6 g, 0.02 mol) and 4-
dimethylaminopyridine (0.2 g) in pyridine (40 ml),
benzoyl chloride (22.5 g, 0.16 mol) was added at
room temperature dropwise during 25-30 min.
The rising temperature was kept at ca. 50 °C by
external cooling. Stirring at room temperature was
continued for another 30 min and the resulting
paste treated with ice concentrated hydrochloric
acid (300 and 60 ml). The separated viscous mate-
rial hardened and broke up to white granules on
being stirred for 1-2 h. This was boiled with etha-
nol (80 ml, removal of benzoic acid) and the undis-
solved fraction (m.p. 248-252 °C, ca. 12.5 g, 90%)
crystallized from acetone - ethanol (250 and 100
ml), producing successive crops of 5, m.p. 256-
2-Acetyl-l,3,4,5,6-pentakisbenzoyImyoinositol (18)
This was prepared from 5 by the zinc chloride -
anhydride procedure (described for 17 above),
and formed opaque microprisms (95%) m.p. 256-
259 °C (from acetone - ethanol). Lit. [33] m.p.
166-167 °C.
Unauthenticated
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77
F. Kurzer-D. Chapman • The Oxidation of Partially Acylated Myoinositols
C 43H 34 0 12 (742.0)
Calcd C 69.5 H4.6%,
dition 10 min, further heating in this range for 20
min, continued stirring 30 min). The crude precipi-
tate gave, after extraction with 0.5 M sodium hy-
droxide and washing with hot water, an ivory pro-
duct (m.p. ca. 275 °C, 8.5 g, 92%). Crystallization
from nitrobenzene - ethanol (6 and 1 ml per g,
recovery 70%) gave 6, m.p. 278-285 °C (decomp.,
rate-dependent). Almost insoluble in the usual
solvents.
Found C 69.9 H4.6%.
IR: 3460 m vbr blunt (H20 ), 3080, 2990 w (CH3,
CH=), 1750-1730 vs (C =0 ester), 1320 ms, 1285
vs mult, 1230 ms (C -O ester), 710 vs, 690 ms (Ph),
1120-1095 vs mult cm-1 (almost identical with IR
of 5, but lacking the “diagnostic quartet”).
m/z 765 [100] (M+ +23,Na), 766 [47] (C43), 683
[28] (M-59, MeCOO), 621 [64] (M-121, PhCOO),
622 [26] (C36), 579 [6] (683-105, PhCO + l,H).
C4ih270 21N5 (925.7)
Calcd
C 53.2 H 2.9 N7.6%,
Found C 53.5 H 3.0 N8.0%.
1.3.4.5.6-Pentakisbenzoylmyoinosose-2 (15)
IR: 3460 s vbr (OH), 1760-1730 vs vbr (C=0
ester), 1545-1530 vs (arom. N 0 2, asym), 1360-
1345 vs, 1325 s (arom. N 0 2, sym), 1290-1250 vs
mult (C -O ester), 870 vs, 845 s (1,4-disub. Ar),
780 mw, 715 vs (Ar), 1125-1090 vs mult, 1015 s
cm-1.
A solution of 5 (1.05 g, 0.0015 mol) in glacial
acetic acid (35 ml) at 95 °C was stirred with chro-
mium(VI)oxide (0.15 g, 0.0015 mol, 0.0023 g-atom
O) for 20 min, the oxidant dissolving gradually.
The brown liquid was set aside for 30 min, then
stirred into ice water containing sodium metabisul-
phite (1 g). The finely divided precipitate (1.0 g,
95%, m.p. ca. 218-222 °C) was crystallized from
nitrobenzene - ethanol (5 ml each, recovery 90%)
or acetone - benzene (100 and 20 ml) giving felted
needles of 15, m.p. 218-224 °C. Very sparingly sol-
uble in ethanol, acetone.
1,3,4,5,6-Pentakis(p-bromobenzoyl)myoinositol (7)
was prepared as the foregoing example. The
crude product (4.9 g, 45%) gave 7 as a microcrys-
talline powder, m.p. 298-304 °C (decomp., rate
dependent) (from acetone - ethanol, 25 and 5 ml
per g, recovery 75%).
C4iH30O n (698.7)
Calcd
C 70.5 H 4.3% M 721.1686 (includg.Na),
C41H27Br5O n (1095.3)
Found C 71.0 H 4.5% M 721.1682.
Calcd
C 45.0 H2.5% ,
Found C 45.1 H2.5%.
IR: 3450 ms (HzO), 1780 ms sh (CO ring),
1750-1735 vs (C=0 ester), 1280-1270 vs vbr,
1120-1100 vs, 1075 vs (C -O ester), 710 vs, 690 m
(Ph), 3080 m, 2980, 2940 mw d, 1610 ms, 1590 m,
1460 ms, 1325 ms, 1185 ms, 1145 s sh, 1030 s, 975
ms, 665 w cm-1.
IR: 3460 s vbr (OH), 1750-1720 vs (C=0),
1290-1260 vs mult, 1180 s, 1120-1090 vs mult (C -
O), 850 s (1,4-disub Ar), 760 vs, 685 w (Ar), 1600
vs, 1020 vs cm-1.
m/z 721 [100] (M+'+23,Na), 722 [45] (C41), 617
[19] (M + 23-105, PhCO + l), 599 [38] (M + 23-
122, PhCOOH or 617-18, H20 ), 577 [26] (M-121,
PhCOO or 594, i.e. M-105 + 1, - 17 OH), 479 [45]
(599-121 + 1), 462 [90] (479-17).
Acknowledgements
We thank Mrs. J. E. Hawkes and Mr. J. Cobb,
of the University of London NMR Spectroscopy
Service at King’s College, London, for the pro-
duction of the 13C NMR spectra. We are also in-
debted to Dr. D. Carter, of the School of Phar-
1.3.4.5.6-Pentakis(p-nitrobenzoyl)myoinositol (6)
was obtained as 5 (0.01 molar scale), using p- macy, University of London, for performing the
nitrobenzoyl chloride (0.06 mol), at 60-70 °C (ad- mass spectrometric measurements.
Unauthenticated
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F. Kurzer-D. Chapman • The Oxidation of Partially Acylated Myoinositols
78
[1]T. Posternak: The Cyclitols, Holden-Day Inc., San
18 G. Höfle, W. Steglich, H. Vorbrüggen, Angew.
Chem., Int. Ed. Eng. 17, 569 (1978).
Francisco (1965);
a) p. 25. b) p. 151-156, c) p. 65.
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Unauthenticated
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