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On the Synthesis of myo-Inositol from Glucose. Condensation of Nitromethane with Dialdehydes (II)

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KNH2 in 100 cm3 solution. Hunt and Boncyk [ 3 ] found the
solubility of KNH2 at +25 "C to be 3.6 g in 100 g of NH3. We
have developed an apparatus for measuring solubilities in
liquefied gases, which will be described elsewhere and which
enables us to investigate not only the solubility diagram over
a wide range of temperature but also any precipitates formed
with only a single initial weighing. For the system KNHz/NH3,
we found the stable precipitate below -42 "C to be KNH2.2
NH3, in agreement with Juza and Mehne [4]. Above this
temperature, we obtained KNH2.NH3 as cubic crystals of
about 3 mm diameter. On slight supercooling below -42 "C,
the monoammoniate, which is metastable under these conditions, is formed instead of the platelet-shaped crystals of the
diammoniate; it proved possible to measure the solubility of
the former. At approximately -50 "C, the system then undergoes a transition with copious separation of the stable diammoniate. The diagram and some numerical results illustrate
the different solubilities and show that Franklin's value is in
good agreement with our findings. All values are quoted in g
of KNH2 per 100 g of NH,.
7
do
/
/"
.O
Em
-32.4
-39.1
-42.2
42.5
43.5
44.1
45.2
46.5
47.1
-50.5
t-
65.8
54.0
49.2
44.3
46.9
32.5
28.9
45.5
43 4
23.6
39.1
Received, October 15th, 1962
[Z3741196 I€]
[I] C. A. Kraus, J. Amer. chem. SOC. 30, 1336 (1908).
[2] E. C. Franklin, Z. Physik. Chem. 69, 290 (1909).
[3] H . Hunt and L . Boncyk, J. Amer. chem. SOC.55, 3529 (1933).
[4] R. Juza and A . Mehne, Z. Anorg. allg. Chem. 299,41 (1959).
On the Synthesis of myo-Inositol from Glucose
pounds, which can be separated easily via the pentaacetates
111 (20 % yield, based on I) and 1V [5]. Since I11 can be
converted into myo-inositol in 55 % yield [6], 2 - W - m y o inositol, which is required for biochemical studies, can be
prepared from I by cyclization with 14C-nitromethane in an
overall yield of 10.6 %.
UH
&cHD
1.HGNOdNaOH
OAc
OAc
I1
111
IV
Sirupy 1,2-isopropylidene-xylo-trihydroxyglutardi~dehyde,
obtained by periodation [7] of 120 g of I, was dissoIved in
800 ml of 0.1 N H2S04 and kept at 100 "C for one hour. The
hot solution was adjusted to pH 5 by addition of powdered
Ba(OHI2, filtered with charcoal, and adjusted to pH 10-11
with 1 N NaOH after addition of 10 ml of nitromethane.
After 10 hours a t room temperature, the solution was neutralized with Amberlite IR-120 (H+-form) and evaporated to
dryness in vacuo. The resulting residue was extracted with
dioxan in a Soxhlet-apparatus for 12 hours, the content of
the thimble being pulverized after 6 hours. The dioxan was
evaporated off in vocuo, and the remaining crystalline mass
was dissolved in a mixture of 200 ml of acetic anhydride and
10 ml of conc. HzSO4 by heating to 60 *C for 3 minutes. On
cooling, a precipitate formed, which was filtered with suction
and recrystallized from a little dioxan; yield: 41.3 g of 111
(18.1 %, based on I); m.p. 254-256 "C (lit. [8]: 254-256 "C).
The mother-liquor remaining after isolation of 111was stirred
into ice-water, and the resulting precipitate was recrystallized
from ethanol, giving 6.15 g of IV (2.7 %, based on I); m.p.
173-176°C (lit. [8]: 174-176OC). The yield of 111 can be
raised to 20 % by repeated conversion of JV into 111 through
the following steps: deacetylation of IV [Sl, isomerization of
the 1-deoxy-1-nitro-myo-inositolformed with NaOH to a
mixture of the scyllo- and myo-1-isomers, and reacetylation
(yield: 31 %).
Received, October 18th. 1962 [Z 3811197 E l
[l] 1st Communication: F. W. Lichtenthaler, Chem. Ber. 96, in
the press.
121 H . H. Baer and H. 0 .L. Fischer, J. Amer. chem. SOC.81, 5184
(1959); 82,3709 (1960); H. H. Baer, Chem. Ber. 93,2865 (1960);
J. Amer. chern. SOC.83, 1882 (1961); 84, 83 (1962); A . C. Richardson and H. 0. L. Fischer, ibid. 83, 1132 (1961); A . C. Richardson, J. chem. SOC.(London) 1962, 2499, 2758; F. W. Lichtenthaler and H. O.L. Fischer, J. Amer. chem. SOC.83,2005 (19611.
[3] In solution, I1 presumably has a cyclic hemialdal structure:
R. D. Guthrie, Adv. Carbohydrate Chem. 16, 105 (1961).
[4] K. Iwadare, Bull. chem. SOC.Japan 16,40 (1941); Chem. Zbl.
1942, I, 1753.
151 Starting from I, J. M. Grosheintz and H . 0. L. Fischer, J.
Amer. chern. SOC.70, 1476, 1479 (1961), obtained similar mixtures by stepwise condensation with nitromethane (see also 181).
[6] G. J . Drummond, J. N . Aronson, and L. Anderson, J. org.
Chemistry 26, 1601 (1961); T . Posternak, W. H . Schopfer and
R. Huguenin, Helv. chirn. Acta 40,1875 (1957).
[7] R. Schaffer and H . S. Isbell, J. Res. nat. Bur. Standards 56,
191 (1956).
[8] F. W. Lichtenthaler, Chem. Ber. 94, 3071 (1961).
CondensationofNitromethane with Dialdehydes @I) [11
By Dr. F. W. Lichtenthaler
Institut fur Organische Chemie
der Technischen Hochschule Darmstadt (Germany)
On application of the dialdehyde/nitromethane cyclization
[1,21 to xylo-trihydroxyglutardialdehyde(11) [3], prepared
from ~,2-isopropylidene-ct-~-glucofuranose
(I) [4], a mixture
of scyllo- and myo-1-deoxynitroinositolis obtained alongside traces of the rnuco-3-isomer upon condensation with
barium hydroxide. With sodium hydroxide, I1 cyciizes
exclusively to give a mixture of the scyllo- and myo-l-com-
662
Synthesis of Oxazole
By Prof. Dr. H. Bredereck and R. Banged
Institut fiir Organische Chemie und Organisch-chemische
Technologie der Technischen Hochschule Stuttgart (Germany)
Oxazole was first prepared by J. W.Cornforth and R. H . Cornforth [l]. We now report briefly on a relatively simple
synthesis.
On heating with formamide at 100-12OoC, hydroxyketosuccinic ester (I) and its isomeric enediols [2] afford .4,5Angew. Chem. internat. Edit. 1 Vol. 1 (1962)
1No. 12
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myo, synthesis, condensation, inositol, dialdehyde, nitromethane, glucose
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