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O-Alkylnitrosoimmonium Salts a New Class of Compounds.

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comp. 169 to 173 "C, (recrystallized from a little glacial acetic
acid) explodes extremely violently on rapid heating.
Received, April 8th, 1963
[Z 490/316IE]
[l] Communication No. XXI on Sulfur Heterocycles and their
Intermediates; Communication No. X X : R. Mayer and M .
Nitzschke, Chem. Ber., in the press.
[2] R. Spindt, D. Stevens, and W. Baldwin, J. Amer. chem. SOC.
73, 3693 (1951); P . Landis and L. Hamilton, J. org. Chemistry 25,
1742 (1960).
[3] F. Boberg, Angew. Chem. 72, 629 (1960).
[4] E. Klingsberg and A . Schreiber, J. Amer. chem. SOC.84, 2941
(1962).
Synthesis of D-Glucosamine-3-phosphate
By Prof. Dr. 0.Westphal and Dr. R. Stadtler [I]
Acetylation in pyridine/acetic anhydride produced a good
yield of crystalline tetraacetate, m. p. 148-150 "C (from
ethanol/ether).
High-voltage electrophoresis of (2) on paper between pH 3
and 8 showed it to be homogeneous and different from
glucosamine-6-phosphate. Degradation of (2) with periodate
[6] yielded ~-arabinose-2-phosphate(3), which behaved on
paper chromatography (ethanol/water/acetic acid, 80: 15: 5)
and in high voltage electrophoresis like the degradation
product of ~-glucose-3-phosphalc[7] and which was different
from ~-arabinose-3-phosphate(obtained by degradation of
~-glucose-4-phosphate
with periodate [7]) and from arabinose
5-phosphate [3]. In the Elson-Morgan test, (2) gives a significantly weaker color reaction as compared to free glucosamine (only about 30 %,; the intensity increases on further
hydrolysis).
Lambert and Zitliken [8] have also synthetized (2) independently by a similar route.
Received, April 24th, 1963
Chemisches Institut der Universitit Freiburg i. Br.
and Max-Planck-lnstitut fur Immunbiologie,
Freiburg-Zlhringen (Germany)
D-Glucosamine-4-phosphate has been identified as a unit in
the lipoid component (lipoid A) [2] of lipopolysaccharides
from Gram-negative bacteria (endotoxin complexes) [3]. Of
all the glucosamine phosphates, only the 6-phosphate had
previously been identified and synthetized [4], hence we
started work upon the synthesis of further glucosamine
phosphates and have first prepared the 3-phosphate(2). Benzyl
N-carbobenzoxyglucosaminide [5] was converted with benzaldehyde/ZnC12 into benzyl N-carbobenzoxy-4,6-O-benzylideneglucosaminide, and treatment of this with diphenylphosphonyl chloride in pyridine gave rise to benzyl Ncarbobenzoxy-3-diphenylphosphoryl - 4,6 - O - benzylideneglu cosaminide ( I ) in about 8 0 % yield. Chromatography on
silica gel with 2 % methanol in benzene gave two crystalline
fractions, one with [cr]3 = +37.5 O and m.p. 98 "C and the
other with [a]% = --39.0° and m.p. 125 "C (chiefly a- and pforms).
Without using strong acids, which displace the phosphoric
ester group from C-3 t o C-6, it was possible t o convert (1)
into (2) by hydrogenolysis. Compound ( I ) was first hydrogenated in ethanol at room temperature with Pd-black.
Water was then added up to 33 % (vol.) and hydrogenation continued at 50 "C and finally for 0.5 hour at 60 "C
after addition of acetic acid to a concentration of 40
The
resulting crude glucosamine-3-diphenylphosphate was hydrogenated in absolute alcohol with Pt-black at room temperature. Glucosamine-3-phosphate (2) was purified by
chromatography on cellulose powder with ethanollwater
(1 : 1). We obtained (2) in 25-30 % yield, calc. from ( I ) . It
was taken up in a very small amount of water, and the
solution treated with acetone. Needles of (2) crystallized out
in the cold, m.p. about 180°C (decomp.); [ M ] $ ' s +70 5'
(c = 0.03 in water), no mutarotation.
x.
*
IZ 488131518]
[l] Part of the Ph.D. thesis of R. Stadiler, Universitlt Freiburg,
1962.
[2] See for example 0. Westphnl, Ann. Inst. Pasteur 98, 789
(1960).
[3] A. Nowotny, A . Closse, 0. Ldderiiz, and 0. Westphal, unpublished observations: se- A . Closse Ph. D. Thesis, Universitlt
Freiburg, 1962.
[4] F. Maley and H . A . Laroy, J. Amer. chern. SOC.78,1393 (1956).
[5] K. Heyes and H . Paulsen, Chcm. Ber. 88, 188 (1955).
[6] R. Jeanloz and E. Forchielli, Helv. chim. Acta 33, 1690 (1960).
[7] P. Szabo and L. Szabo, J. chcni. SOC.(London) 3765 (1960).
[8] R. Lambert and F. Zilliken, Chem. Ber. (1963), in the press.
0-Alkylnitrosoimmonium Salts,
a New Class of Compounds
By Prof. Dr. S. Hiinig, Dr. L. Geldcrn [I]. and Dr. E. Lucke
Chemisches Institut deruniversit l t ~larburg/Lahn(Germany)
and Chemisches Institut der Unibersitlt Wiirzburg (Germany)
By analogy to the smooth 0-alkylation of N,N-dialkylreact with tricarboxamides [2], N,N-dialkyl-N-nitrosamines
ethyloxonium fluoroborate [3] in ethylene chloride, or with
methyl or ethyl iodide and silvcr perchlorate in nitromethane
t o give the immonium salt ( I ) by 0-alkylation. The salts
(3)-(8) exhibit a characteristic band at 1540- 1575 cm-1
which can be attributed to the mesonieric system in ( I ) . The
tautomeric form (2) is absent because there is no band
D
between 1600 and 1700 cm-1 (>C-Ns::
[4]) nor between
3050 and 3500 cm-1 (>N-H). Moreover, proton resonance
spectra show that ( 4 ) , ( 5 ) , and (7) have two equal niethylene
groups adjacent t o the hetcro nitrogen atom. The salts
dissolve without decomposition even in hydroxylic solvents
but evolve nitrogen in strong bases. Salt (4) consumes two
Table I . 0-Alkylnitrosoirnmonium salts
Infrared
0
(CHdzN N 0 - C z H s
BF$
36-39
1575
93
O-C~HS
BF4'
66-67
1570
97
O-CzH5
BF4"
@
(CH2)4NN-N
0
0
CIIO
II
I
( C H ~ ) J NN
505-51
1562
91
I
59-61
0-CH,
C104'
0
011
(C6Hs-CHz)zN
N 0 C2H1 BF40
0
(CaHs--CHz)2N- N 0 -CIl1 C104O 101-102
1560
92
1540 [a]
98
a
(IIO)zP-O-CII
104-
(CH2)sN N
IIC-OH
~
I
IIC-011
I
CHzOH
1540
196
13)
/ I
gew. Cliem. internat. Edit.
1
Vol. 2 (1963)
I No. 6
327
moles of hydrogen on hydrogenation with P t catalysts. NAminopyrrolidine and ethanol are formed, thereby establishing the 0-alkylation.
Received, M a y Znd, 1963
The Preparation of Trimethyl-silanolate
and -germanolate
By Dr. lngeborg Ruidisch and Prof. Dr. Max Schmidt
lnstitut fur Anorganische Chemie
der Universitit Marburg/Lahn (Germany)
A recent paper [I] has prompted us to report on investigations
concerning more advantageous preparations of (CH3)3SiOLi
( I ) a n d (CH3)3GeOLi (2). Cleavage of hexamethyldisiloxane
and hexamethyldigermoxane [2,3] proceeds readily and
quantitatively in diethyl ether t o yield MR4 and ( I ) o r (2).
+ LiR ->
RtMOLi
+ MR4 (R= CH3, M = Si or Ge)
Tetrahydrofuran impedes the isolation of the reaction product and leads t o impure compounds, viz. "colored" solutions
[ l ] of colorless ( I ) or (2). T h e loss of 50% M (as MR1) is
avoided by cleavage of dimethylDolysiloxanes and dimethylpolygermoxanes of any molecular weight, which in diethyl
ether leads t o quantitative yields of pure ( I ) o r (2) according
to the equation:
(RzMO),
+ x LiR + x R3MOLi (R = CH3, M = Si or G e )
These reactions can also be applied t o t h e analogous S [4]
and Se [51 compounds.
Compounds ( I ) and (2) are useful for the synthesis, not
only of (CH3)3SiOSn(C:H3)3 [6] and (CH&SiOGe(CH3)3 [7],
hut also of (CH3)3GeOSn(CH3)3 ( S ) , which cannot be
prepared otherwise [I1. Compound ( 3 ) is obtained quantitatively from (2) and trimethyl-chlorostannane as a colorless
liquid, b.p. 51 "Ci12 m m (identified by analysis a n d infrared
and N M R spectroscopy). As expected, (3) is attacked at the
Sn atom by organo-lithium compounds.
Received, May 3rd, 1963
By Dr. H. Schmidbaur and Dipl.-Chem. H. Hussek
[Z 495/320 IE]
[I] Results partly from the Diploma Thesis, Universitat Marburg, 1960.
[2] H. Meerwein, W . Florinn, N . Schdn, and G. S t o p p , Liebigs
Ann. Chem 641, 1 (1961 ).
[3] H . Meerwein et al., J. prakt. Chem. 147, 257 (1937); 154, 83
(1940).
[4] G. Opitz, H. Hellmrrnn, and H . W . Schubert, Liebigs Ann.
Chem. 623, I17 (1959).
R3MOMR3
Lithium Trimethylstannolate
[Z 497/319 IE]
[l] D . Seyferth and D. L. AIle~ton,Inorg. Chem. 2, 418 (1963).
[2] M . Schmidt and I . Ruidisch, Z. anorg. allg. Chem. 3 I 1 , 331
(I96 I).
[3] I. Ruidisch and M. Schmidt, Chem. Ber. 96, 821 (1963).
[4] I. Ruidisch and M. Schmidt, Chem. Ber., in the press.
[5] I . Ruidisch and M . Schmidt, J. rnetallorg. Chem., in the press.
[6] H. Schmidbnur and M. Schmidt, J . Amer. chem. Soc. 83,2963
(1 96 I ) .
[7] H. Schmidhour and M . Schmidt, Chem. Ber. 94, 1 I38 (1961).
lnstitut fur Anorganische Chemie
der Universitiit Marburg/Lahn (Germany)
Solutions in ether of LiCH3 react rapidly and quantitatively
with hexamethyldistannoxane at room temperature t o yield
tetramethyltin and lithium trimethylstannolate ( I ) [I].
(CH3)3SnOSn(CHd3 1 LiCH, + (CH3)4Sn
+ LiOSn(CHd3
(1)
Compound ( I ) is colorless, crystalline, very sensitive t o
moisture, and is slowly decomposed without melting on
heating t o 200°C in a sealed tube. I t is readily soluble in
organic solvents such as ether, benzene, cyclohexane, and
CC14; in benzene, it exists as the hexamer, as shown by
cryoscopic molecular-weight determinations. I t exhibits
characteristic bands in thc infrared spectrum (Nujol) at
,
and 8.41 E L (8CH3), and also at
3.35 and 3.45 p. ( v C H ~ )7.10
2.95 p. (pCH3). Its N M R spectrum (in CC14) shows only one
proton signal accompanicd by symmetrically arranged
"satellites" resulting from H-l3C, H-C-117Sn, a n d H-C-lI9Sn
coupling (T = 9.76 [ppm] against tetramethylsilane, JH-~3c
= 128, JH-I17Sn -= 54.0, J H - ~ ~ 9 S=
n 56.5 [cisec]).
Alkylstanno-siloxanes and -germoxanes, some of which have
been prepared in the past from alkylchlorostannanes and
alkali silanoxides or germanoxides [ I - 31, can be synthetized
from ( I ) and alkylchlorosilanes o r -germanes. In this way,
for example, (2) b.p. 48 40"C/1.5 mni is obtained in good
yield by the reaction:
(CH3)3SnOLi I- (CZHs)tSiCI + LiCl
+
(CH3)3SnOSi(C2H5)3 I41
(2)
Alkyldistannosiloxanes, such as (CH3)3SnOSi(CH<)2QSn(CH3)3(3),can now beobtainedforthefirsttiniefrom ( I ) and
(CIH3)2SiCIz. T h e structurc of (l), a colorless liquid b.p.
77"C/1 mm, was confirmed by analysis and infrared and
N M R spectroscopy ('1 = 10.12 [pprn] for (CH3)ZSi and
T~ = 9.62 [ppml for (Ct13)3Sn, J H - ~ i 7 S n= 54.7 [cisec],
J H- 1 1 9 =~: ~57.2 [q'sec]). These N M R data show marked
differences from the constants of analogous compounds such
as (CH3)jSiQSi(CH3)20Si(CH3)3 with T = 9.98 for (CH3)3Si,
and (CH3)3SnOSn(Ctf3)3 with r = 9.77 [pprn], J,-r.iC =
128.9, J H - ~ ~ 7 S=n 53.6, and . I H - ~ ~ 9 S =
n 56.0 [cisec]
Received, M a y 3rd, 1963
[Z 498/318 1El
[I] Cf. I . Ruidisch and M . Schmidt, Angew. Chem. 75, 575 (1963);
Angew. Chem. internat. Edit. 2, 328 (1963).
[2] H . Schmidbnur and M . S d ~ m i d tChem.
,
Ber. 94, 1138 (1961).
[3] H . Schmidbnur and M . Sc,hniidt, J. Amer. chem. Soc. 84, I069
(1962).
[4] NMR speclrum: (CH,),Sn: T 9.60 [ppm], J H - ~ ~ c- 129.3
57.2. (CZH5)jSi: AjBz
[c/sec], J H - I ~ ~ S , , 54.3, Jii-119sn
problem with J / A T 0.269. T C H ~ 9.05 [ppml, s C H 2 - . 9.54
8.0 [cisec]. (Measured in CC14; c
5'%,
[ppm], JHCCH
60 Mcps, 23 "C, tetramethylsilane as intcrnal standard).
~
Angew. Chem. intarnnt. Edit.
Val. 2 (1963) I No. 6
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