close

Вход

Забыли?

вход по аккаунту

?

From the Dilithiooctamethylcyclotetrasilazane to the 1 3 5 7-Tetraaza-2 4 6 8 9-pentasilabicyclo[3.3

код для вставкиСкачать
”P-NMR (DICOD): 6 = 15.0 (q, J = 9 2 Hz). “B-NMR (D3COD): 6= -53.5
(9. J = 9 0 Hz). IR (KBr): 2492 c m - ’ (vBH).
Received: April 6, 1988 [Z 2695 IE]
German version: Angew. Chem. 100 (1988) 1135
[ I ] H. Schmidbaur, J . Organomet. Chem. 200 (1980) 287.
121 G. Miiller, U. Schubert, H. Schmidbaur, Chem. Ber. 112 (1979) 3302.
[3] H. Schmidbaur, H.-J. Fuller, G. Miiller, A. Frank, U.Schubert, Chem.
Ber. 112 ( I 979) 1448.
141 H. Schmidbaur, G. Muller, K . C. Dash, B. Milewski-Mahrla, Chem. Ber.
114 (1981) 441.
151 H. Schmidbaur, G. Miiller, Monaah. Chem. I 1 1 (1980) 1233.
[6] G. Muller, D. Neugebauer, W. Geike, F. H. Kohler, J. Pebler,
H. Schmidbaur, OrganometnNics 2 (1983) 257.
[7] H. Schmidbaur, E. Weiss, W. Graf, Organometallics 4 (1985) 1233.
181 H. Schmidbaur, S. Strunk, C. E. Zybill, Chem. Ber. 116 (1983) 3559.
191 Aldrich Chemical Co.
[lo] H. Schmidbaur, E. Weiss, G. Miiller, Synth. React. lnorg. Mef.-Org.
Chem. 15 (1985) 401,415.
[I I] G. Miiller, Dissertation, Technische Universitat Miinchen 1980.
M,=417.88; trigonal, space group P3 (No.
[I21 7 a - H 2 0 : CYHZ8BBr2P3.H20,
143), a=b=15.834(1), c=6.583(1).&, 2 = 3 , p,,,,,=1.456
g cm-’,
@(MoKn)=44.5 cm-’, T=22”C. 4586 unique reflections, 3218 “obA-’,
served” with F024.0a(Fo) ( + h , + k , ‘1, (sin8/A),,,=0.659
Enraf-Nonius CAD4, MoKo radiation, 1=0.71069
Lp and absorption correction, solution by Patterson methods (SHELXS-86); R (R,) =
0.041 (0.031), w = I/u2(Fo)(anisotropic, CH3 as rigid groups, H on B
constant, SHELX-76). Apr,”= + O m -0.88 e/A3 1151.
[I31 H. Schmidbaur, W. Wolfsberger, Synrh. React. Inorg. Met.-Org. Chem. 4
(1974) 149.
[I41 l l a . C,lH20BBr2P,, M,=423.89, orthorhombic, space group P2,2,2,
(NO. 19), 0=9.280(1), b = 14.954(2), C = 12.915(2) 2=4,p,,,,,= 1.571 g
cm-’, p(MoKa)=47.2 cm-’, T = -40°C. 2766 unique reflections, 2380
“observed” with F 0 2 4 . 0 ~ ( F 0()+ h , + k , ‘1, (sin8/A),,,=0.572
A-‘,
Syntex P2,). Data correction and structure solution as for 7 a . H 2 0 1121.
R (R,)=0.061 (0.059). w = l / 0 2 ( F o ) .Apt,.= +2.78/- 1.40 e/A3 1151.
[I 51 The absolute configuration of 7 a . H 2 0 and l l a was confirmed by refinement of the inverse set of coordinates. Further details of the crystal
structure investigation may be obtained from the Fachinforrnationszentrum Energie, Physik, Mathematik GmbH, D-75 14 Eggenstein-Leopoldshafen 2 (FRG), on quoting the despository number CSD-53250, the
names of the authors, and the journal citation.
l b have led to formation of isomeric six- and four-membered rings.14]
Assuming that l b isomerizes according to the same rules
as la,[’.’] we prepared the dilithium compound 2.@]An Xray structure analysis (single crystals grown from THF)
provided information about the ring size and the site of
second lithiation (Fig. 1).
I
>+- 2
(Me,Si-NH),
nBuLi
H
1/2
- 2 nBuH
lb
THF
L
2
12 12
A).
A,
From the Dilithiooctamethylcyclotetrasilazane
to the 1,3,5,7-Tetraaza-2,4,6,8,9pentasiIabicyclo[3.3.llnonane System**
By Kerstin Dippel, Uwe Klingebiel,* Mathias Noltemeyer,
Frank Pauer, and George M . Sheldrick
Dedicated to Professor Ulrich Wannagat on the occasion
of his 65th birthday
The ammonolysis of dichlorodimethylsilane leads to formation of the corresponding cyclotrisilazane l a and cyclotetrasilazane ib.[’-3’
n MezSiClz
+ 3 n NH3
--t
(Me,Si-NH),
+ 2 n NH,CI
la, n = 3
lb. n=4
Fig. 1 . Molecular structure of the dimer [212 of 2 in the crystal (symmetryindependent atoms indicated); symmetry 7. Selected bond lengths [pm] and
angles [“I: Sil-Nl 168.3(3), Nl-SiZ 168.6(2), Si2-N2 174.1(2), N2-Si3 175.5(3),
Si3-N3 168.7(2), N3-Si4 168.6(3), Si4-N4 174.4(2), N4-SiI 173.2(3), NI-Li2
195.0(6), N3-Lil 210.8(5), N3-Lila 215.6(6), NI-Lila 217.3(5), Li2-01
192.5(5), Li2-02 193.5(6); Sil-NI-Si2 135.6(1), Si2-NZ-Si3 130.6(2), Si3-N3Si4 130.3( I), Si4-N4-Sil 132.0(2), Nl-Lila-N3 144.7(3), N3-Lil-N3a 104.9(2),
Lil-N3-Lila 75.1(2).
2 crystallizes as the dimer [Z],. The eight-membered
rings are bound via a perpendicularly oriented planar,
symmetrical (LiN)’ four-membered ring. Lil and Lila are
not, however, located over the centroids of the eight-membered rings: Lila is nearer to N2 while Lil is nearer to
N2a; the distance is 241 pm in each case, whereas the distance between Lila and N4 and between Lil and N4a is
288 pm. Lila and Lil are each bound to two oppositely
disposed N atoms of an eight-membered ring, namely with
N1 and N3 and with N l a and N3a, respectively. The Li
atoms of the four-membered ring are thus threefold coordinated. Li2 and Li2a are each coordinated to two T H F
molecules. The (H)N-Si bonds are systematically 5-7 pm
longer than the (Li)N-Si bonds; this is consistent with ab
initio calculations[71on (H3Si)’NH (Si-N calcd. 176 pm)
and (H3Si)zNe (Si-N calcd. 165 pm).
2
The reaction behavior of the six-membered ring compound l a has recently been the subject of intensive studies.[21In contrast, no reactions of the eight-membered ring
compound l b with retention of the ring moiety[41 have
been reported since its first synthesis some forty years
ago.”] All attempts to carry out substitution reactions with
[*] Prof. Dr.
U.Klingebiel, K. Dippel, Dr. M. Noltemeyer,
0 VCH Verlagsgesellscha~mbH. 0-6940 Weinheim, 1988
i
PhSiF3
I
+ PhSiF3
LiF
-
H
/N\SiMe2
F Me?i
PhSi-N
F. Pauer, Prof. G. M. Sheldrick
Institut fur Anorganische Chemie der Universitat
Tammannstrasse 4, D-3400 Gottingen (FRG)
[**I This work was supported by the Deutsche Forschungsgemeinschaft and
the Fonds der Chemischen Industrie.
1074
+2
\
F
H
3
OS70-0833/88/08O8-1074 $ 02.50/0
4
Angew. Chem. Int. Ed. Engl. 27 (1988) No. 8
2 reacts with fluorosilanes, e.g. with F3SiC6H5, in the
molar ratio 1 2 to give disubstituted ("monomeric") products containing an eight-membered ring.[']
Reaction in the molar ratio 1 : 1 leads to a derivative 4 of
the novel bicyclic system 1,3,5,7-tetraaza-2,4,6,8,9-pentasilabicyclo[3.3.l]nonane (Fig. 2).l9] The N2-N4-Si2-Si3 and
N2-N4-Si4-Si 1 planes of the two six-membered rings are
inclined towards each other. N2, Sil, N1, Si4, and N 4 are
coplanar, whereas N3 of the second six-membered ring is
bent towards the bridging atom Si5, so that N3, Si2, N4,
Si5, N2, and Si3 form a tub-shaped moiety.
191 4 : m.p. 150°C. MS (F1 measurement): m / z 414 (100, M e ) : 'H N M R
(C6D6, TMS int.): 6=0.020, 0.022, 0.223, 0.225, 0.284, 0.286 (6 CH,),
0.470 ( ' 5 ~ ~ = 3 . Hz,
2 CHI), 0.472 ('JHF-3.2 Hz, CH,), 7.5 (CeHX); "C
NMR (COD,, TMS int.): 6=4.09, 6.34 (C-3, C-4, C-5, C-6). 6.46
1.0 Hz, C-I, C-7), 127.64, 129.86,
( 4 J c ~ = 6 . 1Hz, C-2, C-8), 7.83 ( 4 J c ~ =
134.31 ('JcP=2.l Hz), 137.94(2JcF=25.0 Hz, C,H,); "Si NMR(CDC13,
TMS int.): 6= -31.91 (Js,F=263.7 Hz, Si-5). -3.00 ('JSIF=4.7 Hz, Si-I,
Si-4), - 1.65 ('JSIF=1.7 Hz, Si-2, SI-3); space group Pc, a=909.6(2),
b = 1 1 10.1(2), c = 1659.8(3) pm, p= 137.96(2)", 2 = 2 , 1033 independent
reflections with F > 3 a ( F ) and 2%,,,=45"
(+21"C, M o d R=0.060
[lo].
[ I01 Further details of the crystal structure investigations are available on
request from the Fachinformationszentrum Energie, Physik, Mathematik GmbH, D-7514 Eggenstein-Leopoldshafen 2 (FRG), on quoting
the depository number CSD-52963, the names of the authors, and the
journal citation.
Azirineimine as a Structural Unit in the Side Chain
of a Hexofuranose""
By Wolfgang Meyer zu Reekendof* and Norbert Schultz
Fig. 2. Molecular structure of 3 in the crystal. Selected bond lengths [pm] and
angles ["I: Nl-SiI 174.7(15), SiI-N2 173.5(7), N2-Si3 175.3(7), Si3-N3
172.8(13), N3-Si2 172.8(7), Si2-N4 174.3(5), N4-Si4 175.8(8), Si4-NI
171.8(16), N2-Si5 173.2(13), Si5-N4 172.4(12), Si5-Fl 160.4(5); Sil-Nl-Si4
133.9(5), Si2-N3-Si3 127.1(5), Sil-N2-Si3 131.2(5), Sil-N2-SiS lll.5(6), Si3N2-Si5 107.5(4), Si2-N4-Si4 126.4(5), Si2-N4-Si5 108.9(6), Si4-N4-SiS
I10.8(4). N2-Si5-N4 106.1(5).
Experimental
A solution of l b (0.01 mol) in hexane (100 mL) was treated with 0.02 mol of
nC,H,Li ( IS% in hexane) in a three-necked flask fitted with an internal thermometer. For complete cleavage of butane, the sludge was heated under reflux for 2 h. T H F was then added until the lithium salt dissolved at the boiling temperature. 2 crystallized out at room temperature. For the synthesis of
3 and 4 the solution of 2 was cooled to -20°C. After slow dropwise addition of 0.02 mol and 0.01 mol of PhSiF,, respectively, the solutions were
warmed to room temperature for 2 h (I9F-NMR monitoring). After removal
of lithium fluoride, 3 and 4 crystallized out from the solutions: yields 4.5 g
(92%) 2, 4.8 g (84%) 3, 2.6 g (63%) 4 .
Received: March 7, 1988;
revised: April 13, 1988 [Z 2651 IEI
German version: Angew. Chem. 100 (1988) 1093
[ I ] S. D. Brewer, C. P. Haber, J . Am. Chem. Soc. 70 (1948) 3888.
121 U. Klingebiel, Nachr. Chem. Tech. Lab. 35 (1987) 1042.
[3] J. Haiduc, D. B. Sowerby: 7he Chemistry of Inorganic Homo- and
Heferocycles, Academic Press, London 1987.
141 W. Fink, Helv. Chim. Acra 52 (1969) 2261.
[ S ] W. Clegg, U. Klingebiel, G. M. Sheldrick, L. Skoda, N. Vater, Z . Naturforsch. 835 (1980) 1503. For the disubstitution, la is best dilithiated beforehand. Partial contraction of the six-membered ring is observed in
the stepwise disubstitution.
[61 2 : m.p. 130°C; "C NMR (THF, C,D,): 6=6.58, 9.17 (coalescence at
+SO°C,6=7.62); "Si NMR(THF, C6D6):6= -21.19;spacegroup Pi,
a = 1089.6(2), b = liiS.f(2), c= 1241.1(1) pm, a=79.02(1), 8=64.10(1),
y = 8 I .65( I)', 2 = 2 (the two molecules form a dimer [212 via a n inversion
center). 2878 independent reflections with F > 3 a ( F ) and 28,,,=45",
measured at -80°C with MaK, radiation, R=0.046 [lo].
[7] C. Glidewell, C. Thornson, J. Cornput. Chem. 3 (1982) 495.
IS] 3 . m.p. 125"C, MS (70 ev): m / z 561 (100, 1.44-CH,]"), 'H NMR
(CH2C12,TMS int.): 6=0.25 (5J,,,= 1.0 Hz, CH,), 7.35, 7.68 (C,H,); "C
NMR (CH2C12, C6D6, TMS int.): 6=4.93 (4Jc.F=1.9 Hz, Sic2), 128.54,
130.94 ('J,y=28.4 Hz), 131.71, 134.57 (33Jc~=
1.2 Hz, CGHS); " F N M R
(CH,Cl2, C6F6 int.): 6=36.6; 29Si NMR (CH2Cl2, C,D6, TMS int.):
6 = -47.42 (JClF=268.8Hz, SiPh), -5.72 (SiMe2).
Angew. Chem. Inr. Ed. Engl. 27 (1988) No. 8
A series of theoretical papers on the origin of life in the
universe consider reactions of hydrogen cyanide and its
derivatives. Azirineimine is discussed as a possible stable
intermediate in the formation of peptides from hydrogen
cyanide."' We obtained a derivative of this previously unknown compound in a completely surprising way.
All previous attempts to lengthen the chain of carbohydrates or to synthesize branched-chain compounds by
reaction of sulfonic acid esters with cyanides have failed
because the nucleophilicity of the cyanide ion is too low.
Only Grewe and Rockstroh12' were able to synthesize a
~-glucose-6-carbonitri~e
from 1,2-O-isopropylidene-6-O-ptoluenesulfonyl-a-D-glucofuranoseand KCN. However,
since this reaction proceeds via the 5,6-epoxide and therefore does not seem to be applicable to compounds without
neighboring hydroxy groups, we chose 1,2-O-isopropylidene-3,5,6-tri-O-p-toluenesulfonyl-cc-~-glucofuranose
113]
for experiments to investigate the reaction capability of the
sulfonic acid esters in more detail. Upon reaction of 1 with
K C N and tetrabutylammonium chloride in nitromethane/
water under phase-transfer conditions[41(2 d at 5OOC) and
subsequent chromatographic separation we obtained-besides some unchanged starting material, the hydrolysis
product 3, and difficultly isolable byproducts-a crystalline compound of the composition C,,H,,N,O,,S,
as the
main product (150/0), which proved to be the azirineimine
derivative 2.
A\
rO-N=C-C-C-N&
rOH
Ts = p-toluenesulfonyl.
[*] Prof. Dr. W. Meyer zu Reckendorf, Apotheker N. Schultz
Institut fur Pharmazeutische Chemie der Universitat
Hittorfstrasse 58-62, D-4400 Miinster (FRG)
[**I
We thank Dr. I . Lauterwein, Organisch-chemisches Institut der Universitat Miinster (FRG), for invaluable assistance in interpreting the nuclear resonance spectra; we thank the NMR-department for carrying out
the measurements.
0 VCH Verlagsgesellschafr mbH. 0-6940 Weinheim. 1988
0570-0833/88/0808-1075 $ 02.50/0
1075
Документ
Категория
Без категории
Просмотров
0
Размер файла
238 Кб
Теги
tetraaza, pentasilabicyclo, dilithiooctamethylcyclotetrasilazane
1/--страниц
Пожаловаться на содержимое документа