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Germylsiazanes and Stannylsilazanes.

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the hexatrieiie ( 3 h ) (A,,,
260, 251, 247 mp), which is
stable only in solution, but ( l a ) affords a sterically non-uniform dimer (m.p. 184-189 "C) and about 20-25
yield of a
monomeric photo-product, to which we assign the structure of dimethyl bicyclo[3.1 .O]hex-2-ene-I $dicarboxylate
(50) (only terminal absorption at 220 my, E = 1700, cyclopropane ring deformation bandat 1020cm-I, PMR spectrum:
H-1, H-2, H-3, and H-4 two triplets each at T = 3.98; 4.07 to
4.42; 4.51-6.61; 6.90-7.40; 7.69; J i z ~ 6 . 0c.P.s.; J 1 3 =
5 2 3 21 514
524
1.9 c.P.s.; for H-5 and H-6 a doublet each
at T = 7.58 and 9.18; J = 4.0 c.P.s.; arid the H3CO singlet at
T = 6.33). Tke diester ( S u ) can be converted into the dicarboxylic acid and the tricyclic anhydride (6). Irradiation of ( 1 u)
under conditions which preclude excitation of the chromophoric system in (40)has so far produced n3 evidence for the
occurrence of (4u) as an intermediate [3]. We must assume
that the rearrangement of the excited state of ( / a ) to ( S n )
occurs directly. It is significant that diazomethane is inactive
as a sensitizer for valence isomerisation of unsubstituted 1,3cyclohexadiene ( I a). As in the unsensitized irradiation, the
ring of ( I c ) is opened to give 1,3,5-hexatriene ( 3 c ) [4]. Possibly activation of the double bonds i n 1,3-cyclohexadiene by
electronegative substituents is a prerequisite for the sensitizing action of diazomethane.
-
Received, May 16th, 1963
[Z 5091340 IF,]
German version: Angew. Chem. 75, 639 (1963).
[l] H. Prinzbach and J. H . Hartenstein, Angew. Chem. 74, 651
(1962); Angew. Chem. internat. Edit. 1, 507 (1962).
[2] W. G. Dauhen and R . L. Cargill, Tetrahedron 12, 186 (1961).
[ 3 ] H . Prinzbach and H. Hngemann, unpublished work.
[4] D. H . R . Barton, Helv. chim. Acta 42, 2604 (1959); R. J.
deliock, N . G. Minnaurd, and E. Havinga, Rec. Trav. Chim. PaysBas 79, 922 (1960).
absorption spectrum in the visible and ultraviolet regions
(CHCI, solution) contains the following bands: 460 (700);
388 (5000); 312 (8500); 250 (12000) m p (mol. extinction coefficient in brackets). Application of MO-theory leads to a
term-level scheme indicated in Fig. I which shows the predicted stabilization of the b3g and 2blu duroquinone MO's
due to the interaction with the metal orbitals (cf: [lb]).
I n watcr, a furthcr bsnll a1 226 mil. (13 OW), which we
have tentativelq assigned to a Rd-z* (635H5) transition, is observed. The char;icteristic color o f ( I ) is larcely due to the
I l u i o(1~1itioiic~
Coriii)lex i n CHCI,
Fig. 1. Transitions in duroquinonc and duroquinone-cyclopentadienylcobalt (in CHCI3).
band at 460 mu (corresponding to the n-2bzp-transition in
free duroquinone) and thc band in the visible range at 388 m p
(charge-transfer transition). 'i'he high stability of ( I ) in comparison to that of olefin-duroquinone-nickel complexes is
largely attributable to the facl tlia: the latter compounds contain two electrons i n an antib:>iidingorbital, whereas in (/), all
the electrons participating in bonding can be accommodated
i n bonding, or pi-iictically non-bonding orbitals.
Received, May 20tl1, 1963
[Z 51 1/338 JE]
German veryion: Angew. Chem. 75, 641 (1963).
Duroquinone-Cyclopentadienyl-Cobalt [ 1I
By Priv.-Doz. Dr. G. N. Schrauzer and Dr. H. Thyret
lnstitut fur Anorganische Cheniie der Uiiiversitdt Miinchen
(Germany)
On heating duroquinone with cyclopentadienylcobalt dicarbonyl for several hours at 120 "C in a high-boiling solvent,
diamagnetic, red-brown duroquinone-cyclopentadienyl-cobalt ( I ) (decomp. 275 "C) is formed; this is the first x-complex
of t1.k transition metal with a quinone [2]. The compound is
very polar, hygroscopic, can be sublimed in vocuo, is only
sparingly soluble in the usual organic solvents, but is readily
soluble iii water. Its proton magnetic resonance spectra show
only two sharp signals, in CHC13 at 4.86 and 2.20 ppm, in
H20 at 5.10 and 2.12 ppm (at 60 Mc/s with tetramethylsilane
as external standard), with an intensity ratio of 5:12. The
carbonyl groups of ( I ) are protonated in strong acids; in
[I] a) Communication No. 7 011 Quinonen-Complexes of Metals.
b) Communication No. 6: G. N . Schrauzer and H. Thyret, Theoret.
chim. Acta (Berlin) I , 172 (1903).
[2] Analogous complexes of rhodium and iridium have been
prepared in the meantime by another route (experiments with
K . C. Dewhirst); these will be ilcscribcd in detail elsewhere.
[3] G. N . Schrauzer and H . T/i.vr(~t,
Z . Naturforschung 176, 73
(1962).
Germylsilazanes and Stannylsilazanes
By Dr. Otto Schcier and Prof. Dr. Max Schmidt
In\litut f u r Anorganische Chemie
der liniveisitat Marburg (Germany)
In dry organic solvents, trialkylchlorogermanes [l] and trialkylchlorostannanes react with 1,1,1,3,3,3-hexamethyldisihzdn-2-sodium ( I ) [2] according to the following equation
to give good yields of I , I , I ,3,3,3-hexamethyl-2-trimethylgermyldisilazaiie (2), m. p. 29 32 "C, b. p. 54--56 'C/l mm;
1,1,1,3,3,3-hexamethyl-2-trimethylstannyldisila~dne
(3), m. p.
20-22'C, b.p. 58-59'C/l nim; and 1,1,1,3,3,3-hexamethyl2-tri-n-butylstannyldisilazane ( 4 ) , b. p. 140--145 OC/l mm.
conc. H2S04, the proton resonance sigi.als occur at 6.02 and
2.72 ppm. The carbonyl absorption in the infrared of the duroquinone complex in KRr is split into two bands at 1563 and
1536 cm-1 (cf. duroquinone, 1629 cm-1; bis-duroquinonenickel(O), 1577 cm-1; duroquinone- 1,5-cyclooctadienylnickel, 1553 cm-1 [3]). This marked shift to longer wavelengths indicates significant interaction between the 2b2,-MO
of the duroquinone and a suitable 3d14p-orbital of the
cobalt atom.
Besides further duroquinone absorption bandq. the characteristic bands of the symmetrical CsHs-residue at 3086, 1433,
1124, 1026, 836/830 (doublet) cm-1 (KBr) are observed. The
478
[(CH3)3Si12NNa
(1)
+ CIM I<)
--+
[(CH,),Si]2N--MRs
(2) M
=
Ge, R
+ NaCl
= CHI
(3) M = Sn, R = CH3
( 4 ) M = Sn, R = n-C4H9
Whereas (2) forms waxy crystals which are surprisingly
stable towards water, (3) and ( 4 ) are rapidly attacked by
moisture at the Sn-N bond. The proton magnetic resonance
spectra [3] of ( 2 ) and (3) show expected peaks with relative
areas of 2: I. The displacemcnt of the asymmetric Si-N(M)
frequency to higher wave-numbers relative to that of
I ,1, I ,3,3,3-hexamethyl-2-trin~cthyIsilylsilazane
[(CH3)3Sil3N
Angew. Chem. internut. Edit. I Vol. 2 (1963) 1 No. 8
(5) [4]points to an increase in the double bond character of
the bond between silicon and nitrogen [(5) : 916, (2) : 931,
(4): 941, ( 3 ) : 950cm-11.
(CH3)zGeCIz -1- 2 [(CH,)&IzNNa
-
CH3
I
[(CH3)3Sil*N- Ge--N[Si(CH,),lz
-1- 2 NaCl
CH3
Dichlorodimethylgermane reacts with ( 1 ) according to the
equation to give the corresponding bis(disilazy1)germane
(b.p. cn. 135"C/I mm), albeit only in moderate yields (ca.
30-40 %).
Received, May 20th, 1963
[Z 512/345 1EI
German version: Angew. Chem. 75, 642 (1963).
[ I ] M . Schmidt and I . Ruidisch, Z. anorg. allg. Chem. 311, 331
(1961).
[2] U . Wannagat a n d H. Niederpruem, Chem. Ber. 94, 1540(1961).
[3] Varian A60 instrument (60 Mc). Measurements made on
dilute carbon tetrachloride solutions. Tetramethylsilane as
internal standard.
[4] J . Coubeau and J . Jimknez-Barbera, Z . anorg. allg. Chem.
303,217 (1960).
acetonitrile and ether with one mole of acetonitrile, m.p.
178-18OoC. The salt (7) loses I mole of hydrogen bromide
in dimethylformamide/quinolinc at room temperature to
form 4-bromo- 1, I-diphenyl- I -phosphoniocyclohex-2-eneperchlordte (8), where X = C104'), m.p. 175-176"C, 88 %
yield; (8) crystallizes with 1 mole of acetonitrile from a
mixture of acetonitrile and ether. vc=c 1596 cm-1. The salt
(8) is dehydrobrominated in hot anhydrous phosphoric acid
to the'phosphoniocyclohexadiene perchlorate (9), X = C1O4@,
m.p. 117-119"C, VC=C 1626, 1572, 1550 cm-1. IJ-Diphenyl-I-phosphabenzene (10) is precipitated from its
aqueous solution by dilute sodium hydroxide as an amorphous yellow powder (Amax = 400 mp in methanol) which is
stable in water but reforms the salt ( 9 ) in acid.
Like the corresponding phosphanaphthalene derivative [I I,
(10) autoxidizes readily i n solution, forming red and violet
methylenephosphoranes of unclarified structure.
Even i n an atmosphere of nitrogen, dehydrobromination of
(8) or (9) with quinoline or diisopropylethylamine [3] in
boiling dimethylformamide leads beyond (10) to a deepblue stable methylenephosphorane (Amax = 634 m p in
methanol). in addition to small quantities of red compounds,
structural studies of which are in progress.
Received, May ?2nd, 1963
I2 510/343 IEI
German version: Angew. Chem. 75, 669 (1963).
1,l-Diphenyl-1-phosphabenzene11I
By Dr. G. Mlrkl
Chemisches lnstitut der Universitlt Wiirzburg (Germany)
Slow addition of diphenylphosphinopotassium ( I ) [2] in a
mixture of dioxan and tetrahydrofuran to a boiling solution
of an w,w'-dibromoalkane gives the diphenyl-w-bromoalkylphosphine ( 2 ) , which at once quaternizes intramolecularly
to the cyclic phosphonium salt ( 3 ) :
BrH2C-(CHz),-CH2Br
+
H5C6,
--
-
HZ~-(CI-IZ~-CHZBr
P
H 5 C 4 \C&
H5C:
C
''
X"
(21
By Dr. W. Kampe
P O (CH2)n
H2
(1)
Reactions of Di-(oc-pyridyl) Carbonate
Reactive Esters of Heterocyclic Alcohols, I
HZ
H5C6,
PK
H5C6'
[ I ] Communication No. I l l on Cyclic Methylenephosphoranes;
Communication No. 11: G. Murkl, Angew. Chem. 75, 168 (1963);
Angew. Chem. internat. Edit. 2, 153 (1963).
221 K. Issleib and H . 0.Friihlich, Z . Naturforschg. 146,349 (1959),
K. Issleib and A . Tzschach, Chem. Bor. 92, I 1 18 (1959).
[31 S. Hlinig and M . Kiessel, Chem. Ber. 91, 380 (1958).
(3)
( 3 ) : n = 2, X = B(CsH&), m.p. 185-187"C, 77 % yield;
n = 3, X = Br", m.p. 262-263'C, 4 9 % yield; n = 4,
X = C104(1, m.p. 208 "C, 36 g: yield.
1,5-Dibromo-3-methoxypentane affords 4-niethoxy-1 ,l-diphenyl-1-phosphoniocyclohexane bromide (4), m.p. 220 to
221 "C, 46 % yield, and subsequent demethylation with
hydrobromic acid in acetic acid gives the alcohol ( 5 ) , m.p.
148-149 "C, 58 % yield.
lnslitut fur organische Chemie
der Technischen Hochschule Darmstadt (Germany)
a-Hydroxypyridine reacts with phosgene i n a molar ratio of
4:1 (pyridine can also be used to absorb the HCI formed) at
room temperature in dry tetrahydrofuran or benzene to give
di-(a-pyridyl) carbonate ( I ) in almost quantitative yield.
Compound ( I ) is crystalline, m. p. 111--112 "C; it hydrolyses
slowly in water at room temperature with evolution of CO2.
Its infrared spectrum contains ;I carbonyl band shifted to
1796 cm-1 (cf. 1760 1780 cm I Ibr normal carbonic esters).
O
(1)
+ 2 RNH,
(I)
Angew. Chem. internat. Edit.
1 Vol. 2 (1963)
No. 8
(I)
B
+ 2 KO11
0
Compound ( 5 ) can be dehydrated with potassium hydrogen
sulfate at 210-220 "C to give the phosphoniocyclohexene
derivative (6), where X = C1040, m.p. 177-179'C, 6 0 %
yield; VC=C 1637 cm-1; bromination of (6) takes place
smoothly in glacial acetic acid to give (7),X == C 1 0 4 O , m.p.
206-208'C, 68 "/, yield; (7) crystallizes from a mixture of
II
+ RO-P-O"B@
bOB"
(2)
RNII-C-NHR
RO-C-OR
-
RO-P-o
(3)
(5)
&ag@
The reactions of ( I ) usually give high yields [(2), R = C6Hii,
92 % yield; ( 3 ) , R =- C7H7, 91 y, yield; ( 4 ) , R = C6H5. 85 %
yield; ( 5 ) , R = CsHs, 95 yield). Further acylations can be
479
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