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Islolation of Tetracyclo[6.3.1.02 6.05 10]dodecane and Pentacyclo[7.3.1.1.4 12.02 7

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We have obtained 2-t-butylacetoacetic ester (2) in 68 %
yield by treating acetoacetic ester ( I ) with t-butyl perchlorate
in nitromethane; 2-t-pentylacetoacetic ester was prepared
(yield 65 %) similarly. The structure of the product ( 2 ) , b.p.
(CHj)j CC10,
+
::
0
II
C H ~ C - C H ~ - C - O C ~ H-+
S
0
0
II
II
CH~C-CH-C-OCZH, + HClOI
Received: September 29th. 1966
[Z 338 I € ]
German version: Angew. Chem. 78, 1058 (1966)
210°C (corr.)/760 mm; n'," = 1.4291, was proved, byelemental
analysis and N M R spectroscopy [6 = -1.05 (9, s); -1.27
(3, t, J = 7 Hz); -2.13 (3, s); -3.18 (1, s); -4.15 (2, 9, J =
7 Hz) pPm[411, and the mass spectrum is in agreement with the
fragmentation scheme found for ethyl 2-alkylacetoacetates [51.
Further, we have used the reaction
RBr
+ CH2(CN)2 [A'C131 >
(3)
0.16 mole of t-alkyi bromide and kept at 3 "C for 16 hr [for
(4u) and 3,3-dimethylbutane-2,2-dicarbonitrile;48 hr for
(46) and (4c) ; 10 days for ( 4 d ) l . After decomposition of the
aluminum chloride (NaHC03 solution and ice) the mixture
was steam distilled. The product (4a) or 3,3-dimethylbutane-2,2-dicarbonitrile that distilled after nitromethane
was pure [(4b) was distilled, b.p. 82-84OC/2 mm; (4c) was
separated by gas chromatography (polyethylene glycol 20 M;
190 "C) ;(ld)crystallized after decomposition of the aluminum
chloride and removal of the solvent].
[*] We thank the Deutsche Forsrhungsgemeinschafi and the
Fonds der Chemischen Industrie for financial support.
[I] P. Boldr and L . Schulz, Naturwissenschaften 51, 288 (1964).
[2] P. Boldr and H . Militzer, Tetrahedron Letters 30, 3599 (1966).
[3] Cf. also J.T. Adums, B. Abramovitch, and C . R . Hauser,
J. Arner. chem. SOC.65, 552 (1943).
[4] In CCIJ; internal standard tetramethylsilane (= 0 ppm);
relative intensities in parentheses.
[5] .I
H
.
. Bowie, S.-0.Lawesson, G . Schroll, and D . H . Williams,
J. Amer. chem. SOC.87, 5742 (1965).
RCH(CN)z
(4)
to determine whether t-alkyl halides that are more bulky or
have a greater tendency t o eliminate hydrogen halide can be
used in place of t-butyl bromiderll in the acid-catalysed alkylation of CH-acidic compounds. The yields of alkylated
malonodinitriles (4) are given in the table; the structures
are proved by elemental analyses and N M R spectra.
( %)
H CH3
I I
CH3-C-CI
1
H CH3
H CH3
I I
CH3-C-CI I
HSC CH3
H3C CH3
I
I
-I
CH3- C C I
-0.97 (3, t ; J 7 Hz)
-1.20 (6, s)
-1,61(2,q;J=7Hz)
-3.52 ( I , S)
-0.95 (6, d ; J = 6.5 Hz)
-1.14 (6, s)
ca.-1.8 (1, h ; J = 6.5 Hz)
-3.76 ( I , S)
-1.08 (9, S)
-1.26(6, s)
-3.65 ( I , s)
H3C CH3
-1.77 (12,s)
-1.80 (12, s)
ca.-2.15 (3, m )
-3.28 ( I , s)
Lewis acid catalysis also permits acidic methine protons to
be replaced by t-alkyl groups: methylmalonodinitrile,
t-butyl bromide, and aluminum chloride afford 3,3-dimethylbutane-2,2-dicarbonitrile in 38 % yield; its N M R spectrum
includes 6 = -1.23 (3, s) and -1.70 (1, s) ppmr41.
2-t-Butylacetoucetic ester ( 2 ) : A solution of 0.3 mole of
AgC104 in 180 ml of nitromethane was added during 3 hr,
with stirring, t o a mixture of 0.9 mole of the ester ( I ) , 0.3
mole of t-butyl bromide, and 30 ml of nitromethane a t 0 OC.
The whole was kept for 3 hr a t 0 O C , then filtered, washed with
sodium hydrogen carbonate solution and water, dried, and
freed from solvent. The excess of ester ( I ) in the distillation
residue (0.425 mole) was hydrolysed by 45 hours' stirring
with 425 ml of 1 N NaOH at 40°C. The mixture was then
cooled and extracted with ether, and the extracts were united,
dried, and evaporated. Distillation of the residue afforded
37.8 g of product (2), b.p. 95-98 "C/12 mm.
Alkylation of malonodinitrile (3) (or methylmalonodinitrile) :
A solution of 0.1 mole of nitrile (3) and 0.1 mole of aluminum
chloride in 30 ml of nitromethane was treated at -20 OC with
Angew. Chem. internat. Edit.
By Dr. S. HaIa and Prof. S. Landa
Synthetic Fuel and Petroleum Institute, College of Chemical
Technology, Prague (Czechoslovakia)
Yield
R
Isolation of Tetracyclo[6.3.1.02~6.0~J~]dodecane
and Pentacyclo[7.3.1.14J~.0~~7.0~J~]tetradecane
(Diamantane) from Petroleum
/ VoI. 5 (1966) J No.
12
and by Dr. V. HanuS
Physical Chemistry Institute, Academy of Sciences,
Prague (Czechoslovakia)
Work with the naphthenic petroleum obtained in the region
of Hodonin (Czechoslovakia) led some time ago to the
isolation of adamantanerll and recently to that of 1- and
2-methyladamantane [21; we have now obtained from the
same source two further crystalline naphthenes of adamantanoid structure, of which one is tetracyclic and the other
pentacyclic.
These two hydrocarbons, which occar in the petroleum
fraction boiling between 200 and 300 "C, give an adduct with
thiohrea o n extractive crystallization; they concentrate in the
lower portion of the column on separation by thermodiffusion. They can be purified by preparative gas chromatography and subsequent sublimation and crystallization.
The tetracyclic hydrocarbon C12Hl8, which was obtained
with approximately 95 "/, purity[*], melts at 153-154 "C. The
most abundant species in its mass spectrum are the molecule
ion (relative intensity 100) and the fragments CsHs+ and
C&7' (37 and 24, respectively), CgHll+ and C9H12+ (28 and
20, respectively), C7H7+ (19), CloHl3' (ll), C3H5+ (ll), and
CsH7+ (10). In the IR spectrum the C H and CH2 stretching
bands (at 2935, 2920, 2905, 2865, and 2843 cm-1) and the
CH2 deformation bands (at 1480, 1464, and 1450 cm-1) are
accompanied by others of medium or weak intensity, e.g.,
at 1352, 1099, 1075, 996, 965, 928, and 881 cm-1. In the
IH-NMR spectrum (Ha-100) the signals for the protons are
between 7 = 7.80 and 8.84, forming a complex multiplet
comprising several overlapping, relatively narrow bands at
T = 8.05, 8.15, 8.27, 8.64, and 8.78; at T = 8.35 to 8.51 there
is a multiplet with resolved fine structure.
From these data we derive the adamantanoid structure tetracyclo[6.3.1 .Oz,6.05!1o]dodecane (2) for the hydrocarbon
C12H18. This structure accords with the hydrogenative fission
of the hydrocarbon on a rickel catalyst to, almost exclusively,
methane, 2-methyladamantane, and adamantane.
1045
/3/
The pentacyclic hydrocarbon C14H20, which crystallizes in
optically isotropic octahedra. m.p. 237 "C, on slow sublima(3),
tion, is pentacyclo[7.3.1.14~~~.02~7.06~~1]tetradecane
which was recently synthesized [31 and called diamantane [41
(originally songressane [31). The hydrocarbon C14H20 and
authentic diamantane have the same melting point, an undepressed mixed melting point, and the same elution times
on gas chromatography. The mass spectra also are identical
and correspond[**] with the published mass spectrum of
diamantane [31.
W
Received: October 6th. 1966
[ Z 345 IE]
German version: Angew. Chem. 78, 1060 (1966)
[*I Determined by gas chromatography (capillary column);
mass spectrometry indicates that the impurities are predominantly
hydrocarbons C12H20, C13H22 (alkyladamantanes), and C13H20.
[l] S. Landa and V . MachuCek, Collect. czechoslov. chem.
Commun. 5, 1 (1933).
[2] S. Hula and S. Landa, Erdol Kohle-Erdgas-Petrochem., 19,
727 (1966).
[3] C. Cupas, P . v. R . Schleyer, and D . J . Trecker, J. Amer. chem.
SOC.87, 917 (1965); cf. Angew. Chem. 77, 180 (1965); Angew.
Chem. internat. Edit. 4, 169 (1965).
[4] 0. Vogl, B. D. Anderson, and D. M . Simons, Tetrahedron
Letters 1966, 415.
[**I The ratio of the abundance of the molecule ion to that of
the commonest fragment (m/e = 91) is, however, twice as great
as in the published spectrum [3].
Crystal Structure of Carbonyl-
The dimension of the unit cell are
a = 12.28
b,
b = 9.33
c = 12.31 b,
01 =
105.6
p = 109.5
y = 82.4"
Volume (1278 83) and formula weight (196.9) lead to the
density D(ca1c) = 1.54 g/cm3 whereas D(obs) = 1.53 g/cm3.
1594 reflections (CuK,) were registered at room temperature
on film, and intensities were measured photometrically 17-1.
Observable intensities were found only in the range of
0 "-45 "(overall temperature factor Bo N 6 A2). Coordinates
of the Ni atoms could be found from a sharpened Patterson
synthesis. Those of the light atoms (21 C, 6 N, 3 0) were
found on successive Fourier syntheses and refined by leastsquares methods, the R factor decreasing from 45 % to 16 %.
Received: October loth, 1966
[Z 347 IE]
German version: Angew. Chem. 78, 1064 (1966)
(piperidine-N-carbonitrile)nickel(O)
By Dr. K. Krogmann and Dr. R. Mattes
Laboratorium fur anorganische Chemie,
Technische Hochschule Stuttgart (Germany)
The crystal structure of carbonyl(piperidine-N-carbonitrile)
nickel(O), Ni(C5HloNCN)(CO), first prepared by H. Bock
and H . tom Dieckcll reveals a new type of r-complex, involving C = N triple bonds.
Six formula units are contained in the triclinic unit cell
(space group P1) as two trimeric molecules. The nickel atoms
of each trimer occupy the corners of a n equilateral triangle, all having the same coordination of light atoms. Two
nickel atoms (Ni-1 and Ni-2) are relatively close to nickel
atoms of the adjacent trimer (3.20 A), but no effect of metalmetal bonds o n the coordination sphere can be detected.
The figure shows a projection of the molecule on the plane of
the three nickel atoms. Essential bond distances and angles
(averaged) are included. All atoms of the CO and N C N
groups are in the plane of the three Ni atoms or deviate
from it by less than 0.3 A. Every Ni atom is linked by o
bonds to a carbonyl-C and a cyano-N. Three of these monomers form the trimer using x-bonds from the cyano groups.
There are no >N=C=NR2 groups; these would be linear
and perpendicular to the line Ni-Ni. Bond distances and
angles are instead in accordance with -N E C - N R ~ groups,
and N and C atoms of the C N groups are equidistant from
the x-bonded Ni atom (1.99 A). The bond angles
Ni-N-C-NR2
might be expected as a result of the displacements of electron density in the x-system of the N = C
group. The N atom of piperidine is not involved in bonding
to Ni. The rings have the chair conformation; two C N
groups are attached axially, and one is attached equatorially.
1046
[l] H . Bock, Angew. Chem. 74, 695 (1962); Angew. Chem. internat. Edit. I , 550 (1962); H . Bock and H . tom Dieck, Chem. Ber.
99, 213 (1966).
[ 2 ] Crystals were kindly supplied by Drs. H . Bock and H. tom
Dieck.
Preparation of Phosphorus Tribromide from the
Elements
By Dr. F. Schroder
Institut fur Anorganische Chemie,
Universitat Hamburg (Germany)
Preparation of PBr3 from the elements has hitherto required
white phosphorus and/or use of a solvent[l*zl, as well as
complicated apparatus [21. We have now converted red
phosphorus into PBr3 with bromine in the absence of a
solvent, using a three-necked, round-bottomed flask (1 liter)
equipped with a dropping funnel, a reflux condenser with
drying tube, and a stirrer with a glass precision bearing. Red
phosphorus powder (2 g-atoms) is very gently stirred and
treated dropwise with 3 moles of bromine, slowly at first,
then faster. The PBr3 formed may contain suspended phosphorus and is distilled off. Water cooling can be used until
the liquid PBr3 appears. Previous passage of purified nitrogen
through the apparatus and drying of the phosphorus avoids
formation of small amounts of PzO5.
[ Z 346 IE]
Received: October llth, 1966
German version: Angew. Chem. 78, 1102 (1966)
[l] Gmelins Handbuch der anorganischen Chemie. 8th. Edit.,
Verlag Chemie, Weinheim 1965, System No. 16, Part C.
[2] Inorg. Synth. 2, 147 (1946).
Angew. Chem. internat. Edit. / VoI. 5 (1966) / No. I2
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