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Crystal and Molecular Structure of Diethyl 2 4-Bis(diethylamino)cyclobutadiene-1 3-dicarboxylate.

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C 0 M MU N I C AT1 0N S
Crystal and Molecular Structure of Diethyl
2,4-Bis(diethylamino)cyclobutadiene-1,3dicarboxylate[**'
Crystal data: yellow needles, m.p. 50-52°C. M = 338.2,
monoclinic ;lattice c o n s t p s :a= 17.62,b = 13.81,~
=9.76&
p=125.3", U=1954.2 A3, Z=4, D,,,,,=1.1495 g/cm3.
By Hans Jorg Lindner and Brigitte Don Gross[*]
We have carried out an X-ray structure analysis to clarify
the molecular structure of diethyl 2,4-bis(diethylamino)cyclobutadiene-1,3-dicarboxylate
which should
provide further insight into the n-electron system of this
compound. For these measurements single crystals were
sealed under nitrogen in capillaries[*!
[*I Dr. H. J. Lindner and B. von Gross
Institut fur Organische Chemie der Techntschen Hochschuie
61 Darmstadt, Schlossgartenstrasse 2 (Germany)
[ * * I Thls work was supported by the Deutsche Forschungsgemexnschaft.
490
Space group P2,ln. The intensities of 2715 symmetryindependent reflections from layers 0.. . I 4kl were measured
with an automatic Weissenberg diffractorneter with nickelfiltered Cu-K, radiation; of these, 986 reflections were
so weak that they could not be used for determination
of structure.
Angew. Chem. internat. Edit. 1 Vol. 10 (1971)
1 No. 7
The phases of 240 reflections with E > 1.6 were determined
by Karle and Karle's symbol addition method[31.Fourier
synthesis calculated with these E values and phases led to
a complete structural model which has so far been refined
to an R factor of 0.12 by Fourier syntheses and LSQ calculation~[~!
The unit cell contains two pairs of symmetry-independent
centrosymmetric molecules at two-fold special positions.
The mean values of the bond lengths and bond angles of
the two molecules are given ia Fig. 1. Standard deviations
for the bond lengths are 0.015 A and for the bond angles 1'.
dialkyl esters of phosphoramidic acid (2) with chlorine in
aqueous, acetate-buffered solution.
We found that the diethyl ester of ( I ) is obtained in the
form of a stable compound after distilling the reaction
mixture and that its preparation does not present any
problems, even on a kg scale.
Preparation of compound ( I ) , R=CH,, on a 0.5-mole
scale also proceeded in accordance with expectations. When
working with 1.5 mole of starting material, on the other
hand, a violent detonation took place after the reaction
had gone to completion and after the mixture had been
stirred for one hour.
The essential difference between the two preparations lay
in the longer reaction time required when 1.5 mole of the
starting material was reacted (6 hours as compared with
2 hours). It may be assumed that under these conditions
either the amide (2),R=CH,, or the N,N-dichloroamide
( I ) , R = CH,, undergoes partial hydrolytic cleavage of the
P-N-bond, possibly leading to the formation of explosive
nitrogen-chlorine compounds.
[139511
I
Fig. 1. Bond lengths and bond angles of (1)
The four-membered ring of ( I ) contains, within experimental error, sides of equal length (1.46A)and angles of
93 and 87 '.The C-N bond lengths indicate a high doublebond character. The C-C
bonds between the fourmembered ring and the ester groups are shortened.
The four-membered ring is planar within experimental
error. Unlike the amino groups, the ester groups are displaced by about 20" from the plane of the four-membered
ring.
Received: March 15, 1971 [Z 395 IE]
German version: Angew. Chem. 83,489 (1971)
[I]R . Gompper and G . Seyboid, Angew. Chern. 80,804 (1968); Angew.
Chem. internat. Edit. 7,824 (1968); M . Neuenschwander and A . Nieder-
hauser, Helv. Chim. Acta 1970, 529.
[2] We thank Dr. G. SeyboId and Prof. R. Gompper for provision of
the crystals sealed in capillaries.
[3] J . Karle and I.L. Karle, Acta Crystallogr. 21, 849 (1966).
[ 4 ] W R . Busing, K.O. Martin, and H . A . Lecy, ORFLS, a Fortran
Crystallographic Least Squares Program, ORNL-TM-305, 1962.
Dimethyl N,N-DichlorophosphoramidateA Warning
By Hans Dieter Block and Reinhard SchliebsI']
Zwierzak et al."] synthesizeddialkyl esters of N,N-dichlorophosphoramidic acid ( I ) by treating the corresponding
Zwierzak[21himself never observed any explosive decomposition of ( I ) , R=CH,; but on the other hand he never
carried out any preparations using more than 0.15 mole.
It therefore seems advisable not to use amounts greater
than about 0.2 mole when synthesizing ( l ) ,R=CH,, to
keep the reaction time short and to observe the usual
precautions for working with explosive substances.
Received: April 2,1971 [Z 410 IE]
German version: Angew. Chem. 83,537 (1971)
[I] A . Zwierzak er a]., Angew. Chem. 80, 285 (1968); Angew. Chem.
internat. Edit. 7, 292 (1968)
[2] A . Zwierzak, personal communication
Homologation of Cyclic Ketones by
IsocyanomethylIithium[
By Ulrich Schollkopfand Peter Bohine[*l
Isocyanomethyllithium (2),which is obtained from methyl
isocyanide and butyllithium in tetrahydrofuran"], provides
a method of introducing aminomethyl groups into carbony1 compounds conveniently and in good yield^[^.^!
From cycloalkanones one thus obtains I-(aminomethyl)I-cycloalkanols which, inter alia, are important as starting
materials for Tiffeneau-Demjanov ring expansion[51.For
example, cyclohexanone ( I ) and (2) afford I-(isocyanomethyl)-I-cyclohexanol (77% yield), which is converted
by methanolic hydrogen chloride into the amine hydrochloride ( 4 ) (>63%). Diazotization with sodium nitrite
in aqueous acetic acid then yields the intermediates ( 5 )
and (6) and finally cycloheptanone (7). I-(Isocyanomethyl)
derivatives are obtained from cycloheptanone and cyclododecanone in 95% and 90% yield, respectively, and thence
the amine hydrochlorides in about 80% and 67% yields
respectively.
[*] Dr. H. D. Block and Dr. R. Schliebs
Anorganisch-wissenschaftliche Abteilung
Farbenfabriken Bayer A G
509 Leverkusen (Germany)
Angew. Chem. internal. Edit. 1 Vol. 10 (1971) / N o . 7
[*] Prof. Dr. U. Scholikopf and P. Bohme
Organisch-Chemisches Institut der Universitat
34 Gottingen, Windausweg 2 (Germany)
49 1
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crystals, structure, molecular, diethylamino, diethyl, bis, dicarboxylated, cyclobutadiene
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