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Fixation of Molecular Nitrogen on Nickel(0).

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Synthesis of 1,3-Dioxa-6-azacyclooctanesfrom
4,6-Dioxa-l-azabicyclo 13.3 .O]octanes
By R. Feinnuer[*]
On reaction with carboxylic acids or anhydrides [I], phenols,
or secondary amines 121, 4,6-dioxa-l-azabicyclo[3.3.0]octanes
( I ) yield carboxamides by ring fission. The reaction with
aliphatic aldehydes [31 leads to 3-acyloxyalkyl-2-alkyloxazolidines.
We have converted compounds (1) into 1.3-dioxa-6-azacyclooctanes ( 3 ) and ( 4 ) by methylation with dimethyl
sulfate and treatment of the methylation products ( 2 ) with
N a alkoxide.
alkoxide anion and elimination of a proton compete in
formation of (3) or ( 4 ) from ( 2 ) and al koxide. The products
(3) and ( 4 ) are colorless liquids; their structures are proved
by elemental analyses, determination of molecular weights,
and IR, N M R , and mass spectra.
[Z 826 1El
Received: July 3, 1968
German version: Angew. Chem. 80, 703 (1968)
[*I Dr. R. Feinauer
Forschungslaboratorien der Chemische Werke Huls AG
437 Marl (Germany)
[I] R. Feinnuer, Angew. Chem. 7 9 , 189 (1967); Angew. Chem.
internat. Edit. 6, 178 (1967).
[ 2 ] R. Feinauer, unpublished results.
[ 3 ] R. Feinauer and E. Henckel, Liebigs Ann. Chem., in the press.
CH7
Fixation of Molecular Nitrogen on Nickel(0)
CHzR
By P . W. Jolly and K. Jonas[*]
(2a), R = H
(Zb), R = CH3
(la), R = H
(lb), R = CH3
J
Since 1965 several complexes of transition metals (Ru111,
OsL21, CoL31, and 1r[41) have been found that contain nitrogen as ligand. We now report a nitrogen-nickel(0) complex
in which two nickel atoms are bound t o one nitrogen molecule. If nickel acetylacetonate is treated with trimethylaluminum in the presence of tricyclohexylphosphine and nitrogen at -30 t o +2OoC, a yield of ca. 40% of bis[bis(tricyclohexylphosphine)nickel]dinitrogen is obtained as dark red
crystals.
N-OR'
(3a).
(3b),
(3c),
(3d).
K = H, R' = CHs
R = CHj, R'
CH3
R
R
Starting
material
i24
/2a)
i2h1
(26)
=
=
F
3
(4a). R = H
f4b). R = CH3
H, R' = CzH,
CH3, R' = Cz&
B.p. ('Cltorr)
Yield (%)
(3a),38
( 3 ~ )20
.
(361, 42
[ 3 d ) , 10
(4a). -< 5
(40). :c 5
(46). 5
( 4 6 ) , 37
5713
5011
-
1.4546
1.4490
-
6612
70/2
5412
54/2
1.4556
1.4522
1.4780
1.4780
I-Merhyl-5-alkyZ-4,6-dioxa-1-azoniabicyclo[3.3.0]octnne
tnethosulfnte ( 2 ) :
Dimethyl sulfate (0.4 mole) was added with cooling and
stirring t o a solution of ( l a ) or ( I b ) in CH2Cl2 (200 ml) at
such a rate that the internal temperature did not exceed 30 'C.
After 30 minutes' stirring, the vessel was placed in ice. The
colorless crystals of (2a) or (2b) that separated were filtered
off, washed with CH2C12. and dried in a desiccator. (Za),
yield 79%, m.p. 100-101 "C. (2b), yield 82%, m.p. 112 to
113 "C.
2-Alkoxy-2-alkyl- ( 3 ) and 2-alkylidene-6-nzethylI,3-dioxa-6-azacyclooctane (4j :
The nitrogen molecule can easily be replaced by other ligdnds,
such as olefins, phosphines, or CO. When ethylene or the
isomers of 1,5,9-cyclododecatriene are used, known bis(tricyclohexy1phosphine)nickel-olefin complexes (51 are obtained and exactly 1/2 mole of N2 is liberated per g-atom of
Ni.
Cryoscopic determination of the molecular weight in benzene
and the IR spectra show that the complex ( I ) in the dark red
solution presumably exists as an equilibrium mixture of (2)
and (3).
(I) Ar
32 (3)
\
Nr
The band at 2028 cm-1 is probably t o be ascribed t o the N N
stretching vibration; it disappears if argon is passed through
the solution, which then becomes yellow and gives a freezingpoint depression indicating that the equilibrium has been
shifted entirely towards the right. The yellow solution absorbs
nitrogen with red coloration, and the starting system is reformed (mol. wt. and band at 2028 cm-1).
The methosulfate (2) (0.4 mole) was dissolved in methanol
or ethanol (100 mi), and t o it was added at 6OoC with
stirring a solution of N a (0.4 mole) in the corresponding
alcohol (150 ml); the whole was then kept at 6OoC for a
further 2 h. After cooling the solution was filtered from
precipitated NaCH3S04, the excess of alcohol was distilled
off through a column, and the residue was distilled and
fractionated through a rotating band column under vacuum.
The properties of the compounds (3) and ( 4 ) obtained are
summarized in the Table.
X-ray structure analysis is in progress [61 (cell data: P21/,,,
a = 21.83 A, b = 16.54 A, c = 21.24 A, p = 102.7O, Z = 4, d
(X-ray) = 1.12, d (pycn.) = 1.13).
Experimental:
Reaction of (2a) with methoxide or ethoxide gives mainly
(3a) or (3c). respectively; (4uj could only be detected in
traces spectroscopically, presumably because of its lower
stability. With N a methoxide (26) gives mainly (3b) but with
N a ethoxide gives mainly (4b). (36) could not be converted
thermally into (46). This indicates that addition of the
A solution of Al(CH3)3 (2.2 ml) in toluene (5 ml) is added
dropwise and slowly t o a solution of Ni(acac)z (5 g, approx.
20 mmole) and tricyclohexylphosphine (12 g, approx. 40
mmole) in toluene (50 ml) at -20 'C with stirring and passage
of nitrogen. The reaction mixture is allowed to warm to
room temperature and stirred for a further 10 h. Red crystals
Atigew. Chem. internat. Edit. 1 VoI. 7 (1968)
No. 9
( I ) presumably has the structure:
73 I
are precipitated, which are sucked off, washed with ether,
and dried. The compound can be recrystallized from toluene
under nitrogen.
Received: July 3, 1968
[Z 827 1El
German version: Angew. Chem. 80, 705 (1968)
I"] Dr. P. W. Jolly and Dr. K. Jonas
Max-Planck-Institut fur Kohlenforschung
433 Mulheim-Ruhr, Kaiser-Wilhelm-Platz (Germany)
[ l ] A . D. Allen and C . V . Senoff, Chem. Commun. 1965, 621;
F. Bottomley and S. C . Nyburg, ibid. 1966, 89; A. D . Allen,
F. Bottomley, R. 0.Harris, V. P . Reinsalu, and C . V. Senoff, J.
Amer. chem. SOC.89, 5595 (1967); D. E. Harrison and H. Taube,
ibid. 89, 5706 (1967); A . E. Shilov, A . K . Shi/ova, and Y. G . Borod'ko, Kinetika i Kataliz 7, 768 (1966); Chem. Abstr. 65, 19655b
(1966); D . E . Harrison, E. Weissberger, and H . Taube, Science
(Washington) 159, 320 (1968); A . Yarnamota, S. Kitazume, and
S . Ikeda, J . Amer. chem. SOC.90, 1089 (1968).
[2] A . D. Allen and J . R. Sfevens, Chem. Commun. 1967, 1147.
[ 3 ] A. Sacco and M . Rossi, Chem. Commun. 1967, 313; A . Yamamoto, S . Kitazume, L . S. Pu, and S . Ikeda, ibid. 1967, 79;
A . Yamamoto, L. S . Pu, S . Kitazume, and S . Ikeda, J. Amer.
chem. SOC.89, 3071 (1967); A . Misono, Y. Uchida, T. Saito, and
K. M . Song, Chem. Commun. 1967, 419; A . Misono, U . Uchida,
and T. Saito, Bull. chem. SOC.Japan 40,700 (1967); J . H . Enemark, 8. R. Davis, J . A . McCinnety, and J. A. Ibers, Chem.
Commun. 1968, 96.
[4] J. P. Collman and J. W. Kang, J. Amer. chem. SOC.88, 3459
(1966); J . P. Collman, M . Kubota, Y. Sun, and F. Vastine, ibid.
89, 169 (1967).
[5] K . Jonas, Dissertation, Universitat Bochum, 1968.
[6] C . Kruger, unpublished work.
On use of I-14C-labeled (2) autoradiography of the chromatogram shows that the new compound n o longer contains
C-1; apparently the acid ( 5 ) is decarboxylated slowly even
at room temperature. Polarography of the eluted zone
indicates an enediol grouping and an aldehyde group
activated by conjugation. Kdiss for sulfite addition was
determined, also polarographically, as 1.1x 10-3. The IR
spectrum contains a sharp absorption band at 1700 cm-1;
compounds of tetronediol type, such as ( I ) , (3). 3.4-dihydroxy-2,5-dihydrofuranone, and the corresponding deuterated compounds, however, show two sharp bands, one
between 1630 and 1665 cm-1 and the other between 1737 and
1754cm-l.AtpH5 thecompound gave a UVband withhma,=
291 nm, similar to that of triosereductone (Amax= 288 nm).
From these results it is concluded that decomposition of (2)
leads by way of (5) and (6) to ( 7 ) ; and this has been prepared
also from L-arabinose by way of the osazone and osone c6.71.
COOH
H,CsO
I
HO-YH
CHzOH
I
H+-OH
HO - FH
CHzOH
c=o
HO-YH
CHzOH
Constitution and Synthesis of an aci-Reductone
Formed on Non-oxidative Degradation of
Dehydroascorbic Acid[**]
Enolization of the arabosone t o give (7) occurs analogously
to
the proton-catalyzed isomerization of hydroxypyruvaldeBy K. Wisser, W . Heimann, and E. Mogelr*1
hyde to triosereductone [a].
The ~-2,3,4,5-tetrahydroxy-2-pentenal
prepared from L-araOn two-electron oxidation L(+)-ascorbic acid ( 1 ) (vitamin C)
binose is chromatographically, polarographically, and UVis converted into L(+)-dehydroascorbic acid (2), which can
and IR-spectroscopically identical with the non-oxidative
be reduced back to ( I ) in vivo and in vitro. The dehydro acid
degradation product of (2).
(2) decomposes non-oxidatively and non-enzymically to
Substance (71, which was obtained in rng quantities. is a
products that are of interest in food chemistry because they
yellow syrup and decomposes slowly at room temperature
cause discoloration and changes in taste.
with browning. We suggest that it be called L-pentosereducCOz, oxalic acid, threonic acid, furfuryl alcohol, ~-xylosone
(?), ethylglyoxal, and 2-keto-3-deoxy-~-pentono-y-lactone tone or erythroreductone.
The aci-reductone formed on warming (2) in dilute sulfuric
(5-hydroxymethyltetrahydro-2,3-furandione)have been deacid is not compound (3)aspreviouslypostulated [ I ] ; authentic
tected as degradation products 11-51. Little is reliably known
(3) has different UV and IR spectra. The product isolated by
about the course of the degradation. A strongly reducing
the procedure of reference is mainly an as yet unidentified
compound arising o n degradation of (2) has been formulated
reducing compound plus a smaller amount of (7).
as (3) f l l but also as (4)[3J.
[Z 828 IEI
Received: May 9, 1968. Expanded: J u n e 7, 1968
COOH
German version: Angew. Chem. 80, 755 (1968)
Developing a thin-layer chromatogram of an aqueous solution of (2) obtained o n silica gel or aluminum oxide a t room
temperature affords many zones that obviously arise from
products formed by catalytic decomposition of (2) on silica
gel or aluminum oxide but have been held by most authors
t o represent the initial stage of the degradation of (2). 2.3Diketogulonic acid (5) (RF = 0.1) is obtained after about 1 h
at room temperature on thin-layer chromatography on
cellulose with butanol/glacial acetic acidlwater (4:l :l); after
some weeks a new substance of RF = 0.8 appears which is
strongly reducing analogous to ( I ) . This second zone
appears homogeneous in several eluants and o n two-dimensional thin-layer chromatography.
7 32
[*I Dr. K. Wisser, Prof. Dr.-Ing. W. Heimann, and E. Mogel
Institut fur Lebensmittelchernie der Universitat
75 Karlsruhe, Kaiserstr. 12 (Germany)
[*'I We thank the Bundeswirtschaftsministerium and the Forschungskreis der Ernahrungsindustrie e.V. for financial support
of this work.
[l] H . v . Euler and B. Eistert: Chemie und Biochemie der Reduktone und Reduktonate. F. Enke, Stuttgart 1957, pp. 223-237.
121 B. Drevon, C . Nofre, and A. Cier, C. R. hebd. Seances Acad.
Sci. 243, 607 (1956).
[3] C . Nofre, A . Cier, and B. Drevon, Bull. SOC.chim. France 27,
245 (1960).
[4] D . Nomura and T . Uehaba, Hakko-Kogaku Zasshi (J. Ferment. Technol.) 36, 290 (1958).
[5] T. Kurata, H. Wakabayashi, and Y. Sakurai, Agric. biol.
Chem. (Tokyo) 31, 101, 170, 177 (1967).
[6] W . T . Haskins, R . M . Mann, and C . S. Hudson, J. Amer.
chem. SOC.68, 1766 (1946).
[7] S. G . Bayne, G . A . Collie, and J . A. Fewster, J. chem. SOC.
(London) 1952, 2766.
[8] See [I], p. 45.
Angew. Chem. internnt. Edit.
j
Vol. 7 (1968)
/ No. 9
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