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Synthesis of -Functional Nitrosamines.

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decomposition to occur over more than three half-lives with
4 2 5 " C )= (9.05 0.05)x 10- s- I .
2,3-Di-tert-but!,lthiuziri~ine 1,I-dioxide (2)
A solution of (5)l7](2.0g, 11.7mmol) in ether (30ml) is added
dropwise to a solution of (3/[91(1.2g, 12.2mmol) and triethylamine (1.26g, 12.5mmol) in ether (50ml) under N, at -78'C.
for 30 min. After 2 h at - 78°C the reaction mixture is filtered,
the ether distilled off in vucuo at -5O"C, and the residue
sublimed at O"C/10-5 torr on to a finger cooled to -60°C.
Yield: 1.02g (43'%,),dec. p. 40-43°C. IR (CCI,): no NH,
1325, 1177cm-' (SO,).--'H-NMR (CCI,): F=1.03 (s, tBu).
1.33 (s, tBu), 3.72ppm (s, CH).-UV (n-hexane): Only end
absorption above 200nm["'.
Synthesis of x-Functional Nitrosamines
By Mu+d
Wiessled']
Addition of nitrosyl chloride to olefins leads to vicinal chloro
nitroso compounds or their dimers"'. If the reaction proceeds
in the same manner, the addition of nitrosyl chloride to Schiff
bases[" could lead to cc-chloro N-nitroso compounds- ideal
intermediates for the synthesis of x-functional nitrosamines.
In this context, particular interest attaches to the synthesis
of .w-hydroxy nitrosamines or their esters for they are of special
significance for the elucidation of the metabolism of nitrosamines and for studying the carcinogenic action of this class
of compounds. The present communication briefly reports
the addition of nitrosyl chloride to Schiff bases.
Received: August 2. 1974 [Z 89 IE]
German version: Angew. Chem. 86. 816 (1974)
CAS Registry Numbers:
(21. 53111-73-2: i 3 ) . 762-64-1 : i s ) . 33581-95-2
.
.~
.-
[ I ] a ) J. it' Timhe!-/rrkr and M . L. Hodyrs. 1. Amer. Chem. S O ~95. 634
(1973): b) .I. W Timber/akr, M . L. Hodgrs, and A. W Garner, Tetrahedron
Lett. I Y 7 3 . 3843: c) H.-H. Chuny and B. Wrrnsrrrn, J. C. S. Chem. Comm.
1Y73. 397.
H . QIIUSI
and F. K r r s . Tetrahedron Lett 1973, 1655
[?I
[3] a ) B. Johnson and J. B. Doi~&sr, J. Amer Chem. SOC.63, 1571 (1941):
F G. B f J r f / i ! d / and G. D. Cooprr. hid 73, 51 87 (1951): W V. Forrur, J .
Chcm. Soc. IYMI. 3058. b) Norc oridrd i n proof (Oct. IS. 1974): Unsuccessful
attemptsat synthesis have meanwhile been reported: J. C. Skrrhrm. L'. Zo11rr.
and D. B w - k h a i . J Org. Chem. 39. 1817 (1974).
141 H . Q I w r and F. Krrs. Synthesis 1974, 489.
[ 5 ] F. K w a , Diplomarbeit, Universitiit Wurzburg 1972.
[6] Survey: N H. Fi.s(.hcw. Synthesis 1970, 393.
171 W L. Morirr. W 7 Comer. and D. Drirchman, J. Med. Chem. 15, 538
( 1972)
[ X I Regarding the chemistry of the N-sulfonylamines see: B. Wwmrin and
H . H . Chong. Tetrahedron Lett. 1974, 901, and references cited therein.
[9] G. M. Kaufmann, J. A. Smirh, G. G. Van der Siouw, and H . Shrchirr.
J Amer Chem. SOC.87, 935 (1965).
[ 101 The ready decomposition precludes C, H. N analysis
[ I I ] Cf. the spectroscopic data for 2.3-di-ierr-butylthiirane 1.1-dioxide [ S ]
[ I R (CCII): 131 5, I 162cm I (SO?),'H-NMR (CCIaj: 6 = 1.13 Is, tBu), 2.90ppm
Is. CH)] and 2.3-di-rerr-butylthiadiaziridineI,l-dioxlde [Ia. I c].
[ 121 W H i h e r . Titrations in Nonaqueous Solvents. Academic Press, New
York 1967.
[ 131 Identified by comparison with the authentic compound prepared from
( 7 ) [ 141 and perchloric acid.
[I41 R. Bonnrrr. J. Chem. SOC.lY65, 2313; J. C . Sherhan and J. H . Breson,
J Amer. Chem Soc. 89, 362 (1967).
[IS] Apparatus. H . Quusi and E. Schmrir. Lieblgs Ann. Chem. 732.43 (1970).
Angew.
Chrm. rnfernur. Edir. i Vol. 13 (1974) 1 No. I /
If the Schiff base ( l ) [ ' ]is reacted at - 30°C with the stoichiometric amount of NOCI, rapid decoloration occurs. After
addition of CH30H/(CzH5)3N, CH3C02H/(CrH5)3N,or p N02-C6HaC02H/(CrHs)3N at the same temperature and
subsequent work-up, the compound ( 6 u ) , ( 6 b ) , or (6c) can
be isolated. All the compounds of type ( 7 ) - ( 2 0 ) listed in
Table 1 could be synthesized in the same way. Their structures
are confirmed by analytical and spectroscopic data.
In an attempt to prepare compound ( 9 u ) only the starting
materials were isolated. The methyl ether was apparently
formed at - 30°C but liberated methyl nitrite with regeneration of the double bond during work-up. The isolation of
(IOU)demonstrates the feasibility of preparing tertiary methyl
ethers.
It may be assumed that the chlorides ( 6 d ) - ( I O d ) are formed
on addition of NOCl to the Schiff bases (2)-(5). Confirmation of this course is provided by the isolation'of ( 6 d ) [NMR
(CDCI3): ~ = 4 . 9 0(2H, s), 8.35 (9H, s)]. The chloride decomposes already at room temperature. Since the secondary chlorides should be even more reactive we have not attempted
to isolate them. So far, N-chloromethyl-N-nitrosomethyl-
["I
Dr. M Wiessier
Institut fur experimentelleToxikologie und Chemotherapie am Deutschen
K rebsforschungszentrum
69 Heidelberg, Kirschnerstrasse 6 (Germany)
743
amine, which is also accessible cia another route, is the only
representative of this class of compounds that is stable at
room temperat~re'~].
This method supplements and extends Eiter's synthesisi5]of
x-alkoxy nitrosamines. Compounds ( 6 a ) , ( 7 n ) , and ( 8 u )
can also be prepared in low yields by Eiter's method but the
impurities cannot be removed"].
luster (garnet red when viewed by transmitted light) the reaction mixture contained LiNb0313] and some Li,Nb04[41.
which are both colorless.
The same substance was obtained almost pure as a black
powder (streak: wine-red) from corresponding mixtures of
LizO + NbO + NbOz [700"C, 3 d, small nickel bomb, under
argon]. Debye-Scherrer powder photographs show the single
crystals to be identical with the powder, which also contained
a little LiNb03.
The Nb content [70.4 (exp.); calc. 70.46% (LiNbOz),60.02
(Li2Nb0,), and 64.1
(Li4Nb30s), respectively] and the
increase in weight on careful oxidation [O,, 700"C, 12h:
A = +11.3'j/(exp.);calc. +12.14(LiNb02), +5.17(Li2Nb03),
and + 5 S 2 (Li4Nb30H)]as well as structural determination
confirm the presence of LiNb02.
Rotating crystal (above [10.0]), Weissenberg (0k.l-2k.i), and
precession diagrams (kk.0, kk. 1 and k0.1 and kl .I) indicate
a hexagonal unit cell havinga=2.90~A,c= 10.46A, c/a=3.60;
z=2.
Structural determination [I28 Ok.1-2k.1, 10 data recorded
with a two-circle diffractometer (Stadi 2 manufactured by
Stoe, Darmstadt), MoKXradiation] ruled out the space groups
P6imc and P62c, which were also compatible with the extinctions, and confirmed the space group P63/mmc. Interpretation
of the Patterson synthesis followed by Fourier difference syntheses and subsequent least-squares refinement led to the parameters listed in Table 1 ; R=R'=5.2,0/,.
N-rert-Buryl-N-nitrosainiiioinetkyl acetate (6b)
N-Methylene-terr-butylamine ( I ) (25 mmol) in CH2CI is
added dropwise to a 1 M NOCI solution in CH2C12 (25ml)
at -30°C. After lOmin, a solution of triethylammonium acetate (25mmol) in CH2C12 (20mI) is added dropwise at the
same temperature. The cold bath is removed. After the solution
has warmed to room temperature it is shaken several times
with water, the organic phase then being dried over Na2S04,
concentrated, and distilled. ( 6 b ) , b. p. 58T/0.05 torr, yield
2.05g (45%); NMR (CDC13): ~ = 4 . 5 5(2H, s), 7.95 (3H, s),
8.35 (9H, s); IR (CHZC12): 1755, 1480cm-'; UV (diethyl
ether): h,,, = 232 nm (E = 5700).
'x
Received: August 22. 1974 [Z 92 IE]
German version: Angew. Chem. 86, 817 (1974)
CAS Registry Numbers.
( 1 ) . 13987-61-6; ( 2 ) . 7707-70-2; (31. 505-18-0: 141, 622-29-7;
I S ) . 22023-64-9; ( 6 a ) . 53198-37-1 ; 16h), 53198-38-2; ( 6 c J . 53198-39-3:
16di. 53198-40-6; 1 7 ~ )53230-00-5:
.
17h). 53198-41-7; ( 7 c ) . 53198-42-8:
( X U J . 53198-43-9: (Yh), 53198-44-0; (Ya). 53198-45-1 : ( P h i . 53198-46-2:
l Y c J . 53198-47-3: ( I O U ) , 53198-48-4; CH,OH/(C,H,),N. 10510-76-6:
C H ,CO,H/(C,H,),N, 5204-74-0; p-NO,-C,H,CO,H/(C,H,J,N,
51694-06-5; NOCI. 2696-92-6.
Table i. Atomic parameters for LiNbO, (standard deviations in units of
the last decimal place are given in parentheses).
Brrkham. W A. Fessler, and M . A Kisr, Chem Rev. 48, 319
(1951): R. Srroh in Houben-Weyl: Methoden der organischen Chemie. Thieme.
Stuttgart 1962, Vol. V/3, p 934.
[I] L. J
.
[2] J . Turron. Bull. Soc. Chim. Fr 52, 627 (1935)
[3] According t o Houben- Weyl (Methoden der Orgdnischen Chemie Thieme,
Stuttgart 1958. Vol. X1/2, p. 78). this azomethine IS present: however. spectroscopic data indicate that i t is better formulated as perhydro-l,i,5-triazine.
__ -~
~~
-~
~~
Particle
Equiv.
posn.
Y
I'
Li
Nb
2a
2d
4f
0
0
0.6
0.3
0.6
0
0.3
~~
B
0
0.25
0.1263(4)
-.
[A2]
1.4(7)
0.33(2J
0. I3( I I )
[4] L. Kerfer,Tetrahedron Lett., in press: M . Wiessler, ihid.. in press.
[ 5 ] K . Eirer. K . F . Hrhrnhr.ock. and H . J Kuhhu. Liebigs Ann. Chem. 765.
55 (1972).
According to these results the compound has a "filled" layer
structure of MoSl type, which also occurs in NbS,"! Nb3
is in ,a trigonal-prismatic environment of 6 02-(distance
2.1 1 8 A, 6 x ) , which is surprising in view of its "diagonal
relationship" to Ti2+.Li occupies octahedral sites between
the NbOr layers (Li-O=2.13jA, 6 x ) . The 10 data discount
any occupation of the corresponding tetrahedral sites, as
shown by R values and especially B values resulting from
test calculations.
Between 3 and 300 K LiNbOz exhibits temperature-independent magnetism with marked dependence upon field strength,
[6] A4. Wieszier., unpublished experiments
+
The First Oxoniobate(111): LiNbOz['
+
By Gerd Meyer and Rudolf HoppeI';]
During attempts to prepare Li4Nb!?OR, whose existence
appears to be inadequately substantiatedl2],we unexpectedly
obtained inhomogeneous wine-red reaction products
[2Li20+3NbOz; 90O0C, 35d, small nickel bomb, under
argon]. Apart from hexagonal plate2ers having a bluish-black
Table 2. Madelung part of the lattice energy (MAPLE) of LiNbO? [kcdlmol].
- -
~
binai-y
from
+
0 2
0
'
0'
Li 3 0
Nb O
2'-N bO
Li :O
N bO
%'-NbO,
A
ZA
215.1
+
+689
-40.7
- 63.3
0
f51.9
- 24.3
X
-
Li
Nb"
Nb"
ternary
146.2
1067.0
I 1 12.2
543.5
474.2
515.9
_
- -
1
0.5
05
0.5
0 75
0.75
-
~
146.2
533.5
556. I
27 I .8
355.7
431.9
9x5 7
543.5
(2 x J
689
- 81.3
- 126.5
0
+ 69.3
- 32.4
~
___
.
[*] Prof. Dr. R. Hoppe and DiplLChem. G. Meyer
Institut fur Anorganische und Analytische Chemie der UniversitPt
63 Giessen, Sudanlage 6 (Germany)
744
~~
2 : 2295.2
2287.8
-
_ _
_
7.5 (0.3"<,)
and resembles NbOl['' to such a degree that, as with VOz,
it is presumably antiferromagneti~~''
(with T., > 300 K).
The agreement between the Madelung part of the lattice energy
Angrw. Chrm. i n r m m t . Edir.
/ Vol. 13 f 1974) I No. I 1
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