LITERATURE CITED

i. Y. Wilkinson and F. Stone (eds.), Comprehensive Organometallie Chemistry, Vol. 8, Pergamon Press; Oxford (1982), pp. 434, 446.

2. Jiro Tsuji, Organic Synthesis with Palladium Compounds, Springer-Verlag, Berlin (1980), p. 93.

3. U.M. Dzhemilev, V. V. Sidorova, and R. V. Kunakova, Izv. Akad. Nauk SSSR, Ser. Khim., 584 (1983).

4. R.V. Kunakova, V. V. Sidorova, and U. M. Dzhemilev, Abstracts of the Fourth All-Union Conference on the Reactivity and Biological Activity of Noble Metal Complexes [in Russian], (1982), p. 55.

REACTION OF THE TETRAETHYLAMMONIUM SALT OF N-METHYL-N-NITROSOHYDROXYLKMINE

WITH ALLYL BROMIDE

I. N. Zyuzin UDC 542.91:547.238-38:547.323

N-Alkyl-N-nitrosohydroxylamines (NHA) and their salts are alkylated at both oxygen atoms, although there is no information available on the ratio of the alkylation products since the desired product of this reaction is, as a rule, an N-alkyl-N'-alkoxydiazene N-oxide, while alkylalkoxynitrosoamines decompose under the synthesis and separation conditions [i] :

R - - N - - 0

o o

In this work, we have shown that the reaction of the tetraethylammonium salt of N-methyl- N-nitrosohydroxylamine (I) with allyl bromide proceeds exothermally at 20~ to form N-methyl- N'-allyloxydiazene N-oxide (II) and methylallyloxynitrosamine (III) in 1:1.6 ratio with a to- tal yield of 89%:

�9 CH~--i~__0 MeCN -- N+N~ "~ CH~=CHCH~Br _Et,NBr> CHsaN+(0-) =

=NOCHz b H d

\C=C / + CHaaN(N0)OCH~ bt H d ,

H= / \H e \'C=C / " (II) (III) H~ XHe

The structures of (II) and (III) were supported by their elemental analysis, molecular re- fraction indices, and IR, UV, and PMR spectra. The purity of (II) and (III) were checked by gas--liquid chromatography. The amount of the impurity of (III) in (II) was monitored by UV spectroscopy relative to the n--~* transition (%max 373 nm in heptane). A shift in the n--~* transition toward longer wavelengths and the appearance of fine structure are noted in the UV spectrum of (II), as in the case of dialkylnitrosamines [2], in going from water to hydrocarbon solution. As a result, this band is better resolved from the strong ~-~* transition band in (II), which reduces the limit for the observation of an impurity of (III) in (II) by almost an order of magnitude. Oxide (II) is a colorless liquid, while (I!l) is a yel!ow liquid which de-

Division of the Institute of Chemical Physics, Academy of Sciences of the USSR, Cherno- golovka. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. Ii, pp. 2626- 2628, November, 1985. Original article submitted January 16, 1985.

0568-5230/85/3411- $09.50 �9 1986 Plenum Publishing Corporation 2433

composes slowly at 80oc in the liquid phase and rapidly at 130~ in the gas phase. The decomp- osition kinetics of (III) is first-order (kso o = 2.8.10 -6 , k o = 4.9.10 -~ sec-1). On the

30 O other hand, the decomposition of (II) becomes significant only above 200 C. This difference in thermal stability was used to remove traces of (III) from (II).

In the case of the reaction of salt (I) with allyl bromide, mild conditions for the al- kylation of tetraalkylammonium salts of NHA permit the use of this reaction as a convenient means for the concurrent preparation of N-alkyl-N'-alkoxydiazene N-oxides and alkylalkoxyni- trosamines.

EXPERIMENTAL

The IR spectra were taken on a UR-20 spectrometer. The UV spectra were taken on a Specord UV-VIS spectrometer with 10-mm pathlength. The PMR spectra were taken on an NMR spectrometer with a cryogenic magnet developed and constructed at the Chernogolovka Division of the Insti- tute of Chemical Physics of the Academy of Sciences of the USSR at 294 MHz with TMS as the in- ternal standard. The gas--liquid chromatographic analysis was carried out on an LKhM-8~/5 chromatograph, using a flame ionization detector and 30 ml/min nitrogen flow rate with 2 m • 3 mm steel columns packed with 15% Carbowax 20M on Chromosorb W-HMDS (80-100 mesh). The column temperature was 180~

Tetraethylammonium Salt of N-Methyl-N-nitrosohydroxylamine (I). A sample of a 30% aque- ous solution of Et4NOH was poured into a hot solution of 0.15 mole of the copper salt of N- methyl-N-nitrosohydroxylamine [3] in 300 ml water and heated at reflux for 0.5 h, filtered to remove Cu(OH) 2, and evaporated in vacuum. The residue crystallized at ~20~ PMR spectrum (30% solution in MeCN, 8, ppm) 3.48 s (3H, CH3N), 3.36 q (SH, NCH2), 1.19 t (12H, C--CH~).

NTMethyl-N'-allyloxydiazene N-Oxide (II) and Methylallyloxynitrosamine (III). A solution of 0.3 mole (I) in 70 ml acetonitrile was added dropwise over 1 h at a temperature not exceed ~ ing 25~ tO a solution of 0.33 mole allyl bromide in 30 ml acetonitrile. The reaction mixture after the addition of i00 ml CH2C12 and the removal of Et4NBr precipitate was diluted with 150 ml water, extracted with CH2C12, and dried over MgS04. After distilling off the solvent, the residue was fractionated in vacuum to give a 34% yield of (II). After purification by maintenance for 1.5 h at 140~ and further repeated distillation in vacuum, the toHal content of impurity detectable by gas--liquid chromatography was 0.1%; an impurity of (IIl) could not be detected (<0.05%), bp 72~ (4 mm), n_ 2~ 1.4751, d4 2~ 1.0749. Found: C 40.6; H 6.8; N 24.0%; MR~ 30.42. Calculated for C4HsN202: C ~1.37; H 6.94; N 24.12%; MR D 30.31. UV spectrum (~max, nmY in water: 234 (s 9060). IR spectrum (~, cm-i): 1325, 1435, i~20 [N+(O-)=N--O]. PMR spec- trum withou~ solvent (8, ppm): 3.82 s (3H, Ha), 4.67 d. t (2H, HD), 5.25 d.q (IH, He), 5.34

d. q (IH, H ), 5.98 m (IH, HC), Jbc = 5.5, Jce= i0, Jcd = 17 Hz, Jbe ~ J~A = Jde ~ 1 Hz. The yield of (IIi) was 55%. After distillation thrice in vacuum, the content~f the impurity of (II) was 0.2%, bp 33~ (3 mm), nD2~ 1.4555, d~ 2~ 1.0491. Found: C 41.3; H 6.5; N 23.8%; MR D 30.06. Calculated for C4HsN202: C 41.37; H 6.94; H 24.12%; MRn 30,40. UV spectrum (%max, nm) in water: 234 (s 6340), 335 (s 93.1); in heptane: 373 (E 88.7)~ IR spectrum (n, cm-i): 1225, 1285, 1445 (ONN~O). PMR spectrum without solvent (8, ppm~ the lines are broadened): 3.81 s (3H, He), 4.13 d (IH, Hb) , 5.31 d (IH, He), 5.36 d (IH, HU), 5.97 m (IH, HC), Jbc = 6, J ii, and Jcd = 18 Hz. ce

CONCLUSIONS

Allyl bromide alkylates the tetraethylammonium salt of N-methyl-N-nitrosohydroxylamine at both oxygen atoms to form N-methyl-N'-allyloxydiazene N-oxide and methylallyloxynitrosamine in 1:1.6 ratio.

1. 2. 3.

LITERATURE CITED

V. N. Yandovskii, B. V. Gidaspov, and I. V. Tselinskii, Usp. Khim., 49, 452 (1980). R. N. Hazeldine and B. J. H. Mattinson, J. Chem. Soc., 4172 (1955). J. Y. Johnson and G. W. Johnson, British Patent No. 815,537 (1959); Chem. Abstr. 54, 3270 (1960).

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