A CONVENIENT SYNTHESIS OF BIS(AMINOOXY)METHANE DIHYDROCHLORIDE
125
166 (2) [M NC(CH3)C6H4F]+, 136 (100) [M
OCH2ON(CH3)CC6H4F]+, 95 (31) [C6H4F]+. Found, %:
C 64.14; H 5.07; F 11.85; N 8.70. C17H16F2N2O2. Cal-
culated, %: C 64.15; H 5.10; F 11.94; N 8.72.
catalysis. However, a proper choice of both alkylating
agent and the system basephase-transfer catalyst is
necessary to achieve a good preparative yield of dimeric
products IIaIIt [7, 8]. For example, oxime Ib was quan-
titatively converted into compound IIb by the action of
methylene chloride in the system potassium carbonate
rown ether, whereas complete transformation of oxime
Ie into compound IIe was effected with the use of me-
thylene bromide and the system alkaliquaternary am-
monium salt.Also, success in the acid hydrolysis of com-
pounds IIaIIt strongly depended on the R and R' sub-
stituents. We failed to obtain product III by hydrolysis of
compounds IIc and IId despite wide variation of the re-
action conditions. On the other hand, the simplest deriva-
tives IIa and IIb were readily hydrolyzed in aceto-nitrile
by the action of concentrated hydrochloric acid; here, the
yield and purity of compound III were better in the reac-
tion with IIb. Bis(aminooxy)methane dihydrochloride (III)
can readily be converted into N,N,N',N'-tetraacetyl de-
rivative IV (which is more convenient to handle with) by
heating in boiling acetic anhydride.
Bis(3-fluoro-a-methylbenzylideneaminooxy)-
methane (IIl). Yield 89%. Colorless crystals, mp 88 90°C
1
(from CCl4). H NMR spectrum (CDCl3), d, ppm:
7.547.58 m (2H, p-H), 7.417.51 m (4H, o-H),
7.147.21 m (2H, m-H), 5.87 s (2H, CH2), 2.26 s (6H,
CH3). Mass spectrum, m/z (Irel, %): 318 (3) M+, 166 (2)
[MNC(CH3)C6H4F]+,
136
(100)
[M
OCH2ONC(CH3)C6H4F]+, 95 (33) [C6H4F]+. Found, %:
C 64.12; H 5.08; F 11. 87; N 8.76. C17H16F2N2O2. Cal-
culated, %: C 64.15; H 5.10; F 11.94; N 8.72.
Bis(4-fluoro-a-methylbenzylideneamino-
oxy)methane (IIm). Yield 96%. Colorless crystals, mp
1
104106°C (from CCl4). H NMR spectrum (CDCl3),
d, ppm: 7.627.69 m (4H, o-H), 7.007.19 m (4H, m-H),
5.82 s (2H, CH2), 2.25 s (6H, CH3). Mass spectrum, m/z
(Irel, %): 318 (2) M+, 166 (3) [M NC(CH3)C6H4F]+,
136 (100) [M OCH2ONC(CH3)C6H4F]+, 95 (30)
[C6H4F]+. Found, %: C 64.11; H 5.12; F 11. 83; N 8.68.
C17H16F2N2O2. Calculated, %: C 64.15; H 5.10; F 11.94;
N 8.72.
The NMR spectra were recorded on a Varian XL-
100 spectrometer. The mass spectra were run on
a Finnigan MAT-113 instrument with direct sample ad-
mission into the ion source. The properties of previously
known compounds were in a good agreement with pub-
lished data [1, 2, 7, 8].
Bis(2,4-difluoro-a-methylbenzylideneamino-
oxy)methane (IIn). Yield 83%. Colorless crystals,
mp 127129°C (from CCl4). 1H NMR spectrum (CDCl3),
d, ppm: 7.507.57 m (2H, m-H), 6.826.93 m (4H, o-H,
m-H), 5.83 s (2H, CH2), 2.28 s (6H, CH3). Mass spec-
trum, m/z (Irel, %): 354 M +, 200 (3) [M
Bis[bis(ethoxycarbonyl)methyleneaminooxy]-
methane (IId). Yield 85%. Colorless crystals, mp 100
102°C (from CCl4). 1H NMR spectrum (CDCl3), d, ppm:
5.92 s ( 2H, CH2), 4.43 q (8H, OCH2CH3), 1.31 t (12H,
CH3). Mass spectrum, m/z (Irel, %) : 390 (2) M +, 202 (3)
[MNC(CO2Et)2]+, 172 (100) [M OCH2ONC(CO2Et)2]+,
73 (30) [CO2Et]. Found, %: C 47.00; H 5.60; N 7.00.
C15H22N2O10. Calculated, %: C 47.15; H 5.68; N 7.18.
NC(CH3)C6H3F2]+,
154
(100)
[M
OCH2ONC(CH3)C6H3F2]+, 114 (35) [C6H3F2]. Found,
%: C 64.14; H 5.07; F 21.12; N 8.80. C17H14F4N2O2.
Calculated, %: C 57.63; H 3.98; F 21.45; N 7.91.
Bis(2-fluoro-4-methoxy-a-methylbenzylidene-
aminooxy)methane (IIq). Yield 90%. Colorless crys-
Bis(a-aminobenzylideneaminooxy)-methane
(IIe). Yield 80%. Colorless crystals, mp 185187°C (from
CHCl3). 1H NMR spectrum (CD3OD), d, ppm: 7.30
7.80 m (10H, Ph), 5.50 s (2H, CH2), 4.70 s (4H, NH2).
Mass spectrum, m/z (Irel, %): 284 (3) M+, 165 (3) [M
NC(NH2)Ph]+, 119 (100) [M OCH2ONC(NH2)Ph]+, 77
(35) [Ph]+. Found, %: C 63.20; H 5.54; N 19.65.
C15H16N4O2. Calculated, %: C 63.40; H 5.70; N 19.90.
1
tals, mp 128130°C (from CCl4). H NMR spectrum
(CDCl3), d, ppm: 7.457.51 m (2H, m-H), 6.616.73 m
(4H, o-H, m-H), 5.82 s (2H, CH2), 3.77 s (6H, CH3O),
2.30 s (6H, CH3). Mass spectrum, m/z (Irel, %): 378 (3)
M+, 212 (2) [M NC(CH3)C6H3FOCH3]+, 166 (100)
[M OCH2ONC(CH3) C6H3FOCH3]+, 126 (38)
[C6H3FOCH3Ar]+. Found, %: C 60.25; H 5.28; F 10.00;
N 7.36. C19H20F2N2O4. Calculated, %: C 60.31; H 5.33;
F 10.04; N 7.40.
Bis(2-fluoro-a-methylbenzylideneaminooxy)-
methane (IIk). Yield 92%. Colorless crystals, mp 89
90°C (from CCl4). 1H NMR spectrum (CDCl3), d, ppm:
7.517.56 m (2H, o-H), 7.337.40 m (2H, p-H),
7.107.18 m (4H, m-H), 5.86 s (2H, CH2), 2.30 s
Bis(3-fluoro-4-methoxy-a-methylbenzylidene-
aminooxy)methane (IIr). Yield 81%. Colorless crys-
tals, mp 148150°C (from CCl4). 1H NMR spectrum
(CDCl3), d, ppm: 7.477.56 m (4H, o-H, m-H), 7.12
+
(6H, CH3). Mass spectrum, m/z (Irel, %): 318 (2) M ,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 1 2004