Phosphoryl-containing α-thiocyanatoaldehydes

Full text of DOI:10.1023/A:1020982316890

Russian Journal of Organic Chemistry, Vol. 38, No. 8, 2002, pp. 1216 1217. From Zhurnal Organicheskoi Khimii, Vol. 38, No. 8, 2002,
pp. 1267 1268.
Original English Text Copyright
2002 by Guseinov, Asadov, Burangulova.
SHORT
COMMUNICATIONS
Phosphoryl-containing -Thiocyanatoaldehydes
F. I. Guseinov, Kh. A. Asadov, and R. N. Burangulova
Kazan State Technological University, Kazan, Tatarstan, 420015 Russia
Received December 21, 2001
-Thiocyanatoamides and -ketones as synthetic
equivalent of two-carbon electrophilic synthons are
used in the synthesis of heterocyclic structures [1 3]
some of which possess useful properties [4, 5].
Unlike these carbonyl compounds the procedures for
preparation and chemical properties of -thiocyanato-
aldehydes are poorly known.
Thiocyanatoaldehydes IVa, b are colorless crystal-
line substances; their structure was proved by IR,
1H and 31P NMR spectroscopy.
Aldehyde IVa exists in solution exclusively as enol
in a mixture of cis- and trans-isomers in 1: 2 ratio.
Therewith the methylene protons give in the 1H NMR
spectrum doublet signals at 7.63 and 7.43 ppm with
3JPH 5 Hz. Basing on data from [6] the doublet at
7.63 ppm was assigned to the trans-isomer, and that
at 7.43 ppm to the cis-isomer.
Aiming at the synthesis of previously unknown
-thiocyanatoaldehydes we studied reactions of phos-
phorylated -haloaldehydes (II) with alkali metals
thiocyanates (III). The initial haloaldehydes IIa, b
were obtained by reaction of enolate I with halogens
in CH2Cl2 at 30 40 C.
Heating of compound IVa or its treating with
bases results in formation of O,O-diisopropyl(2-
imino-1,3-oxathiol-4-yl)phosphonate (V).
Hlg = Cl (a), Br (b).
In the IR spectra of compounds IIa, b the aldehyde
group appears as an absorption band is the region
1
1770 1780 cm , and in the 1H NMR spectra at 9.59
9.65 ppm as an intense doublet with 3JPH 6.25 Hz.
The reaction of halocarbonyl compounds IIa, b
with nucleophilic reagents III proceeded in boiling
acetone for 6 7 h giving rise to -thiocyanato-
aldehydes IVa, b in 75 80% yield.
The heterocyclization is confirmed by the 1H NMR
data. In the spectrum of compound V appears only
one doublet of methylene protons at 7.35 ppm (3JPH
5 Hz), the signal of imine group is observed as a
singlet at 7.40 ppm.
-(Diethoxyphosphoryl)phenylchloroacet-
aldehyde (IIa). Through a suspension of 139 g
(0.5 mol) of enolate I in 500 ml of dichloromethane
at room temperature while stirring was passed gaseous
II, Hlg = Cl (a, c), Br (b); R = Et (a, b), i-Pr (c);
X = Ph (a, b), H (c); IV, R = i-Pr, X = H (a);
R = Et, X = Ph (b); M = Na, K.
1070-4280/02/3808-1216$27.00 2002 MAIK Nauka/Interperiodica

PHOSPHORYL-CONTAINING -THIOCYANATOALDEHYDES
1217
chlorine till the solution turned yellow, and heat
evolution stopped. Then the reaction mixture was
heated to 40 C, and chlorine was passed for 2 h more.
The precipitate was filtered off, the solvent was
removed, and fractional distillation of the residue
furnished aldehyde IIa, yield 135 g (93%), bp 115
cyanate, yield 76%, mp 178 180 C. IR spectrum, ,
1
cm : 1250 (P=O), 1660 (C=C), 2130 (C N), 3160
(OH). 1HNMR spectrum [(CD3)2SO], , ppm: 1.10d.t
(6H, 2CH3); 4.0 m (4H, 2OCH2); 7.35 m (3H, Ph);
7.75m (2H, Ph); 9.8 s (1H, CHO). 31PNMR spectrum:
6.59 m.d. Found, %: N 4.54; P 9.81; S 10.14.
C13H16NO4PS. Calculated, %: N 4.47; P 9.90;
S 10.22.
116 C (0.05 mm Hg), n2D0 1.5133. IR spectrum,
,
1
1
cm : 1260 (P=O), 1750 (CHO). H NMR spectrum
[(CD3)2CO], , ppm: 1.15 d.t (6H, 2CH3), 4.05 m
(4H, 2OCH2), 7.35 m (3H, Ph), 7.50 m (2H, Ph),
9.65 d (1H, CHO, J 6.25 Hz). 31P NMR spectrum:
8.0 ppm
O,O-diisopropyl(2-imino-1,3-oxathiol-4-yl)phos-
phonate (V). In 15ml of 2-propanol 2.65g (0.01mol)
of aldehyde IVa was boiled for 8 h. The reaction
mixture was filtered, the filtrate was evaporated by
60% and left overnight in a refrigerator. The pre-
cipitated crystals of compound V were filtered off,
washed with ethyl ether, and dried. Yield 1.9 g
-(Diethoxyphosphoryl)bromophenylacet-
aldehyde (IIb). To a suspension of 83.4 g (0.3 mol)
of enolate I in 300 ml of dichloromethane at room
temperature was added dropwise 0.3 mol of bromine.
The reaction mixture was heated to 40 C for 2 h, the
precipitate was filtered off, the solvent was removed,
and fractional distillation of the residue furnished
aldehyde IIb, yield 90 g (90%), bp 129 130 C
1
(72%), mp 169 170 C. IR spectrum, , cm : 1280
1
(P=O), 1620(C=C), 2500(=NH). HNMR spectrum
[(CD3)2SO], , ppm: 1.20 t (12H, 4CH3); 4.50 m
(2H, 2OCH); 7.35 d (1H, =CH, J 5 Hz); 7.40 s (1H,
=NH). 31P NMR spectrum: 10.00 ppm Found, %:
N 5.22; P 11.64; S 12.16. C19H16NO4PS. Calculated,
%: N 5.28; P 11.70; S 12.07.
(0.05 mm Hg), n2D0 1.5131. IR spectrum, , cm :
1
1260 (P=O), 1750 (CHO). 1H NMR spectrum
[(CD3)2CO], , ppm: 1.20 d.t (6H, 2CH3); 4.01 m
(4H, 2OCH2); 7.30 m (3H, Ph); 7.65 m (2H, Ph);
9.50 d (1H, CHO, J 6.25 Hz). 31P NMR spectrum:
8.2 ppm.
IR spectra were recorded on spectrophotometer
UR-20. 1H NMR spectra were measured on spectrom-
eter Tesla BW-567 (100 MHz), reference HMDS.
31P NMR spectra were registered on spectrometer
Bruker WP-80 (32.38 MHz), reference % H3PO4.
-Diisopropoxyphosphoryl- -thiocyanatoacet-
aldehyde (IVa). A mixture of 0.02 mol of aldehyde
IIc [7] and 0.02 mol of sodium or potassium thio-
cyanate in 30 ml of acetone was boiled for 6 h. The
separated precipitate was filtered off, the filtrate was
evaporated. To the oily substance obtained was added
a mixture acetone ethyl ether (1: 2). The separated
crystalline aldehyde IVa was filtered off and recrystal-
lized from 2-propanol, yield 80%, mp 172 173 C.
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1
IR spectrum, , cm : 1251 (P=O), 1736 (CHO),
1
2154 (C N). H NMR spectrum [(CD3)2CO], , ppm:
1.20 d.t (12H, 4CH3); 4.25 q (1H, OH); 4.60 m (2H,
2OCH); 7.43, 7.63 d (1H, =CH, J 7.5 Hz). 31PNMR
spectrum: 10.00 ppm Found, %: N 5.24; P 11.78;
S 11.98. C9H16NO4PS. Calculated, %: N 5.28;
P 11.7; S 12.07.
-Diethoxyphosphoryl- -thiocyanatoacet-
aldehyde (IVb) was prepared under similar condi-
tions from aldehyde IIa or IIb and potassium thio-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 8 2002