Synthesis of O-aryl N4-glycosyl(thiosemicarbazido) phosphonothioates

Article abstract of DOI:10.1023/B:RUJO.0000013135.25430.40

A reaction of aryl(aryloxy)thiophosphonic acids hydrazides with glycosyl isothiocyanates was studied. Amides of N-(glycosylthioureylene)aryl(aryloxy) thiophosphonic acids were synthesized. The structure and composition of the new compounds were confirmed by the data of IR, ¹H and ³¹P NMR and mass spectra, and by results of elemental analyses.

Full text of DOI:10.1023/B:RUJO.0000013135.25430.40

Russian Journal of Organic Chemistry, Vol. 39, No. 11, 2003, pp. 1608 1612. Translated from Zhurnal Organicheskoi Khimii, Vol. 39, No. 11, 2003,
pp. 1678 1682.
Original Russian Text Copyright
,
2003 by Tsao, Chzhou, Sun , Koroteev.
Synthesis
4
of O-Aryl N -Glycosyl(thiosemicarbazido)phosphonothioates
L. Tsao1, Ch. Chzhou1, Ts. Sun,2, and A. M. Koroteev3
1Chemical Department of Xinjiang University, People,s Republic, of China
2Central State Organoelemental Laboratory of Nanchang University, People s Republic of China;
e-mail: cehxj@xju.edn.cn
3Moscow State Pedagogical University, Moscow, 119992 Russia; e-mail: chemdept@mtunet.ru
Received April 11, 2003
Abstract A reaction of aryl(aryloxy)thiophosphonic acids hydrazides with glycosyl isothiocyanates was
studied. Amides of N-(glycosylthioureylene)aryl(aryloxy)thiophosphonic acids were synthesized. The
1
structure and composition of the new compounds were confirmed by the data of IR, H and 31P NMR and
mass spectra, and by results of elemental analyses.
Phosphoric acids hydrazides and their derivatives
possess cytostatic, pesticidal, and other bioregulator
properties. For instance, thiosemicarbazide is an
efficient insecticide [1].
thiosemicarbazides. The introduction of a carbo-
hydrate fragment into the structure of phospho-
hydrazides would evidently diminish their toxicity
and increase the solubility in water.
In view of above we studied the modification of
these compounds with glycosyl isothiocyanates and
obtained the first representatives of glycosylated
The glycosyl isothiocyanates constitute a large class
of accessible organic substances which can serve as
intermediate products in the organic synthesis [2, 3].
Ia, IIa, IV: R1 = Ph, R2 = PhO; Ib, IIb, V: R1 = Ph, R2 = n-MePhO; Ic, IIc, VI: R1 = Ph, R2 = t-BuPhO;
Id, IId, VII: R1 = p-EtPh, R2 = PhO; III VII, gly: tetra-O-acetyl- -D-glucosyl isothiocyanate (a), tetra-O-acetyl-
-D-mannosyl isothiocyanate (b), tri-O-acetyl- -D-xylosyl isothiocyanate (c), hepta-O-acetyl-D-lactosyl isothio-
cyanate (d).
As initial sugars for preparation of glycosyl iso-
thiocyanates were used glucose, mannose, xylose, and
lactose. We established that reaction of acylhalo-
genoses of the above carbohydrates with lead(II)
thiocyanate afforded glycosyl isothiocyanates. The
hydrazides of aryl(aryloxy)thiophosphonic acids IIa
d were obtained by treating with hydrazine aryl(aryl-
oxy)thiophosphonic chlorides. The study of reactions
between phosphorus-containing hydrazides IIa d
with carbohydrates isothiocyanates IIIa d revealed
that the process occurred readily. Evidently the
anomeric effect operating through the semiacetal bond
C1 Ocycle reduced the electron density on the carbon
atom of the isothiocyanate group and thus significant-
ly increased the electrophilicity of NCS group attach-
ed to the glycoside center of the monosaccharide.
Therefore glycosyl isothiocyanates IIIa d turned out
to be more reactive than common isothiocyanates.
1070-4280/03/3911-1608$25.00 2003 MAIK Nauka/Interperiodica

SYNTHESIS OF O-ARYL N-4-GLYCOSYL(THIOSEMICARBAZIDO)PHOSPHONOTHIOATES
1609
In the IR spectra of compounds IV VII lacks the
characteristic band of NCS group (2100 cm ) and
Glycosyl isothiocyanates IIIa d were prepared by
1
procedure [2]. Tetra-O-acetyl- -D-glucosyl isothio-
cyanate (IIIa), yield 54%, mp 109 110 C. Tetra-O-
acetyl- -D-mannosyl isothiocyanate (IIIb), yield
55%, syrupy substance, Rf 0.84. Tri-O-acetyl- -D-
xylosyl isothiocyanate (IIIc), yield 41%, mp 88
appear absorption bands of the following groups:
1
NH CS NH(1510 1490cm ) and C=S (1240
1
1
1220cm ), P=S (705 685 cm ), P N (915
1
905 cm ).
1
90 C.
Hepta-O-acetyl-D-lactosyl
isothiocyanate
In the H NMR spectra of compounds IVa VIIa
(IIId), yield 50%, mp 169 171 C.
signals are observed in the region 5.5 3.2 ppm cor-
responding to the protons of glucose fragment. The
coupling of anomeric proton of glucose H1 with
protons H2 and N4H gives rise to a doublet of
Aryl(aryloxy)thiophosphonic chlorides. To a
solution of 0.079 mol of PhP(S)Cl2 in 20 ml of
anhydrous ether at 20 25 C was added dropwise
with stirring 0.079 mol of an appropriate phenol and
0.079 mol of pyridine in 5 ml of anhydrous pyridine.
The solution was heated at reflux for 2 h, the pre-
cipitated pyridine hydrochloride was filtered off, the
filtrate was concentrated under reduced pressure and
left standing in a refrigerator for 12 h. Then it was
filtered, the syrupy residue was distilled in a vacuum
collecting the appropriate fraction.
doublets at 5.61 ppm (2JH1H2
=
2JH1N4H 8.7 Hz).
The proton of N1H group also appears as a doublet
of doublets at 7.75 ppm with coupling constants
2JHN1,P 16 Hz and JHN1,HN2 4.6 Hz. To determine the
2
chemical shifts of NH protons the compounds under
study were subjected to the exchange with D2O.
Actually, on replacing the labile hydrogen by deuter-
ium in the spectrum, for instance, of compound Va
disappeared doublets of doublets at 7.36, 7.43, and
7.55 ppm, whereas the doublet of doublets of the ano-
meric proton an 5.60ppm transformed into a doublet
of triplets (since for deuterium I = 1). Thus it was
confirmed that the fragment N4HCSN2HN1HPSRR.‘
was actually linked to carbon C1 of the mono-
saccharide skeleton and that it contained labile
hydrogen atoms attached to nitrogens.
Phenyl(phenoxy)thiophosphonic chloride (Ia),
yield 51%, bp 214 218 C (0.5 mm Hg). Phenyl(p-
tolyloxy)thiophosphonic chloride (Ib), yield 30%,
bp 180 188 C (0.3 mm Hg). Phenyl(p-tert-butyl-
phenyloxy)thiophosphonic chloride (Ic), yield 45%,
bp 218 220 C (0.5 mm Hg). p-Ethylphenyl(phenoxy)-
thiophosphonic chloride (Id), yield 38%, bp 205
209 C (0.5 mm Hg).
In the 31P NMR spectra of compounds IV VII
Aryl(aryloxy)thiophosphonic acids hydrazides
IIa d. To 0.3 mol of hydrazine hydrate at cooling
below 12 C with vigorous stirring was added drop-
wise 0,022 mol of an appropriate aryl(aryloxy)thio-
phosphonic chloride Ia d, the reaction mixture was
stirred for 5 h, the precipitate was filtered off, washed
with ethanol and ether, and recrystallized from a
mixture tetrachloromethane petroleum ether, 3: 1.
The corresponding compounds IIa d were thus
obtained.
characteristic signals of the P=S moiety appear in
2
the region
64 78 ppm, JHN1,P 12 20 Hz (see
P
EXPERIMENTAL).
In the mass spectra of all reaction products
molecular ion peaks are observed evidencing the
stability of compounds IV VII under electron impact.
EXPERIMENTAL
All synthesis were carried out in anhydrous sol-
vents. The TLC analyses were performed on GF-254
plates (China). As eluent was used a mixture benz-
ene ethyl acetate, 2: 1. Melting points were measured
on heating block Yanaco MP-S3 (Japan). Optical
activity of compounds was determined on Perkin-
Elmer-241 MC instrument. Elemental analyses were
performed on analyzers MT-3 and Perkin-Elmer-2400.
IR spectra were recorded on spectrophotometer
Perkin-Elmer-325 from samples pelletized with
Phenyl(phenoxy)thiophosphonic acid hydrazide
(IIa), yield 62%, mp 123 125 C. Phenyl(p-tolyloxy)-
thiophosphonic acid hydrazide (IIb), yield 82%, mp
10 112 C.
Phenyl(p-tert-butylphenyloxy)thiophos-
phonic acid hydrazide (IIc), yield 56%, mp 92 94 C.
p-Ethylphenyl(phenoxy)thiophosphonic acid hydra-
zide (IId), yield 72%, mp 107 108.5 C.
N-(glycosylthioureylene)aryl(aryloxy)thiophos-
phonic acids amides. A mixture of 1 mmol of an
appropriate aryl(aryloxy)thiophosphonic acid hydra-
zide IIa d and 1 mmol of glycosyl isothiocyanate
IIIa d in 10 ml of chloroform was heated at reflux
under TLC monitoring. On cooling the separated
precipitate was filtered off, the solvent was distilled
1
KBr. H and 31P NMR spectra were registered on
spectrometer Bruker AC 80 at operating frequencies
80 and 32.4 MHz respectively using TMS as internal
reference (1H) and 85% phosphoric acid as external
reference (31P), solvents CDCl3 or D2O. Mass spectra
were measured on VG-ZAB-HS instrument.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 11 2003

1610
TSAO et al.
off in a vacuum, and 2 ml of anhydrous ether was
added to the residue. The separated precipitate was
filtered off and recrystallized from a mixture of 95%
ethanol and water.
331 (41). Found, %: C 49.67; H 5.10; N 4.49;
P 3.32. C39H48N3O18PS2. Calculated, %: C 49.73;
H 5.14; N 4.46; P 3.29.
4-[2,3;4,6-Tetra-O-acetyl- -D-glucopyranosyl]-1-
[phenyl(p-tolyloxy)thiophosphoryl]thiosemicarb-
azide (Va). Yield 47%, mp 193 194 C. IR spectrum,
4-[2,3,4,6-Tetra-O-acetyl- -D-glucopyranosyl]-
1-[phenyl(phenoxy)thiophosphoryl]thiosemicarb-
azide (IVa). Yield 81%, mp 165 168 C. IR spec-
1
, cm : 1754 (C=O), 1506 (NH C=S), 1220 (P O
1
1
trum, , cm : 1754 (C=O), 1505 (NH C=S), 1460
Ar), 907 (P N), 697 (P=S). H NMR spectrum, ,
1
(P Ph), 1225 (P O Ar), 920 (P N), 696 (P=S). H
ppm: 1.80 2.06 q (12H, CH3), 2.02 2.10 s (3H,
CH3), 3.68 4.35 m (2H, H6 of sugar), 4.79 5.61 m
NMR spectrum, , ppm: 1.79 2.13 m (12H, CH3),
3.25 3.98 m ( 2H, H6 of sugar), 4.71 5.71 m (5H,
(5H, H1 of sugar), 7.04 7.55 m (10H, H arom,
5
H1 of sugar), 7.27 8.16 m (13H, H arom, NH).
5
NH), 8.17 br.s (1H, NH). 31P NMR spectrum, ppm
(J, Hz): 75 “ (2JPH 16) . Mass spectrum, m/z (Irel,
%): 667 ([M]+ , 100), 331 (10). Found, %: C 50.44;
H 5.16; N 6.31; P 4.59. C28H34N3O10PS2. Calculated,
%: C 50.37; H 5.13; N 6.29; P 4.64.
31P NMR spectrum, , ppm (J, Hz): 66.7d ( 2JPH 14).
Mass spectrum, m/z (Irel, %): 653 ([M]+ , 100), 331
(57). Found, %: C 50.01; H 4.89; N 6.47; P 4.78.
C27H32N3O10PS2. Calculated, %: C 49.61; H 4.93;
N 6.43; P 4.74.
4-[2,3,4,6-Tetra-O-acetyl- -D-mannopyranosyl]-
1-[phenyl(p-tolyloxy)thiophosphoryl]thiosemicarb-
4-[2,3,4,6-Tetra-O-acetyl- -D-mannopyranosyl]-
1-[phenyl(phenoxy)thiophosphoryl]thiosemicarb-
azide (Vb). Yield 62%, Rf 0.42. IR spectrum,
,
azide (IVb). Yield 38%, Rf 0.54. IR spectrum,
,
1
1
cm : 1751 (C=O), 1507 (NH C=S), 1119 (P O
cm : 1755 (C=O), 1498 (NH C=S), 1447 (P Ph),
1210(P O Ar), 909 (P N), 695 (P=S). 1H NMR
spectrum, , ppm: 1.77 2.12 m (12H, CH3), 3.24
1
Ar), 914 (P N), 690 (P=S). H NMR spectrum, ,
ppm: 1.77 2.04 q (12H, CH3), 2.28 s (3H, CH3),
3.70 4.32 m (2H, H6 of sugar), 4.81 5.62 m (5H,
3.96 m (2H, H6 of sugar), 4.68 5.70 m (5H, H1 of
5
H1 of sugar), 7.06 7.58 m (10H, H arom, NH);
sugar), 7.15 8.17 m (13H, H arom, NH). 31P NMR
spectrum, , ppm (J, Hz): 66 “ (2JPH 14.5). Mass
spectrum, m/z (Irel, %): 653 ([M]+ , 100), 331 (38).
Found, %: C 50.11; H 4.90; N 6.57; P 4.82.
C27H32N3O10PS2. Calculated, %: C 49.61; H 4.93;
N 6.43; P 4.74.
5
8.15 br.s (1H, NH ). 31P NMR spectrum, , ppm (J,
Hz): 75 d (2JPH 16). Mass spectrum, m/z (Irel, %):
667 ([M]+ , 100), 331 (24). Found, %: C 50.41;
H 5.10; N 6.25; P 4.61. C28H34N3O10PS2. Calculat-
ed, %: C 50.37; H 5.13; N 6.29; P 4.64.
4-[2, 3, 4, 6-Tetra-O-acetyl- -D-xylopyra-
nosyl]-1-[phenyl(phenoxy)thiophosphoryl]thio-
semicarbazide (IVc). Yield 44%, mp 97 99 C. IR
4-[2, 3, 4-Triacetyl-O- -D-xylopyranosyl]-1-
[phenyl(p-tolyloxy)thiophosphoryl]thiosemicarb-
azide (Vc). Yield 90%, mp 109 111 C. IR spectrum,
1
1
spectrum, , cm : 1750 (C=O), 1492 (NH C=S),
, cm : 1753(C=O), 1504(NH C=S), 1221 (P O
1
1458 (P Ph), 1234 (P O Ar), 910 (P N), 690 (P=S).
Ar), 910 (P N), 692 (P=S). H NMR spectrum, ,
1H NMR spectrum, , ppm: 1.81 2.12 m (9H, CH3),
ppm: 1.87 2.10 m (9H, CH3), 2.27 s (3H, CH3),
3.20 5.69 m (5H, H1 of sugar), 7.10 8.15 m (13H,
5
3.68 4.35 m (2H, H5 of sugar), 4.79 5.61 m (4H,
H arom, NH). 31P NMR spectrum, , ppm (J, Hz):
66 d (2JPH 12.5). Mass spectrum, m/z (Irel, %): 697
([M]+ , 100), 259(48). Found, %: C 51.22; H 4.91;
N 7.31; P 5.39. C24H28N3O8PS2. Calculated, %:
C 49.56; H 4.85; N 7.22; P 5.33.
H1 of sugar), 7.06 7.53 m (10H, H arom, NH),
4
8.20 br.s (1H, NH). 31P NMR spectrum, , ppm (J,
Hz): 75 d (2JPH 16). Mass spectrum, m/z (Irel, %):
596 ([M]+ , 100), 259 (15). Found, %: C 50.35;
H 5.10; N 7.11; P 5.25. C25H30N3O8PS2. Calculated,
%: C 50.41; H 5.08; N 7.05; P 5.20.
4-[2,3,4,6-Tetra-O-acetyl- -D-lactosyl]-1-[phenyl-
(phenoxy)thiophosphoryl]thiosemicarbazide (IVd).
4-[Hepta-O-acetyl- -D-lactosyl]-1-[(p-
tolyloxy)thiophosphoryl]thiosemicarbazide (Vd).
1
Yield 60%, Rf 0.37. IR spectrum, , cm : 1751
1
(C=O), 1506 (NH C=S), 1440 (P Ph), 1210 (P O
Yield 56%, Rf 0.25. IR spectrum, , cm : 1748
1
Ar), 911 (P N), 701 (P=S). H NMR spectrum, ,
(C=O), 1505(NH C=S), 1220(P O Ar), 912 (P N),
1
ppm: 1.79 2.01 m (21H, CH3), 3.18 5.64 m (13H,
H of sugar), 7.08 8.09 m (13H, H arom, NH).
31P NMR spectrum, , ppm (J, Hz): 67 d (2JPH 15.5).
Mass spectrum, m/z (Irel, %): 941 ([M]+ , 100),
689 (P=S). H NMR spectrum, , ppm: 1.75 2.04 m
(21H, CH3), 2.18 s (3H, CH3), 3.50 5.41 m (13H,
H of sugar), 6.97 8.19 m (11H, H arom, NH).
31P NMR spectrum, , ppm (J, Hz): 78 d (2JPH 15).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 11 2003

SYNTHESIS OF O-ARYL N-4-GLYCOSYL(THIOSEMICARBAZIDO)PHOSPHONOTHIOATES
1611
Mass spectrum, m/z (Irel, %): 955 ([M]+ , 100), 331
(30). Found, %: C 50.70; H 5.32; N 4.38; P 3.21.
C40H50N3O18PS2. Calculated, %: C 50.26; H 5.27;
N 4.40; P 3.24.
(11H, H arom, NH). 31P NMR spectrum, , ppm (J,
75 d (2JPH 19.5) . Mass spectrum, m/z (Irel, %): 998
Hz): ([M]+ , 100), 973 (54), 331 (17%). Found, %:
C 50.26; H 5.53; N 4.26; P 3.14. C43H56N3O18PS2.
Calculated, %: C 51.75; H 5.66; N 4.21; P 3.10.
4-[2,3,4,6-Tetra-O-acetyl- -D-glucopyranosyl]-
1-[phenyl(p-tert-butylphenoxy)thiophosphoryl]thio-
semicarbazide (VIa). Yield 82%, mp 196 197 C. IR
4-[2,3,5,6-Tetra-O-acetyl- -D-glucopyranosyl]-
1-[p-ethylphenyl(phenoxy)thiophosphoryl]thiosemi-
carbazide (VIIa). Yield 56%, mp 147 149 C. IR
1
spectrum, , cm : 1751 (C=O), 1508 (NH C=S),
1
1438 (P Ph), 1220 (P O Ar), 912 (P N), 692
(P=S). 1H NMR spectrum, , ppm: 1.28 s (9H,
CH3), 1.77 2.04 q (12H, CH3), 3.25 5.57 m (7H,
H of sugar), 6.80 8.29 m (11H, H arom, NH).
spectrum, , cm : 1756 (C=O), 1501 (NH C=S),
1440 (P Ph), 1221 (P O Ar), 910 (P N), 700(P=S).
1H NMR spectrum, , ppm: 1.30 t (3H, CH3), 1.77
2.07 q (12H, CH3), 2.81 m (2H, CH2), 3.20 3.82 m
31P NMR spectrum, , ppm, (J, Hz): 77.5 d (2JPH 20). (2H, H6 of sugar), 4.72 5.74 m (5H, H1 of sugar),
5
Mass spectrum, m/z (Irel, %): 710 ([M]+ , 100),
652 (80), 331 (24). Found, %: C 51.90; H 5.57;
N 5.96; P 4.39. C31H40N3O10PS2. Calculated, %:
C 52.46; H 5.68; N 5.92; P 4.36.
7.00 8.15 m (12H, H arom, NH). 31P NMR spec-
trum, , ppm (J, Hz): 68 d (2JPH 17). Mass spectrum,
m/z (Irel, %): 681 ([M]+ , 100), 331 (61). Found, %:
C 50.88; H 5.29; N 6.20; P 4.56. C29H36N3O10PS2.
Calculated, %: C 51.09; H 5.32; N 6.16; P 4.54.
4-[2,3,4,6-Tetra-O-acetyl- -D-mannopyranosyl]-
1-[phenyl(p-tert-butylphenoxy)thiophosphoryl]-
thiosemicarbazide (VIb). Yield 52%, mp 135
4-[2,3,5,6-Tetra-O-acetyl- -D-mannopyranosyl]-
1-[p-ethylphenyl(phenoxy)thiophosphoryl]thiosemi-
carbazide (VIIb). Yield 45%, Rf 0.66. IR spectrum,
1
136 C. IR spectrum, , cm : 1755 (C=O), 1506
(NH C=S), 1437(P Ph), 1220 (P O Ar), 911 (P N),
1
, cm : 1751 (C=O), 1495 (NH C=S), 1412 (P
1
690 (P=S). H NMR spectrum, , ppm: 1.27 s (9H,
Ph), 1220 (P O Ar), 915 (P N), 687 (P=S).
1H NMR spectrum, , ppm: 1.30 t (3H, CH3), 1.78
2.09 q (12H, CH3), 2.82 m (2H, CH2), 3.20 3.81 m
CHd3), 1.77 2.02 q (12H, CH3), 3.25 5.54 m (7H,
H of sugar), 6.81 8.28 m (11H, H arom, NH).
31P NMR spectrum, , ppm, (J, Hz): 77 d (2JPH 19).
Mass spectrum, m/z (Irel, %): 710 ([M]+ , 100),
652 (63), 331 (38%). Found, %: C, 51.38; H, 5.57;
N 5.83; P 4.48. C31H30N3O10PS2. Calculated, %:
C 52.46; H 5.68; N 5.92; P 4.36.
(2H, H6 of sugar), 4.69 5.76 m (5H, H1 of sugar),
5
7.01 8.14 m (12H, H arom, NH). 31P NMR spec-
trum, , ppm (J, Hz): 64.5 d (2JPH 16) . Mass
spectrum, m/z (Irel, %): 681 ([M]+ , 100), 331 (14).
Found, %: C 50.79; H 5.35; N 6.11; P 4.51.
C29H36N3O10PS2. Calculated, %: C 51.09; H 5.32;
N 6.16; P 4.54.
4-[2, 3, 4-Tri-O-acetyl- -D-xylopyranosyl]-1-
[phenyl(p-tert-butylphenoxy)thiophosphoryl]thio-
semicarbazide (VIc). Yield 74%, mp 102 104 C. IR
4-[2,3,4-Tri-O-acetyl- -D-xylopyranosyl]-1-[p-
ethylphenyl(phenoxy)thiophosphoryl]thiosemicarb-
1
spectrum, , cm : 1757 (C=O), 1508 (NH C=S),
1438 (P Ph), 1221 (P O Ar), 912 (P N), 693
(P=S). 1H NMR spectrum, , ppm: 1.26 s (9H,
CH3), 1.28 2.00 q (9H, CH3), 3.26 5.54 m (6H,
H of sugar), 6.78 8.30 m (11H, H arom, NH).
31P NMR spectrum, , ppm, (J, Hz): 78 d (2JPH 21).
Mass spectrum, m/z (Irel, %): 637 ([M]+ , 100), 580
(77), 259 (48%). Found, %: C 52.51; H 5.71;
N 6.63; P 4.81. C28H36N3O8PS2. Calculated, %:
C 52.74; H 5.69; N 6.59; P 4.86.
azide (VIIc). Yield 67%, Rf 0.57. IR spectrum,
,
1
cm : 1754 (C=O), 1502 (NH C=S), 1440 (P Ph),
1
1216 (P O Ar), 908 (P N), 701 (P=S). H NMR
spectrum, , ppm: 1.30t (3H, CH3), 1.81 2.10t (9H,
CH3), 2.79 m (2H, CH2), 3.21 5.70 m (6H, H1 of
5
sugar), 7.04 8.10 m (12H, H arom, NH). 31P NMR
spectrum, , ppm, (J, Hz): 67 d (2JPH 16.5) . Mass
spectrum, m/z (Irel, %): 610 ([M]+ , 100), 259 (22).
Found, %: C 50.89; H 5.24; N 6.92; P 5.10.
C26H32N3O8PS2. Calculated, %: C 51.22; H 5.29;
N 6.89; P 5.08.
4-[Hepta-O-acetyl- -D-lactosyl]-1-[phenyl(p-tert-
butylphenoxy)thiophosphoryl]thiosemicarbazide
1
(VId). Yield 71%, Rf 0.39. IR spectrum, , cm :
4-[Hepta-O-acetyl- -D-lactosyl]-1-[p-ethylphenyl-
(phenoxy)thiophosphoryl]thiosemicarbazide (VIId).
1756 (C=O), 1507 (NH C=S), 1437 (P Ph), 1224
1
1
(P O Ar), 910 (P N), 705 (P=S). H NMR spec-
Yield 41%, Rf 0.35. IR spectrum, , cm : 1755
trum, , ppm): 1.20 2.00 m (21H, CH3), 1.25 s (9H,
CH3), 3.20 5.48 m (13H, H of sugar), 6.77 8.24 m
(C=O), 1506 (NH C=S), 1450 (P Ph), 1220 (P O
Ar), 910 (P N), 707 (P=S). H NMR spectrum, ,
1
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 11 2003

1612
TSAO et al.
ppm: 1.29 t (3H, CH3), 1.75 2.03 m (21H, CH3),
2.77 m (2H, CH2), 3.19 5.61 m (13H, H of sugar),
6.94 8.07 m (12H, H arom, NH). 31P NMR spec-
trum, , ppm, (J, Hz): 66 d (2JPH 17) . Mass spec-
trum, m/z (Irel, %): 970 ([M]+ , 100), 331 (14).
Found, %: C 51.20; H 5.44; N 4.29; P 3.21.
C41H52N3O18PS2. Calculated, %: C 50.77; H 5.40;
N 4.33; P 3.19.
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The authors are grateful for support to the State
Foundation for Natural Sciences of People‘s Republic
of China (no. 29962002).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 11 2003