New methods of synthesis of boron, germanium, and tin derivatives of pentavalent phosphorus thioacids

Article abstract of DOI:10.1002/hc.1103

The reaction of S-trimethysilyl esters of S-propyl-4-methoxyphenyltrithiophosphonic, bis-(dialkylamido)dithiophosphoric, and S-ethyl-diethylamidotrithiophosphoric acid with trialkyl borates, triorganylbromogermanes, trimethyl(isobutylthio)germane, and tri

Full text of DOI:10.1002/hc.1103

Heteroatom Chemistry
Volume 13, Number 1, 2002
New Methods of Synthesis of Boron,
Germanium, and Tin Derivatives of Pentavalent
Phosphorus Thioacids
Il’yas S. Nizamov, Tat’yana P. Sorokina, Il’nar D. Nizamov, Nailya G.
Galimullina, Elvira S. Batyeva, and Vladimir A. Alfonsov
A. E. Arbuzov Institute of Organic and Physical Chemistry, Russian Academy of Sciences,
Arbuzov Str. 8, 420088 Kazan, Russia
Received 14 February 2001; revised 10 May 2001
have recently been studied. 2-(O,O0-Dialkyl and al-
ABSTRACT: The reactions of S-trimethylsilyl esters
kylenedithiophosphato)-1,3,2-dioxaborinanes have
of S-propyl-4-methoxyphenyltrithiophosphonic, bis-
been prepared by the reactions of the correspond-
(dialkylamido)dithiophosphoric, and S-ethyl-diethyl-
ing dithiophosphoric acids or their ammonium
amidotrithiophosphoric acids with trialkyl borates,
salts with 2-chloro-1,3,2-dioxaborinanes or with
triorganylbromogermanes, trimethyl(isobutylthio)ger-
trimethylaminoboranes [1,2]. O-Ethyl-S,S0-bis(o-
mane, and trialkylchlorostannanes were studied.
carborane-9-yl)dithiophosphate, -trithiophosphate,
On the basis of these studies, new methods of synthe-
and -diphenyldithiophosphinate have also been
sizing S-boron, S-germyl, and S-stannyl derivatives
obtained by addition of elemental sulfur to the
of pentavalent phosphorus thioacids were developed.
corresponding (o-carborane-9-yl)thiophosphite, -di-
S-Diethylaminomethyl O-isopropyl-4-ethoxyphenyl-
thiophosphite, and -diphenyldithiophosphinite,
dithiophosphonate was obtained by the reaction of
respectively [3–7]. Organogermyl alkylenedithio-
the diisopropylboron derivative of the corresponding
phosphates and heterocycles with the P(S)SGe
C
dithiophosphonic acid with the aminal 6. 2002 John
structural fragment were obtained by the reactions
Wiley & Sons, Inc. Heteroatom Chem 13:27–35, 2002;
of ammonium alkylenedithiophosphonic acids
DOI 10.1002/hc.1103
with organogermanium mono- and dichlorides
[12–15]. The common methods of synthesizing
organotin dithiophosphates, dithiophosphinates,
INTRODUCTION
and tetrathiophosphates are usually based on the
reactions of the corresponding pentavalent phos-
phorus thioacids or their salts with organotin
halides (also in the presence of ␤-diketones),
oxides, hydroxides, tetraalkyltin, and tributyltin
isocyanates [7–9,16–25]. Bis(trimethylstannyl) tert-
butyltrithiophosphonate was obtained by the reac-
tion of 2,4-bis(tert-butyl)-1,3,2,4-dithiadiphosphe-
tane-2,4-disulfide with bis(trimethylstannyl)sulfide
[26].
There is a considerable interest in main group III
and IV element derivatives of pentavalent phos-
phorus thioacids containing the P(S)SE (E = B,
Si, Sn) structural fragment because of their biolog-
ical activity, their high reactivity, and their use as
synthetic intermediates in the preparation of new
organothiophosphorus compounds [1–11]. Boron
dithiophosphates containing the P(S)SB linkage
Over the past few years, we have been in-
volved in the development of alternate methods of
synthesizing boron, germanium, and tin derivatives
Correspondence to: Il’yas S. Nizamov.
2002 John Wiley & Sons, Inc.
c
27

28 Nizamov et al.
of pentavalent phosphorus thioacids. We have
recently developed convenient methods for the
synthesis of S-(O,O0-dialkyl)boron O,O0-dialkyl-
dithiophosphates and -aryldithiophosphonates by
the reactions of tetraphosphorus decasulfide and
1,3,2,4-dithiadiphosphetane-2,4-disulfides with alkyl
borates, O,O0-dialkyl dithiophosphoric acids with tri-
alkyl borates promoted by ultrasonic irradiation, and
ammonium O,O0-dialkyldithiophosphates with fluo-
rodialkyl borates [27–30], which were summarized
in a review [31]. S-Triphenyl or trialkylgermyl esters
of dialkyl dithiophosphoric and tetrathiophosphoric
acids, and 4-methoxyphenyldithiophosphonic and
-trithiophosphonic acids were easily obtained by
the reactions of tetraphosphorus decasulfide and
Lawesson’s reagent with triphenyl and trialkyl
(alkoxy)germanes, and with -(alkylthio)germanes
[32–34]. Reactions of tetraphosphorus decasul-
fide and Lawesson’s reagent with trialkyl(alkoxy)
stannanes, and with -(alkylthio)stannanes, and
bis(trialkylstannyl)sulfide result in S-trialkylstannyl
dialkyldithiophosphates, S-trialkylstannyl tetrathio-
phosphates, tris(trialkylstannyl) tetrathiophospha-
tes, and S-trialkylstannyl 4-methoxyphenyldithio-
phosphonates and -trithiophosphates, respectively
[35–41]. In this article, new methods are presented
for synthesizing boron, germanium, and tin deriva-
tives of pentavalent phosphorus thioacids by use
of S-trimethylsilyl esters of the corresponding
pentavalent phosphorus thioacids.
established that tri-isobutyl borate reacts with O,O0-
dialkyldithiophosphoric acids under the influence
of low frequency ultrasonic irradiation (22 kHz,
power 130 W) at 25–60 C for 0.5h to give S-(O,O0-di-
isobutyl)boron O,O0-dialkyldithiophosphates with
the elimination of isobutyl alcohol [29]. In this
connection, we expected to observe the same low
reactivity of trialkyl borates in the substitution
reactions with S-trimethylsilyl esters of pentavalent
phosphorus thioacids. Indeed, we have now found
that the reactions of S-trimethylsilyl S0-propyl-4-
methoxyphenyltrithiophosphonate (1) with trialkyl
borates (2a,b) proceed only under severe condi-
tions (170 C, 6 h) to yield S-(S0-propyl-4-methoxy-
phenyltrithiophosphonato)
(3a,b) and trimethyl(alkoxy)silanes (4a,b) (Reac-
tion 1, Tables 1–5).
O,O0-dialkylborates
(1)
Note that trialkyl borates (2a,b) take part in reac-
tion 1 via the cleavage of only one O B bond under
the conditions used. Other alkoxy groups remained
attached to the boron atom. We believe that the
compounds (3a,b) are a new type of boron(III)
derivative of pentavalent phosphorus thioacids
containing the S(C)P(S)SB structural fragment.
Alkoxysilanes (4a,b) were easily removed from the
reaction mixtures by evaporation at reduced pres-
sure (see Experimental). They were purified by a
subsequent distillation. Compounds (3a,b) are yel-
low, oily liquids. They are nonvolatile even under
reduced pressure, and stable at room temperature.
The thermal stabilities of boron trithiophospho-
nates (3a,b) are lower than those of the boron
aryldithiophosphonates previously obtained by the
treatment of 2,4-diaryl-1,3,2,4-dithiadiphosphetane-
2,4-disulfides with alkyl borates [44] or boron dithio-
phosphates [28,29]. Compound 3a was isolated
by column chromatography, whereas substance 3b
tended to decompose partially when falling-film dis-
tillations were used in attempted purification.
RESULTS AND DISCUSSION
S-Trimethylsilyl esters of dithiophosphoric and
tetrathiophosphoric acids are efficient intermediates
for the synthesis of useful organothiophosphorus
compounds [10,11,42]. The substitution reactions
of S-trimethylsilyl O,O0-dialkyldithiophosphates or
S,S0-bis(trimethylsilyl) trithiophosphonates with
trialkyl-isocyanatostannane and its thioanalogue,
trialkyl(N,N0-dialkylamino)stannanes, trimethylben-
zyl- or 4-vinylbenzylstannanes or trimethylchloro-
stannane have been reported to result in
S-trialkylstannyl dithiophosphates and bis(tri-
methylstannyl) trithiophosponates [26,43].
Taking into account the rather high reactivity
of the S Si bond, we have studied the reactions
of S-trimethylsilyl esters of pentavalent phos-
phorus thioacids with trialkyl borates. However,
trialkyl borates possess a low reactivity in the
reactions, which proceed with the rupture of
the O B bond. Thus, trialkyl borates do not ap-
pear to react with dithiophosphoric acids in the
absence of any additives [1]. We have recently
The 31P NMR spectra of boron trithiophospho-
nates (3a,b) (Table 2) show singlets in the range
of = 88.1–90.8 in benzene solutions. These reso-
nances are shifted toward low field in comparison
with the 31P NMR data of initial S-trimethylsilyl
trithiophosphonate 1 ( = 69 [40]). Substitution
of the silicon atom on the boron atom in the

New Methods of Synthesis of Boron, Germanium, and Tin Derivatives of Pentavalent Phosphorus Thioacids 29
TABLE 1 Experimental Data and Yields of the Products Obtained
Reaction Conditions
Initial Compounds a
Temp. ( C)
Time (h)
Product Yield b
1
1
5
6.0 (17.1); 2a 3.2 (17.0)
6.3 (18.0); 2b 4.1 (17.8)
2.0 (5.0); 0.7 (5.1)
170
170
20
50
120
6
6
3
2
3
3a 2.2 (31)c; 4a 0.5 (22)d
3b 7.3 (94)e; 4b 0.8 (31)d
6
7
0.7 (39) f
9a 2.7 (10.5); 10a 4.0 (10.4)
9b 4.7 (15.1); 10b 3.0 (15.1)
11a 2.3 (47)e 12 0.8 (50)d
11b 2.8 (52)e/1.5 (28)g;
12
15
0.9 (39)d
13
5.8 (19.3); 14 4.0 (19.4)
170
20
5
5
4.4 (66)e; 16 0.7 (23)d
9b 4.1 (13.1); 17a 2.6 (13.1)
18a 4.4 (83)e/2.2 (42)g;
19
18b 9.4 (90)e/6.3 (60)g;
19
1.3 (59)d
0.9 (64)d
9b 6.2 (19.9); 17b 6.5 (20.0)
20
5
aBold numbers indicate reactants; values that follow indicate quantity in grams (mmols).
bBold numbers indicate the products obtained; values that follow indicate the product yield in grams (percentage).
cYield of product isolated by column chromatography.
dYield of product isolated by a distillation.
eYield of crude product.
f Yield of crystalline product.
gYield of product isolated by a falling-film distillation.
molecules of the derivatives of trithiophosphonic
acids was confirmed by the data of H NMR spec-
of the alkoxy groups at the boron atom. Bands of
strong intensity in the region 1032 and 1020 cm
1
1
tra of 3a,b (Table 4). Although a signal of the
in the IR spectra of 3a,b (Table 3) are assigned to the
trimethylsilyl group [45] is absent in the range of
0.05–0.08, they reveal the characteristic resonances
=
C
O(C
O C) and the O B valence vibrations,
respectively. Valence vibrations of the P S bond
TABLE 2 Physical, Analytical, and 31P NMR Data of the Products Obtained
Found/Calc. %
Molecular
Formula
20
31
P NMR, (C H )
Compounds
bp ( C)a
n
(Mol. mass)
E
P
S
D
5
6
3ab
3b
C16H28BO3PS3
(406.6)
C18H32BO3PS3
(434.0)
C16H28NO2PS2
(361.2)
2.72B
2.66B
2.51B
2.49B
7.80
7.63
7.21
7.14
8.50
8.57
6.11
6.36
9.07
8.68
8.52
8.96
8.18
7.69
6.05
5.85
23.21
23.63
22.60
22.10
17.38
17.70
13.55
13.14
17.70
17.92
27.34
27.74
15.37
15.87
12.02
12.09
79.0c
78.1
7
113–115d
102.8e
88.4
11a
11b
15
C22H27GeN2PS2
14.96Ge
14.91Ge
20.04Ge
20.35Ge
21.06Ge
21.00Ge
29.42Sn
29.46Sn
22.17Sn
22.43Sn
(486.8)
1.4880 C11H29GeN2PS2
(356.8)
95–100 (0.03) f
110–120 (0.03)g
120–125 (0.03)
135–140 (0.03)
65.7
C9H24GeNPS3
(345.7)
78.3
18a
18b
1.5500
C11H29N2PS2Sn
86.8
(402.9)
1.5290 C20H47N2PS2Sn
(529.1)
87.7
aTemperature of thermal element of a falling-film distillation.
b Rf 0.75 (CHCl3).
cIn CDCl3.
dM.p
eIn CD3CN.
f Values in parentheses in this column indicate pressure (mm/Hg).
gTemperature of decomposition.

30 Nizamov et al.
TABLE 3 IR Data of the Products Obtained
1
Compounds
(cm
)
3a
3080, 3010
(
C H, Ar); 2975, 2932, 2875, 2841 (CH3 as, s; CH2 as, s; CH); 1594, 1570, 1499,
1463 (C C, Ar); 1440, 1410 (CH3 as); 1387, 1375 [(CH3)2C gem s]; 1292 (C C, Ar);
1256 ω, (CH2); 1181, 1100, 1032 (C O), (C
O
C); 693 (P S); 646, 623 (C S);
543, 510 (P S, S B).
3b
7a
3070, 3010
( C H, Ar); 2965, 2940, 2900, 2880 (CH3 as, s; CH2 as, s; CH); 1596, 1502, 1470
(C C, Ar); 1420 (CH3 as, s; CH2); 1380, 1352 [(CH3)2C gem s]; 1260 ω, (CH2); 1031
(OC C); 1020 (O B); 852 (S B); 695 (P S); 625 (C S); 540, 516 (P S).
3090, 3060, 3030
1300 (C C, Ar); 1250 ω, (CH2); 1182 (C
922 [(N)C C]; 875 [P O(C)]; 678 (P S); 630 (C S]; 572 (P S); 530 (CNC).
3070, 3050, 3030, 3010, 3000 H, Ar); 2960, 2885, 2800 (CH3 as, s); 1580, 1480 (C C,
Ar); 1190 (C C as); 1030, 1000 (P C as); 695 (P S); 679, 623 (P C as);
(C S); (P S); (C S); 500 (C C); 410 (S Ge).
2970, 2938, 2905, 2878 (CH3 as, s; CH2 as, s); 1467, 1380 (CH3 as, CH2); 1259 [CH3(Ge)];
1180 (C C as); 1030, 997 (P C as); 950 [(N)C C]; 710 (P S); 535 (P S);
540 (CNC); 428 (S Ge).
2963, 2935, 2910, 2888 (CH3 as, s; CH2 as, s); 1465, 1380 (CH3 as, s); 1260 [CH3(Ge)]; 1020
(P C as); 700 (P S); 535, 520 (P S); 420 (S Ge).
(
C
H, Ar); 1596, 1500, 1470 (C C, Ar); 1390, 1370 [(CH3)2C gem s];
N
C as); 1060 (C C as); 958 [(OC) C];
N
11a
11b
( C
N
N
N
N
N
N
15
N
18a
18b
N
C as); 790
aIn vaseline oil.
1
As we can see, reaction 1 resulted in the forma-
tion of the organothiophosphorus compounds 3a,b
containing the P(S)SB structural fragment. Sub-
stances of this type contain the reactive S B bond
and a readily leaving boryl group. They may be
were observed in the region ␯ 695–693 cm
for 3a,b. The electron impact mass spectrum
of 3b exhibits the mass peak m/e 406 that
may be attributed to its molecular ion [M]+.
(Table 5).
TABLE 4 1H NMR Data of the Products Obtained
Compounds
, J(Hz)
3aa
3ba
7b
1.00 (t, 3H, CH3CH2CH2SP, 3J HH 7.0); 1.02 (d, 12H, [(CH3)2CHO]2B, 3J HH 7.0); 1.21–1.97 (m, 2H,
CH3CH2CH2SP; 1H, (CH3)2CHO); 2.23 (d. T, 2H, CH3CH2CH2SP, 3J HH 7.0, 3 J PH 15.5); 3.84 (s,
3H, CH3OC6H4); 6.92 (d. D, 2H, 3,5-H2C6H2, 3J HH 9.0, 4J PH 3.0); 7.76 (d. d, 2H, 2,6-H2C6H2,
3J HH 9.0, 3J PH 14.0).
0.91 (t, 12H, [(CH3)2CHCH2O]2B, 3J HH 7.0); 0.92 (t, 3H, CH3CH2CH2SP, 3J HH 7.0); 1.35–2.08 (m,
2H, [(CH3)2CHCH2O]2B; 2H, CH3CH2CH2SP); 2.92 (d. t, 2H, CH3CH2CH2SP, 3J HH 7.0, 3J PH
15.0); 3.57 (d, 4H, [(CH3)2CHCH2O]2B, 3 J HH 7.0); 3.85 (s, 3H, CH3OC6H4); 6.92 (d. d, 2H,
3,5-H2C6H2, 3J HH 9.0, 4J PH 3.0); 7.85 (d. d, 2H, 2,6-H2C6H2, 3J HH 9.0, 3J PH 14.0).
1.11 (d, 6H, (CH3)2CHOP, 3J HH 6.0); 1.25 (t, 6H, (CH3CH2)2N, 3J HH 6.8); 1.34 (t, 3H,
CH3CH2OC6H4, 3J HH 6.8); 3.02 (q, 4H, (CH3CH2)2N, 3J HH 6.8); 3.04–3.14 (m, 2H,
CH3CH2OC6H4, 3J HH 6.8; 1H, CH2SP); 5.40–6.10 (m, 1H, (CH3)2CHOP); 6.84 (d. d, 2H,
3,5-H2C6H2, 3J HH 8.3, 4J PH 2.3); 7.96 (d. d, 2H, 2,6-H2C6H2, 3J HH 8.3, 3J PH 13.0).
2.62 (d, 12H, [(CH3)2N]2P, 3J HH 14.0); 7.26–7.58 and 7.62–7.93 (rwo m, 15H, (C6H5)3Ge).
11aa
11ba
0.78 (s, 9H, (CH3)3Ge); 1.04 (t, 12H, [(CH33CH2)2P, 3J HH 7.0); 3.05 (d. q, 8H, [(CH3CH2)2N]2P,
3J HH 7.0, 3J PH 13.0).
18ac
18bc
0.67 (s, 9H, (CH3)3Si); 1.18 (t, 12H, (CH3CH2)2NP, 3J HH 6.5); 3.20 (d. q, 8H, (CH3CH2)2NP, 3J HH
6.5; 3J PH 13.0).
0.84–1.97 (m, 27H, (C4H9)3Sn + 12H, (CH3CH2)2NP); 3.21 (d. q, 8H, (CH3CH2)2NP, 3J HH 6.5; 3J PH
13.0).
aIn CDCl3.
bIn CD3CN.
cIn CCl4.

New Methods of Synthesis of Boron, Germanium, and Tin Derivatives of Pentavalent Phosphorus Thioacids 31
used as efficient intermediates for the synthesis of
occurrence of the substitution reactions of disilyl
trithiophosphonates with chlorostannanes [26], we
have involved in a corresponding manner bromoger-
manes in the reactions with silyl esters of pentava-
lent phosphorus thioacids. Thus, the reactions of
S-trimethylsilyl bis(dialkylamido)dithiophosphates
(9a,b) with triphenyl and trimethylbromogermanes
(10a,b) have been found to bring about the
formation of S-triphenyl and S-trimethylgermyl
bis(dialkylamido)dithiophosphates (11a,b) and tri-
methylbromosilane (12) (Reaction 3, Tables 1–5).
organothiophosphorus compounds. Thus, 2-(O,O0-
dipropyldithiophosphato)-1,3,2-dioxaborinane has
been reported to react with dibutyl oxide in a
molar ratio of 2:1 in benzene at room tem-
perature, with the rupture of the S B bond
to give the corresponding bis(dithiophosphato)
dibutyltin and bis(1,3,2-dioxaborinane) oxide [1].
Moreover, we have previously shown that S-
trimethylsilyl dialkyltetrathiophosphates react with
aminals, with the cleavage of the S Si bond
to form dialkylaminomethyl tetrathiophosphates
and trimethyldialkylaminosilanes [46]. We have
now found that the reaction of S-(O-isopropyl-4-
ethoxyphenyldithiophosphonato) O,O0-di-isopropyl
borate 5 with bis(diethylamino)methane (6) gives
S-diethylaminomethyl O-isopropyl-4-ethoxypheny-
ldithiophosphonate 7 and O,O0-di-iso-butyldiethyla-
minoborate 8 (Reaction 2, Tables 1–5).
(3)
The reaction of S-trimethylsilyl diamidodithio-
phosphate (9a) with triphenylbromogermane (10a)
proceeds in anhydrous benzene at 50 C for 2 h.
In contrast to this, trimethylbromogermane (10b)
reacts with S-trimethylsilyl bis(diethylamido)dithio-
phosphate (9b) only at 120 C for 3 h. S-Germyl di-
amidodithiophosphates (11a,b) are a new type of
germanium derivatives of pentavalent phosphorus
thioacids. S-Triphenylgermyl derivative 11a was ob-
tained as a semisolid. It is nonvolatile in a high vac-
uum and tended to decompose when column chro-
matography (silica gel with benzene as an eluant)
was used in an attempted purification. We have man-
aged to isolate the S-trimethylgermyl derivative 11b
in distillate form by means of a falling-film distil-
lation. Trimethylbromosilane (12) was evaporated
from the reaction mixtures under vacuum and pu-
rified by a subsequent distillation.
(2)
Reaction 2 is exothermic and occurs at room tem-
perature for 3 hours. Compound 7 is a white crys-
talline solid. The 31P NMR spectral signal of 7 re-
veals a significant change ( = 101.8) with respect to
5 ( = 83.0). It should be noted that the 31P nuclei
of the corresponding dialkylaminomethyl tetrathio-
phosphates are reported to resonate in practically
the same region ( = 98.5–101 [44]) as observed in 7.
The attachment of the diethylaminomethyl group to
the sulfur atom of 7 was confirmed by IR, 1H NMR,
and mass spectroscopy (Tables 3–5). Bands in the
1
region of ␯ 922 and 530 cm in the IR spectra of 7
(Table 3) are due to the (N)C C valence vibrations
and the CNC deformation vibrations, respectively.
The mass peak m/e 362 observed in the chemical ion-
ization mass spectrum of 7 is due to its molecular ion
[M + H]+.
The 31P NMR spectrum of 11a in benzene solu-
tion (Table 2) reveals a singlet at 88.4. As we can
see, the 31P NMR spectral signal of 11a shows no
significant change with respect to 9a ( = 89.9 [47]).
Broad bands of medium intensities in the region of
Aminoborate 8 was removed from the reaction
mixture by vacuum distillation. The electron impact
mass spectrum of the volatile liquid, collected in a
liquid nitrogen cooled trap from the crude reaction
mixture of reaction 2, shows the mass peak m/e 201
that can be attributed to the molecular ion [M]+. of
aminoborate (8) (calculated molecular mass of 8 is
201.1).
1
␯ 428–410 cm in the IR spectra of 11a,b (Table 3)
are due to the S Ge valence vibrations. Bands in the
1
range of ␯ 710–690 cm are assigned to the P
S
valence vibrations. These bands appear in practi-
cally the same region as those for 9a,b (␯ (P S)
1
1
727–692 cm [47]). The H NMR spectrum of 11b
in CDCl3 solution shows a low field shift of the sin-
glet of the trimethylgermyl group ( = 0.78) with re-
spect to the isostructural 9b ( = 0.78 in CH2Cl2 solu-
tion [47]). The electron impact mass spectrum of 11b
(Table 5) exhibits the mass peaks m/e 357, 342, and
325 due to its molecular ions [M]+., [M Me]+., and
In continuation of a study of the reactivity of the
Si bond of S-trimethylsilyl esters of pentavalent
phosphorus thioacids, we have tried to extend these
substitution reactions to derivatives of main group
IV elements, containing labile X E bonds (X Cl,
Br, S; E Ge, Sn). Taking into account the facile
S
[M
S]+., respectively. The phenyl and sulfur

32 Nizamov et al.
TABLE 5 Mass Spectral Data of the Products Obtained
S-Germyl derivatives of pentavalent phosphorus
thioacids including the S(N)P(S)S-Ge structural
fragment remained unknown before our work. Low
reactivity of (isobutylthio)germane (14) is mainly
determined by the rather strong S Ge bond. The
S-germyl amidotrithiophosphate 15 formed in reac-
tion 4 was obtained in 66% yield. Compound 15 con-
Compounds
i -C4 H10, m/e (Irel, %)
3aa
3ab
406 [M]+. (1); 288 [M 2i PrO]+. (3)
364 [M + H Pr]+ (2); 348 [M + H 2i
PrO]+. (2)
7b
362 [M + H]+ (4)
11aa
410 [M Ph]+. (1); 378 [M Ph S]+. (2);
301 [M 2Ph S]+. (12); 333 [M
2Ph]+. (1); 224 [M 3Ph S]+. (2)
444 [M + H NMe2]+ (16); 412 [M + H
NMe2 S]+ (1)
taining the P S, P N, and P
S Ge bonds tended
to partially decompose when a falling-film distilla-
tion was used at the temperature of the thermal el-
ement of the apparatus, 110–120 C (0.03 mm Hg).
Trimethyl(isobutylthio)silane (16) was isolated by
distillation.
11ab
11ba
357 [M]+. (7); 342 [M Me]+. (5); 325 [M
S]+. (33); 328 [M Et]+. (2); 327 [M
2Me]+. (12); 312 [M 3Me]+. (16);
299 [M 2 Et]+. (10)
The 31P NMR chemical shift value of 15 is shifted
to high field ( = 78.3) with respect to 13 ( = 88.3).
Bands of valence vibrations of the S Ge bond of 15
15b
301 [M]+. (1); 285 [M + Et S]+. (2); 274
[M
Et2N]+. (2); 270 [M Et Me
S]+. (2); 256 [M 2Et S]+. (43)
1
appeared at ␯ 420 cm similarly to 11a,b. The IR
15a
275 [M + H Et2N]+.(3); 257 [M + H
spectrum of 15 also reveals a bond of the P S va-
2Et
S]+ (3); 241 [M + H 3 Me Et
1
lence vibrations (␯ 700 cm ) in the same region as
S]+ (2)
1
18aa
403 [M]+. (3); 388 [M Me]+. (75); 374 [M
Et]+. (9); 373 [M 2Me]+. (4); 371 [M
S]+. (5); 358 [M 3 Me]+. (2); 356 [M
that for 11a,b (␯ (P S) 710–690 cm ). The electron
impact mass spectrum of 15 (Table 5) exhibits the
mass peak m/e 301 of its molecular ion [M]+.. The
mass peaks m/e 285 and 274 were also observed in
the electron impact mass spectrum of 15, those be-
ing attributed to the ions [M Et S]+. and [M
Et2N]+., respectively.
Taking into account the results of the reac-
tions of S-trimethylsilyl diamidodithiophosphates
(9a,b) with bromogermanes (10a,b) (Reaction 3),
we developed a convenient method of synthe-
sizing the corresponding S-trialkylstannyl diami-
dodithiophosphates. The reactions of 9b with tri-
alkylchlorostannane (17a,b) at room temperature
for 5 h brought about the formation of S-trialkylsilyl
bis(diethylamido)dithiophosphates (18a,b) (Reac-
tion 5, Tables 1–5).
S
Me]+. (2); 239 [M SnMe3]+. (2);
164 [M 2Et2N PS2]+. (17)
359 [M + H 3Me]+ (6)
18ab
18ba
529 [M]+. (1); 497 [M S]+. (1); 472 [M
Bu]+. (4); 239 [M SnBu3]+. (1); 290
[M (Et2N)2PS2]+. (15)
18bb
530 [M + H]+ (2); 498 [M + H S]+ (3); 416
[M + H 2Bu]+ (1); 360 [M + 2H 3Bu]+
(3)
aElectron impact, 70 eV.
bChemical ionization, 100 eV.
fragments are split out from the molecule of 11a
under the conditions of the recording of the mass
spectra. Thus, the mass peaks m/e 410, 378, and 301
in the electron impact mass spectrum of 11a are due
to ions [M
Ph]+., [M
Ph
S]+., and [M
2Ph
S]+., respectively.
Thus, the Br Ge bond possesses a rather
high reactivity in the substitution reactions with
S-trimethylsilyl esters of pentavalent phosphorus
thioacids. However, when the bromine atom was
exchanged on the alkylthio group, we encountered
difficulties owing to the low reactivity of the alkyl-
thiogermanes. Thus, the reaction of S-trimethylsilyl
S0-ethyldiethylamidotrithiophosphate (13) with tri-
methyl(isobutylthio)germane (14) proceeds only at
170 C for 5 h to give S-trimethylgermyl S0-ethyl-
diethylamidotrithiophosphate (15) and trimethyl
(isobutylthio)silane (16) (Reaction 4, Tables 1–5).
(5)
Compounds 18a,b containing the new N2P(S)S Sn
structural fragment were formed as oily liquids in
high yields (83–90%). They were purified by use of
a falling-film distillation. Trimethylchlorosilane 19
was also isolated when the crude reaction mixtures
were evaporated under vacuum with use of a trap
cooled by liquid nitrogen.
In the case of S-trialkylstannyl diamidodithio-
phosphates (18a,b), their 31P signals in benzene so-
lutions are shifted to lower field ( = 86.8 and 87.7,
respectively) in comparison with that of 9b ( = 83.6
(4)

New Methods of Synthesis of Boron, Germanium, and Tin Derivatives of Pentavalent Phosphorus Thioacids 33
[40]). Thus, an observed tendency of the low field
S-(S0-Propyl-4-methoxyphenyltrithiophosphonato)
O,O0-diisopropylborate (3a). The mixture of 1 (6.0 g,
17.1 mmol) and 2a (3.2 g, 17.0 mmol) was stirred
at 170 C for 6 h under dry argon. The mixture was
evaporated at reduced pressure (0.5 mm Hg) at 40 C
for 1 h and under a higher vacuum (0.03 mm Hg)
at 40 C for 1 h with use of a trap cooled by liquid
nitrogen. The residue was chromatographed on a
silica gel column with CHCl3 as eluant to yield 2.2 g
(31%) of pure 3a (see Tables 1–5). Distillation of
the contents of the liquid nitrogen trap gave pure
trimethyl(isopropoxy)silane 4a (0.5 g, 22%), b.p.
87–88 C, n20 1.3789 (cf. lit. [51]: b.p. 87 C, n20
shift of the 31P resonances of the isostructural di-
amidodithiophosphoric derivatives of the group 14
elements increases when passing from the top to the
bottom of this group. This effect indicates a bidentate
coordination of the diamidodithiophosphato ligands
with the tin atom similar to the chelating behavior of
dithiophosphato ligands with the tin atom [48–50].
1
Broad bands at ␯ 623–621 cm in the IR spectra
of 18a,b (Table 3) are assigned to the P S valence
vibrations, showing a shift to lower frequency with
1
respect to 9b (␯ (P S 680 cm ) that also suggests
a chelating behavior of the diamidodithiophosphato
ligands. The mass peaks m/e 403 and 529 were ob-
served by examination of the electron impact mass
spectrum of 18a and 18b, respectively; these may
be attributed to their molecular ions (Table 5). This
method provides important information about the
fragmentation of these molecules. Thus, the mass
peaks of ions formed via the rupture of the S Sn
bond of 18a,b were established in their mass spec-
tra. We have observed the mass peak m/e 239 in the
the electron impact mass spectra of both 18a and
18b that may be attributed to the ions [M SnMe3]+.
and [M SnBu3]+..
Thus, the above substitution reactions of S-
silyl esters of pentavalent phosphorus thioacids with
trialkyl borates, germanium and tin halides, and
alkylmercaptides have a fundamental significance as
they lead to new types of boron, germanium, and tin
derivatives of pentavalent phosphorus thioacids con-
taining the P(S)SE (E = B, Ge, Sn) structural frag-
ment. Besides, the reactions studied are of interest
from the point of view of preparative organophos-
phorus chemistry. A series of main group element
derivatives of pentavalent phosphorus thioacids,
which may be prepared on the basis of the approach
developed here, is in progress.
D
D
1.3782).
The product 3b was obtained similarly (see
Tables 1–5).
S-(1-N,N0-Diethylaminomethyl) O-isopropyl-4-eth-
oxyphenyldithiophosphonate (7). Compound 6 (0.7
g, 5.1 mmol) was added dropwise under dry argon
with stirring at 20 C to 2.0 g (5.0 mmol) of 5. After
the exothermic period (up to 35 C) of the reaction
had been completed, the stirring of the reaction
mixture was continued for 3 h at 20 C. The mixture
was evaporated at reduced pressure (0.05 mm Hg)
at 40 C for 2 h with use of a liquid nitrogen trap.
The residue was crystalline. The crystalline solid
was washed with benzene, and dried at reduced
pressure (0.06 mm Hg) at 40 C for 2 h. The yield of
7 was 0.7 g (39%) (see Tables 1–5).
S-Trimethylgermyl bis(diethylamido)dithiophos-
phate (11a). The mixture of 9b (4.7 g, 57.1 mmol)
and 10b (3.0 g, 15.1 mmol) was stirred at 120 C
for 3 h. The mixture was evaporated at reduced
pressure (0.5 mm Hg) at 40 C for 0.5 h and under
a higher vacuum (0.06 mm Hg) at 40 C for 2.5 h
with use of a trap cooled by liquid nitrogen and
gave 2.8 g (52%) of crude 11b. Product 11b (1.5 g,
28%) was isolated from the residue by means
of a falling-film distillation (see Tables 1–5). Dis-
tillation of the contents of the liquid nitrogen
trap gave pure trimethylbromosilane (12) (0.9 g,
EXPERIMENTAL
General Data
39%), b.p. 80–81 C, n20 1.4205 (cf. lit. [51]: b.p.
D
The 31P NMR spectra were recorded with a Bruker
MSL 400 (162 MHz) instrument in CDCl3, C6H6, or
CD3CN with 85% H3PO4 as an external reference.
80 C, n20 1.4211).
D
The product 11a was obtained similarly (see
Tables 1–5) and trimethylbromosilane (12) (0.8 g,
50%) was also isolated from the volatile fractions.
1
The H NMR spectra were taken on a Bruker MSL-
400 (400 MHz) spectrometer and a Varian T-60 (60
MHz) spectrometer in CDCl3, CD3CN, or CCl4 with
(Me3Si)2O as an internal reference. The IR spectra
were obtained in KBr pellets with an UR-20 infrared
spectrophotometer. Mass spectra (EI, 70 eV; CI, 100
eV) were determined on an M 80 B Hitachi chro-
matomass spectrometer.
S-Trimethylgermyl S0-ethydiethylamidotrithiophos-
phate (15). The mixture of 13 (5.8 g, 19.3 mmol)
and 14 (4.0 g, 19.4 mmol) was stirred at 170 C
for 5 h. The mixture was evaporated at reduced
pressure (0.03 mm Hg) at 40 C for 2 h with use
of a liquid nitrogen trap and gave 4.4 g (66%)

34 Nizamov et al.
[15] Barrau, J.; Rima, G.; Satge´, J. Phosphorus Sulfur Sil-
icon Relat Elem 1995, 107, 99–105.
[16] Baker, D. R. USA Patent 3992425, 1976; Chem Abstr
1977, 86, 90031.
[17] Cray, R. A.; Hyzak D. L. USA Patent 4652298, 1987.
[18] McDermott, J. P.; Springfield, N. J. USA Patent
2786812, 1957; Chem Abstr 1957, 51, 10892f-n.
of crude 15 (see Tables 1–5). Distillation of the
contents of the liquid nitrogen trap gave pure
trimethyl(isobutylthio)silane 16 (0.7 g, 23%), b.p.
165–166 C, n20 1.4511. Mass spectrum (CI) m/e 162
D
[M + H]+ (1%).
S-Trimethylstannyl bis(diethylamido)dithiophos-
phate (18a). Compound 17a (2.6 g, 13.1 mmol) was
added dropwise under dry argon with stirring at 20 C
to 4.1 g (13.1 mmol) of 9b, and stirring of the re-
action mixture was continued for 5 h at 20 C. The
mixture was filtered. The filtrate was evaporated at
reduced pressure (0.5 mm Hg) at 40 C for 1 h and
under a higher vacuum (0.07 mm Hg) at 40 C for
0.5 h with use of a trap cooled by liquid nitrogen and
gave 4.4 g (83%) of crude 18a. Product 18a (2.2 g,
42%) was isolated from the residue by means of a
falling-film distillation (see Tables 1–5). Distillation
of the contents of the liquid nitrogen trap gave pure
trimethylchlorosilane (19) (0.9 g, 64%), b.p. 57 C,
n20 1.3890 (cf. lit. [51]: b.p. 57.5 C, n20 1.3885).
[19] Rao, R. J.; Srivastava, G.; Mehrotra, R. C.
Organomet Chem 1983, 258, 155–161.
[20] Rao, R. J.; Srivastava, G.; Mehrotra, R. C.; Saraswat,
B. S.; Mason, J. Polyhedron 1984, 3, 485–490.
[21] Rao, R. J.; Srivastava, G.; Mehrotra, R. C. Phosphorus
Sulfur Relat Elem 1985, 25, 183–191.
[22] Lefferts, J. L.; Molloy, K. C.; Zuckerman, J. J.; Haiduc,
I.; Guta, C.; Ruse, D. Inorg Chem 1980, 19, 2861–
2868.
[23] Parulekar, C. S.; Jain, V. K.; Kesavadas, T. Phosphorus
Sulfur Silicon Relat Elem 1989, 46, 145–151.
[24] Chaturvedi, A.; Nagar, P. N.; Srivastava, G. Phospho-
rus Sulfur Silicon Relat Elem 1992, 70, 303–315.
[25] Kutyrev, G. A.; Kakurina, V. P.; Cherkasov, R. A. USSR
Patent 631519; Bull Izobr Russ 1978, No. 41.
[26] Hahn, J.; Nataniel, T. Z Anorg Allg Chem 1986, 543,
7–21.
[27] Nizamov, I. S.; Sergeenko, G. G.; Batyeva, E. S.; Pu-
dovik, A. N. Zh Obshch Khim 1996, 66, 520.
[28] Nizamov, I. S.; Sergeenko, G. G.; Batyeva, E. S.;
Azancheev, N. M.; Al’fonsov, V. A. Heteroatom Chem
2000, 11, 102–106.
J
D
D
The product 18b was obtained similarly (see
Tables 1–5) and trimethylchlorosilane (19) (0.9 g,
64%) was also isolated from the volatile fractions.
[29] Nizamov, I. S.; Sergeenko, G. G.; Batyeva, E. S.;
Azancheev, N. M.; Al’fonsov, V. A. Phosphorus Sulfur
Silicon Relat Elem 2000, 158, 157–166.
[30] Nizamov, I. S.; Sergeenko, G. G.; Batyeva, E. S.;
Azancheev, N. M.; Al’fonsov, V. A. Main Group Chem
2000, 3, 129–138.
[31] Nizamov, I. S.; Batyeva, E. S. Main Group Chem 2000,
3, 117–127.
[32] Nizamov, I. S.; Kuznetzov, V. A.; Batyeva, E. S.
Phosphorus Sulfur Silicon Relat Elem 1994, 88,
67–73
REFERENCES
[1] Singh, B. P.; Mehrotra, R. K.; Srivastava, G. Phospho-
rus Sulfur Silicon Relat Elem 1991, 60, 147–158.
[2] Chaturvedi, A.; Nagar, P. N.; Srivastava, G. Phospho-
rus Sulfur Silicon Relat Elem 1994, 90, 229–233.
[3] Balema, V. P.; Rys, E. G.; Godovikov, N. N.;Kabachnik,
M. I. Izv Akad Nauk, Ser Khim 1990, 2857–2859.
[4] Balema, V. P.; Rys, E. G.; Godovikov, N. N. Izv Akad
Nauk, Ser Khim 1992, 459–461.
[5] Balema, V. P.; Rys, E. G.; Godovikov, N. N.; Polyakov,
A. V.; Struchkov, Yu. T. Izv Akad Nauk, Ser Khim 1992,
180–186.
[6] Godovikov, N. N.; Balema, V. P.; Rys, E. G. Usp Khimii
(Russ) 1997, 66, 1125–1140 and references therein.
[7] Lefferts, J. L.; Molloy, K. C.; Zuckerman, J. J.; Haiduc,
I.; Guta, C.; Ruce, D. Inorg Chem 1980, 19, 1662–
1672.
[33] Nizamov, I. S.; Kuznetzov, V. A.; Batyeva, E. S.
USSR Patent 2059645, 1994; Bull Izobr Russ 1996,
No. 3.
[34] Nizamov, I. S.; Kuznetzov, V. A.; Batyeva, E. S. USSR
Patent 2059644, 1994; Bull Izobr Russ 1996, No. 3.
[35] Nizamov, I. S.; Kuznetzov, V. A.; Al’fonsov, V. A.;
Batyeva, E. S.; Pudovik, A. N. USSR Patent 1735299;
Bull Izobr Russ 1992, No. 19.
[8] Singh, B. P.; Srivastava, G.; Mehrotra, R. C. J
Organomet Chem 1979, 171, 35–41 and references
therein.
[9] Spiridonov, Yu. Ya.; Shcheglov, Yu. V.; Spiridonova,
G. S.; Mitishchev, A. I.; Khokhlov, P. S.; Bliznyuk, N.
K. USSR Patent 292683, 1971; Bull Izobr Russ 1971,
No. 5.
[36] Nizamov, I. S.; Kuznetzov, V. A.; Al’fonsov, V. A.;
Batyeva, E. S.; Pudovik, A. N. Zh Obshch Khim 1992,
62, 1665–1666.
[37] Nizamov, I. S.; Kuznetzov, V. A.; Al’fonsov, V. A.;
Batyeva, E. S. Izv Akad Nauk, Ser Khim 1992, 2457–
2458.
[38] Nizamov, I. S.; Kuznetzov, V. A.; Batyeva, E. S.;
Alfonsov, V. A.; Pudovik A. N. Heteroatom Chem 1993,
4, 379–382.
[10] Cherkasov, R. A.; Kutyrev, G. A. Usp Khimii (Russ)
1983, 53, 1675–1708.
[11] Cherkasov, R. A.; Kutyrev, G. A.; Pudovik, A. N. Tetra-
hedron 1985, 41, 2567–2624.
[12] Rao, R. J. Phosphorus Sulfur Silicon Relat Elem 1990,
53, 203–209.
[13] Drake, J. E.; Mislankar, A. G.; Ratnani R. Can J Chem
1994, 72, 1830–1838.
[14] Barrau, J.; El Amine, M.; Rima, G.; Satge´, J. Can J
Chem 1986, 64, 615–620.
[39] Nizamov, I. S.; Kuznetzov, V. A.; Batyeva, E. S. Russ
Patent 2005723; Bull Izobr Russ 1994, No. 1.
[40] Nizamov, I. S.; Kuznetzov, V. A.; Batyeva, E. S.;
Al’fonsov, V. A.; Pudovik, A. N. Heteroatom Chem
1994, 5, 107–111.
[41] Nizamov, I.; Al’metkina, L.; Kuznetzov, V. XIIth In-
ternational Conference on Phosphorus Chemistry,
Toulouse, 1992, pp. 1–12; Abstracts of Posters.

New Methods of Synthesis of Boron, Germanium, and Tin Derivatives of Pentavalent Phosphorus Thioacids 35
[42] Nizamov, I. S.; Popovich, A. E.; Batyeva, E. S.; Al-
[46] Nizamov, I. S.; Kuznetzov, V. A.; Batyeva, E. S.
Phosphorus Sulfur Silicon Relat Elem 1994, 90,
249–257.
[47] Roesky, H. W.; Remmers, G. Z Anorg Allg Chem 1977,
431, 221–226.
[48] Haiduc, I. Rev Inorg Chem 1981, 3, 353–370.
[49] Silvestru, C.; Haiduc, I. Coord Chem Rev 1996, 147,
117–146.
[50] Glidwell, C. Inorg Chim Acta 1977, 25, 159–163.
[51] Bazˇant, V.; Chvalovsky´, V.; Rathousky´, J. Organosili-
con Compounds; Publishing House of the Czechoslo-
vak Academy of Sciences: Prague, 1965; Vol. 2, parts
1 & 2.
fonsov, V. A. Heteroatom Chem 2000, 11, 276–280.
[43] Kutyrev, G. A.; Lygin, A. V.; Kapura, A. A.; Cherkasov,
R. A.; Pudovik, A. N. Organo-metallic Compounds
of Non-transition Metals in Synthesis and Catalysis,
Perm, 1983, p. 59; Abstracts of Vsesoyz Soveshch
Russ.
[44] Nizamov, I.; Al’fonsov, V.; Batyeva, E. Phosphorus Sul-
fur Silicon Relat Elem 1996, 109–110, 453–456.
[45] Raman, I. R. NMR Spectroscopy of Si, Ge, Sn and Pb
Organic Compounds; Licht, K.; Reich, P. (Eds.); VEB
Deutscher Verlag der Wissenschaften: Berlin, 1971;
p. 623.