Phosphorus-substituted carbothioamides

Article abstract of DOI:10.1023/B:RUCB.0000037865.24497.d8

A facile procedure was developed for the synthesis of phosphorus- substituted carbothioamides by the reaction of the corresponding nitriles with O,O-diisopropyl dithiophosphate in the presence of methanol. The structural features and hydrogen bonding in c

Full text of DOI:10.1023/B:RUCB.0000037865.24497.d8

Russian Chemical Bulletin, International Edition, Vol. 53, No. 4, pp. 925—931, April, 2004
925
Phosphorusꢀsubstituted carbothioamides
V. A. Kozlov, I. L. Odinets,ꢀ K. A. Lyssenko, S. G. Churusova, S. V. Yarovenko,
P. V. Petrovskii, and T. A. Mastryukova
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (095) 135 5085. Eꢀmail: odinets@ineos.ac.ru
A facile procedure was developed for the synthesis of phosphorusꢀsubstituted carboꢀ
thioamides by the reaction of the corresponding nitriles with O,Oꢀdiisopropyl dithiophosphate
in the presence of methanol. The structural features and hydrogen bonding in crystals of
structurally different Pꢀthioamides are discussed.
Key words: phosphorusꢀsubstituted acetonitriles, thionation, O,Oꢀdiisopropyl dithioꢀ
phosphate, thioacetamides, thiobenzamides, Xꢀray diffraction analysis, intramolecular and
intermolecular hydrogen bonds.
Various methods were developed for the synthesis of
carbothioamides based on thionation of the correspondꢀ
ing nitriles with hydrogen sulfide and phosphorus monoꢀ
thio and dithio acids.1 In the latter case, the synthesis of
the target products requires either the use of an excess of
dithio acid2 or the involvement of the third component3—6
(hydrogen chloride, alcohol, water, or organic acids)
which can decompose intermediate imidoyl dithioꢀ
phosphates.
phosphorusꢀsubstituted analogs as the most convenient
laboratory procedure. This procedure has been proposed4
for the synthesis of thiobenzamides ArC(S)NH2 from the
corresponding aromatic nitriles. It appeared that various
phosphorusꢀsubstituted thioacetamides can easily be preꢀ
pared in high yields, the procedure being preparatively
much more convenient compared to the known approach
to the synthesis of (EtO)2P(O)CH2C(S)NH2 with the use
of hydrogen sulfide.7—11
On the contrary, data concerning the procedures for
the synthesis of primary thioamides of the corresponding
phosphorusꢀsubstituted carboxylic acids are scarce. Only
several examples of mercaptolysis of diethoxyphosphorylꢀ
acetonitrile in a basic medium giving rise to diethoxyꢀ
phosphorylthioacetamide were reported.7—11 The formaꢀ
tion of this compound in the reaction of diethoxyꢀ
phosphorylacetonitrile with diphenyldithiophosphinic
acid was mentioned,12 but data on the yield of the target
product were lacking in the publication. In addition, ringꢀ
opening of 1,3ꢀdithietanes with carboxylic acid hydrazides
resulted in phosphorylthioacetamides containing the
1,3,4ꢀoxadiazole ring.13
In spite of the fact that alkanenitriles behave ambiguꢀ
ously in this reaction,4 the reactions of acetonitriles conꢀ
taining the electronꢀwithdrawing phosphoryl fragment
(1a—d) as well as the phosphonium (1e) or (thiophosꢀ
phoryl)thio group (1f) with the aboveꢀmentioned thionatꢀ
ing system based on O,Oꢀdiisopropyl dithiophosphate (2)
proceeded smoothly to give the corresponding thioamides
3a—f (~20 °C, 2 days) in satisfactory yields (Scheme 1).
Scheme 1
In our opinion, phosphorusꢀcontaining carbothioꢀ
amides are of obvious interest as chelating agents analoꢀ
gously to phosphorusꢀsubstituted thioureas14 and also as
building blocks for the preparation of various fiveꢀ and
sixꢀmembered heterocyclic compounds. Therefore, it is
worth developing a general preparative procedure for the
synthesis of such compounds.
Taking into account the advantages and drawbacks of
methods developed earlier for the preparation of carboꢀ
thioamides,1—6 we chose thionation of nitriles with
O,Oꢀdiisopropyl dithiophosphate in the presence of
methanol (1 : 1 : 2 reagent ratio) for the synthesis of their
RP = (EtO)2P(O) (a), Me(PriO)P(O) (b), Ph(EtO)P(O) (c),
Ph2P(O) (d), Ph3P+Cl– (e), (EtO)2PSS (f)
Although the introduction of an additional substituent
into the methylene fragment of acetonitrile 1 has no efꢀ
fect on the final result of the process, it leads to deceleraꢀ
tion of the reaction rate and a slight decrease in the yield
of the target products. For example, 5—6 days are reꢀ
quired for completion of the reactions of (benzyl)phosꢀ
phorylacetonitrile (4) and 2,3,5,6ꢀtetramethylꢀ1,4ꢀ
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 887—893, April, 2004.
1066ꢀ5285/04/5304ꢀ0925 © 2004 Plenum Publishing Corporation

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Russ.Chem.Bull., Int.Ed., Vol. 53, No. 4, April, 2004
Kozlov et al.
Scheme 2
Scheme 3
bis[(2ꢀphosphorylꢀ2ꢀcyano)ethyl]benzene (5) with
O,Oꢀdiisopropyl dithiophosphate (2) (Scheme 2). It should
be noted that the reaction of compound 5 led to thionation
of both nitrile groups of the molecule.
As mentioned above, these reaction conditions have
earlier been used4 for the preparation of thiobenzamides
from benzonitrile and its pꢀbromoꢀ and pꢀdimethylamino
derivatives. Using 2ꢀ(diphenylphosphorylmethyl)benzoꢀ
nitrile (8) as an example, we demonstrated that this proꢀ
cedure makes it also possible to perform thionation of the
nitrile group in orthoꢀsubstituted benzonitriles. After mixꢀ
ing of the reagents and storage of the reaction mixture at
~20 °C for 2 days, the corresponding thioamide 9 was
isolated in ~80% yield (Scheme 3).
All primary thioamides were prepared as crystalline
compounds. Their compositions and structures were conꢀ
firmed by data from elemental analysis and IR and NMR
spectroscopy (Tables 1 and 2).
In the IR spectra of thioamides 3a—d, 6, 7, and 9
(KBr) containing the phosphoryl fragment, absorption of
Table 1. Yields, melting points, and data from elemental analysis and IR spectroscopy for phosphorusꢀsubstituted thioamides
Comꢀ Yield
pound (%)
M.p.
/°C
Found
Calculated
Molecular
formula
IR spectrum,
(%)
ν/cm–1
С
H
N
—
ν(P=O)
ν(C=S) + δ(CH2) + δ(NH) + ν(N—C=S)
3a
3b
75
68
72—74а
152—154
—
—
—
1230
1205
1315, 1435—1445 br
1300, 1315, 1442, 1450
36.82
36.92
49.68
49.37
61.04
61.08
—
7.37 7.11
7.23 7.17
6.19 5.56
5.80 5.76
5.07 5.07
5.13 5.09
C6H14NO2PS
C10H14NO2PS
C14H14NOPS
C20H19ClNPSb
3c
3d
78
75
146—148
250—251
1220
1195
1315, 1385, 1450 br
1300, 1320, 1438, 1455
3e
3f
6
70
35
58
255—257
30—32
268—270
—
—
—
—
—
658d
1175
1440—1490 br
1380, 1450—1465
1300, 1430, 1457
с
—
C6H14NO2PS2
68.88
69.02
49.68
49.64
68.41
68.36
5.36 4.02
5.52 3.83
4.75 7.29
4.82 7.29
5.21 3.98
5.16 3.99
C21H20NOPS
C24H42N2O6P2S2
C20H18NOPS
7
9
63
79
262—263
295—297
1235
1300, 1395, 1445, 1450
1180—1190 br
1320, 1380, 1445, 1460
a Cf. lit. data11,12: m.p. 73—75 °C.
b Found (%): P, 8.53; S, 8.40. Calculated (%): P, 8.33; S, 8.62.
c Found (%): P, 12.30; S, 37.24. Calculated (%): P, 11.94; S, 37.09.
d
ν(P=S).

Phosphorylꢀsubstituted carbothioamides
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 4, April, 2004
927
Table 2. Selected parameters of the 1H and 31P NMR spectra of thioamides (in DMSOꢀd6)
Comꢀ
pound
NMR (δ, J/Hz)
31P
1H
3а
22.35
1.29 (t, 6 Н, CH3СН2, 3JH,H = 6.8); 3.25 (d, 2 Н, РСН2, 2JР,H = 22.5); 4.11—4.03 (m, 4 Н, ОСН2);
9.05, 9.45 (both s, 1 Н + 1 Н, NH2)
3ba
47.26
37.80
37.01
1.31 (d, 3 Н (СН3)2СН, 3JH,H = 6.0); 1.33 (d, 3 Н, (СН3)2СН, 3JH,H = 6.4); 1.63 (d, 3 Н, РMe,
2JР,H = 11.6); 3.34 (t, 1 НА, СНАНВ, 2JН,H = 2JР,H = 14.0); 3.43 (dd, 1 НB, СНАНВ, 2JН,H = 14.0,
2JР,H = 19.2); 4.64—4.72 (m, 1 Н, ОСН); 8.04, 8.77 (both s, 1 Н + 1 Н, NH2)
1.31 (t, 3 Н, Me, 3JH,H = 6.4); 3.51 (t, 1 НА, СНАНВ, 2JН,H = 2JР,H = 15.0); 3.61 (dd, 1 НB,
СНАНВ, 2JН,H = 15.0, 2JР,H = 18.0); 3.94—4.18 (m, 2 Н, ОСН2); 7.35—7.80 (m, 5 Н, Ph);
7.83, 8.75 (both s, 1 Н + 1 Н, NH2)
3ca
3с
3
1.21 (t, 3 Н, Me, JH,H = 7.0); 3.55 (d, 2 Н, РСН2, 2JР,H = 19.3); 3.89—3.93, 4.00—4.05
(both m, 2 Н, ОСН2); 7.52—7.55, 7.59—7.63, 7.74—7.79 (three m, 4 Н + 2 Н + 4 Н, Ph—P); 9.11, 9.48
(both s, 1 Н + 1 Н, NH2)
2
3d
3e
3f
27.96
23.67
92.26
3.91 (d, 2 Н, РСН2, JР,H = 13.4); 7.49—7.84 (m, 10 Н, Ph); 9.01, 9.42 (both s, 1 Н + 1 Н, NH2)
5.49 (d, 2 Н, РСН2, 2JР,H = 16.0); 7.35—7.80 (m, 15 H, Ph); 9.85, 10.45 (both s, 1 Н + 1 Н, NH2)
1.35 (t, 6 Н, СН3СН2, 3JH,H = 7.2); 3.82 (d, 2 Н, РСН2, 3JР,H = 12.7); 4.10—4.30 (m, 4 Н, ОСН2);
9.24, 9.63 (both s, 1 Н + 1 Н, NH2)
2
2
6
29.62
2.86 (t, 1 НА, СНАНВAr, JH,H = 3JH,H = 11.7); 3.49 (dt, 1 НВ, СНАНВAr, JH,H = 3JH,H = 11.7,
3JР,H = 5.52); 4.37 (br.t, 1 Н, Р(О)СН, JР,H = JH,H = 11.7); 7.12—7.20, 7.45—7.56, 7.91—8.02
(3 m, 5 Н + 6 Н + 4 Н, СН2С6Н5 + Ph2Р); 8.90, 9.20 (both s, 1 Н + 1 Н, NH2)
1.18 (m, 12 Н, СН3СН2); 2.20 (s, 12 Н, MeAr); 3.42—3.49 (m, 6 Н, СН2Ar + CH); 3.94—4.00
(m, 8 H, OCH2); 9.10, 9.47 (both s, 2 Н + 2 Н, NH2)
2
3
7
24.76
33.13
9b
4.05 (d, 2 Н, РСН2, 2JР,H = 13.0); 6.60 (d, 1 Н, С6Н4, 3JH,H = 7.6); 7.05 (t, 1 Н, С6Н4, 3JH,H = 7.6);
7.20 (t, 1 Н, С6Н4, 3JH,H = 7.6); 7.48 (d, 1 Н, С6Н4, 3JH,H = 7.6); 7.53—7.70 (m, 6 Н pꢀ, mꢀPhР);
7.84—7.89 (m, 4 Н, оꢀPhР)
a The spectra were recorded in CDCl3.
b 13C NMR (DMSOꢀd6), δ: 33.81 (d, CH2, JP,C = 64.0 Hz); 125.47 (d, C(1), JP,C = 8.4 Hz); 126.59 (d, C(3), JP,C = 2.0 Hz);
1
3
3
3
2
1
128.48 (C(4)); 128.92 (d, mꢀPhP, JP,C = 11.9 Hz); 129.86 (C(5)); 130.88 (d, oꢀPhP, JP,C = 9.6 Hz); 132.01 (d, ipsoꢀPhP, JP,C
=
98.8 Hz); 135.32 and 132.50 (pꢀPhP); 144.52 (d, C(2), 2JP,C = 5.4 Hz); 201.92 (C=S).
the P=O group is observed at 1180—1230 cm–1, the band
being shifted as expected to a lower frequency as the
number of P—C bonds in the molecule increases. The
absorption band at 1315—1320 cm–1 was assigned to
stretching vibrations of the C=S group by analogy with
the published data.12 Only weak bands at 1300 and
1340 cm–1 are observed for thioacetamide 3e containing
the phosphonium substituent. The band of the C=S group
in the spectra of thioacetamide 3f and bisꢀthioamide 7 is
shifted to 1380 and 1395 cm–1, respectively. Overlapꢀ
ping of the bending bands of the CH2 and NH groups
and the ν(N—C=S) band is responsible for the appearꢀ
ance of a broad mediumꢀintensity absorption band at
1435—1455 cm–1. In the spectra of all the thioamides
synthesized, a broadened stretching band of the amido
group is observed as a doublet in the region of
3100—3300 cm–1, the band being shifted by ~100 cm–1
compared to NH2 vibrations in the spectra of amides of
the corresponding carboxylic acids. Broadening of this
vibrational band, the appearance of a series of additional
bands in this region, and the shift of the band are indicaꢀ
tive of the presence of intraꢀ and intermolecular associꢀ
ates formed through hydrogen bonds involving the amide
protons.
The 31P NMR spectra of compounds 3a—f, 6, and 9
show singlets in regions characteristic of this type of enviꢀ
ronment about the P atom. It should be noted that a
singlet is observed also for bisꢀthioamide 7 in spite of the
presence of two asymmetric centers in the molecule (corꢀ
respondingly, 7 is formed as the meso and d,l forms).*
In the 1H NMR spectra of thioacetamides 3a,c—f in
DMSOꢀd6, the signals for the protons of the PCH2C(S)
group appear as doublets. In the spectra (in CDCl3) of
compounds 3b,c containing the asymmetrical P atom,
these signals are observed as ABX systems. The magnetic
nonequivalence of the methylene protons in the spectra
of compounds 3b,c in CDCl3 is apparently indicative of
sterically hindered rotation about the P—C bond in this
solvent due to specific solvation. The spinꢀspin coupling
constant of the protons of the CH2 group with the P atom
and δ for this signal are close to the analogous parameters
for the starting nitriles and decrease on going from
phosphonates to phosphinates and then to phosphine oxꢀ
ides. The position of the signal for these protons depends
* The starting bisꢀnitriles 5 represented mixtures of meso and
d,l isomers, which are characterized by individual signals in the
31P NMR spectra (see Ref. 15).

928
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Kozlov et al.
O(1B)
H(1N)
S(1A)
H(2N)
C(2)
N(1A)
H(2NA)
N(1)
C(1)
H(1NB)
O(1)
N(1B)
C(7)
C(8)
S(1)
P(1)
C(3)
C(6)
C(5)
C(9)
C(14)
C(4)
C(10)
C(11)
C(12)
C(13)
Fig. 1. Overall view of molecule 3d and a fragment of a hydrogenꢀbonded chain in the crystal.
directly on the acidifying effect of the phosphorusꢀconꢀ
taining fragment, i.e., the signal is shifted downfield as
the CHꢀacidity increases.16
C(3)—P(1)—C(9) bond angle decreases on going from
3d to 9. The mutual arrangement of the phosphoryl group
and the substituent at the C(1) atom (the aryl fragment
in 9 or the C(S)NH2 group in 3d) is nearly synꢀperiplanar;
the corresponding torsion angles are 53.6 and 59.8°, reꢀ
spectively. Due to steric repulsion, the carbothioamide
group in compound 9 is twisted with respect to the plane
of the phenyl ring by 52.5°.
Comparison of the main geometric parameters of molꢀ
ecules 3d and 9 shows that the presence of the electronꢀ
withdrawing thioamide substituent at the C(1) atom in 3d
leads to a substantial shortening of the P(1)—O(1) bond
(to 1.482(2) Å) compared to the analogous bond in 9
(1.497(1) Å). In spite of the fact that this effect of the
electronꢀwithdrawing substituent on the P=O bond length
has been noted in our earlier study,17 it is also not inconꢀ
ceivable that the observed differences in the bond lengths
in molecules 3d and 9 are associated with hydrogen
bonding.
Analysis of the crystal packing demonstrated that
the C(S)NH2 group in both compounds is involved in
N—H...O and N—H...S hydrogen bonds (see Table 3). In
spite of rather high acidity of the methylene protons, they
are not involved in C—H...O contacts in the crystals.
In both structures, the N—H...S hydrogen bonds give
rise to centrosymmetrical dimers with a planar eightꢀmemꢀ
bered Hꢀbonded ring. The geometric parameters of these
hydrogen bonds in two compounds are approximately
the same.
It should also be noted that the signals for the amide
protons are magnetically nonequivalent and appear as
two singlets in the spectra of all the thioamides syntheꢀ
sized regardless of the solvent in which the spectra were
recorded, whereas the positions of the signals depend on
the solvent. In DMSO, these signals are substantially
shifted downfield compared to their chemical shifts in
CDCl3 (cf. the 1H NMR spectra of 3c in CDCl3 and
DMSO, see Table 2).
Since most of the compounds synthesized contain the
carbothioamide and phosphoryl groups along with the
methylene fragment characterized by rather high acidity
of CH protons, it was of interest to study their molecular
and, in particular, crystal structures* with special emphaꢀ
sis on specific interactions. For this purpose, we carried
out singleꢀcrystal Xꢀray diffraction study of diphenylꢀ
phosphorylthioacetamide (3d) and 2ꢀ(diphenylphosꢀ
phorylmethyl)thiobenzamide (9). The overall views of
molecules 3d and 9 are shown in Figs. 1 and 2, respecꢀ
tively. Their selected geometric parameters are given in
Table 3. In both molecules, the P atoms are characterized
by a slightly distorted tetrahedral coordination. The
* It should be noted that the NH2 group in the only known
crystal structure of phosphorylated carbothioamides, viz., diꢀ
ethyl [5ꢀ(pꢀtolyl)ꢀ1,3,4ꢀoxadiazolꢀ2ꢀyl]thiocarbamoylmethylꢀ
phosphonate,13 forms hydrogen bonds (intraꢀ and intermolecuꢀ
lar) only of the N—H...O type, whereas the C=S bond is not
involved in specific interactions.
In contrast, the type of N—H...O bonds in 3d differs
substantially from that in 9. In the crystal of thioacetꢀ

Phosphorylꢀsubstituted carbothioamides
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 4, April, 2004
929
C(6)
C(7)
C(5)
C(8)
C(4)
C(3)
S(1A)
P(1)
C(9)
C(14)
O(1)
C(13)
C(12)
H(2N)
N(1A)
H(2NA)
H(2NA)
C(1)
H(1N)
C(10)
N(1)
C(11)
C(15)
C(20)
C(2)
C(16)
O(1A)
S(1)
C(17)
C(19)
C(18)
Fig. 2. Overall view of molecule 9 and centrosymmetrical N—H...S dimers in the crystal.
Table 3. Selected bond lengths (d) and bond
angles (ω) in the crystals of 3d and 9
amide 3d, the molecules are linked in infinite chains
through intermolecular N—H...O bonds (see Fig. 1). In
thiobenzamide 9, the N—H...O bond is, on the contrary,
intramolecular and is involved in the formation of the
second eightꢀmembered Hꢀbonded ring (see Fig. 2). It
should be noted that the N...O distances generally used as
estimates of the strength of hydrogen bonds are equal in
3d and 9. Consequently, the observed differences in the
geometry of the molecules are determined primarily by
inductive effects of the substituents rather than are associꢀ
ated with the difference in the crystal packing.
Parameter
3d
9
Bond
d/Å
P(1)—O(1)
P(1)—C(1)
P(1)—C(3)
P(1)—C(9)
S(1)—C(2)
C(2)—N(1)
C(1)—C(2)
C(1)—C(15)
Angle
1.482(2)
1.816(3)
1.805(3)
1.798(3)
1.663(3)
1.304(3)
1.500(3)
—
1.497(1)
1.821(2)
1.801(2)
1.797(2)
1.684(2)
1.314(2)
—
Thus, phosphorusꢀsubstituted nitriles can easily and
efficiently be transformed into the corresponding thioꢀ
amides with the use of O,Oꢀdiisopropyl dithiophosphate
as the thionating agent.
1.491(2)
ω/deg
O(1)—P(1)—C(1) 113.0(1)
O(1)—P(1)—C(3) 113.0(1)
O(1)—P(1)—C(9) 111.3(1)
C(3)—P(1)—C(9) 107.7(1)
S(1)—C(2)—N(1) 124.4(2)
112.16(7)
113.13(7)
112.27(8)
105.35(8)
123.50(1)
Experimental
N(1)—H(2N)...S(1A) bonda
The NMR spectra were recorded on Bruker WPꢀ200SY and
Bruker AMXꢀ400 instruments in CDCl3 and DMSOꢀd6 using
residual signals for the protons of the deuterated solvents as the
internal standards (1H and 13C) and 85% H3PO4 as the external
standard (31P). The 13C NMR spectra were recorded in the
JMODECHO mode; the signals for the C atoms bearing odd
and even numbers of protons have opposite polarities. The IR
spectra were recorded on a MagnaꢀIR 750 (Nicolet) Fourierꢀ
Bond
N(1)...S(1A)
Angle
d/Å
3.416(2)
3.432(2)
ω/deg
N(1)—H(1)—S(1A) 176
168
N(1)—H(1N)...O(1A) bondb
Bond
d/Å
2.817(2)
N(1)...O(1A)
Angle
N(1)—H(1)—O(1A) 163.5
2.813(2)
169.0
ω/deg
transform spectrometer; the spectral resolution was 2 cm–1
128 scans (KBr pellets).
;
a The atom was generated from the basis atom by
the symmetry transformations (–x + 1, –y + 2,
–z) and (–x + 1, –y, –z + 1) in 3d and 9.
b The atom was generated from the basis atom
by the symmetry transformation (–x + 1, y,
–z + 1/2) in 3d.
Xꢀray diffraction data sets for thioamides 3d and 9 were
collected on an automated threeꢀcircle SMART CCDꢀ1000
diffractometer (MoꢀKα radiation, graphite monochromator,
ω scanning technique). Single crystals were prepared by slow
crystallization of compounds 3d and 9 from dilute solutions in a
1 : 1 MeCN—EtOH mixture. The structures were solved by diꢀ

930
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Kozlov et al.
Table 4. Principal crystallographic data and details of structure refinement for 3d and 9
Parameter
3d
9
Formula
T/K
C
14H14NOPS
298
C20H18NOPS
120
Crystal system
Space group
Monoclinic
С2/с
Triclinic
P–1
a/Å
b/Å
c/Å
α/deg
9.320(2)
17.052(3)
17.383(4)
—
98.018(4)
—
9.448(1)
9.592(1)
11.535(1)
77.833(2)
78.494(2))
63.592(2)
908.5(2)
2 (1)
β/deg
γ/deg
V/Å3
2735.7(9)
8 (1)
Z (Z´)
M
µ/cm–1
275.29
3.40
351.38
2.72
F(000)
dcalc/g cm–3
1152
1.337
368
1.285
2θmax/deg
57.00
58.00
Number of measured reflections (Rint
Number of independent reflections
)
6505 (0.0302)
3330
7978 (0.0260)
4519
Number of observed reflections
2110
3895
with I > 2σ(I )
Number of parameters
R1
296
0.0563
289
0.0448
wR2
0.1392
0.1153
GOOF
(ρmax/e•Å–3)/ρmin/e•Å–3
1.088
0.524/–0.262
1.065
0.588/–0.352
)
2
rect methods and refined anisotropically by the fullꢀmatrix leastꢀ
squares method against F 2hkl. The H atoms were revealed from
difference Fourier syntheses and refined isotropically. All calcuꢀ
lations were carried out using the SHELXTL PLUS program
package. The principal crystallographic data are given in Table 4.
The atomic coordinates were deposited with the Cambridge
Structural Database.
The starting phosphorylacetonitriles 1a—d were prepared by
the reactions of the corresponding esters of trivalent phosphorus
acids with chloroacetonitrile involving the Arbuzov rearrangeꢀ
ment according to a known procedure.18 Phosphorusꢀsubstiꢀ
tuted acetonitriles 1e 19 and 1f 20 were synthesized according to
the published procedures. Nitriles 4 and 5 were prepared by
alkylation of phosphorylacetonitriles with benzyl bromide and
1,4ꢀbis(bromomethyl)ꢀ2,3,5,6ꢀtetramethylbenzene, respectively,
according to a procedure described earlier.15
29.15. 1H NMR (CDCl3), δ: 3.89 (d, 2 H, CH2P, JP,H
=
13.6 Hz); 7.44—7.47 (m, 4 H, Ph); 7.51—7.53 (m, 4 H, C6H4);
7.66—7.75 (m, 6 H, Ph). 13C NMR (CDCl3), δ: 36.05 (d, CH2,
1JP,C = 63.8 Hz); 113.04 (d, C(1), 3JP,C = 6.0 Hz); 117.62 (CN);
3
127.32 (C(3)); 128.61 (d, mꢀPhP, JP,C = 12.1 Hz); 129.84 (d,
1
2
ipsoꢀPhP, JP,C = 99.0 Hz); 131.03 (d, oꢀPhP, JP,C = 9.6 Hz);
131.31 (C(4)); 132.27 (pꢀPhP); 132.38 (C(5)); 132.71 (C(6));
135.23 (C(2)).
Diethyl thiocarbamoylmethylphosphonate (3a). A mixture of
equimolar amounts of diethoxyphosphorylacetonitrile (1a) and
diisopropyldithiophosphoric acid 2 and 2 mol. equiv. of MeOH
was kept at ~20 °C for 2 days. Then Et2O was added to
the reaction mixture. The oil that formed was separated and
washed additionally with diethyl ether, after which the resiꢀ
due crystallized to give the target product in 75% yield (see
Tables 1 and 2).
2ꢀ[(Diphenylphosphoryl)methyl]benzonitrile (8) was prepared
upon the Arbuzov rearrangement starting from methyl diphenylꢀ
phosphinite and 2ꢀ(bromomethyl)benzonitrile.21 OꢀMethyl
diphenylphosphinite (2.4 g, 11.1 mmol) was added dropwise to
a boiling solution of 2ꢀ(bromomethyl)benzonitrile (1.96 g,
0.01 mol) in xylene (20 mL) under a weak stream of argon for
15 min. The reaction mixture was refluxed for 2 h. A white
precipitate that formed after cooling was filtered off and recrysꢀ
tallized from a benzene—ethanol system. The yield of product 8
was 1.8 g (56.8%), m.p. 168—169 °C (benzene—ethanol).
Found (%): C, 75.90; H, 4.92; N, 4.55; P, 9.68. C20H16NOP.
Thioacetamides 3, 6, 7, and 9 were prepared analogously.
In the case of compound 3f, the oil that was precipitated
with diethyl ether was additionally purified by column chromaꢀ
tography on silica gel using benzene as the eluent.
Thioamides 3b—e, 6, 7, and 9 crystallized from the reaction
mixtures in the course of reactions. These compounds were
separated by filtration, washed on a filter with diethyl ether, and
recrystallized from EtOH (see Tables 1 and 2).
This study was financially supported by the Russian
Foundation for Basic Research (Project No. 02ꢀ03ꢀ
33073), the Federal Program for the Support of Leading
Scientific Schools of the Russian Foundation (Project
Calculated (%): C, 75.70; H, 5.08; N, 4.41; P, 9.76. IR, ν/cm–1
2230 (ν(CN)); 1195 (ν(P=O)). 31P—{1H} NMR (CDCl3), δ:
:

Phosphorylꢀsubstituted carbothioamides
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 4, April, 2004
931
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Heterocycles, 1994, 39, 185.
14. D. J. Birdsall, J. Green, T. Q. Ly, J. Novosad, M. Necas,
A. M. Z. Slavin, J. D. Woolins, and Z. Zak, Eur. J. Inorg.
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No. NShꢀ1100.2003.3), and the Government contract
No. 10002ꢀ251/Pꢀ09/118ꢀ125/100603ꢀ589.
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Received November 14, 2003;
in revised form January 23, 2004