Reaction of N-thioamido amidines with phosphoramide derivatives: Synthesis of 2-substituted-1,3,5,2-triazaphosphorines

Article abstract of DOI:10.1002/hc.20546

The reaction of N-thioamido amidines 1 with tris(dimethylamino) phosphine or bis(diethylamino) phenylphosphine in refluxing toluene leads to the 1,3,5,2λ³-triazaphosphorines 2 and 3, respectively. The condensation results in the release of two

Full text of DOI:10.1002/hc.20546

Heteroatom Chemistry
Volume 20, Number 5, 2009
Reaction of N-Thioamido Amidines with
Phosphoramide Derivatives: Synthesis of
2-Substituted-1,3,5,2-Triazaphosphorines
Noureddine Raouafi, Akila Khlifi, Khaled Boujlel,
and Mohamed Lamine Benkhoud
Laboratoire de Chimie Analytique et Electrochimie, De´partement de Chimie, Faculte´ des Sciences
de Tunis, Campus Universitaire, Tunis El Manar 2092, Tunisia
Received 4 October 2008; revised 26 April 2009
rine rings, the latter are the least studied [1–10].
ABSTRACT: The reaction of N-thioamido
Since 1966 when Latscha isolated triazaphospho-
amidines
1
with tris(dimethylamino)phosphine
rines as byproducts of the reaction of phospho-
rus pentachloride with dimethylurea [11], much
work was devoted to the development of new routes
to these heterocycles [12–14]. Recently Schmut-
zler and his coworkers described many syntheses
and applications of triazaphosphorines [15–18]. We
have previously developed access to 2-substituted-
1,3,5,2-triazaphosphorines via the condensation of
trivalent or tetravalent phosphorus derivatives with
compounds bearing two nucleophilic sites in 1,5-
positions [19–21]. In this paper, we report the syn-
thesis of new families of triazaphosphorines by
condensation of N-thioamido amidines with phos-
phoramide derivatives and their oxidation by ele-
mental sulfur.
or bis(diethylamino)phenylphosphine in refluxing
toluene leads to the 1,3,5,2λ3-triazaphosphorines
2 and 3, respectively. The condensation results in
the release of two molecules of dialkylamine. The
sulfuration of the trivalent phosphorus atoms was
achieved by the reaction with elemental sulfur,
followed by heating in toluene. The structure of the
triazaphosphorines 2 and 3 and their thione deriva-
1
tives 4 and 5 were readily elucidated by means of H,
13C, and 31P NMR spectroscopy and mass spectrom-
ꢀ
C
etry.
2009 Wiley Periodicals, Inc. Heteroatom Chem
20:272–277, 2009; Published online in Wiley InterScience
(www.interscience.wiley.com). DOI 10.1002/hc.20546
INTRODUCTION
RESULTS AND DISCUSSION
Among the five- and six-membered heterocycles con-
taining carbon, nitrogen, and phosphorus atoms
and in particular those containing more than
two heteroatoms such as diazaphosphole, triaza-
phosphole, diazaphosphorine, and triazaphospho-
Synthesis of 1,3,5,2-Triazaphosphorines
Tris(dimethylamino)phosphine and bis(diethyl-
amino)phenylphosphine are much less reactive
than halogenated phosphorus derivatives such as
phosphorus trichloride and phosphorus oxytrichlo-
ride. The conversion of phosphoramides requires
more drastic conditions such as refluxing for several
hours in high boiling solvents such as toluene or
xylene, to effect cyclization reaction with com-
pounds bearing two nucleophilic sites in 1,4- or
Correspondence to: Noureddine Raouafi; e-mail: rdnnin@fst.
rnu.tn.
Contract grant sponsor: Tunisian Ministe`re de l’Enseignement
Supe´rieure, de la Recherche Scientifique et de la Technologie.
Contract grant number: Lab-CH-02.
2009 Wiley Periodicals, Inc.
c
ꢀ
272

Synthesis of a New Family of Triazaphosphorines 273
SCHEME 1
1,5-positions [21,22]. On the other hand, this kind
of reaction, i.e. when hexamethylphosphoramide
or bis(diethylamino)phenylphosphine are used in
excess, gives pure products, whereas the use of
halogenated phosphorus derivatives require more
steps to separate the desired product from the
hydrochloride salt. Only the release of dialkylamine
gas was detected during the course of the reaction.
The end of the reaction could easily be monitored
by 31P NMR spectroscopy or simply by testing the
decrease of the evolution of dialkylamine gas using
a pH paper.
two highest chemical shifts (δ = 122 and 100 ppm)
are attributed to the starting phosphoramide deriva-
tives (P(NMe2)3 or PhP(NEt2)2), and the third one
is assigned to the corresponding cyclic products 2
and 3. The reaction is completed after heating the
mixture for 22–24 h. Thus all reaction mixtures are
refluxed for 24 h, followed by a standard workup.
The different products are summarized in
Table I. The reaction yield depends strongly on the
steric hindrance caused by the R2 and R3 moieties,
i.e. the yield increases by decreasing of strain (R3 =
phenyl to benzyl to ethyl, when R2 = benzyl). The
final oily product could easily be purified by wash-
ing several times with small amounts of petroleum
ether.
When the starting N-thioamido amidines 1
[23–25] are refluxed in anhydrous toluene with a
small excess of tris(dimethylamino)phosphine or
bis(diethylamino)phenylphosphine, the reaction
leads to the corresponding 2-dimethylamino-
The reaction presumably proceeds via the forma-
tion of two possible intermediates A (Aꢀ) and B (Bꢀ)
(Scheme 2). The first is obtained by phosphorylation
1,3,5,2λ3-triazaphosphorines
2
and 2-phenyl-
respectively
1,3,5,2λ3-triazaphosphorines
3,
(Scheme 1). During the reaction for each com-
pound, the 31P NMR spectra show essentially two
major signals at δ = 122 ppm and δ = 70–80 ppm or
δ = 100 ppm (Ph) and δ = 70–80 ppm (Table 1); the
S
S
R3
H
R3
N
N
N
N
N
NMe2
NMe2
or
or
P
NMe2
NMe2
R1
R1
N
R2
S
P
NH
R2
TABLE 1 Triazaphosphorines 2 and 3
A
B
31
Compound
R1
R2
R3
P NMR
S
R3
R3
2a
2b
2c
2d
2e
2f
3a
3b
3c
3d
Ph
Bn
Ph
Ph
Ph
Bn
Ph
Bn
Bn
Ph
Bn
Bn
Bn
Bn
Bn
Et
Ph
Ph
Bn
Ph
Bn
Ph
78.6
81.4
73.8
77.2
81.4
81.5
77.4
81.0
70.9
77.3
N
N
N
H
NEt2
CH3 CH Ph
P
NEt2
Ph
R1
R1
Bn
NH
N
P
Ph
CH2 C5H4N
R2
R2
Bn
A'
B'
CH3 CH Ph
Bn
Bn
Bn
R1– R3: see Table 1
SCHEME 2
Heteroatom Chemistry DOI 10.1002/hc

274 Raouafi et al.
TABLE 2 Triazaphosphorine-2-thiones 4 and 5
31
Compound
R1
R2
R3
P NMR
4a
4b
4c
4d
4e
4f
5a
5b
5c
5d
Ph
Bn
Ph
Ph
Ph
Bn
Ph
Bn
Bn
Ph
Bn
Bn
Bn
Bn
Bn
Et
Ph
Ph
Bn
Ph
Bn
Ph
58.5
56.8
63.8
57.9
59.3
58.5
61.1
59.3
59.6
60.0
CH3 CH Ph
Bn
CH2 C5H4N
Bn
CH3 CH Ph
Bn
Bn
Bn
SCHEME 3
assigned to the stretching vibration of the C N func-
tion. The IR spectra of the final products 2 and 3 do
not display any band in the region between 3200
and 3400 cm−1. The other bands show no major dif-
ference as compared to those of the starting com-
pounds. However, the spectra reveal the presence of
a new sharp, intense band at 1235 cm−1, attributed
to the P N bond.
of the amidinic nitrogen atom and the second one
by reaction of the thioamidinic nitrogen atom and
P(NMe2)3 or Ph-P(NEt2)2. This is followed by a sec-
ond intramolecular nucleophilic substitution of the
dialkylamine to furnish the final products 2 and 3.
AM1 and PM3 semiempirical calculations of the
charges at different nitrogen atoms show that the
electron density at the amidinic nitrogen atom, to
which R2 is linked, is higher than at the thioami-
dinic nitrogen atom, to which R3 is linked and which
is conjugated to the thiocarbonyl function. It is,
therefore, more likely that the intermediate A (Aꢀ) is
formed during this reaction, although the formation
of intermediate B (Bꢀ) cannot be totally excluded.
NMR Spectroscopies. The 1H NMR spectra con-
firm the absence of the proton signals of the N H
functions and the presence of those related to the
dimethylamino group introduced by the phospho-
rus substrate. In addition, a peak splitting due to
3
phosphorus–proton coupling JPH (3 J = 10–11 Hz)
when R2 and/or R3 = benzyl is observed. These ob-
servations are confirmed by 13C NMR spectroscopy.
All 31P NMR spectra show a signal about 70–80 ppm,
assigned to λ3-P, which is in agreement with the lit-
erature and confirmed by our previous work [19–20].
The sulfuration of the products 2 and 3 by addition
of elemental sulfur shifted the 31P signal to higher
field (δ = 60 ppm). No major changes are detected in
the 1H or 13C NMR spectra.
Synthesis of 1,3,5,2-Triazaphosphorine-
2-thiones
Heating the triazaphosphorines 2 and 3 in toluene
for 3 h in the presence of a small excess of ele-
mental sulfur leads to the corresponding 1,3,5,2λ4-
triazaphosphorine-2-thiones 4 and 5, respectively
(Scheme 3).
The 31P NMR spectra show a shift to higher field
of about 20 ppm, compared to that observed for the
initial products (Table 2). The 1H and 13C NMR spec-
tra do not reveal any significant changes with respect
to the data of the starting compounds.
Mass Spectra. Owing to the low stability of
the triazaphosphorines 2 and 3 in the ionization
medium, the CI-MS spectra do not show the molec-
ular M+ peaks. The oxidation by sulfur addition
stabilizes the products 4 and 5, and (M + H)+
is detected as the base peak. Moreover, the spec-
tra of triazaphosphorines and triazaphosphorine-
2-thiones reveal the existence of some common
fragments such as (M R2 NCS)+ or (M R3)+ and
some other phosphorus-containing moieties such as
S C NHPh P N(CH3)2 or Ph CH2 N P Ph.
Spectroscopic Studies
IR Spectroscopy. The IR spectra of the starting
amidines 1 show two characteristic bands at about
3200 and 3430 cm−1 related to the stretching vibra-
tions of the two amidinic N H bonds, and two other
bands, the first at 1190 cm−1 due to the C S vibration
and the second one in the region of 1620–1660 cm−1
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of a New Family of Triazaphosphorines 275
CONCLUSION
128.6; 128.8; 130.9; 137.2; 157.7 (C N); 188.6 (C S);
31P NMR (121 MHz, CDCl3): δ 78.6.
In this paper, a short and straightforward synthesis
of 2-substituted-1,3,5,2-triazaphosphorines from N-
thioamido amidines and phosphoramide derivatives
is described. The derivatization of these compounds
is possible through oxidation with elemental sulfur.
2b: Oil. Yield: 59%. IR (CHCl3 solution 0.01
M): 3113 (νC H), 1596 (νC N), 1235 (νP N), 1188
1
(νC S) cm−1. H NMR (300 MHz, CDCl3): δ 2.23 (d,
6H, J = 10.4 Hz, CH3 N); 2.77 (d, 2H, J = 8.0 Hz,
CH2 C); 4.17 (d, 2H, J = 7.1 Hz, CH2 N); 4.54
(d, 6H, J = 6.8 Hz, CH2 N); 6.91–8.08 (m, Harom);
13C NMR (75 MHz, CDCl3): δ 36.7 (N CH3); 41.4
(CH2 C); 45.6 (CH2 N); 48.6 (CH2 N); 125.6; 126.9;
129.1; 135.1; 140.4 C; 158.5 (C N); 181.9 (C S);
31P NMR (121 MHz, CDCl3): δ 81.4. Anal. Calcd for
C25H27N4PS(446): H: 6.09; C: 67.24; N: 12.55; Found:
H: 6.15; C: 67.29; N: 12.57.
EXPERIMENTAL
Melting points were determined in open capillaries
with an Electrothermal 9100 apparatus and are un-
corrected. NMR spectra were recorded on a Bruker
AC 300 spectrometer at 300 MHz (1H), 75 MHz (13C),
and 121 MHz (31P). Chemical shifts are given in ppm,
2c: Oil. Yield: 54%. IR (CHCl3 solution 0.01 M):
3105 (νC H), 1598 (νC N), 1237 (νP N), 1184 (νC
)
1
S
using TMS as an internal standard for the H and
cm−1. 1H NMR (300 MHz, CDCl3): δ 1.20 (t, 3H,
J = 7.0 Hz, CH3 CH); 2.33 (d, 6H, J = 10.4 Hz,
CH3 N); 4.19 (q, 2H, J = 7.7 Hz, CH N); 4.85 (d, 2H,
J = 7.3 Hz, CH2 N); 6.71–8.03 (m, Harom); 13C NMR
(75 MHz, CDCl3): δ 38.6 (N CH3); 54.8 (CH2 N);
59.3 (CH N); 126.4; 128.2; 129.4; 129.9; 133.1; 136.7;
158.9 (C N); 192.5 (C S); 31P NMR (121 MHz,
CDCl3): δ 73.8. Anal. Calcd for C25H27N4PS (446): H:
6.09; C: 67.24; N: 12.55; Found: H: 6.01; C: 67.13; N:
12.60.
13C NMR and 85% H3PO4 as an external standard
for 31P NMR spectra. The IR spectra were recorded
on a Perkin–Elmer Paragon 1000 spectrophotome-
ter as CHCl3 solution in the range 4000–400 cm−1.
CI-MS spectra were recorded on a JOEL MX 700
at ENS Paris. Elemental analyses were conducted
by the Service de Microanalyse, CNRS at Gif-sur-
Yvette, France.
N-thioamido imidines 1 were synthesized ac-
cording to the literature [26], and the purity of
the products was checked by the comparison of
the melting point and by 1H and 13C NMR spec-
troscopy. Bis(diethylamino)phenylphosphine was
obtained following the literature from aminolysis of
commercial dichlorophenylphosphine; the product
was collected by distillation, and purity was verified
by 1H and 31P NMR spectroscopies [27].
2d: Oil. Yield: 53%. IR (CHCl3 solution 0.01 M):
3109 (νC H), 1592 (νC N), 1236 (νP N), 1186 (νC
)
S
cm−1. 1H NMR (300 MHz, CDCl3): δ 1.33 (t, 3H,
J = 6.8 Hz, CH3 CH2); 2.24 (d, 6H, J = 10.5 Hz,
CH3 N); 3.37 (q, 2H, J = 6.8 Hz, CH2 CH3); 4.51
(d, 2H, J = 7.1 Hz, CH2 N); 7.05–7.93 (m, Harom);
13C NMR (75 MHz, CDCl3): δ 14.2 (CH3 CH2); 37.6
(N CH3); 44.6 (CH2 CH3); 57.3 (CH2 N); 125.7;
127.6; 127.8; 129.9; 132.4; 137.2; 157.3 (C N); 189.9
(C S); 31P NMR (121 MHz, CDCl3): δ 77.2. Anal.
Calcd for C19H23N4PS (370,5): H: 6.21; C: 61.60; N:
15.12; Found: H: 6.35; C: 61.73; N: 15.24.
Synthesis of the Dimethylamino-1,3,5,2-
triazaphosphorines 2 and 3
A mixture of 5.0 mmol of the N-thioamido amidine
1 and 5.5 mmol of tris(dimethylamino)phosphine
in 20 mL of anhydrous toluene was heated to re-
flux in a nitrogen atmosphere for 24 h. The solvent
was then evaporated under reduced pressure, and
the resulting oily product was washed three times
with 20 mL of petroleum ether to remove the excess
of tris(dimethylamino)phosphine; the product was
then heated (70◦C) to dryness under reduced pres-
sure (18 mmHg).
2e: Oil. Yield: 58%. IR (CHCl3 solution 0.01
M): 3114 (νC H), 1599 (νC N), 1232 (νP N), 1189
1
(νC S) cm−1. H NMR (300 MHz, CDCl3): δ 2.57 (d,
6H, J = 11.0 Hz, CH3 N); 4.61 (d, 2H, J = 8.0 Hz,
CH2 N); 7.15–8.08 (m, Harom); 13C NMR (75 MHz,
CDCl3): δ 37.9 (N CH3); 57.3 (CH2 N); 126.7; 127.6;
128.4; 129.1; 136.5; 155.5 (C N); 193.1 (C S); 31P
NMR (121 MHz, CDCl3): δ 81.4. MS (CI, NH3):
m/z (%) = 420 (100) [M+ + H]; 419; 211 (45)
[S C NHPh P N(CH3)2]+.
2a: Oil. Yield: 65%. IR (CHCl3 solution 0.01
M): 3109 (νC H), 1642 (νC N), 1227 (νP N), 1179
2f: Oil. Yield: 51%. IR (CHCl3 solution 0.01
M): 3106 (νC H), 1591 (νC N), 1238 (νP N), 1190
(νC S) cm−1. 1H NMR (300 MHz, CDCl3): δ 2.61
(d, 6H, J = 10.7 Hz, CH3 N); 3.84 (d, 2H, J = 6.1
Hz, CH2 C); 4.48 (d, 2H, J = 8.5 Hz, CH2 N); 7.11–
7.84 (m, Harom). 13C NMR (75 MHz, CDCl3): δ 38.3
(N CH3); 55.3 (CH2 N); 57.8 (CH2 N); 126.8; 127.5;
1
(νC S) cm−1. H NMR (300 MHz, CDCl3): δ 2.48 (d,
6H, J = 11.1 Hz, CH3 N); 4.41 (d, 2H, J = 8.0 Hz,
CH2 N); 4.54 (d, 2H, J = 6.4 Hz, CH2 N); 6.88–
7.89 (m, Harom); 13C NMR (75 MHz, CDCl3): δ 38.6
(N CH3); 54.8 (CH2 N); 57.3 (CH2 N); 127.0; 128.4;
Heteroatom Chemistry DOI 10.1002/hc

276 Raouafi et al.
184.7 (C S); 31P NMR (121 MHz, CDCl3): δ 77.3.
MS (CI, NH3): m/z (%) = 451 (8) [M]+; 346 (40)
[M N CH2 Ph]+; 211 (47) [Ph CH2 N P Ph]+.
Anal. Calcd for C27H22N3PS (451): H: 4.91; C: 71.82;
N: 9.31; Found: H: 5.01; C: 72.05; N: 9.47.
128.6; 129.3; 134.1; 139.7; 159.2 (C N); 193.6 (C S);
31P NMR (121 MHz, CDCl3): δ 81.5. Anal. Calcd For
C24H25N4PS (432): H: 5.83; C: 66.65; N: 12.95; Found:
H: 5.91; C: 66.72; N: 13.01.
Synthesis of the Phenyl-1,3,5,2-
triazaphosphorines 3
Synthesis of the 2-Substituted-1,3,5,2-
triazaphosphorine-2-thiones 4 and 5
To a solution of N-thioamido amidine 1 (5.0
mmol) in 20 mL of anhydrous toluene, 5.5 mmol
of phenyl(diethylamino)phosphine was added. The
mixture was heated to reflux in a nitrogen atmo-
sphere for 24 h. The solvent was then removed un-
der reduced pressure, the resulting oily residue was
washed three times with 20 mL of petroleum ether to
remove excess of phenyl(diethylamino)phosphine;
the product was dried under reduced pressure (18
mmHg).
1.0
mmol
of
the
2-substituted-1,3,5,2-
triazaphosphorine 2 or 3 was dissolved in 10 mL
of anhydrous toluene, and 1.1 mmol of elemental
sulfur was added. The mixture was heated to reflux
for 3 h. After cooling, the solvent was evaporated
under reduced pressure and 10 mL of anhydrous
petroleum ether was added to the residue. A yellow-
ish precipitate was formed; the solid was collected
by filtration and was used as it was without further
purification.
3a: Oil. Yield: 69%. IR (CHCl3 solution 0.01
M): 3107 (νC H), 1598 (νC N), 1235 (νP N), 1196
1
4a: mp: 116–118◦C; Yield: 75%. H NMR (300
1
(νC S) cm−1. H NMR (300 MHz, CDCl3): δ 1.22 (d,
MHz, CDCl3): δ 2.31 (d, 6H, J = 10.7 Hz, CH3 N);
4.57 (d, 2H, J = 5.6 Hz, CH2 N); 4.70 (d, 2H, J = 9.2
Hz, CH2 N); 6.59–7.94 (m, Harom); 13C NMR (75
MHz, CDCl3): δ 38.3 (N CH3); 54.4 (CH2 N); 56.8
(CH2 N); 125.1–127.7; 129.7; 131.9; 133.3; 136.8;
158.6 (C N); 187.2 (C S); 31P NMR (121 MHz,
CDCl3): δ 58.5. DCI-MS m/z (%) = 466 (32) [M +
H]+; 465 (100) [M]+; 360 (60) [M–N−CH2 Ph]+.
3H, J = 8.3 Hz, CH3 CH); 4.21 (q, 1H, J = 8.2 Hz,
CH3 CH); 4.58 (d, 2H, J = 10.9 Hz, CH2 N); 7.17–
7.83 (m, Harom); 13C NMR (75 MHz, CDCl3): δ 14.6
(CH3 CH); 42.7 (CH2 C); 65.8 (CH3 CH); 125.6;
126.8; 128.2; 130.9; 141.9; 142.2; 155.9 (C N); 178.3
(C S); 31P NMR (121 MHz, CDCl3): δ 77.4. Anal.
Calcd for C29H26N3PS (479): H: 5.46; C: 72.63; N:
8.76; Found: H: 5.48; C: 72.87; N: 8.81.
1
4b: mp: 129–131◦C; Yield: 59%. H NMR (300
3b: Oil. Yield: 60%. IR (CHCl3 solution 0.01
M): 3111 (νC H), 1597 (νC N), 1233 (νP N), 1194
(νC S) cm−1. 1H NMR (300 MHz, DMSO-d6): δ
3.57 (d, 2H, J = 7.2 Hz, CH2 C); 4.44 (d, 2H,
J = 8.4 Hz, CH2 N); 6.49–8.43 (m, Harom); 13C NMR
(75 MHz, CDCl3): δ 42.4 (CH2 C); 45.1 (CH2 N);
125.6; 126.9; 129.1; 129.5; 134.8; 139.9; 140.9; 154.5
(C N); 183.9 (C S); 31P NMR (121 MHz, CDCl3): δ
81.0. MS (CI, NH3): m/z (%) = 465 (8) [M]+; 225
(100) [M − (Ph N C S + Ph CH N)]+; 209 (37)
[Ph CH2 CH N CH2 Ph]+.
MHz, CDCl3): δ 2.33 (d, 6H, J = 11.0 Hz, CH3 N);
3.88 (d, 2H, J = 6.9 Hz, CH2 C); 4.51 (d, 2H, J = 5.8
Hz, CH2 N); 4.77 (d, 2H, J = 9.2 Hz, CH2 N);
6.33–7.97 (m, Harom); 13C NMR (75 MHz, CDCl3): δ
36.3 (N CH3); 41.8 (CH2 C); 45.3 (CH2 N); 49.2
(CH2 N); 125.9; 127.2; 129.9; 138.3; 142.7; 159.3
(C N); 186.4 (C S); 31P NMR (121 MHz, CDCl3): δ
56.8.
1
4c: mp: 144–146◦C; Yield: 54%. H NMR (300
MHz, CDCl3): δ 1.23 (d, 3H, J = 7.0 Hz, CH3 CH);
2.34 (d, 6H, J = 10.5 Hz, CH3 N); 4.19 (q, 2H, J = 7.0
Hz, CH–CH3); 4.78 (d, 2H, J = 6.2 Hz, CH2 N); 6.76–
8.05 (m, Harom); 13C NMR (75 MHz, CDCl3): δ 27.2
(CH3 CH); 38.6 (CH3 N); 54.8 (CH2 N); 59.3 (CH–
CH3); 124.5; 127.7; 128.3; 130.2; 134.6; 138.8; 161.5
(C N); 196.2 (C S); 31P NMR (121 MHz, CDCl3): δ
63.8.
3c: Oil. Yield: 63%. IR (CHCl3 solution 0.01 M):
3112 (νC H), 1594 (νC N), 1234 (νP N), 1207 (νC
)
S
cm−1. H NMR (300 MHz, CDCl3): δ 4.22 (d, 2H,
J = 7.5 Hz, CH2 C); 4.46 (d, 2H, J = 7.4 Hz, CH2 N);
4.65 (d, 2H, J = 7.8 Hz, CH2 N); 7.07–7.84 (m,
Harom); 13C NMR (75 MHz, CDCl3): δ 42.4 (CH2 C);
45.1 (CH2 N); 48.1 (CH2 N); 127.1; 127.8; 128.4;
131.0; 136.6; 138.9; 154.5 (C N); 183.9 (C S); 31P
NMR (121 MHz, CDCl3): δ 70.9.
1
1
4d: mp: 131–132◦C; Yield: 78%; H NMR (300
MHz, CDCl3): δ 1.42 (t, 3H, J = 7.3 Hz, CH3 CH2);
2.33 (d, 6H, J = 10.8 Hz, CH3 N); 3.48 (q, 2H, J = 7.3
Hz, CH2 CH3); 4.64 (d, 2H, J = 11.2 Hz, CH2 N);
6.95–7.93 (m, Harom); 13C NMR (75 MHz, CDCl3):
δ 16.6 (CH3 CH2); 36.4 (N CH3); 45.9 (CH2 CH3);
58.7 (CH2 N); 124.2; 126.5; 127.6; 128.3; 135.1;
137.9; 158.4 (C N); 192.2 (C S); 31P NMR (121 MHz,
CDCl3): δ 57.9. Anal. Calcd for C19H23N4PS2(402): H:
3d: Oil. Yield: 69%. IR (CHCl3 solution 0.01
M): 3115 (νC H), 1587 (νC N), 1229 (νP N), 1198
(νC S) cm−1. 1H NMR (300 MHz, CDCl3): δ 4.73
(d, 2H, J = 7.7 Hz, CH2 N); 7.11–7.95 (m, Harom);
13C NMR (75 MHz, CDCl3): δ 46.5 (CH2 N); 125.5;
127.4; 129.2; 131.7; 133.5; 137.6, 139.3; 155.7 (C N);
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of a New Family of Triazaphosphorines 277
5.72; C: 56.72; N: 13.93; Found: H: 5.85; C: 56.89; N:
14.06.
ACKNOWLEDGMENTS
The authors thank Dr. Bernd Scho¨llhorn for his use-
ful help during the preparation of the manuscript.
1
4e: mp: 127–129◦C; Yield: 58%. H NMR (300
MHz, CDCl3): δ 2.63 (d, 6H, J = 10.3 Hz, CH3 N);
4.62 (d, 2H, J = 11.2 Hz, CH2 N); 7.07–8.14 (m,
Harom); 13C NMR (75 MHz, CDCl3): δ 36.3 (N CH3);
55.7 (CH2 N); 124.4; 126.2; 127.0; 129.6; 138.7;
145.2; 158.9 (C N); 195.3 (C S); 31P NMR (121 MHz,
CDCl3): δ 59.3.
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4f: mp: 116–118◦C; Yield: 68%; H NMR (300
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3.77 (d, 2H, J = 6.6 Hz, CH2 C); 4.75 (d, 2H, J = 7.2
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1
5a: mp: 114–115◦C; Yield: 82%. H NMR (300
MHz, CDCl3): δ 1.28 (d, 2H, J = 10.8 Hz, CH3 CH);
4.31 (q, 2H, J = 10.8 Hz, CH3 CH); 4.65 (d, 2H,
J = 7.2 Hz, CH2 N); 7.02–7.88 (m, Harom); 13C NMR
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67.5 (CH3 CH); 126.7; 128.4; 129.6; 131.5; 140.7;
145.0; 157.6 (C N); 185.7 (C S); 31P NMR (121
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(10) [Ph P(S) N CH2 Ph+2H]+. Anal. Calcd for
C29H26N3PS2(497): H: 5.09; C: 68.10; N: 8.22; S: 12.52;
Found: H: 5.17; C: 68.23; N: 8.41; S: 12.73.
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1
5b: mp: 124–125◦C; Yield: 60%. H NMR (300
MHz, DMSO-d6): δ 3.92 (d, 2H, J = 6.7 Hz, CH2 C);
4.44 (d, 2H, J = 7.3 Hz, CH2 N); 6.49–8.43 (m,
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47.7 (CH2 N); 124.3; 126.9; 129.8; 130.2; 134.8;
141.5; 144.2; 157.7 (C N); 188.2 (C S); 31P NMR
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1
5c: mp: 114–116◦C; Yield: 72%. H NMR (300
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4.35 (d, 2H, J = 7.4 Hz, CH2 N); 4.49 (d, 2H,
J = 7.0 Hz, CH2 N); 7.01–7.94 (m, Harom); 13C NMR
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48.4 (CH2 N); 125.3; 128.8; 129.4; 133.1; 138.8;
140,1; 157.3 (C N); 185.7 (C S); 31P NMR (121
MHz, CDCl3): δ 59.6. MS (CI): m/z (%) = 271(31)
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5d: mp: 131–133◦C; Yield: 69%. 1H NMR
(300 MHz, CDCl3): δ 4.78 (d, 2H, J = 7.4 Hz,
CH2 N); 7.11–7.95 (m, Harom); 13C NMR (75 MHz,
CDCl3): δ 49.7 (CH2 N); 122.7; 124,1; 127.4; 128.8;
130.5; 133.9; 137.5, 140.2; 159.5 (C N); 189.3
(C S); 31P NMR (121 MHz, CDCl3): δ 60.0. MS
(CI, NH3): m/z (%) = 484 (100) [M + H]+;
211 (47) [Ph CH2 N P Ph]+. Anal. Calcd for
C28H24N3PS2(483): H: 4.55; C: 67.08; N: 8.69; Found:
H: 4.73; C: 67.22; N: 8.79.
Heteroatom Chemistry DOI 10.1002/hc