Reaction of Lawesson's reagent with ester hydrazones: Synthesis of novel 3-thioxo-1,2,3-diazaphospholine derivatives

Article abstract of DOI:10.1080/17415993.2011.594053

The reaction of ester hydrazones with Lawesson's reagent leads to a variety of new 3-thioxo-1,2,3-diazaphospholine derivatives. The reaction shows relative regioselectivity and gives in some cases a mixture of two diastereoisomers. The electronic and steric factors influencing the regioselectivity of the reaction are discussed.

Full text of DOI:10.1080/17415993.2011.594053

This article was downloaded by: [University of Calgary]
On: 19 June 2013, At: 00:47
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Journal of Sulfur Chemistry
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/gsrp20
Reaction of Lawesson's reagent with
ester hydrazones: synthesis of novel
3-thioxo-1,2,3-diazaphospholine
derivatives
Emna Chebil a & Soufiane Touil a
a Laboratoire de Chimie Organique des Hétéroéléments,
Département de Chimie, Faculté des Sciences de Bizerte,
Université de Carthage, 7021, Jarzouna, Tunisie
Published online: 22 Jun 2011.
To cite this article: Emna Chebil & Soufiane Touil (2011): Reaction of Lawesson's reagent with
ester hydrazones: synthesis of novel 3-thioxo-1,2,3-diazaphospholine derivatives, Journal of Sulfur
Chemistry, 32:4, 297-302
To link to this article: http://dx.doi.org/10.1080/17415993.2011.594053
PLEASE SCROLL DOWN FOR ARTICLE
Full terms and conditions of use: http://www.tandfonline.com/page/terms-and-
conditions
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden.
The publisher does not give any warranty express or implied or make any representation
that the contents will be complete or accurate or up to date. The accuracy of any
instructions, formulae, and drug doses should be independently verified with primary
sources. The publisher shall not be liable for any loss, actions, claims, proceedings,
demand, or costs or damages whatsoever or howsoever caused arising directly or
indirectly in connection with or arising out of the use of this material.

Journal of Sulfur Chemistry
Vol. 32, No. 4, August 2011, 297–302
Reaction of Lawesson’s reagent with ester hydrazones: synthesis
of novel 3-thioxo-1,2,3-diazaphospholine derivatives
Emna Chebil and Soufiane Touil*
Laboratoire de Chimie Organique des Hétéroéléments, Département de Chimie, Faculté des Sciences de
Bizerte, Université de Carthage, 7021-Jarzouna, Tunisie
(Received 30 April 2011; final version received 1 June 2011)
The reaction of ester hydrazones with Lawesson’s reagent leads to a variety of new 3-thioxo-1,2,3-
diazaphospholine derivatives. The reaction shows relative regioselectivity and gives in some cases a mixture
of two diastereoisomers. The electronic and steric factors influencing the regioselectivity of the reaction
are discussed.
O
OR2
R1
C
(CH2)
n
P
N
S
N
Ar
Ph
2
LR
OR2
R1
(CH2)
C
O
C
N
CH2
n
Toluene/80°C
O
C
OR2
R1
(CH )
2 n-1
CH2
NHPh
1
N
P
S
N
Ar
Ar
S
S
S
Ph
LR :
P
P
S
Ar
2¢
:
Ar
O
CH3
Keywords: 3-thioxo-1,2,3-diazaphospholines; ester hydrazones; ketoesters; Lawesson’s reagent;
regioselectivity; diastereoisomers
*Corresponding author. Email: soufiane.touil@fsb.rnu.tn
ISSN 1741-5993 print/ISSN 1741-6000 online
© 2011 Taylor & Francis
DOI: 10.1080/17415993.2011.594053
http://www.informaworld.com

298 E. Chebil and S. Touil
1. Introduction
The use of 2,4-bis(p-methoxyphenyl)-1,3,2,4-dithiaphosphetane-2,4-disulfide, commonly
known as Lawesson’s reagent (LR), for the synthesis of five- and six-membered phosphorus-
containing heterocycles has been well documented (1–4). One of its important applications
involves the synthesis of 3-thioxo-1,2,3-diazaphospholine derivatives by reaction with hydra-
zones (5). In this area, we have previously shown that β- and γ -phosphonylhydrazones react with
LR to give 3-thioxo-1,2,3-diazaphospholine derivatives bearing an alkylphosphonate group (6,
7). We report, in the present investigation, the extension of this reaction to ester hydrazones 1. Our
main objective here was to study the effect of the ester group on the course of the reaction, in order
to identify the factors which appear to govern regioselectivity in reactions of LR with hydrazones.
Thesecondgoalofthisworkwasthesynthesisofavarietyofnew3-thioxo-1,2,3-diazaphospholine
derivatives, bearing an ester group.
It is important to note here that diazaphospholine derivatives are known for their useful
properties ranging from antifungal (8, 9) to anticholinesterase (10) and antitumor (11) activities.
2. Results and discussion
The reaction of LR with an equimolar amount of ester hydrazone 1, performed in toluene, at 80◦C,
leads according to the nature of substituents at the α, αꢀ positions to the C = N double bond either
O
OR2
R1
C
(CH2)
n
P
N
S
N
Ar
Ph
2
LR
OR2
R1
(CH2)
C
O
C
N
CH2
n
Toluene/80°C
O
C
OR2
R1
(CH )
CH2
2 n-
1
NHPh
1
N
P
S
N
Ar
Ar
S
S
S
Ph
LR :
P
P
S
Ar
2¢
:
Ar
O
CH3
2a
2b
2c
2d
2
¢a
2
¢
b
2
¢
c
2
¢e
R1
R2
n
H
Et
2
H
Et
0
H
Et
2
H
Et
1
Me
Me
1
H
Et
1
Me
Me
1
(*)
Et
1
Note: (*) –CH2-R1: Ph
Scheme 1. Synthesis of 3-thioxo-1,2,3-diazaphospholines 2 and 2ꢀ.

Journal of Sulfur Chemistry 299
to the diazaphospholine derivative 2 or 2ꢀ or to a mixture of isomeric diazaphospholines (2 + 2ꢀ)
(Scheme 1). The reaction times (r.t.) range from 4 to 8 h depending on the nature of the substrate.
The overall yield of the reaction is about 80%.
The reaction pathway was assumed to proceed via an equilibrium mixture of enehydrazines
which react with LR leading to intermediates I and Iꢀ. These underwent intramolecular cyclization
through the nucleophilic attack of the NH group at the phosphorus atom to give the final products
2 and 2ꢀ (Scheme 2).
S
Ar
S
S
S
S
2
Ar
:
P
LR
P
P
Ar
S
O
C
1
S
S
R
(CH )
2 n
OR2
1
R
(
)
C
O
OR2
Ar
H
CH2
P
Ar
S
n
1
H
R
OR2
S
C
O
C
H
P
N
(CH2)
C
C
(CH2)
C
OR2
C
O
P
N
1
R
n
n
Ar
N
N
Ar
HS
NH
S
N
P
Ph
Ph
HS
I
NHPh
NHPh
2
1
R
CH2
CH2 (CH )
2 n-
OR2
C
C
N
1
O
NHPh
1
O
O
S
1
Ar
P
R
CH2
C
1
(CH )
Ar
S
OR2
(CH )
2 n-
1
OR2
C
2 n-
1
R
CH2
S
C
OR2
C
OR2
1
1
(CH )
1C
R
CH2
CH
R
CH2
(CH )
Ar
S
C
N
N
P
CH
P
H
2 n-
2 n-
1
N
P
S
Ar
N
SH
N
O
NH
PhHN
O
Ph
SH
Ph
I
¢
PhHN
2
¢
Scheme 2. Reaction mechanism for the synthesis of compounds 2 and 2ꢀ.
We shall note here that the reaction shows relative regioselectivity. Indeed, when a mixture of
2 and 2ꢀ regioisomers is possible, the reaction leads to an approximately 3:1 ratio of compounds
2:2ꢀ. The regioselectivity of the reaction is governed by electronic and steric factors and depends
essentially on the reactivity of carbons at the α and αꢀ positions relative to the C = N double
bond (Scheme 2). In the case of hydrazones 1a and b, we can easily realize that the αꢀ-carbon is
less nucleophilic than the other one because of the conjugation with the ester group (Scheme 3).
As for the hydrazone 1c, and in the absence of conjugation with the ester function, the reaction
becomes subject to steric control and takes place mainly at the less hindered α-carbon.
Less reactive
More reactive
a
a'
OR2
OR2
OR2
R1
R1
R1
N
O
NH
O
NH
O
NHPh
1a and b
NHPh
NHPh
Scheme 3. Effect of the conjugation with the ester group on the reactivity of α and αꢀ carbons.
Compounds 2 and 2ꢀ were characterized on the basis of their IR, NMR (1H, 31P, 13C) and
mass spectral data, which indicate that they are obtained, in some cases, as a mixture of two

300 E. Chebil and S. Touil
Table 1.
δ
31P in ppm and % of diastereoisomers for compounds 2 and 2ꢀ.
Compound
δ
2a
75.7
–
2b1
92.4
55
2b2
79.3
45
2c
93.2
–
2d
75.6
–
2ꢀa1
69.9
65
2ꢀa2
77.1
35
31P
% diastereoisomers
Compound
2ꢀb1
99.0
56
2ꢀb2
83.5
44
2ꢀc1
93.5
58
2ꢀc2
93.8
42
2ꢀe1
63.9
62
2ꢀe2
79.5
38
δ
31P
% diastereoisomers
diastereoisomers. This is due to the presence of a chiral carbon in addition to the asymmetric
phosphorus atom. The major diastereoisomer will be designated by index 1 and the minor by
index 2. The relative proportions of these diastereoisomers were estimated from the 31P NMR
spectra where a singlet for each diastereoisomer is present (Table 1).
The 13C NMR spectra display the characteristic signals of all carbons and particularly those
corresponding to the diazaphospholine ring. The C = N carbon resonates at 140–150 ppm. The
C4 carbon at the α position to the phosphorus atom gives a doublet toward 30 ppm. Such a doublet
comes from the coupling with phosphorus with a 1JCP coupling constant of about 60–90 Hz.
3. Experimental section
1H, 31P and 13C NMR spectra were recorded with CDCl3 as the solvent, on a Bruker-300 spec-
trometer. The chemical shifts are reported in ppm relative to TMS (internal reference) for 1H and
13C NMR and relative to 85% H3PO4 (external reference) for 31P NMR. The coupling constants
are reported in Hz. For the 1H NMR, the multiplicities of signals are indicated by the following
abbreviations: s: singlet, d: doublet, t: triplet, q: quartet, m: multiplet.
Mass spectra were determined on an Agilent 5975B spectrometer, under electronic impact
(EI) conditions. IR spectra were recorded on a Perkin Elmer Paragon 1000 PC spectrometer.
The progress of the reactions was monitored by TLC. Purification of products was performed by
column chromatography using silica gel 60 (Fluka).
3.1. Synthesis of ester hydrazones 1
To a mixture of phenylhydrazine (0.02 mol) in absolute ethanol (20 ml), cooled at 0◦C, was added
dropwise with stirring, a solution of ketoester (0.02 mol) in absolute ethanol (10 ml). Stirring
at 0◦C was continued for 12 h. The reaction mixture was then concentrated in vacuo. The solid
obtained was washed with petroleum ether.
3.2. Synthesis of 3-thioxo-1,2,3-diazaphospholines 2 and 2ꢀ
A mixture of ester hydrazone 1 (0.01 mol), LR (0.01 mol) and dry toluene (30 ml) was heated at
80◦C with stirring for the r.t. (the reaction was monitored by TLC). The reaction mixture was then
concentrated in vacuo. The residue obtained was chromatographed on a silica gel column using
ether as the eluent.
2a: Yellow oil; Yield = 64%; r.t. = 5 h; 1H NMR (CDCl3): δ = 1.15 (t, 3H, 3JH
= 6.0 Hz,
−
H
3
−
−
−
CH3 CH2); 2.27 (s, 2H, CH2 CO2Et), 3.71 (s, 3H, CH3 O); 3.90 (q, 2H, JH
= 6.0 Hz,
−
H
CH3 CH2); 3.93 4.11 (m, 2H, CH2 P(S)); 6.10 7.67 (m, 9H, arom-H); 13C NMR (75.5 MHz,
−
−
−
−
−
−
−
−
CDCl3): δ (JCP): 13.5 (CH3 CH2 O); 27.7 (CH2 C = O); 30.9 (87.2 Hz; CH2 P(S)); 55.5
−
−
−
(CH3 O); 65.8 (CH3 CH2 O); 149.2 (C = N); 191.4 (C = O); Phenyl carbons: 113.2; 113.3;
113.5, 125.3; 127.9; 128.0; 128.5; 132.57; 132.63; 161.6; IR (neat): νC=N = 1585 cm−1
;

Journal of Sulfur Chemistry 301
νP=S = 1135 cm−1; νC=O = 1784 cm−1; EI-HRMS: calculated for C19H21N2O3PS, 388.1011
(M+); found: 388.1018.
2b:Yellow oil;Yield = 53%; r.t. = 6 h; H NMR (CDCl3): δ = 1.26 1.46 (m, 3H, CH3 CH);
1
−
−
−
−
−
−
2.08 (s, 2H, CH2 CO2Me, 2b2); 2.26 (s, 2H, CH2 CO2Me, 2b1); 3.37 3.53 (m, 1H, CH P(S),
− −
−
−
2b1), 3.59 3.70 (m, 1H, CH-P(S), 2b2); 3.68 (s, 3H, CH3 O C = O); 3.71 (s, 3H, CH3 O);
6.07 7.77 (m, 9H, arom-H); 13C NMR (75.5 MHz, CDCl3): δ (JCP): 11.9 (CH3 CH, 2b1); 12.9
−
−
−
−
−
−
(CH3 CH, 2b2); 20.5 (CH2 C = O, 2b1); 21.3 (CH2 C = O, 2b2); 28.8 (59.2 Hz; CH P(S));
− −
− −
−
−
51.6 (CH3 O CO, 2b2); 51.7 (CH3 O CO, 2b1); 55.4 (CH3 O, 2b1); 55.5 (CH3 O, 2b2);
154.4 (C = N, 2b1); 154.5 (C = N, 2b2); 195.8 (C = O, 2b2); 195.9 (C = O, 2b1); Phenyl car-
bons: δ = 102.1; 111.6; 112.67; 112.72; 112.8; 112.9; 116.1; 117.67; 117.70; 124.4; 124.5;
125.3; 126.0; 126.1; 126.4; 128.4; 131.8; 138.0; 160.1; 161.9; IR (neat): νC=N = 1562 cm−1
;
νP=S = 1135 cm−1; νC=O = 1760 cm−1; EI-HRMS: calculated for C19H21N2O3PS, 388.1011
(M+); found: 388.1034.
2c: Yellow oil; Yield = 58%; r.t. = 4 h; 1H NMR (CDCl3): δ = 1.02 (t, 3H, 3JH
=
−
H
3
3
−
−
6.0 Hz, CH3 CH2); 2.11 (t, 2H, JH
= 6.0 Hz, CH2 C = N); 2.15 (t, 2H, JH
= 6.0 Hz,
−
−
H
H
3
−
−
−
−
CH2 C = O); 2.72 2.85 (m, 2H, CH2 P(S)); 3.55 (s, 3H, CH3 O); 4.05 (q, 2H, JH
=
−
H
6.0 Hz, CH3 CH2); 6.74 7.77 (m, 9H, arom-H); 13C NMR (75.5 MHz, CDCl3): δ (JCP):
−
−
−
−
−
−
−
11.8 (CH3 CH2 O); 25.5 (CH2 C = N); 28.3 (CH2 C = O); 31.4 (55.1 Hz; CH2 P(S));
−
−
−
55.6 (CH3 O); 60.4 (CH3 CH2 O); 144.7 (C = N); 194.9 (C = O); Phenyl carbons: 103.9;
110.8; 102.3; 120.9; 122.5; 125.4; 128.3; 133.1; 138.1; 162.9; IR (neat): νC=N = 1598 cm−1
;
νP=S = 1127 cm−1; νC=O = 1732 cm−1; EI-HRMS: calculated for C20H23N2O3PS, 402.1167
(M+); found: 402.1170.
2d: Yellow oil; Yield = 84%; r.t. = 4 h; 1H NMR (CDCl3): δ = 1.26 (t, 3H, 3JH
= 9.0 Hz,
−
H
3
−
−
−
−
CH3 CH2); 3.78 (s, 3H, CH3 O); 3.75 3.83 (m, 2H, CH2 P(S)); 4.07 (q, 2H, JH
=
−
H
9.0 Hz, CH3-CH2); 6.77-8.28 (m, 9H, arom-H); 13C NMR (75.5 MHz, CDCl3): δ (JCP): 14.3
−
−
−
−
−
−
(CH3 CH2 O); 30.3 (98.1 Hz; CH2 P(S)); 55.3 (CH3 O); 65.9 (CH3 CH2 O); 144.3 (C =
N); 189.6 (C = O); Phenyl carbons: 113.4; 113.5; 113.7; 113.9; 113.0; 114.2; 129.0; 132.7;
134.6; 162.4; IR (neat): νC=N = 1573 cm−1; νP=S = 1127 cm−1; νC=O = 1772 cm−1; EI-HRMS:
calculated for C18H19N2O3PS, 374.0854 (M+); found: 374.0859.
2ꢀa:Yellow oil;Yield = 22%; r.t. = 5 h; 1H NMR (CDCl3): δ = 1.06 (t, 3H, 3JH
= 6.0 Hz,
−
H
ꢀ
3
ꢀ
−
− −
= 6.0 Hz, CH3 CH2, 2 a1); 1.99 (s, 3H, CH3 C = N,
ꢀ ꢀ
CH3 CH2, 2 a2); 1.23 (t, 3H, JH
−
H
2ꢀa2); 2.17 (s, 3H, CH3 C = N, 2 a1); 3.57 (s, 1H, CH P(S), 2 ); 3.60 (s, 3H, CH3 O, 2 a1);
ꢀ
−
−
−
ꢀ
3
ꢀ
−
−
3.63 (s, 3H, CH3 O, 2 a2); 3.83 (q, 2H, JH
= 6.0 Hz, CH3 CH2, 2 a2); 3.95 (q, 2H,
−
H
ꢀ
ꢀ
3JH
= 6.0 Hz, CH3 CH2, 2 a1); 5.37 (s, 1H, CH P(S), 2 a1); 6.60 7.60 (m, 9H, arom-
−
−
−
−
H
H); 13C NMR (75.5 MHz, CDCl3): δ (JCP): 14.6 (CH3 CH2 O, 2 a1); 14.7 (CH3 CH2 O,
ꢀ
−
−
−
−
ꢀ
−
−
−
−
−
2 a2); 29.9 (71.7 Hz; CH P(S)); 34.2 (CH3 C = N); 55.7 (CH3 O); 61.3 (CH3 CH2 O,
2ꢀa2); 61.4 (CH3 CH2 O, 2 a1); 148.9 (C = N, 2 a2); 154.5 (C = N, 2 a1); 187.0 (C = O,
2ꢀa2); 187.4 (C = O, 2ꢀa1); Phenyl carbons: 112.9; 113.1; 113.3; 113.4; 122.5; 122.8; 124.1;
125.5; 126.6; 127.0; 127.6; 128.2; 128.7; 129.2; 131.2; 131.9; 135.8; 137.2; 161.4; 161.9; IR
(neat): νC=N = 1564 cm−1; νP=S = 1157 cm−1; νC=O = 1732 cm−1; EI-HRMS: calculated for
C19H21N2O3PS, 388.1011 (M+); found: 388.1020.
ꢀ
ꢀ
ꢀ
−
−
2ꢀb:Yellow oil;Yield = 20%; r.t. = 6 h; 1H NMR (CDCl3): δ = 1.17 (t, 3H, 3JH
= 6.0 Hz,
−
H
ꢀ
ꢀ
3
ꢀ
3
−
−
CH3 CH2, 2 b1); 1.20 (t, 3H, JH
= 6.0 Hz, CH3 CH2, 2 b2); 2.59 (q, 2H, J
= 6.0 Hz,
−
−
CH3 CH2, 2 b1); 2.61 (q, 2H, J H = 6.0 Hz, CH3 CH2, 2 b2); 3.67 (s, 3H, CH3 O C = O);
−
−
H−H −
3
ꢀ
−
H
H
3.72 (s, 3H, CH3 O); 5.75 (s, 1H, CH P(S)), 6.07 7.77 (m, 9H, arom-H); 13C NMR (75.5 MHz,
−
−
−
ꢀ
ꢀ
ꢀ
−
−
−
CDCl3): δ (JCPꢀ ): 13.6 (CH3 CH2, 2 b2); 13.7 (CH3 CH2, 2 b1); 17.4 (CH3 CH2, 2 b1); 20.5
ꢀ
−
−
− −
− −
(CH3 CH2, 2 b2); 32.2ꢀ (95.2 Hz; CH P(S)); 51.3 (CH3 O CO, 2 b2); 51.4 (CH3 O CO,
2ꢀb1); 55.2 (CH3 O, 2 b1); 55.3 (CH3 O, 2 b2); 154.2 (C = N, 2 b1); 154.3 (C = N, 2 );
196.1 (C = O); Phenyl carbons: 105.4; 112.5; 113.0; 114.0; 119.6; 123.5; 123.6; 124.4;
124.7; 124.8; 124.9; 125.0; 127.8; 128.1; 128.3; 131.6; 132.4; 138.5; 162.0; 163.2; IR (neat):
ꢀ
ꢀ
ꢀ
−
−

302 E. Chebil and S. Touil
νC=N = 1562 cm−1; νP=S = 1135 cm−1; νC=O = 1760 cm−1; EI-HRMS: calculated for C19H21N2
O3PS, 388.1011 (M+); found: 388.1026.
2ꢀc:Yellow oil;Yield = 31%; r.t. = 4 h; 1H NMR (CDCl3): δ = 1.09 (t, 3H, 3JH
= 6.0 Hz,
−
H
ꢀ
3
ꢀ
ꢀ
−
−
−
CH3 CH2, 2 c1);1.14(t, 3H, JH
= 6.0 Hz, CH3 CH2, 2 c2);1.67(s, 3H, CH3 C = N, 2 c2);
−
H
ꢀ
3
−
−
−
1.86 (s, 3H, CH3 C = N, 2 c1); 2.68 2.82 (m, 2H, CH2 C = O); 2.88 (t, 1H, JH
= 9.0 Hz,
= 6.0 Hz,
−
H
ꢀ
ꢀ
3
−
−
−
CH P(S)); 3.55 (s, 3H, CH3 O, 2 c2); 3.57 (s, 3H, CH3 O, 2 c1); 3.90 (q, 2H, JH
−
H
ꢀ
3
ꢀ
−
−
−
CH3 CH2, 2 c2); 3.94 (q, 2H, JH
= 6.0 Hz, CH3 CH2, 2 c1); 6.74 7.77 (m, 9H, arom-
−
H
H); 13C NMR (75.5 MHz, CDCl3): δ (JCP): 16.2 (CH3 CH2 O, 2 c1); 16.3 (CH3 CH2 O,
ꢀ
−
−
−
−
ꢀ
ꢀ
ꢀ
2ꢀc2); 20.9 (CH3 C = N, 2 c1); 23.1 (54.3 Hz; CH P(S), 2 c1); 24.6 (CH3 C = N, 2 c2); 31.2
−
−
−
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
−
−
−
−
(50.6 Hz; CH P(S), 2 c2); 36.9 (CH2 C = O, 2 c1); 39.9 (CH2 C = O, 2 c2); 55.6 (CH3 O,
2ꢀc1); 55.7 (CH3 O, 2 c2); 60.5 (CH3 CH2 O, 2 c1); 66.3 (CH3 CH2 O, 2 c2); 159.5 (C = N,
2ꢀc1); 159.6 (C = N, 2ꢀc2); 192.4 (C = O, 2ꢀc2); 192.8 (C = O, 2ꢀc1); Phenyl carbons: 113.9;
114.0; 114.11; 114.15; 114.3; 115.6; 127.0; 128.0; 129.0; 129.1; 129.2; 129.3; 129.4; 132.5; 132.6;
ꢀ
−
−
−
−
−
132.7; 132.8; 132.9; 163.0; 163.1; IR (neat): νC=N = 1598 cm−1; νP=S = 1127 cm−1; νC=O
=
1732 cm−1; EI-HRMS: calculated for C20H23N2O3PS, 402.1167 (M+); found: 402.1168.
2ꢀe:Yellow oil;Yield = 41%; r.t. = 8 h; 1H NMR (CDCl3): δ = 1.10 (t, 3H, 3JH
= 6.0 Hz,
−
H
ꢀ
3
ꢀ
−
−
−
CH3 CH2, 2 e2); 1.17 (t, 3H, JH
= 6.0 Hz, CH3 CH2, 2 e1); 3.65 (s, 1H, CH P(S)); 3.68
−
H
ꢀ
ꢀ
3
−
−
−
= 6.0 Hz, CH3 CH2,
(s, 3H, CH3 O, 2 e1); 3,71 (s, 3H, CH3 O, 2 e2); 3.95 (q, 2H, JH
−
H
2ꢀe1); 3.97 (q, 2H, 3JH
= 6.0 Hz, CH3 CH2, 2 e2); 6.66 7.75 (m, 14H, arom-H); 13C
ꢀ
−
−
−
H
ꢀ
ꢀ
−
−
−
−
NMR (75.5 MHz, CDCl3): δ (JCP): 14.2 (CH3 CH2 O, 2 e2); 15.0 (CH3 CH2 O, 2ꢀe1); 30.7
ꢀ
ꢀ
ꢀ
−
−
−
−
(142.0 Hz; CH P(S)); 55.4 (CH3 O, 2 e1); 55.6 (CH3 O, 2 e2); 61.7 (CH3−CH2 O, 2 e2); 66.0
ꢀ
ꢀ
−
−
(CH3 CH2 O, 2 e1); 151.7 (C = N, 2 e2), 151.9 (C = N, 2 e1); 192.8 (C = O); Phenyl carbons:
108.7; 112.5; 113.4; 113.6; 113.8; 114.3; 125.3; 125.9; 126.0; 126.3; 126.4; 127.4; 128.8; 128.9;
129.0; 129.3; 131.0; 131.3; 131.8; 134.2; 134.6; 135.4; 135.9; 137.7; 138.48; 138.54; 162.3; 162.5;
IR (neat): νC=N = 1581 cm−1; νP=S = 1140 cm−1; νC=O = 1728 cm−1; EI-HRMS: calculated for
C24H23N2O3PS, 450.1167 (M+); found: 450.1164.
References
(1) Cherkasov, R.A.; Kutyrev, G.A.; Pudovik, A.N. Tetrahedron 1985, 41, 2567–2624.
(2) Jesberger, M.; Davis, T.P.; Barner, L. Synthesis 2003, 13, 1929–1958.
(3) Ozturk, T.; Ertas, E.; Mert, O. Chem. Rev. 2007, 107, 5210–5278.
(4) Seijas, J.A.; Vázquez-Tato, M.P.; Crecente-Campo, J. Tetrahedron 2010, 66, 8210–8213.
(5) El Barbary, A.A.; Lawesson, S.O. Tetrahedron 1981, 37, 2647–2650.
(6) Boukraa, M.; Ayed, N.; Ben Akacha, A.; Zantour, H.; Baccar, B. Phosphorus Sulfur Silicon Relat. Elem. 1995, 105,
17–21.
(7) Touil, S.; Ben Dhia, M.T.; Zantour, H.; Baccar, B. Phosphorus Sulfur Silicon Relat. Elem. 1996, 119, 295–302.
(8) Ali, H.M.; Ali, M.K. Bull. Environ. Contam. Toxicol. 2000, 65, 421–426.
(9) Hussein, M.A.; El-Sayed, W.; Tomader, A.R.G. Aust. J. Basic Appl. Sci. 2007, 1, 593–599.
(10) Hussein, M.A. Phosphorus Sulfur Silicon Relat. Elem. 1999, 155, 157–166.
(11) Ying, H.Z.; Sun, M.T.; Liu, T.; Hu, Y.Z. Chin. J. Struct. Chem. 2008, 27, 1171–1174.