Kinetics and mechanism of the anilinolysis of dimethyl and diethyl chloro(thiono)phosphates

Article abstract of DOI:10.1002/poc.1314

The deuterium kinetic isotope effects (KIEs) involving deuterated aniline nucleophiles (XC₆H₄ND₂) are reported for the reactions of dimethyl chlorophosphate (1), dimethyl chlorothionophosphate (2), diethyl chlorophosphate

Full text of DOI:10.1002/poc.1314

Research Article
Received: 15 October 2007,
Revised: 25 November 2007,
Accepted: 28 November 2007,
Published online in Wiley InterScience: 24 January 2008
(www.interscience.wiley.com) DOI 10.1002/poc.1314
Kinetics and mechanism of the
anilinolysis of dimethyl and diethyl
chloro(thiono)phosphates
Nilay Kumar Deya, Md. Ehtesham Ul Hoquea, Chan Kyung Kima,
a
a
*
*
Bon-Su Lee and Hai Whang Lee
The deuterium kinetic isotope effects (KIEs) involving deuterated aniline nucleophiles (XC6H4ND2) are reported for the
reactions of dimethyl chlorophosphate (1), dimethyl chlorothionophosphate (2), diethyl chlorophosphate (3) and
diethyl chlorothionophosphate (4) in acetonitrile at 55.0 8C. The obtained kH/kD values are 0.798–0.979, 0.945–1.06,
0.714–0.919 and 1.01–1.10 for 1, 2, 3 and 4, respectively. A concerted mechanism with dominant backside nucleophilic
attack is proposed for the reactions of 1 and 3. A concerted mechanism involving partial frontside attack through a
hydrogen-bonded four-centre-type transition state (TS) is proposed for the reactions of 2 and 4. Copyright ß 2008
John Wiley & Sons, Ltd.
Supplementary electronic material for this paper is available in Wiley InterScience at http://www.mrw.interscience.wiley.com/
suppmat/0894-3230/suppmat/
Keywords: deuterium kinetic isotope effect; anilinolysis; dimethyl and diethyl chlorophosphates; dimethyl and diethyl
chlorothionophosphates
substituted anilines and deuterated anilines (XC6H4NH2 and
INTRODUCTION
XC6H4ND2) in acetonitrile at 55.0 8C, Eqn (1), to clarify the phos-
phoryl transfer mechanism, as well as to compare the anilinolysis
of aryl ethyl chlorophosphate [5; (YPhO)(EtO)P(O)Cl],[22] aryl ethyl
chlorothionophosphate [6; (YPhO)(EtO)P(S)Cl],[22] aryl phenyl chlo-
rophosphate [7; (YPhO)(PhO)P(O)Cl][23] and aryl phenyl chlor-
othionophosphate [8; (YPhO)(PhO)P(S)Cl].[19]
Phosphoryl transfer reactions have been studied extensively and
a considerable amount of work has been carried out to clarify the
mechanism. Two main types of mechanisms, the stepwise mecha-
nism involving a trigonal bipyramidal pentacoordinate (TBP-5C)
intermediate and the concerted mechanism through a single
pentacoordinate transition state (TS), are known to occur in
neutral phosphoryl transfer reactions.[1–4] When the attacking
and leaving groups occupy apical positions [ap(Nu)-ap(Lg)], that
is, backside nucleophilic attack, the configuration is inversed. But
when the nucleophile attacks frontside towards the leaving
group, that is, when nucleophile and leaving groups occupy
apical and equatorial positions [ap(Nu)-eq(Lg)], respectively or
when nucleophile and leaving groups occupy equatorial and
apical positions [eq(Nu)-ap(Lg)], respectively, the configuration is
retained.[5–16] When backside and frontside nucleophilic attacks
occur simultaneously, the relative importance of the reaction
pathways leads to products with inversion or retention of the
configuration, depending on the nucleophile, the leaving group
and the reaction conditions.[5]
MeCN
R2PðLÞC1 þ 2XC6H4NH2ðD2Þ ꢀ! R2PðLÞNHðDÞC6H4X
55:0ꢁC
þXC6H4NHþ3 ðD3ÞC1ꢀ
1 :L ¼ O; R ¼ MeO
(1)
2 :L ¼ S; R ¼ MeO
3 :L ¼ O; R ¼ EtO
4 :L ¼ S; R ¼ EtO
X ¼ 4ꢀMeO; 4ꢀMe; 3ꢀMe; H; 3ꢀMeO; 4ꢀC1; 3ꢀC1
RESULTS AND DISCUSSION
In our preceding papers, partial frontside nucleophilic attack
was suggested for the reactions of: aryl bis(4-methoxyphenyl)
phosphates with less basic pyridines;[17] aryl phenyl isothiocya-
nophosphates with more basic pyridines;[18] aryl phenyl
chlorothionophosphates with anilines;[19] diphenyl phosphinic
chlorides with anilines;[20] diphenyl thiophosphinic chlorides with
more basic pyridines[21] and aryl ethyl chlorophosphates and
chlorothionophosphates with anilines.[22]
The observed pseudo-first-order rate constants (kobsd) for the
reactions obey Eqn (2) with negligible k0 in acetonitrile. The
second-order rate constants, kH(D), were determined using Eqn (2)
with at least five concentrations [An]. No third-order or higher-
*
Department of Chemistry, Inha University, 253 Yonghyundong, Namgu,
Incheon 402-751, Korea.
E-mail: hwlee@inha.ac.kr; bslee@inha.ac.kr
In this work, we investigate the aminolysis of dimethyl chlo-
rophosphate (1), dimethyl chlorothionophosphate (2), diethyl
chlorophosphate (3) and diethyl chlorothionophosphate (4) with
a
N. K. Dey, Md. E. Ul Hoque, C. K. Kim, B.-S. Lee, H. W. Lee
Department of Chemistry, Inha University, Incheon 402-751, Korea
J. Phys. Org. Chem. 2008, 21 544–548
Copyright ß 2008 John Wiley & Sons, Ltd.

ANILINOLYSIS OF DIMETHYL AND DIETHYL CHLORO(THIONO)PHOSPHATES
Table 1. Second-order rate constants, kH(D) ꢃ 104 Mꢀ1 sꢀ1
and selectivity parametersa for the reactions of dimethyl
chlorophosphate (1) with XC6H4NH2 and XC6H4ND2 in
acetonitrile at 55.0 8C
,
Table 3. Second-order rate constants, kH(D) ꢃ 104 Mꢀ1 sꢀ1
and selectivity parametersa for the reactions of diethyl
chlorophosphate (3) with XC6H4NH2 and XC6H4ND2 in
acetonitrile at 55.0 8C
,
b
b
kHb
kDb
kH
kD
(ꢃ 104 Mꢀ1 sꢀ1
)
(ꢃ 104 Mꢀ1 sꢀ1
)
kH/kD
X
(ꢃ 104 Mꢀ1 sꢀ1
)
(ꢃ 104 Mꢀ1 sꢀ1
)
kH/kD
X
4-MeO
4-Me
3-Me
H
3-MeO
4-Cl
3-Cl
229 ꢄ 3
126 ꢄ 4
234 ꢄ 5
132 ꢄ 5
0.979 ꢄ 0.026
0.955 ꢄ 0.048
0.934 ꢄ 0.024
0.922 ꢄ 0.042
0.843 ꢄ 0.025
0.815 ꢄ 0.020
0.798 ꢄ 0.030
4-MeO
4-Me
3-Me
H
3-MeO
4-Cl
3-Cl
170 ꢄ 1
83.6 ꢄ 1.0
40.4 ꢄ 0.9
28.2 ꢄ 0.1
12.2 ꢄ 0.3
5.40 ꢄ 0.20
2.00 ꢄ 0.01
ꢀ2.99 ꢄ 0.04
(r ¼ 0.999)
1.06 ꢄ 0.03
(r ¼ 0.999)
185 ꢄ 4
93.0 ꢄ 1.5
47.4 ꢄ 0.7
33.4 ꢄ 1.1
16.0 ꢄ 0.4
7.40 ꢄ 0.2
2.80 ꢄ 0.11
ꢀ2.80 ꢄ 0.04
(r ¼ 0.999)
0.993 ꢄ 0.023
(r ¼ 0.999)
0.919 ꢄ 0.022
0.899 ꢄ 0.018
0.852 ꢄ 0.022
0.844 ꢄ 0.043
0.763 ꢄ 0.027
0.730 ꢄ 0.033
0.714 ꢄ 0.028
62.4 ꢄ 1.3
42.8 ꢄ 1.5
21.4 ꢄ 0.5
10.6 ꢄ 0.2
3.99 ꢄ 0.01
ꢀ2.72 ꢄ 0.04
(r ¼ 0.999)
0.962 ꢄ 0.019
(r ¼ 0.999)
66.8 ꢄ 1.1
46.4 ꢄ 1.4
25.4 ꢄ 0.5
13.0 ꢄ 0.2
5.00 ꢄ 0.20
ꢀ2.56 ꢄ 0.05
(r ¼ 0.999)
0.907 ꢄ 0.020
(r ¼ 0.999)
rX
rX
bX
bX
a The s and pKa values were taken from References [24] and
[25], respectively.
b Correlation coefficients (r) were better than 0.998.
a,bSame as in Table 1.
order terms were detected,
Figure 1 shows the rate ratios of the anilinolysis (C6H5NH2) of 1,
2, 3 and 4 in acetonitrile at 55.0 8C. The reaction rate of 1 is
3.9 times faster than that of 2 and the rate of 3 is 5.5 times faster
than that of 4. Phosphate systems are more reactive than
their thionophosphate counterparts for several reasons, the
so-called thio effect, which is mainly the electronegativity
difference between O and S that favours O over S.[26–29]
The methoxy group (sI ¼ 0.30)[30] has slightly stronger electron
withdrawing ability inductively than the ethoxy group (sI ¼
0.28).[30] Solely considering the difference of inductive effects
between methoxy and ethoxy groups, the positive charge of the
reaction centre P in 1 (and 2) would be a little greater than that in
3 (and 4). Figure 1 shows the natural bond order (NBO) charges,
kobsd ¼ k0 þ kHðDÞ½Anꢂ
(2)
and no complications were found in the determination of kobsd or
in the linear plots of Eqn (2). This suggests that there is no
base-catalysis or noticeable side reaction and that the overall
reactions follow the route given by Eqn (1). The kH and kD values
are summarized in Tables 1–4, together with the deuterium
kinetic isotope effects (KIEs), kH/kD, and the selectivity parameters,
rX and bX. The magnitudes of rX and bX values of the reactions of
1–4 with deuterated anilines (XC6H4ND2) are somewhat smaller
than those with anilines (XC6H4NH2), suggesting less sensitivity to
substituent effect of deuterated anilines than of anilines.
Table 2. Second-order rate constants, kH(D) ꢃ 104 Mꢀ1 sꢀ1
,
Table 4. Second-order rate constants, kH(D) ꢃ 104 Mꢀ1 sꢀ1
,
and selectivity parametersa for the reactions of dimethyl
and selectivity parametersa for the reactions of diethyl
chlorothionophosphate (2) with XC6H4NH2 and XC6H4ND2 in
acetonitrile at 55.0 8C
chlorothionophosphate (4) with XC6H4NH2 and XC6H4ND2 in
acetonitrile at 55.0 8C
kHb
kDb
kHb
kDb
X
(ꢃ 104 Mꢀ1 sꢀ1
)
(ꢃ 104 Mꢀ1 sꢀ1
)
kH/kD
X
(ꢃ 104 Mꢀ1 sꢀ1
)
(ꢃ 104 Mꢀ1 sꢀ1
)
kH/kD
4-MeO
4-Me
3-Me
H
3-MeO
4-Cl
3-Cl
77.9 ꢄ 1.1
31.0 ꢄ 0.6
73.4 ꢄ 0.8
29.8 ꢄ 0.7
1.06 ꢄ 0.02
1.04 ꢄ 0.03
4-MeO
4-Me
3-Me
H
3-MeO
4-Cl
3-Cl
41.3 ꢄ 0.1
17.4 ꢄ 0.3
37.7 ꢄ 0.4
16.1 ꢄ 0.3
1.10 ꢄ 0.01
1.08 ꢄ 0.03
1.06 ꢄ 0.03
1.05 ꢄ 0.04
1.04 ꢄ 0.04
1.03 ꢄ 0.03
1.01 ꢄ 0.04
16.8 ꢄ 0.2
16.3 ꢄ 0.1
1.03 ꢄ 0.02
7.19 ꢄ 0.18
5.12 ꢄ 0.07
2.51 ꢄ 0.06
1.57 ꢄ 0.03
0.607 ꢄ 0.019
ꢀ2.75 ꢄ 0.14
(r ¼ 0.993)
6.78 ꢄ 0.12
4.86 ꢄ 0.16
2.41 ꢄ 0.06
1.53 ꢄ 0.03
0.602 ꢄ 0.011
ꢀ2.70 ꢄ 0.14
(r ¼ 0.993)
10.9 ꢄ 0.2
11.0 ꢄ 0.2
0.991 ꢄ 0.026
0.974 ꢄ 0.031
0.955 ꢄ 0.036
0.945 ꢄ 0.029
4.95 ꢄ 0.14
2.33 ꢄ 0.08
1.20 ꢄ 0.03
ꢀ2.81 ꢄ 0.10
(r ¼ 0.997)
0.993 ꢄ 0.050
(r ¼ 0.994)
5.08 ꢄ 0.08
2.44 ꢄ 0.04
1.27 ꢄ 0.03
ꢀ2.73 ꢄ 0.10
(r ¼ 0.997)
0.963 ꢄ 0.047
(r ¼ 0.994)
rX
rX
bX
bX
0.977 ꢄ 0.045
(r ¼ 0.995)
0.957 ꢄ 0.044
(r ¼ 0.995)
a,bSame as in Table 1.
a,bSame as in Table 1.
J. Phys. Org. Chem. 2008, 21 544–548
Copyright ß 2008 John Wiley & Sons, Ltd.
www.interscience.wiley.com/journal/poc

N. KUMAR DEY ET AL.
Figure 1. B3LYP/6-311þG(d,p)[31] geometries and NBO charges of 1, 2, 3 and 4 in the gas phase.
using the B3LYP/6-311þG(d,p) level,[31] on reaction centre P, 2.226
(1) < 2.236 (3) and 1.687 (2) < 1.701(4), which are not consistent
with the expectations for the inductive effects of the ligands. The
obtained rate ratios of kH (1)/kH(3) ¼ 1.5 and kH (2)/kH(4) ¼ 2.1
cannot be rationalized by the inductive effects of the ligands or
the NBO charges on the reaction centre.
Eqn (3) for the four phosphates (1, 3, 5[22] and 7[23]) and the four
thionophosphates (2, 4, 6[22] and 8[19]) are roughly linear, giving
d ¼ 0.12 (r ¼ 0.967) and d ¼ 0.18 (r ¼ 0.959), respectively.
log kH ¼ dSEs þ C
(3)
Moreover, taking into account the NBO charges on reaction
centre P in 5 (2.233),[22] 7 (2.230),[23] 6 (1.687)[22] and 8 (1.661),[19]
the sequence of reactivity for 1: 3: 5: 7 ¼ 4.8: 3.2: 2.2: 1 and 2: 4: 6:
8 ¼ 10.8: 5.1: 2.8: 1 (when X ¼ Y ¼ H) cannot be rationalized (refer
Buncel and coworkers reported that the second-order rate
constants, kꢀEtO, for the ethanolysis of the phosphinates, Ph2P(O)
(OPh-4-NO2), PhMeP(O)(OPh-4-NO2) and Me2P(O)(OPh-4-NO2)
give relative rates of 1: 69: 235, contrary to the expectations
also to Table 5). The plots of log kH against Taft steric constants
for the inductive effects of the ligands [sI ¼ ꢀ0.01(Me) and
P
P
Es: Es ¼ 0.00 (Me), ꢀ0.07 (Et) and ꢀ2.48 (Ph)][32,33] according to
0.12(Ph)].[34–37] A plot of log kꢀEtO against
Es for the three
[
—
Table 5. Summary of second-order rate constants and selectivity parameters for the anilinolysis of R R P( L)Cl in acetonitrile at
—
1
2
55.0 8C
a
L
R1
R2
kH (ꢃ104 Mꢀ1 sꢀ1
)
kH/kD
–rX
bX
rY
–rXY
References
O
1:
MeO
EtO
YPhO
YPhO
MeO
EtO
MeO
EtO
EtO
PhO
MeO
EtO
EtO
PhO
42.8
28.2
20.0
8.91
10.9
5.12
2.80
1.01
0.80–0.98
0.71–0.92
1.07–1.80
0.61–0.87
0.95–1.06
1.01–1.10
1.06–1.27
1.11–1.33
2.72
2.99
3.09–3.40
3.42–4.63
2.81
2.75
3.15–3.33
3.81–4.01
0.96
1.06
1.09–1.20
1.24–1.68
0.99
0.98
1.11–1.17
1.34–1.41
—
—
0.41–0.90
0.22–0.87
—
—
0.75–0.95
0.67–0.73
—
—
0.60
1.31
—
—
0.19
0.22
This work
This work
[22]
3:
5:
7:
2:
4:
6:
8:
[23]
S
This work
This work
[22]
YPhO
YPhO
[19]
a X ¼ Y ¼ H.
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Copyright ß 2008 John Wiley & Sons, Ltd.
J. Phys. Org. Chem. 2008, 21 544–548

ANILINOLYSIS OF DIMETHYL AND DIETHYL CHLORO(THIONO)PHOSPHATES
phosphinates yields d ¼ 1.32 (r ¼ 0.954), which leads to the
conclusion that the sequence of reactivity for the phosphinates is
determined mainly by steric factors.[34–37] Large steric effects on
the ethanolysis of the phosphinates can be rationalized by the
backside nucleophilic attack towards the 4-NO2PhO leaving
group since large steric effects on the reaction rates cannot be
substantiated by frontside nucleophilic attack regardless of
ap(Nu)-eq(Lg) or eq(Nu)-ap(Lg) positions in the TS. The smaller
magnitudes of d values in the present work compared to that of
the phosphinates may be ascribed to the intervening oxygen
atoms in the phosphates which render more available space to
attacking nucleophiles.
kD ¼ 0.798–0.979) and 3 (kH/kD ¼ 0.714–0.919) and that front
side attack (TS I) is dominant for the anilinolysis of 4 (kH/
kD ¼ 1.01–1.10).
Another plausible TS structure with kH/kD > 1 could be TS III
where there is a hydrogen bond between the oxygen (or sulphur)
—
atom in P O(S) and the hydrogen (deuterium) of the N—H(D)
—
moiety in aniline. A four-membered TS IV was proposed in the
ethanolysis of the phosphinates, paraxon and parathion with
alkali metal ions by Buncel[44,45] and Um.[46]
Selectivity parameters and deuterium KIEs for the anilinolysis
of 1–8 in acetonitrile at 55.0 8C are summarized in Table 5. The
¨
magnitudes of both Hammett rX (rnuc) and Bronsted bX (bnuc
)
values of 1–4 are large, suggesting extensive bond formation in
the TS. However, these values are somewhat smaller than those of
5–8, indicating a lesser degree of bond formation in the
anilinolyses of 1–4 than in those of 5–8.
However, positive charge development on the hydrogen
(deuterium) of the N—H(D) moiety in the TS would be much
smaller than that on Mþ ions, so a hydrogen bond involving the
In our previous work on the anilinolysis of 7,[23] a backside
nucleophilic attack concerted mechanism with a late, product-
like TS was proposed on the basis of large rX (and bX), large
negative cross-interaction constant,[38–40] rXY ¼ ꢀ1.31 and the
secondary inverse KIEs, kH/kD ¼ 0.61–0.87, with deuterated
aniline nucleophile. However, in the anilinolysis of 5,[22] 6[22]
and 8,[19] a partial frontside nucleophilic attack concerted
mechanism through a hydrogen-bonded four-centre type TS I
was suggested for several reasons, mainly based on the primary
KIEs, kH/kD ¼ 1.07–1.80, 1.06–1.27 and 1.11–1.33, respectively.
—
acceptor P O(S), as in TS III, is not feasible. In addition, the
—
difference between the secondary inverse KIEs in 1, 3 and 7[23]
and the primary normal KIE in 5[22] cannot be substantiated by TS
III. Moreover, the KIEs, kH/kD ¼ 0.945–1.06, in 2 cannot be
rationalized by TS III at all. So we can neglect TS III with kH/kD > 1.
CONCLUSIONS
The reactions of dimethyl chlorophosphate (1), dimethyl
chlorothionophosphate (2), diethyl chlorophosphate (3) and
diethyl chlorothionophosphate (4) with substituted anilines and
deuterated anilines (XC6H4NH2 and XC6H4ND2) are studied
kinetically in acetonitrile at 55.0 8C. By comparing the kinetics
and mechanism of these reactions with those of similar reactions,
we reached the following conclusions: (i) 1 and 3 react with
anilines through a concerted mechanism involving dominant
backside nucleophilic attack in the TS; (ii) a concerted mechanism
involving a partial frontside attack through a hydrogen-bonded
four-centre-type TS is proposed for the reaction of 2; (iii) 4 reacts
with anilines through a concerted mechanism involving domi-
nant frontside nucleophilic attack in the TS and (iv) steric effect is
the major factor that determines the reactivities of the studied
phosphate and thionophosphate systems.
In the present work on the anilinolysis of 1 and 3, the KIEs are
less than unity, kH/kD ¼ 0.798–0.979 and 0.714–0.919, respect-
ively. In the anilinolysis of 2, the KIEs gradually change from less
than unity to greater than unity, kH/kD ¼ 0.945–1.06, as the
nucleophiles change from less basic to more basic. In the
anilinolysis of 4, the KIEs are greater than unity, kH/kD ¼ 1.01–1.10.
In an SN2 mechanism, the secondary inverse KIE, kH/kD < 1, is
ascribed to the increment of vibrational frequencies of N—H(D)
in the TS II due to an increase in steric crowding in the
bond-making process.[41,42] In contrast, the primary normal KIE,
kH/kD > 1, indicates that partial deprotonation of the aniline
nucleophile occurs in the rate-limiting step by hydrogen
bonding.[43] Therefore, the KIEs in 2, kH/kD ¼ 0.945–1.06, imply
that steric congestion in TS II is dominant for less basic
nucleophiles, X ¼ 3-Cl—H (kH/kD ¼ 0.945–0.991), while partial
deprotonation in TS I is dominant for more basic nucleophiles,
X ¼ 4-MeO—3-Me (kH/kD ¼ 1.06–1.03). These results can be
rationalized in that backside attack (TS II) is dominant for less
basic nucleophiles, while frontside attack (TS I) involving
hydrogen bond between the Cl leaving group and the hydrogen
(deuterium) atom of the N—H(D) moiety in aniline is dominant
for more basic nucleophiles. We can also suggest that backside
attack (TS II) is dominant for the anilinolyses of 1 (kH/
EXPERIMENTAL
Materials
Aldrich GR grade dimethyl chlorophosphate (96%), diethyl chloro-
phosphate (97%), dimethyl chlorothionophosphate (97%) and
diethyl chlorothionophosphate (97%) were used without further
purification. The other materials are the same as previously
described.[19]
Kinetics procedure
Rates were measured conductometrically as described pre-
viously.[19,23] [1 and 3] ¼ 2 ꢃ 10ꢀ3 M; [An] ¼ 0.1–0.3 M and [2 and
J. Phys. Org. Chem. 2008, 21 544–548
Copyright ß 2008 John Wiley & Sons, Ltd.
www.interscience.wiley.com/journal/poc

N. KUMAR DEY ET AL.
4] ¼ 1 ꢃ 10ꢀ3 M; [An] ¼ 0.3–0.15 M were used for the present
REFERENCES
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Product analysis
Dimethyl chlorophosphate, dimethyl chlorothionophosphate,
diethyl chlorophosphate and diethyl chlorothionophosphate
were reacted with excess 4-chloroaniline, aniline and
4-methylaniline, respectively, for more than 15 half-lives at
55.0 8C in acetonitrile as described previously.[19] Analysis data of
the products gave the following results:
—
(CH O) P( O)NHC H -4-Cl
—
3
2
6 4
Brown, gummy solid, 1H NMR (400 MHz, CDCl3) d 3.76 (3H, s,
OCH3), 3.79 (3H, s, OCH3), 5.457 (1H, d, J ¼ 7.6 Hz, NH), 6.91 (2H, d,
J ¼ 8.8 Hz, phenyl), 7.20 (2H, d, J ¼ 8.8 Hz phenyl); 13C NMR
(100 MHz, CDCl3) d 53.37 (OCH3), 114.17, 118.59, 126.99, 129.21,
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137.85 (C C, aromatic); 31P NMR (162 MHz, CDCl3) d 9.83 (s, 1P,
—
—
—
P
O); MS m/z, 235 (Mþ); (found: C 41.2, H 5.0, N 6.1; C H NO PCl
—
8
11
3
requires C 40.8, H 4.7, N 6.0%).
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(3rd ed.), Macmillan, New York, 1996. 693.
—
(CH O) P( S)NHC H
6 5
—
3
2
Brown liquid, 1H NMR (400 MHz, CDCl3) d 3.73–3.77 (6H, d,
J ¼ 16 Hz, OCH3), 5.34–5.38 (1H, d, J ¼ 16 Hz, NH), 6.96–7.01 (3H,
m, phenyl), 7.23–7.27 (2H, m, phenyl); 13C NMR (100 MHz, CDCl3) d
53.52–53.55 (d, J ¼ 3 Hz, OCH3), 117.59, 117.565, 122.30, 129.32,
138.95,138.99 (C C, aromatic); 31P NMR (162 MHz, CDCl3) d 74.79
—
—
—
(s, 1P, P O); MS m/z, 217 (Mþ); (found: C 44.2, H 5.7, N 6.9, S
—
14.3; C8H12NO2PS requires C 44.2, H 5.6, N 6.5, S 14.7%).
—
(C H O) P( O)NHC H
6 5
—
2
5
2
[26] A. C. Hengge, I. Onyido, Curr. Org. Chem. 2005, 9, 61.
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Trans. 2 2001, 324.
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7178.
Brown solid, m.p. 92–94 8C, 1H NMR (400 MHz, CDCl3) d 1.29–1.33
(6H, m, CH3), 4.08–4.17 (4H, m, CH2), 5.42 (1H, d, J ¼ 8.8 Hz, NH),
6.96–6.98 (2H, d, J ¼ 7.6 Hz, phenyl), 7.22–7.26 (3H, t, J ¼ 7.6 Hz
phenyl); 13C NMR (100 MHz, CDCl3) d 16.2 (CH3), 62.9 (CH2), 117.2,
[29] R. J. Hondal, K. S. Bruzik, Z. Zhao, M. D. Tsai, J. Am. Chem. Soc. 1997,
119, 5477.
121.6, 129.2, 129.21, 139.4 (C C, aromatic); 31P NMR (162 MHz,
—
—
—
[30] M. Charton, Prog. Phys. Org. Chem. 1987, 16, 287.
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Chemistry, RSC, Cambridge, UK, 2003, Chapter 7.
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2526.
CDCl ) d 7.24 (s, 1P, P O); MS m/z, 229 (Mþ); (found: C 52.8, H 7.4,
—
N 6.1; C10H11NO3PCl requires C 52.4, H 7.0, N 6.1%).
3
—
(C H O) P( S)NHC H -4-CH
3
—
2
5
2
6
4
1
Pink liquid, H NMR (400 MHz, CDCl3) d 1.29–1.33 (6H, m, CH3),
4.08–4.17 (4H, m, CH2), 5.377 (1H, d, J ¼ 14.8 Hz, NH), 6.88–6.90
(2H, q, phenyl), 7.03–7.05 (2H, d, J ¼ 8 Hz phenyl); 13C NMR
(100 MHz, CDCl3) d 15.77–15.86 (CH3, d, J ¼ 8.4 Hz), 20.6 (CH3),
63.09–63.14 (CH2, d, J ¼ 4.5 Hz), 117.6, 117.7, 129.6, 131.4, 136.6,
136.7 (C C, aromatic); 31P NMR (162 MHz, CDCl3) d 70.36 (s, 1P,
—
—
—
P
S); MS m/z, 259 (Mþ); (found: C 51.0, H 7.0, N 5.8, S
—
12.2; C11H18NO2PS requires C 50.9, H 7.2, N 6.2, S 11.8%).
[43] L. Melander, W. H. Saunders, Jr, in Reaction Rates of Isotopic Molecules,
Wiley, New York, 1981, Chapter 5.
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Acknowledgement
This study was funded by Korea Science and Engineering Founda-
tion (R01-2004-000-10279-0).
www.interscience.wiley.com/journal/poc
Copyright ß 2008 John Wiley & Sons, Ltd.
J. Phys. Org. Chem. 2008, 21 544–548