Dichlorodimethyl hydantoin: An efficient reagent for one-pot synthesis of CWC-related O,O-dialkyl, N,N-dialkyl phosphoramidates

Article abstract of DOI:10.1080/10426500701724514

A simple, rapid, economical, and efficient one-pot synthetic method for preparation of O,O-dialkyl, N,N-dialkylphosphoramidates (DADAPs) and phosphates has been developed. Copyright Taylor & Francis Group, LLC.

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Dichlorodimethyl Hydantoin:
An Efficient Reagent for One-
Pot Synthesis of CWC-Related
O,O-dialkyl, N,N-dialkyl
Phosphoramidates
a
a
Arvind K. Gupta , Devendra K. Dubey & M. P.
a
Kaushik
a
Process Technology Development Division, Defence
R & D Establishment, Jhansi Road, Gwalior, India
Published online: 24 Jun 2008.
To cite this article: Arvind K. Gupta , Devendra K. Dubey & M. P. Kaushik (2008):
Dichlorodimethyl Hydantoin: An Efficient Reagent for One-Pot Synthesis of CWC-
Related O,O-dialkyl, N,N-dialkyl Phosphoramidates, Phosphorus, Sulfur, and Silicon
and the Related Elements, 183:7, 1641-1658
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Phosphorus, Sulfur, and Silicon, 183:1641–1658, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500701724514
Dichlorodimethyl Hydantoin: An Efficient Reagent
for One-Pot Synthesis of CWC-Related O,O-dialkyl,
N,N-dialkyl Phosphoramidates
Arvind K. Gupta, Devendra K. Dubey, and M. P. Kaushik
Process Technology Development Division, Defence R & D
Establishment, Jhansi Road, Gwalior, India
A simple, rapid, economical, and efficient one-pot synthetic method for preparation
of O,O-dialkyl, N,N-dialkylphosphoramidates (DADAPs) and phosphates has been
developed.
Keywords CWC; dichlorodimethyl hydantoin; O,O-dialkyl, N,N-dialkylphosphorami-
dates; phosphates
INTRODUCTION
Development of efficient synthetic procedures for retrospective detec-
tion and identification of chemical warfare agents (CWAs) and related
compounds is a prominent area of research that has attracted the atten-
tion of several workers due to the strict verification program of Chemical
1−6
Weapons Convention (CWC).
The convention entered into the force
on 29 April 1997 and prohibits the development, production, stockpil-
ing and use of chemical weapons. By April 2006, 176 countries had
ratified the convention. An international organization, known as the
Organisation for the Prohibition of Chemical Weapons (OPCW) ensures
implementation of CWC by implementing the verification program. Ver-
ification involves collection of samples from production, storage and sus-
7
pected sites by inspectors appointed by the OPCW. Inspectors perform
on-site analysis of collected samples to detect and identify CWC related
chemicals. Where there is ambiguity, the samples are sent to at least two
off-site laboratories designated by the OPCW for unambiguous identi-
fication of the CWC related chemicals.7 Thus, a laboratory willing to
undertake the challenging task of off-site analysis of such chemicals
,8
Received 11 August 2007; accepted 29 August 2007.
Address correspondence to M. P. Kaushik, Process Technology Development Divi-
sion, Defence R & D Establishment, Jhansi Road, Gwalior 474002 (MP), India. E-mail:
mpkaushik@rediffmail.com
1641

1
642
A. K. Gupta et al.
for verification should first achieve the status of ‘designated laboratory’
from the OPCW. Laboratories become and stay designated by prov-
ing their analytical capability in Official Proficiency Tests (OPTs) con-
ducted by the OPCW.9 The performance of participating laboratory
in OPTs mainly depends on availability of spectral data of CWC-related
chemicals, sample preparation, analytical skills of chemists, judgment
and reporting.
,10
Schedules of compounds are based on commercial use and alleged use
8
of chemicals as CWAs. As the total number of scheduled compounds is
7
,8
several million, their synthesis (in pure form) by reported methods
and the recording of spectral data base is a daunting task. To over-
come such problems, there is an urgent need to develop efficient and
rapid synthetic procedures, which provide the pure compounds with
minimal work up. Rapid synthesis of these compounds in pure form
is also required to report the correct formula of isomeric compounds
3
1
by overlapping their spectra with the GC-MS and P NMR spectra of
spiked compounds.. The perfect match of test sample spectra with syn-
thesized compounds is one of the unique ways to report the results of
analysis as it does not require much expertise in the field of interpre-
tation of spectra.9
(
,11−14
O-alkyl N,N-dialkylphosphoramidocyanidates
ADAPCs) are analogues of highly toxic nerve agent tabun (O-ethyl
N,N-dimethyl phosphoramidocyanidate) and fall in Schedule 1.A.2 of
7
the CWC Annex. Based on commercially available C1-C10 alcohols, the
estimated number of compounds belonging to Schedule 1.A.2 is 48,000
and their corresponding O,O-dialkyl, N,N-dialkyl phosphoramidates
(
DADAPs) are often produced when tabun or its derivatives are pro-
8
duced in laboratories or chemical plants. Hence, DADAPs are impor-
tant chemical markers because of their stability and persistency in the
environment and their confirmed presence provides evidence for the
presence of tabun and related compounds for verification. Because of
this property DADAPs, appear in Schedule 2 B6 category of CWC and
probably this the reason they are quite often used in Official Profi-
ciency Test (12, 14, and 18 tests). This fact prompted us to develop
an efficient one-pot synthesis of phosphoramidates from dialkyl phos-
phites. A plethora of effective chemical approaches have been devised
for the preparation of phosphoramidates.1
5−25
However, these methods
suffer from several draw backs such as non-availability of intermedi-
ates (N,N-dialkylphosphoramidic dichlorides), requires an additional
step, time consuming, poor atom economy (requires extra equivalents
of base as acid scavenger), and use of organic solvents. The reaction is
◦
also performed at high temperature 240 C resulting in tar formation,
3
,25
which reduces the yields of the desired products.

Dichlorodimethyl Hydantoin
1643
Recently, there has been increasing emphasis on finding out low
2
6
moleculer weight recyclable environmentally friendly reagents. This
is essentially required to reduce the amount of toxic waste and by-
products arising from a chemical process.27 One such reagent is N,N -
dichlorodimethyl hydantoin (DCDMH) a cheap, commercially available
reagent and recently used as an excellent reagent for deoximation of ke-
tones, preparation of gem- chloro nitroso alkanes, nitrosation of amines
ꢀ
2
8
and in neutralization of chemical warfare agents, and also has two
positive chlorine.
In continuation of our earlier work,29,30 we report a rapid, efficient,
economic, and easy to scale-up method for the effective one pot con-
version of dialkyl phosphites to their corresponding phosphoramidates
at moderate temperature using DCDMH (non toxic and commercially
available reagent) followed by addition of dialkylamines. To investigate
the simplicity and effective transformation of phosphoramidates via in-
situ generation of dialkyl chlorophosphates approach (Scheme 1) was
followed. The phosphites were reacted with DCDMH to generate di-
alkyl chlorophosphate followed by phosphorylation reactions with var-
◦
ious dialkyl amines in presence of CsF-celite at 0 C without isolating
the intermediate (dialkyl chlorophosphates).
Cl
O
RO
RO
H3C
N
R'
C
C O
N Cl
P H H3C
O C
NH
R''
O
CsF -celite 0 -50 C
H
N
H C
RO O
3
R'
C
C O
N H
H C
P
N
3
O C
RO
R''
SCHEME 1
The results of this study indicates, that the work-up procedure of
reaction of dialkyl phosphites 1 and DCDMH 2 was simple and suit-
able for the preparation DADAPAs due to easy removal of by-product
dimethyl hydantoin (DMH) from the reaction mixture as it is insoluble
in diethyl ether and DADAPAS are soluble in ether. In order to optimize
the mole ratio, various reactions were carried out and the optimum yield
was obtained when a reaction was carried out in 1: 0.5: 2:1 molar ratios
of dialkyl phosphite, DCDMH, CsF-celite, and dialkylamines, respec-
tively. It is important to note that CsF-celite should be added first and

1
644
A. K. Gupta et al.
◦
dialkylamines should be added later at 0 C slowly to the stirred reac-
tion mixture. The desired phosphoramidates were obtained in excellent
yield with exceptionally high purities (Scheme 1 and Table I). To find
out effectiveness of CsF-celite,31 a model reaction between diisopropyl
phosphite and DCDMH was performed with various solid supports such
as anhydrous sodium sulfate, silica, charcoal, active carbon, CsF, celite,
and basic alumina, followed by the addition of diethylamine. Combina-
tion of CsF-celite gave better results in terms of reduced reaction time,
isolation of pure product and yield of the product.
It was observed that when CsF alone was used as a solid support,
unreacted diisopropyl fluorophosphate (DFP) along with tetra isopropyl
31
pyrophosphate was found ( PNMR and GC-MS analysis). It indicated
that isolation of pure product became difficult from contaminated flu-
orophosphates. Furthermore, to examine the role of CsF-celite, a con-
trol experiment was performed except in the absence of CsF-celite and
monitored by GC and 31P NMR after drawing few milligrams sam-
ple and washed with diethyl ether. The results of ethereal solution
analysis showed that the formation of DADAPAs was invariably poor
(
15–25% only) and contaminated with corresponding unreacted dialkyl
chlorophosphate as a major product and an unidentified product (5–
0%) in each case. The poor yield of DADAPAs can be explained by
1
consumption of same amine to form their corresponding hydrochloride
salt. Furthermore, in the absence of CsF-celite, these reactions required
longer reaction times for completion of the reaction. Most probably CsF-
celite brought the reactants closure to each other which enhances the
3
1
reactivity on the surfaces and facilitated the reactions. To study the
applicability of DCDMH, various reactions of diethylphosphite and di-
ethylamine in absence of DCDMH but in presence CsF-celite under
neat conditions were also performed by varying the mole ratio and
temperature, but there was no formation of corresponding diethyl,
N,N-diethylphosphoramidate on TLC. It indicated that DCDMH is gen-
erating the corresponding dialkyl chlorophosphate which subsequently
reacting with dialkylamines in presence of CsF-celite.
In order to study the effect of substituents, various reactions of differ-
ent dialkyl phosphites were performed with diethyl amine in presence
of DCDMH and CsF-celite under identical reaction conditions. We ob-
served that the reaction of dimethyl phosphite and diethyl amine in
presence of DCDMH and CsF-celite completed within 35 min and cor-
responding phosphoramidates were obtained in 84% yield. However,
phosphorylation of diisopropyl phosphite with diethyl amine was rel-
atively slow and took 50 min under same reaction conditions. It in-
dicated that, as the size of alkyl group of dialkylphosphite increases,
the reactivity of diethyl amine decreased. Furthermore, to study the

Dichlorodimethyl Hydantoin
1645
ꢀ
TABLE I One-Pot Synthesis of O,O-dialkyl, N,N -dialkyl
Phosphoramidates from Dialkylphosphites, DCDMH and
Dialkyl Amine in Presence of CsF-celite
O
RO
R'
P
N
RO
R''
ꢀ
ꢀꢀ
◦
a
Entry
R
R
R
Time (min) Temp ( C) Yield (%)
1
2
3
4
5
6
7
8
9
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
C2H5
C2H5
C2H5
C2H5
C2H5
C2H5
C2H5
CH3
C2H5
CH3
20
20
35
40
20
25
30
25
30
25
25
40
30
50
25
25
40
30
45
25
30
30
40
65
30
30
50
30
65
35
40
50
50
90
30
60
35
40
75
45
25
35
35
40
25
25
30
30
50
30
30
35
35
50
30
30
35
30
30
35
30
30
40
50
30
30
40
30
40
30
30
40
50
60
35
35
40
35
50
35
89
84
83
86
86
85
86
82
87
85
82
80
88
83
88
84
81
80
82
84
88
86
84
84
82
84
84
85
87
82
82
83
80
80
81
83
82
84
85
80
C2H5
n-C3H7
i-C3H7
C2H5
C2H5
C2H5
CH3
n-C3H7
CH3
CH3
C2H5
n-C3H7
i-C3H7
C2H5
C2H5
C2H5
CH3
n-C3H7
CH3
CH3
C2H5
n-C3H7
i-C3H7
C2H5
C2H5
C2H5
CH3
n-C3H7
CH3
CH3
C2H5
n-C3H7
i-C3H7
C2H5
C2H5
C2H5
CH3
n-C3H7
i-C3H7
CH3
n-C3H7
i-C3H7
n-C3H7
i-C3H7
i-C3H7
CH3
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
C2H5
n-C3H7
i-C3H7
CH3
n-C3H7
i-C3H7
n-C3H7
i-C3H7
i-C3H7
CH3
C2H5
C2H5
C2H5
n-C3H7
n-C3H7
n-C3H7
n-C3H7
n-C3H7
n-C3H7
n-C3H7
n-C3H7
n-C3H7
n-C3H7
i-C3H7
i-C3H7
i-C3H7
i-C3H7
i-C3H7
i-C3H7
i-C3H7
i-C3H7
i-C3H7
i-C3H7
C2H5
n-C3H7
i-C3H7
CH3
n-C3H7
i-C3H7
n-C3H7
i-C3H7
i-C3H7
CH3
C2H5
n-C3H7
i-C3H7
CH3
n-C3H7
i-C3H7
n-C3H7
i-C3H7
i-C3H7
n-C3H7
CH3
aReactions were monitored by 31P NMR in CDCl3 at 162 MHz, and the
products had satisfactory I.R, NMR and Mass data; GC-MS data were
3
2
compared with literature values.

1
646
A. K. Gupta et al.
effect of various amines with in situ formed dialkyl chlorophosphates,
we found that reaction of dimethyl amine completed more quickly than
ethyl methyl amine. We also noticed that by increasing the size of chain
length, the reactivity of these amines decreased. However, diisopropyl
amine somewhat took little longer time (40–90 min) in each case. The
reaction of diisopropyl phosphite and diisopropyl amine was slowest and
took maximum time (90 min). It is essentially due to presence of steri-
cally hindered diisopropyl amino group in both substrate and reagent,
which might have reduced the reactivity.
The positive feature of this method is that the product can be ob-
tained simply by filtration. The filtrate contains the desired products
and residue after washings with sufficient acetone can be recycled
for the preparation of DCDMH. The solid residue can be reused after
◦
activating it in oven at 150 C for 2 h. The important advantage of this
method is minimum use of solvent, easy work up, and its occurrence at
mild temperatures. In terms of atom economy, it does not require extra
base to scavenge HCl. Another advantage is that the by-product DMH
is not reacting with amines under these conditions. To examine the
reproducibility of one-pot concept at higher mole ratio, 200 mmol of di-
ethyl phosphite was reacted with 10.0 mmol of the reagent DCDMH in
diethyl ether at room temperature. The reaction mixture was stirred for
1
5 min and monitored by 31P NMR; it showed complete conversion of the
diethyl phosphite to the corresponding diethyl chlorophosphate within
1
5 min The CsF-celite was added followed by the slow addition of ethyl
◦
methyl amine (0.1mol) in the heterogeneous reaction mixture at 0 C.
The reaction mixture was stirred on vortex shaker for the period given
in Table I and periodically monitored by 31P NMR by drawing few mil-
ligram of sample from the reaction mixture. The results of NMR studies
indicated that signal of diethyl chlorophosphate at δ 4.14 completely dis-
appeared and a new signal appeared at δ 13.58 clearly demonstrated
that the rapid conversion of diethyl chlorophosphate to the correspond-
ing O,O-diethyl, N-ethyl, N-methylphosphoramidates. Filtration of het-
erogeneous reaction mixture and concentration of the solvent provided
the pure product in 88% isolated yield.
CONCLUSIONS
In conclusion, we have developed a simple, rapid, economical and ef-
ficient one-pot synthetic method for the preparation of DADAPs and
the phosphates. The method is very useful for spectral up-gradation
for CWC verification and for the synthesis of biologically active com-
pounds. The method can be extended for the synthesis of various pseudo
phosphates. Thus, it will make a useful and an important addition to

Dichlorodimethyl Hydantoin
1647
existing methodologies. In addition to this, the recycling of the reagent,
and the easy and clean work-up with high yields, makes this an attrac-
tive methodology. Further, the application of DCDMH in the synthesis
of various organic compounds is in progress and will be reported in due
course.
EXPERIMENTAL
IR spectra were recorded on Bruker FT-IR spectrometer model Tensor
1
31
2
7 on KBr disk. H and P NMR spectra were recorded on Bruker DPX
Avance FT- NMR in CDCl3 using tetramethylsilane as an internal stan-
1
31
dard for H and 85% H3 PO4 as an external standard for P NMR at 400
and 162 MHz, respectively. A Chemito GC model 1000 instrument was
used with flame ionization detector (FID). A capillary column (30 m ×
0
.25 mm I.D-BP5) packed with 5% phenyl and 95% dimethyl polysilox-
ane (SGE) coated on fused silica was employed. The injection port and
◦
◦
detector block were maintained at 280 C and 260 C respectively and
the column oven was at programmed temperature profile started at
5
◦
◦
◦
0 C, ramped up to 280 C at 25 C/min Nitrogen was used as a carrier
gas (at a flow rate of 30ml/min). Air for FID was supplied at 300ml/min
and hydrogen at 30ml/min In all analyses, 1µl sample was injected
and peaks were recorded on computerized data acquisition station. The
GC-MS analyses were performed in EI (70 eV) in full scan mode with
an Agilent 6890 GC equipped with a model 5973 mass selective detec-
tor (Agilent Technologies, USA). An SGE BPX5 capillary column with
3
0 m length × 0.32 mm internal diameter × 0.25 µm film thickness
◦
◦
◦
was used at temperature program of 80 C (2 min)-20 C/min-280 C (3
min). Helium was used as the carrier gas at a constant flow rate of
1
.2 ml/min. The samples were analyzed in splitless mode at injection
◦
◦
temperature of 250 C, EI source temperature 230 C and quadrupole
analyzer at 150 C.
◦
Preparation of Solid-Surface Material CsF-Celite
The preparation of CsF-Celite substance was carried out in the same
33
manner as we described in literature. 152 g (1000 mmol) of cesium
@
fluoride was added to a solution of 100g (1660 mmol) of Celite 521 in
1000 ml of distilled water. This heterogenous mixture was stirred for 1 h
at room temperature and then water was removed under vacuum using
Heidolph rotary evaporator until dry It was shaken with 3 × 100 ml
acetonitrile, filtered and washed with 3 × 25 ml acetonitrile. The CsF-
Celite substance was dried under vacuum and stored in desiccators.

1
648
A. K. Gupta et al.
General Experimental Procedure
In a typical experimental procedure, dialkylphosphite (50.0 mmol) was
added in suspended solution of DCDMH (4.92 g, 25.0 mmol) in 15 ml ace-
tonitrile and reaction mixture was stirred for 10–30 min. The progress
of the reaction mixture was monitored by 3 P NMR by drawing a few
milligrams of reaction mixture to find out the consumption of dialkyl
phosphite. A white amorphous precipitate of DMH 4 was formed. When
1
0
precipitation of four ceased, reaction mixture was cooled at 0 C, sol-
vent was removed under reduced pressure at r.t. and CsF-celite (25.32 g,
100 mmol CsF and 160 mmol of Celite) mole was added. The dialky-
lamine (50.0 mmol) was added slowly with shaking in heterogeneous
reaction mixture on a vortex shaker. The progress of the reaction was
further monitored by 31 P NMR to find out the consumption of dialkyl
chlorophosphate by drawing a few milligrams of reaction mixture after
extracting with ether. After completion of reaction (as time and tem-
perature mentioned in Table I), reaction mixture was extracted with
ether and a white solid substance (mixture of 4 and solid support) was
removed by filtration and washed with acetonitrile (3x10 ml). The sol-
vent was removed from the filtrate and the product was distilled under
vacuum to get pure DADAPs.
Dimethyl–N,N-dimethylphosphoramidate
◦
31
1
Bp: 82–83 C (6 mmHg); P NMR (161.98 MHz, CDCl3): δ = 14.07. H-
NMR (400.13 MHz, CDCl3): δ = 3.72(d, 6H, OCH3 JH-P = 12.0Hz), 2.9(d,
6H, N-CH3). IR: Neat (KBr) υ(max): 2972, 2899, (C H Str.), 1380(C H
−
1
bend), 1272(P O), 1160(P-N-C), 1090, 1050(P-O-C) cm . MS (EI): m/z
%) = 153(21), 120(20), 109 (39), 79(15), 44 (100).
(
Dimethyl-N, N-diethylphosphoramidate
◦
31P
Bp: 98–99 C (5 mmHg);
NMR (161.98 MHz, CDCl3): δ = 13.57.
H-NMR (CDCl3): δ = 3.75 (d, 6H, OCH3 JH-P = 12.0 Hz), 3.3(m,4H,-
CH2N-),1.2(t,6H,CH3-). IR: (Neat) (KBr) υ (max): 2943, 2989(C H str.),
1
−
1
1
385 C H bend), 1268 (P O), 1163 (P-NC), 1090, 1050(P-O-C) cm .
MS (EI): m/z (%) = 181(10), 166(100), 138 (33), 109(45), 72 (15).
Dimethyl-N, N-dipropylphosphoramidate
◦
31
Bp: 92–93 C (2 mmHg); P NMR (161.98 MHz, CDCl3): δ = 13.81.
H-NMR (CDCl3): δ = 3.78 (d, 6H, OCH3, JH-H = 12.0 Hz), 3.3 (m, 4H,-
1
CH2-N-), 1.75(m, 4H, -CH2-), 1.0 (t, 3H, CH3) . IR: (neat) (KBr) υ (max):
2
978, 2947, 2889 (C H str.), 1385 (C H bend), 1262(P O), 1167 (P-N-
−1
C), 1080, 1040(P-O-C) cm . MS (EI): m/z (%) = 209(4), 194(68), 152
(
100), 166(17), 109 (33) 79 (17).

Dichlorodimethyl Hydantoin
1649
Dimethyl-N, N- diisopropylphosphoramidate
◦
31
Bp: 95–96 C (3 mmHg); P NMR (161.98 MHz, CDCl3): δ = 11.51.
H-NMR (CDCl3): δ = 3.80 (d,6-H,OCH3 JH-H =12.0 Hz), 3.4(m, 2H,-
1
CH-), 1.4 (d, 12H, CH3). IR (neat) (KBr) υ (max): 2977, 2940, 2896
(
C H str), 1382 (C H bend), 1275 (P O), 1174(P-N-C),1090,1050 (P-
−
1
O-C)cm . MS(EI):m/z(%) = 209 (4), 194(68), 152(100), 166(17), 109(33),
7
9(17).
Dimethyl-N-ethyl-N-methylphosphoramidate
◦
31
Bp: 83–85 C (5 mmHg);
P NMR (161.98 MHz, CDCl3): δ =
1
1
(
3.87. H-NMR (CDCl3): δ = 3.78 (d,6-H,OCH3 JH-H = 12.0Hz), 3.25
m,2H,-CH2-), 2.75(d,3H, N-CH3), 1.5 (t,3H,CH3).IR: (neat) (KBr)
υ (max): 2970, 2945, (C H str), 1382 (C H bend), 1273(P O),
−1
1
174(P-N-C), 1090, 1050 (P-O-C)cm . MS (EI): m/z (%) = 167(12),
152(100),122(45), 109(67), 79 (13).
Dimethyl-N-ethyl-N-propylphosphoramidate
◦
31
Bp: 93–95 C (3 mmHg); P NMR (161.98 MHz, CDCl3): δ = 13.75.
H-NMR (CDCl3): δ = 3.80 (d, 6-H, OCH3 JH-H = 12.0 Hz), 3.25 (m,4H,-
1
CH2-N-), 1.55 (m,2H,-CH2-)1.15(t,3H,CH3-), 0.88(t,3H, CH3-).IR: (neat)
(
1
1
KBr) υ(max): 2977, 2950, (C H Str), 1387(C H bend), 1272 (P O),
−1
160(P-N-C), 1090, 1050(P-O-C) cm . MS (EI): m/z (%) = 195(5),
66(100), 138 (44), 109(36), 79 (11).
Dimethyl-N-ethyl-N- isopropylphosphoramidate
◦
31
Bp: 84–86 C (4.5 mmHg); P NMR (161.98 MHz, CDCl3): δ = 11.17.
H-NMR (CDCl3): δ = 3.79 (d,6-H, OCH3 JH-H = 12.0 Hz), 3.9(m,1H,-
1
CH-), 3.20 (m,2H,-CH2-), 1.25 (t,3H,CH3), 1.2(d,6H,CH3-).IR: (neat)
(
1
1
KBr) υ (max): 2975, 2947, (C H str), 1380 (C H bend), 1267 (P O),
−1
167 (P-N-C),1090,1050 (P-O-C) cm . MS (EI): m/z (%) = 195(4),
80(100), 138 (52), 152 (67), 120 (24), 109 (46), 79 (20)
Dimethyl-N-methyl-N- propylphosphoramidate
◦
31
Bp: 98–99 C (6 mmHg); P NMR (161.98 MHz, CDCl3): δ = 13.72.
H-NMR (CDCl3): δ = 3.80 (d,6-H, OCH3 JH-H = 12.0Hz), 3.1 (m, 2H,
1
-
(
(
CH2-N), 2.75 (d,3H,CH3-N)1.55(m,2H,-CH2-), 0.89(t,3H, CH3-). IR:
neat) (KBr) υ (max): 2976, 2953 (C H str.), 1382 (C H bend), 1265
P O), 1174 (P-N-C), 1085, 1045 (P-O-C) cm . MS (EI): m/z (%) =
81(8), 152(100), 122 (45), 109(51), 79, (11), 42(20).
−
1
1
Dimethyl-N-propyl-N-isopropylphosphoramidate
◦
31
Bp: 98-99 C (2 mmHg); P NMR (161.98 MHz, CDCl3): δ = 11.17.
H-NMR (CDCl3): δ = 3.80 (d, 6-H, OCH3 JH-H = 12.0 Hz), 3.6(m, 1H,-
1
CH-), 3.21(m,2H,-CH2-N-),1.6(m,2H,-CH2-),1.2(d,6H,CH3-), 0.88 (t, 3H,

1
650
A. K. Gupta et al.
CH3-).IR: (neat) (KBr) υ (max): 2976, 2953 (C H str.), 1375(C H bend),
−
1
1
2
266(P O), 1165(P-N-C), 1090, 1050(P-O-C) cm .MS (EI): m/z (%) =
09(2), 194(47), 180, (54), 166 (12), 152(43), 138 (100), 109 (31), 79 (11).
Dimethyl-N-methyl-N-sopropylphosphoramidate
◦
31
Bp: 88–89 C (6 mmHg); P NMR (161.98 MHz, CDCl3): δ = 11.19.
H-NMR (CDCl3): δ = 3.80 (d, 6-H, OCH3 JH-H = 12.0 Hz), 3.75 (m,
1
1
2
1
1
H, -CH-) 2.73(d, 3H, CH3-N-),1.15(d, 6H,CH3).IR: (neat) (KBr) υ(max):
980, 2955, (C H str),1372 (C H-bend), 1272(P O), 1168(P-NC), 1090,
−1
055(P-O-C) cm .MS (EI): m/z (%) = 181(2), 166(100), 136 (4), 134 (16),
09(27), 79 (11), 56 (42), 42 (16).
Diethyl-N, N-dimethylphosphoramidate
◦
31
Bp: 82–83 C (5 mmHg); P NMR (161.98 MHz, CDCl3): δ = 11.45.
H-NMR (CDCl3): δ = 4.25(m, 4-H, -OCH2, JH−H =7.0 JH-P = 8.0 Hz),
1
2
.79(d, 6H, N-CH3), 1.33(t, 6-H, -CH3 JH-H = 7.0 Hz). IR: (neat) (KBr)
υ (max): 2972, 2899, (CH Str.), 1380 (C H bend), 1267(P O), 1160(P-
−
1
N-C), 1090, 1053(P-O-C) cm .MS (EI):m/z (%) = 181(18),152(6),136
6),124(34),109(5), 111(11),110(12),108(38),44(100).
(
Diethyl-N, N-diethylphosphoramidate
◦
31
Bp: 109–110 C (1 mmHg); P NMR (161.98 MHz, CDCl3): δ =
1
1
0.87. H-NMR(CDCl3): δ = 4.25(m,4-H,-OCH2,JH-H = 7.0 JH−P = 8.0
Hz),3.3(m, 4H,-CH2-), 1.33 (t, 6-H, CH3 JH-H = 7.0Hz), 1.2 (t, 6H, CH3-
)
1
, IR: (neat) (KBr) υ(max): 2943, 2989(C H str.), 1385 C H bend),
−
1
268 (P O), 1163 (P-NC), 1085,1052 (P-O-C) cm . MS (EI): m/z (%)
209(12), 194(74), 180, (6), 166 (37), 152(16), 138 (100), 110 (39),72
17).
=
(
Diethyl-N, N-dipropylphosphoramidate
◦
31
Bp: 110–111 C (2 mmHg); P NMR (161.98 MHz, CDCl3): δ =
1
1
8
7
1.09. H-NMR (CDCl3): δ = 4.25(m,4-H,-OCH2, JH-H = 7.0 JH−P =
.0 Hz),3.3(m,4H,-CH2-N-),1.75 (m,4H,-CH2-), 1.33(t,6-H, CH3 JH-H =
.0 Hz),1.0(t,6H,CH3); IR: (neat) (KBr) υ(max):2975,2947,2883(C H
−
1
str.), 1362, 1270(P O),1166(P-N-C),1080,1040 (P-O-C)cm .MS (EI):
m/z (%) = 237(8), 222(47), 180(31), 152(23), 138(100), 110(29), 72(21).
Diethyl-N,N-diisopropylphosphoramidate
◦
31
Bp: 116–117 C (1 mmHg); P NMR (161.98 MHz, CDCl3): δ = 8.80.
H-NMR (CDCl3): δ = 4.25(m,4-H, -OCH2, JH-H =7.0 JH−P = 8.0 Hz),
1
3
(
.4(m,2H,-CH-), 1.4(d,12H,CH3-), 1.31(t,6-H, CH3 JH-H =7.0Hz). IR:
neat) (KBr) υ(max): 2978, 2945, 2893 (C H str), 1380(C H bend),

Dichlorodimethyl Hydantoin
1651
−
1
1
2
170(P-N-C), 1275, (P O),1088, 1045 (P-O-C) cm . MS (EI): m/z (%) =
37(4), 222(10), 180(11), 138(100), 110(16), 72(13).
Diethyl-N-ethyl-N-methylphosphoramidate
◦
31
Bp: 109–110 C (1 mmHg);
P NMR (161.98 MHz, CDCl3): δ
1
=
=
10.77. H-NMR (CDCl3): δ = 4.25(m,4-H,-OCH2,JH-H =7.0JH−P
8.0Hz),3.25(m,2H,-CH2-), 2.75 (d,3H,CH3),1.5(t,3H,CH3),1.33(t,6-
H,CH3JH-H =7.0Hz). IR: (neat) (KBr) υ(max): 2973, 2944, (C H str),
−
1
1
379(C H bend.) 1267(P O), 1165(P-N-C), 1087, 1048(P-O-C) cm
MS (EI): m/z (%) = 195(13), 180(74), 152(40), 138 (12), 124 (100),
10(11), 58 (35).
.
1
Diethyl-N-ethyl-N-propylphosphoramidate
◦
31
Bp: 121–122 C (1 mmHg);
P NMR (161.98 MHz, CDCl3):
1
δ = 11.06. H-NMR (CDCl3): δ = 4.25(m,4-H, -OCH2, JH-H =7.0
JH−P =8.0Hz),3.26(m,4H,-CH2-N-), 1.54(m,2H,-CH2-),1.34(t,6-H,-CH3
JH-H = 7.0Hz),1.14 (t,3H, CH3-), 0.89(t,3H, CH3-).IR: (neat) (KBr)
υ(max): 2978, 2954, (C H Str), 1385(C H bend),1266(P O), 1164(P-
N-C), 1091,1047(P-O-C) cm .MS (EI): m/z (%) = 233(3), 208(7), 194
100), 180 (5), 166 (45), 152(9), 138 (82), 110 (39), 86 (7).
−1
(
Diethyl-N-ethyl-N-isopropylphosphoramidate
◦
31
Bp: 92–93 C (10 mmHg);
P NMR (161.98 MHz, CDCl3):
1
δ = 8.66. H-NMR (CDCl3): δ = 4.23(m,4-H, -OCH2, JH-H =7.0
JH−P =8.0Hz),3.91(m,1H,-CH-), 3.21 (m, 2H,-CH2-), 1.33(t,6-H,-CH3
JH-H = 7.0Hz), 1.21 (d,6H, CH3-), 1.24(t,3H,-CH3).IR: (neat) (KBr)
υ(max): 2975, 2947, (C H stn), 1380 (C H bend),1267 (P O), 1167
P-N-C), 1090,1050(P-O-C) cm .MS (EI): m/z (%) = 233(4), 208( 100),
80 (35), 152 (92), 166 (21),152(90), 138 (12), 124 (25), 110 (21), 86 (11).
−
1
(
1
Diethyl-N-methyl-N-propylphosphoramidate
◦
31
Bp: 81–82 C (1 mmHg); P NMR (161.98 MHz, CDCl3): δ = 11.02.
H-NMR (CDCl3): δ = 4.25(m,4-H, -OCH2, JH-H =7.0 JH−P =8.0 Hz),
1
3
.1(m,2H,-CH2-N), 2.75(d,3H,CH3-N) 1.55(m,2H,-CH2-), 1.33(t,6-H, -
CH3 JH-H =7.0Hz), 0.89(t,3H, -CH3 ).IR: (neat) (KBr) υ(max): 2976,
2
1
1
953 (C H str.), 1375(C H bend), 1265(P O), 1174(P-N-C), 1085,
−1
045(P-O-C) cm . MS (EI): m/z (%) = 209(7), 208( ), 180 (85), 152(41),
24 (100), 110 (5), 72 (14).
Diethyl-N-propyl-N-isopropylphosphoramidate
◦
31
Bp: 95–96 C (1 mmHg); P NMR (161.98 MHz, CDCl3): δ = 11.57.
H-NMR (CDCl3): δ = 4.25(m,4-H, -OCH2, JH-H = 7.0 JH−P = 8.0 Hz),
1

1
652
A. K. Gupta et al.
3.6(m,1H,-CH-), 3.1(m,2H,CH2-N-), 1.6(m,2H,-CH2-), 1.33(t,6-H, -
CH3 JH-H = 7.0Hz), 1.2(d,6H,CH3-), 0.88(t,3H,CH3-).IR: (neat) (KBr)
υ(max): 2976, 2953 (C H str.), 1375(C H bend), 1266(P O), 1165(P-
−1
N-C), 1090, 1050(P-O-C) cm . MS (EI): m/z (%) = 237(3), 222 (38), 208
87), 194(17),180 (13), 166 (100), 152(57), 124 (26), 100 (9).
(
Diethyl-N-methyl-N- isopropylphosphoramidate
◦
31
Bp: 98–990 C (0.5 mmHg); P NMR (161.98 MHz, CDCl3): δ =
1
1
0.77. H-NMR (CDCl3): δ = 4.25(m,4-H, -OCH2, JH-H =7.0 JH−P =8.0
Hz), 3.75(m, 1H, -CH-) 2.65(d,3H,CH3-N-), 1.33(t,6-H, -CH3 JH-H =
7
1
.0Hz), 1.15(d,6H,CH3).IR: (neat) (KBr) υ(max): 2980, 2955, (C H str),
−
1
372(C H-bend), 1273(P O), 1168(P-NC), 1090, 1050(P-O-C) cm .MS
(
(
EI): m/z (%) = 209(3), 194(7), 166 (25), 138 (100), 124 (60), 120 (15), 72
11).
Diproyl-N,N-dimethylphosphoramidate
◦
31
Bp: 92–93 C (3 mmHg);
P NMR (161.98 MHz, CDCl3): δ =
1
1
1.51. H-NMR (CDCl3): δ = 4.05(m,4-H, -OCH2, JH-H = 7.0 JH−P =8.0
Hz), 2.9(d,6H, -NCH3), 1.74( m, 4H, -CH2), 0.97(t,6-H, -CH3 JH-H =
7
1
2
.0Hz);IR: (neat) (KBr) υ(max): 2972, 2899, (CH Str.), 1380, (C H bend),
−
1
272(P O), 1160(P-N-C), 1090,1050(P-O-C) cm . MS (EI): m/z (%) =
09(3), 168 (20), 150(7), 138 (100), 126 (63), 124 (33),108 (31), 44 (100).
Diproyl-N,N-diethylphosphoramidate
◦
31
Bp: 119–120 C (1 mmHg); P NMR (161.98 MHz, CDCl3): δ = 10.27.
H-NMR (CDCl3): δ = 4.05(m,4-H, -OCH2, JH-H = 7.0 JH−P =8.0 Hz),
1
3
.3(m,4H,-CH2-), 1.74( m, 4H, CH2),1.2(t,6H,CH3-), 0.97(t,6-H, -CH3
JH-H = 7.0Hz);IR: (neat) (KBr) υ(max): 2943, 2989(C H str.), 1385
−
1
(
(
(
C H bend), 1268 (P O), 1163 (P-NC), 1090,1050(P-O-C) cm . MS
EI): m/z (%) = 237(3), 222(42), 180 (25), 138 (100), 124(12), 110 (19),72
25).
Dipropyl-N,N-dipropylphosphoramidate
◦
31
Bp: 113–114 C (1 mmHg); P NMR (161.98 MHz, CDCl3): δ = 11.22.
H-NMR (CDCl3): δ = 4.05(m,4-H, -OCH2, JH-H = 7.0 JH−P =8.0 Hz),
1
3
.3(m,4H,-CH2-N-), 1.72- 1.76 ( m, 8H, -CH2-), 1.02(t,3H,CH3), 0.97(t,6-
H, -CH3 JH-H = 7.0Hz); IR: (neat) (KBr) υ(max): 2978, 2947, 2889 (C H
str.), 1365, (C H bend), 1262(P O), 1167(P-N-C), 1080,1040(P-O-C)
−
1
cm . MS (EI): m/z (%) = 265(2), 236(67), 194 (30), 152(100), 134 (11)
38 (8), 110 (45), 100 (9).
1

Dichlorodimethyl Hydantoin
1653
Dipropyl-N,N-diisopropylphosphoramidate
◦
31
Bp: 123–124 C (1 mmHg); P NMR (161.98 MHz, CDCl3): δ = 8.90.
H-NMR (CDCl3): δ = 4.05(m,4-H, -OCH2, JH-H = 7.0 JH−P =8.0 Hz),
1
3
.4(m,2H,-CH-), 1.74( m, 4H, CH2),1.4(d,12H,CH3-),0.97(t,6-H, -CH3
JH-H = 7.0 Hz);IR: (neat) (KBr) υ(max): 2977, 2940, 2896 (C H str),
−
1
1
382(C H bend), 1265(P O), 1174(P-N-C), 1090, 1050(P-O-C) cm
MS (EI): m/z (%) = 265(3), 250(78), 208 (45),166 (47), 124(100), 180 (4)
38 (20).
.
1
Dipropyl-N-ethyl-N-methylphosphoramidate
◦
31
Bp: 109–110 C (1 mmHg); P NMR (161.98 MHz, CDCl3): δ = 10.37.
H-NMR (CDCl3): δ = 4.05(m,4-H, -OCH2, JH-H = 7.0 JH−P = 8.0 Hz),
1
3
.25(m,2H,-CH2-), 2.75(d,3H,CH3), 1.74( m, 4H, CH2),1.5(t,3H,CH3),
0
.97(t,6-H, -CH3 JH-H = 7.0 Hz).IR: (neat) (KBr) υ(max): 2970, 2945,
(
C H str), 1378(C H bend.), 1265(P O), 1174(P-N-C), 1090, 1050(P-
−1
O-C) cm . MS (EI): m/z (%) = 233(4), 208(39), 166 (31), 124(100), 138
(
11), 110 (9), 106 (7), 58 (35).
Dipropyl-N-ethyl-N-propylphosphoramidate
◦
31
Bp: 1127–1128 C (1 mmHg); P NMR (161.98 MHz, CDCl3): δ =
1
1
8
1.14. H-NMR (CDCl3): δ = 4.05(m,4-H, -OCH2, JH-H = 7.0 JH−P =
.0 Hz), 3.25(m,4H,-CH2-N-), 1.74( m, 4H, CH2),1.55 (m,2H,-CH2-
)
)
1
2
,1.15(t,3H,CH3-), 0.97(t,6-H, -CH3 JH-H =7.0 Hz), 0.88(t,3H, CH3-
.IR: (neat) (KBr) υ(max): 2977, 2950, (C H Str), 1387(C H bend),
−
1
262(P O),1160(P-N-C), 1090, 1050(P-O-C)cm .MS (EI): m/z (%) =
51(2), 220(69), 180 (35), 138(100), 110 (24) 86(11).
Dipropyl-N-ethyl-N-isopropylphosphoramidate
◦
31
Bp: 109–110 C (7 mmHg); P NMR (161.98 MHz, CDCl3): δ = 8.76.
H-NMR (CDCl3): δ = 4.05(m, 4-H, -OCH2, JH-H = 7.0 JH−P =8.0 Hz),
1
3
.62(m,1H,-CH-), 3.20(m,2H,-CH2-), 1.74( m, 4H,CH2), 1.2(d,6H,CH3-
)
, 1.25(t,3H,CH3), 0.97(t,6-H, -CH3 JH-H = 7.0 Hz).IR: (neat) (KBr)
υ(max): 2975, 2947, (C H stn), 1380 (C H bend),1267 (P O), 1167
−1
(
1
PNC), 1090,1050(P-O-C) cm . MS (EI): m/z (%) = 251(2), 236(50),
94(18), 152(100), 124(23). 110 (21) 86(10).
Dipropyl-N-methyl-N-propylphosphoramidate
◦
31
1
Bp: 97–98 C (2 mmHg); P NMR (161.98 MHz, CDCl3): δ = 11.12. H-
NMR (CDCl3): δ = 4.05(m,4-H, -OCH2, JH-H = 7.0 JH−P = 8.0 Hz),
3.1(m,2H,-CH2-N), 2.75 (d,3H,CH3-N) 1.74( m, 4H, -CH2),1.55(m,2H,-
CH2-), 0.97(t,6-H, -CH3 JH-H = 7.0 Hz), 0.89(t,3H, -CH3). IR: (neat)
(
KBr) υ(max): 2976, 2953 (C H str.), 1375(C H bend), 1382(C H bend),

1
654
A. K. Gupta et al.
−
1
1
2
265(P O),1174(P-N-C), 1085, 1045(P-O-C) cm . MS (EI): m/z (%) =
37 (4), 208(61), 166 (39), 124(100), 110 (4) 152(9), 72(13).
Dipropyl-N-propyl-N-isopropylphosphoramidate
◦
31
Bp:118–119 C (1 mmHg); P NMR (161.98 MHz, CDCl3): δ = 8.77.
H-NMR (CDCl3): δ = 4.05(m,4-H, -OCH2, JH-H = 7.0 JH−P = 8.0 Hz),
1
3
.6(m,1H,-CH-), 3.1(m,2H,CH2-N-), 1.74(m,4H,CH2), 1.6(m,2H,-CH2-
)
)
1
2
1
, 1.2(d, 6H, CH3), 0.97(t,6-H, -CH3 JH-H =7.0 Hz), 0.88(t,3H,CH3-
.IR: (neat) (KBr) υ(max): 2976, 2953 (C H str.), 1375(C H bend),
−
1
266(P O),1165(P-N-C),1090, 1050(P-O-C) cm .MS (EI): m/z (%) =
65(6), 250(33), 236(100), 208 (16), 194(33), 166 (47), 152(50), 110(81),
24 (24), 110 (10).
Dipropyl-N-methyl-N-isopropylphosphoramidate
◦
31
Bp: 104–105 C (1 mmHg); P NMR (161.98 MHz, CDCl3): δ =
1
1
8
1
0.97. H-NMR (CDCl3): δ = 4.05(m,4-H, -OCH2, JH-H = 7.0 JH−P =
.0 Hz), 3.75(m, 1H, -CH-), 2.65(d,3H,CH3-N-), 1.74( m, 4H, CH2),
.15 (d, 6H, CH3), 0.97(t,6-H, -CH3 JH-H =7.0 Hz).IR: (neat) (KBr)
υ(max): 2980, 2955, (C H str), 1372(C H-bend), 1265(P O), 1168 (P-
−1
NC), 1090,1050(P-O-C) cm .MS (EI): m/z (%) = 237(2), 222(31), 180
19), 138(100), 124 (40) 120(13), 72(10).
(
Diisopropyl-N,N-dimethylphosphoramidate
◦
31
1
Bp: 92 C (1 mmHg); P NMR (161.98 MHz, CDCl3):δ = 9.33. H-
NMR (CDCl3):δ = 4.55(sept,2-H,-OCH-, JH-H = 6.0, JH−P = 6.0, Hz),
2
.9(d,6H, -NCH3), 1.25(d,12-H, -CH3 JH-H = 6.0 Hz); IR: (neat) (KBr)
υ(max): 2972, 2899, (C H Str.), 1380, (C H bend), 1262(P O), 1160(P-
−1
N-C), 1090, 1050(P-O-C) cm . MS (EI): m/z (%) = 209(3), 166 (7), 152(7),
50 (9), 126 (13), 124 (19), 108 (25), 44 (100)
1
Diisopropyl-N,N-diethylphosphoramidate
◦
31
Bp: 115–116 C (1 mmHg); P NMR (161.98 MHz, CDCl3): δ = 8.17.
H-NMR (CDCl3): δ = 4.55(sept,2-H, -OCH-, JH-H = 6.0, JH−P =6.0Hz),
1
3
(
(
.3(m,4H,-CH2-), 1.25(d,12-H, -CH3 JH-H = 6.0 Hz),1.2(t,6H,CH3-). IR:
neat) (KBr) υ(max): 2943, 2989(C H str.), 1385 C H bend), 1268
−1
P O), 1163 (P-NC), 1090,1050(P-O-C) cm
.
Diisopropyl-N,N-dipropylphosphoramidate
◦
31
Bp: 107–108 C (1 mmHg);
P NMR (161.98 MHz, CDCl3):
1
δ = 9.06. H-NMR (CDCl3): δ = 4.55(sept,2-H, -OCH-, JH-H = 6.0,
JH−P = 6.0 Hz), 3.3(m,4H,-CH2-N-), 1.75(m,4H, -CH2-), 1.25(d,12-H,
-
CH3, JH-H =6.0 Hz), 1.04 (t,6H,CH3).IR: (neat) (KBr) υ(max): 2978,

Dichlorodimethyl Hydantoin
1655
2
1
947, 2889 (C H str.), 1365, (C H bend.),1262(P O), 1167(P-N-C),
−1
080,1040(P-O-C) cm
.
Diisopropyl-N,N-diisopropylphosphoramidate
◦
31
Bp: 119–120 C (1 mmHg); P NMR (161.98 MHz, CDCl3): δ = 6.89.
H-NMR (CDCl3): δ = 4.55(sept,2-H, -OCH-, JH-H = 6.0, JH−P = 6.0 Hz),
1
3
.4(m,2H,-CH-N-), 1.4(d,12H,CH3-),1.25(d,12-H, -CH3, JH-H = 6.0 Hz).
IR: (neat) (KBr) υ(max): 2977, 2940, 2896 (C H str), 1382(C H bend),
−
1
1
265(P O), 1174(P-N-C), 1090, 1050(P-O-C) cm . MS (EI): m/z (%) =
2
65(4), 250(32), 208(25), 180(7),166 (5), 138(100), 124(75).
Diisopropyl-N-ethyl-N-methylphosphoramidate
◦
31
Bp: 104–105 C (1 mmHg); P NMR (161.98 MHz, CDCl3): δ =
1
8
6
.27. H-NMR (CDCl3): δ = 4.55(sept,2-H, -OCH-, JH-H = 6.0, JH−P =
.0 Hz), 3.25(m,2H,-CH2-), 2.75(d,3H,CH3), 1.5(t,3H,CH3), 1.25(d,12-
H, -CH3, JH-H = 6.0 Hz).IR: (neat) (KBr) υ(max): 2970, 2945, (C H
str), 1378(C H bend.), 1267(P O), 1165(P-N-C), 1090, 1050(P-O-C)
−
1
cm .MS (EI): m/z (%) = 237(4), 222(11), 180(10), 152 (5), 138(100),
20(11).
1
Diisopropyl-N-ethyl-N-propylphosphoramidate
◦
31
Bp: 125–126 C (1 mmHg); P NMR (161.98 MHz, CDCl3): δ =
1
9
6
1
2
1
1
.04. H-NMR (CDCl3): δ = 4.55(sept,2-H, -OCH-, JH-H = 6.0, JH−P =
.0 Hz), 3.25(m,4H,-CH2-N-), 1.55 (m,2H, -CH2-), 1.15(t,3H,CH3-),
.25(d,12-H, CH3-JH-H = 6.0), 0.88(t,3H, CH3-).IR: (neat) (KBr) υ(max):
977, 2950, (C H Str), 1387(C H bend), 1272(P O), 1160(P-N-C),
−1
088, 1047(P-O-C) cm . MS (EI): m/z (%) = 251(3), 222(22), 180(22),
66 (7), 138(100), 110(20).
Diisopropyl-N-ethyl-N-isopropylphosphoramidate
◦
31
Bp: 115–116 C (1.5 mmHg); P NMR (161.98 MHz, CDCl3): δ =
1
6
6
.91. H-NMR (CDCl3): δ = 4.55(sept,2-H, -OCH-, JH-H = 6.0, JH−P =
.0 Hz), 3.9(m,1H,-CH-), 3.20(m,2H,-CH2-), 1.23(t,3H,CH3), 1.25(d,12-
H, CH3-, JH-H =6.0 Hz), 1.2(d, 6H, CH3-).IR: (neat) (KBr) υ(max): 2975,
2
1
947, (C H str), 1380 (C H bend), 1267 (P O), 1167 (PNC), 1090,
050(P-O-C) cm .MS (EI): m/z (%) = 251(2), 236(19), 194(12), 152
−1
(
100), 138(100), 124(20), 110 (15).
Diisopropyl-N-methyl-N-propylphosphoramidate
◦
31
Bp:112–113 C (1.5 mmHg);
P NMR (161.98 MHz, CDCl3):
1
δ = 9.02. H-NMR (CDCl3): δ = 4.55(sept,2-H, -OCH-, JH-H = 6.0,
JH−P = 6.0 Hz), 3.1(m,2H,-CH2-N), 2.75(d,3H,CH3-N) 1.55(m,2H,-CH2-
)
, 1.25(d,12-H, CH3-JH-H = 6.0 Hz),0.89(t,3H, CH3-).IR: (neat) (KBr)

1
656
A. K. Gupta et al.
υ(max): 2976, 2953 (C H str.), 1375(C H bend), 1265(P O), 1174(P-
−1
N-C), 1085, 1045(P-O-C) cm . MS (EI): m/z (%) = 237(7), 208(46), 166
17), 124(100), 152(9).
(
Diisopropyl-N-propyl-N-isopropylphosphoramidate
◦
31
Bp: 116–117 C (1.2 mmHg); P NMR (161.98 MHz, CDCl3): δ = 6.88.
H-NMR (CDCl3): δ = 4.55(sept,2-H, -OCH-, JH-H = 6.0, JH−P = 6.0 Hz),
1
3
.6(m,1H,-CH-), 3.1(m,2H,CH2-N-), 1.6(m,2H,-CH2-), 1.2(d,6H,CH3),
1
.25(d,12-H, CH3- JH-H = 6.0 Hz),0.88(t,3H,CH3-).IR: (neat) (KBr)
υ(max): 2976, 2953 (C H str.), 1375(C H bend), 1270(P O), 1165(P-
−1
N-C), 1090, 1050(P-O-C) cm .MS (EI): m/z (%) = 265(4), 250(11), 236
31), 180(4),166 (67), 124(17), 110(60).
(
Diisopropyl-N-methyl-N-isopropylphosphoramidate
◦
31
1
Bp: 99–100 C (1 mmHg); P NMR (161.98 MHz, CDCl3): δ = 6.90. H-
NMR (CDCl3): δ = 4.55(sept, 2-H, -OCH-, JH-H = 6.0, JH−P = 6.0 Hz),
3
6
1
.75(m, 1H, -CH-N-),2.65(d,3H,CH3,-N-), 1.25 (d,12-H, CH3-, JH-H =
.0 Hz),1.15(d,6H,CH3).IR: (neat) (KBr) υ (max): 2980, 2955,(C H str),
−
1
372(C H-bend), 1265(P O), 1168(P-N-C), 1090, 1050(P-O-C) cm
.
MS (EI): m/z (%) = 237(3),222(11),180(10), 138(100), 124(35), 120(20).
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