Reaction of P(III) chlorides with aldehydes: III. Reaction of primary intermediates with oxidants and chlorinating agents

Article abstract of DOI:10.1134/S1070363214010113

Primary intermediates of P(III) chlorides reaction with aldehydes have been converted into the corresponding phosphates by treating with oxidants: dimethylsulfoxide and tert-butyl hypochlorite. In reactions of the intermediates with chlorinating agents (P

Full text of DOI:10.1134/S1070363214010113

ISSN 1070-3632, Russian Journal of General Chemistry, 2014, Vol. 84, No. 1, pp. 75–81. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © M.B. Gazizov, R.A. Khairullin, R.F. Karimova, 2014, published in Zhurnal Obshchei Khimii, 2014, Vol. 84, No. 1, pp. 79–85.
Reaction of P(III) Chlorides with Aldehydes:
III.1 Reaction of Primary Intermediates with Oxidants
and Chlorinating Agents
M. B. Gazizov, R. A. Khairullin, and R. F. Karimova
Kazan National Research Technological University, ul. K. Marksa 68, Kazan, Tatarstan, 420015 Russia
e-mail: mukattisg@mail.ru
Received January 14, 2013
Abstract—Primary intermediates of P(III) chlorides reaction with aldehydes have been converted into the
corresponding phosphates by treating with oxidants: dimethylsulfoxide and tert-butyl hypochlorite. In reactions
of the intermediates with chlorinating agents (PCl5 and Cl2) the oxidation products are formed (due to the
ligand exchange at quasiphosphonium center) along with the expected P(IV) acid chlorides.
DOI: 10.1134/S1070363214010113
Oxidation has used as an efficient chemical method
to elucidate the structure of primary reaction inter-
mediates. In [2] we have demonstrated phosphorus
atom of compounds I bears the substituents exhibiting
different donor-acceptor properties. Therefore, it is
necessary to find the suitable agents capable of oxidizing
both the electrophilic and nucleophilic P(III) derivatives.
oxidation. The oxidation product IVc had significantly
higher boiling point than that of paraldehyde and thus
could be isolated by vacuum distillation. The
intermediates Ik, and Il (obtained by treating of
compound Ie with alcohols in the presence of tertiary
base) were oxidized in heavily diluted ether solution
right after removing the amine salt. Physical
parameters and elemental analysis data of compounds
IV are given in the Experimental section. The com-
pounds structures were confirmed by 1H and 31P NMR
spectroscopy (see the table).
The following compounds have been known to
oxidize various P(III) derivatives: oxygen [3–8], ozone
[9, 10], alkyl- [11], and dialkyl peroxides [12–16],
tertiary amine oxides [17–19], dimethylsulfoxide [20,
21], and alkyl hypochlorites [17, 22–25]. Analysis of
the above-listed reference has suggested that
dimethylsulfoxide II and tert-butyl hypochlorite III
are suitable candidates to oxidize the primary
intermediates. Both II and III are readily available,
easy and safe in handling, and oxidation can be
performed under the conditions of stability of I.
Electrophilic as well as nucleophilic P(III) derivatives
can likely be oxidized with these reagents.
Scheme of the intermediates oxidation could be
presented as follows.
R1R2POCHClR3 + Me2SO → R1R2P(O)OCHClR3 + Me2S,
I
II
IV
R1 + R2 = C6H4O2, R3 = Me (a), Pr (b); R1 = R2 = Cl, R3 =
Me (c), CCl3 (d), i-Pr (e); R1 = R2 = CCl3CH2O, R3 = i-Pr
(f); R1 = Cl, R2 = MeCHClO, R3 = Me (g); R = CCl3CH2O,
R2 = MeCHClO, R3 = Me (h), R2 = i-PrCHClO, R3 = i-Pr (i).
R1R2POCHClR3 + t-BuOCl → R1R2P(O)OCHClR3 + t-BuCl,
The experiments confirmed that both oxidants were
efficient oxidizers of the primary intermediates. The
oxidation was carried out under mild conditions: in the
solution and upon cooling. In all the cases, the stable
oxidation products IV were isolated. The mixture of
intermediates Ic with paraldehyde (could not be
separated by distillation) was also subjected to
I
III
IV
R1 = R2 = Cl, R3 = Me (c), Pr (j); R1 = R2 = MeO, R3 = i-Pr
(k); R1 = R2 = EtO, R3 = i-Pr (l).
It should be noted that tert-butyl hypochlorite
oxidized the intermediates Ic and Ij (with phosphorus
atom being an electrophile) under mild conditions. In
1
For communication II, see [1].
75

76
GAZIZOV et al.
1H and 31P NMR parameters of phosphates R1R2P(O)OCHClR3
Comp. no.
R1
R2
R3
δ, ppm (JHH and JPH, Hz)
δP, ppm
O
Me
Pr
1.5 d (3Н, Ме, JHH 5.0), 6.12 d.q (1Н, РОСН, JРH 9.0, JНH 5.0), 6.92–
7.09 m (4Н, Ar)
11.0
IVа
O
O
0.93 t (3H, CH2CH2CH3, JHH 6.5), 1.37–1.63 m (2H, CH2CH2CH3),
1.78–2.02 m (2H, CH2CH2CH3), 6.23 d.t (1H, POCH, JPH 8.0, JHH
5.5), 6.90–7.10 m (4H, Ar)
11.0
5.0
IVb
IVc
O
Cl
Cl
Me
1.80 d (3Н, Ме, JHH 5.0), 6.30 sextet (1Н, РОСН, JРH 10.0,
JНH
5.0)
Cl
Cl
Cl
Cl
CCl3
6.52 d (1Н, РОСН, JРH 11.3)
8.0
6.0
IVd
IVe
CHMe2
0.95 d (6Н, Ме, JHH 5.0), 1.78–2.00 m (1Н, CH), 6.30 d.t (1Н,
РОСН, JРH 10.0, JНH 5.0)
CCl3CH2O CCl3CH2O
CHMe2
0.99 d (6Н, Ме, JHH 6.3), 2.0–2.3 m (1H, CHMe2), 4.55 d (4H,
CH2OP, JРH 5.0), 5.92 d.d (1Н, РОСН, JРH 9.0, JHH 5.0)
–6.0
IVf
Cl
Cl
OCHClCH3 Me
1.79 d (6Н, Ме, JHH 7.0), 6.13–6.43 m (2H, CH)
2.42, 1.2, 0.7
6.0
IVg
IVj
Cl
Pr
0.90 t (3H, CH2CH2CH3, JHH 6.3), 1.38 sextet (2Н, CH2CH2CH3, JHH
6.3), 1.88 d.t (2H, CH2CH2CH3, JРH 5.0, JНH 6.3), 6.25 d.t (1Н,
РОСН, JРH 5.0, JНH 6.3)
MeO
EtO
MeO
EtO
CHMe2
CHMe2
0.99 d (6Н, Ме, JHH 6.3), 1.93–2.20 m (1H, CHMe2), 3.70 d and 3.74
d (6H, OMe, JРH 12.5), 5.83 d.d (1Н, РОСН, JРH 8.8, JHH 5.0)
0
IVk
IVl
1.42 d (6H, CHMe2, JHH 6.3), 1.2 t (6H, OCH2CH3, JHH 7.5), 1.9–2.2
m (1H, CHMe2), 4.00–4.04 m (4H, OCH2CH3), 5.85 d.q (1H, POCH,
JPH 9.0, JHH 6.3)
–3.0
O
O
CHMe2
0.98 d (6Н, Ме, JHH 6.0), 1.85–2.25 m (1H, CHMe2), 6.12 d.d (1Н,
РОСН, JРH 8.0, JHH 5.0), 0.85–7.12 m (4Н, Ar)
10.6
IVm
IVn
MeO
MeO
CH3CHClO Me
1.50–1.72 m (6H, Me), 3.61 d and 3.63 d (3H, OMe, JPH 12.0, JPH
–3.89,
–4.86,
–5.14
15.0), 5.90–6.16 m (2H, POCH)
MeO
Me
1.42 d (6Н, Ме, JHH 6.3), 5.85 d.q (1Н, РОСН, JРH 9.0, JHH 6.3), 3.40 d
and 3.44 d (6H, OMe, JРH 12.0)
–1
IVo
order to demonstrate that the reaction was common for
the electrophilic P(III) derivatives, we performed the
oxidation of PCl3 and ethyl phosphorodichloridite as
well; the reaction gave the corresponding phosphates
with good yields under mild conditions.
Some of the compounds IV were synthesized by
other methods. For example, compounds IVn and IVo
were prepared via the reaction of the products of
oxidation of Ic and Ig with methanol in the presence of
tertiary amine.
nEt3N
Cl(MeCHClO)P(O)X + nMeOH
MeO(MeCHClO)P(O)Y,
–nEt3N·HCl
IVc, IVg
IVn, IVo
X = Cl (c), MeCHClO (g); Y = MeCHClO (n), MeO (o).
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REACTION OF P(III) CHLORIDES WITH ALDEHYDES: III.
77
In order to extend the knowledge on chemical
properties of the primary intermediates I, we studied
the reactions of compounds Ia and Im with PCl5 and
gaseous Cl2. The structures of (Ia and Ib) and (Im and
In) intermediates were those of trisubstituted phos-
phite. Trialkyl phosphites are known to react with
halogens, in particular, with chlorine, to form dialkyl
chlorophosphates [17, 24]. Phosphorus pentachloride
may act as source of chlorine.
the second major reaction product being dialkyl
chlorophosphate [26, 27].
(RO)3P + PCl5 → (RO)2P(O)Cl + PCl3 + RCl.
In the excess of trialkyl phosphite, it can
disproportionate via interaction with PCl3 [27].
3P(OR)3 + PCl5
PCl3 + (RO)2P(O)Cl + 2P(OR)3
–RCl
+
→ (RO)2P(O)Cl + 3(RO)2PCl.
(RO)3P + Cl2 → [(RO)3PCl2 ⇄ (RO)3PCl Cl–]
→ (RO)2P(O)Cl+ RCl.
We proposed that the intermediates Ia and Ib
should react with PCl5 and Cl2 similarly to trialkyl
phosphites, to give chlorophosphate V (pathway a).
It reacts with trialkyl phosphites to give PCl3, and
Cl
O
O
POCHR + PCl5
POCHR
O
−PCl3
or
O
Cl
Cl
Cl
Cl2
I
VI
O
O
P(O)Cl + RCHCl2
Cl
+
POCHR
а
O
O
V
Cl−
b
Cl
VII
O
+I
O
+
P(OCHR)2 Cl−
P(O)OCHR + RCHCl2
O
IV
O
VIII
Cl
Cl
R = Me (а), i-Pr (m).
However, chlorophosphate V was not the only
phosphorus-containing reaction product; trisubstituted
phosphates IV (the products of oxidation of
intermediates I) were formed as well (pathway b). The
ratio of the products IV and V depended on the order
of mixing of reagents. In view of that, using PCl5
seemed more convenient. When the intermediate Im
was added dropwise to the benzene solution of PCl5,
chlorophosphate V was the only product. With the
reversed mixing order, both IV and V were obtained
with 1 : 1 ratio. 31P NMR spectrum of reaction mixture
after evaporating all the volatile products contained
two singlets of equal intensity at δP 19 and 10.5 ppm.
The first fraction of the first vacuum distillation
contained chlorophosphate V (δP 19 ppm). Slow
distillation of the third fraction (containing V and IVm
in the 1 : 4 ratio) gave the pure compound IVm.
In the course of chlorination with gaseous chlorine,
the reversed reagents mixing order could not be carried
out. Therefore, in all the cases the chlorine gas was
passed through the solution of intermediate Im in
methylene chloride. The major reaction product was
chlorophosphate V, the ratio of δP 19 and 10.5 ppm
signals being of 10 : 1. By distillation with reflux
condenser, compound V was isolated in pure form in
78% yield. Chlorination of the intermediate Ia in
toluene the major fraction contained the products V
and IVa in the 1 : 3 ratio. Repeated distillation of that
fraction with reflux condenser gave the mixture
majorly containing the trisubstituted phosphate
IVa (V : IVa ratio of 1 : 10). In the 1H NMR spectrum
of that fraction, all the characteristic signals of IVa
were observed. Hence, the reactions of intermediates
I with PCl5 and Cl2 proceeded via different path-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 1 2014

78
GAZIZOV et al.
ways: chlorination and oxidation took place simul-
taneously.
Noteworthily, such ligand exchange at quasiphos-
phonium center is a well known organophosphorus
compounds reaction [17, 29, 30].
We propose that the intermediates I first reduced
PCl5 to PCl3, being simultaneously chlorinated to give
the quasiphosphonium compound VII via the
phosphorane intermediate VI. Then, the quasiphos-
phonium compound VII was subjected to ligand
exchange with the initial trisubstituted phosphite I to
give the quasiphosphonium compound VIII that was
further dealkylated to give the oxidation product IV.
Reaction with PCl5 was also used for confirmation
of tris(1-chloroethyl) phosphite In structure. The
reaction product was bis(1-chloroethyl) chlorophos-
phate IVg that could be prepared as well by oxidation
of phosphoromonochloridite Ig with DMSO, as
discussed above. The spectral properties of compound
IVd obtained by different methods were identical.
Cl
(MeCHO)3P
(MeCHO)2PCl
(MeCHO)3P + PCl5
−PCl3
−RCHCl2
Cl
Cl
Cl
O
Cl
In
IVg
EXPERIMENTAL
21.01; H 3.50; Cl 47.15; P 13.68. C4H8Cl3O2P.
Calculated, %: C 21.29; H 3.54; Cl 47.18; P 13.74.
1H (300 MHz), 13C (75.5 MHz), and 31P (121.5 MHz)
NMR spectra were registered with 7.0 T IBM/Bruker
Pyrocatechol(1-chloroethyl) phosphate IVa.
Similar reaction of 33 g (0.151 mol) of pyrocatechol(1-
chloroethyl) phosphite Ia and 11.8 g (0.151 mol) of
DMSO gave 13.11 g (38%) of phosphate IVa, bp 95–
98°C (0.03 mm Hg), nD20 1.4985, d420 1.3005. Found,
%: C 40.86; H 3.32; Cl 15.10; P 13.15. C8H8ClO4P.
Calculated, %: C 40.94; H 3.41; Cl 15.13; P 13.20.
1
AF 300 spectrometer. H (100 MHz) NMR spectra
were recorded with Tesla BS-567A device, and 31P
(162 MHz) NMR spectra were recorded with Bruker
MSL-400 spectrometer. Chemical shifts of hydrogen
and carbon are given with reference to TMS. Chemical
shifts of phosphorus are given with reference to 85%
phosphoric acid.
Pyrocatechol(1-chlorobutyl) phosphate IVb.
Similar reaction of 33.56 g (0.136 mol) of pyro-
catechol(1-chlorobutyl) phosphite Ib and 10.64 g
(0.136 mol) of DMSO gave 14 g (53%) of phosphate
IVb, bp 98–100°C (0.02 mm Hg), nD20 1.5022; d420
1.2999. Found, %: C 45.35; H 4.46; Cl 13.48; P 11.45.
C10H12ClO4P. Calculated, %: C 45.71; H 4.57; Cl
13.52; P 11.79.
1-Chloroethyl dichlorophosphate IVc. 2.79 g
(0.036 mol) of DMSO in benzene was added dropwise
at 0–5°C to solution of 6.47 g (0.036 mol) of 1-chloro-
ethyl phosphorodichloridite Ic (containing admixture
of paraldehyde) in benzene. Vacuum distillation gave
2.13 g (30%) of dichlorophosphate IVc, bp 30°C
(0.04 mm Hg), nD20 1.4531, d420 1.4854. Found, %: C
11.92; H 1.92; Cl 53.80; P 15.63. C2H4Cl3O2P. Cal-
culated, %: C 12.15; H 2.02; Cl 53.92; P 15.69.
1,2,2,2-Tetrachloroethyl dichlorophosphate IVd.
Solution of 9.2 g (0.118 mol) of DMSO in diethyl
ether was added dropwise at 0–3°C to solution of 33.6 g
(0.118 mol) of crude 1,2,2,2-tetrachloroethyl dichloro-
phosphite Id in diethyl ether. Vacuum distillation gave
20.5 g (58%) of phosphate IVd, bp 106–108°C
(0.01 mm Hg). Found, %: C 7.89; H 0.38; Cl 70.69; P
10.17. C2HCl6PO. Calculated, %: C 7.27; H 0.33; Cl
70.76; P 10.29.
1-Chlorobutyl dichlorophosphate IVj. Reaction
of 5.48 g (0.026 mol) of 1-chlorobutyl dichlorophos-
phite Ij and 2.04 g (0.026 mol) of DMSO yielded 2 g
(31%) of dichlorophosphate IVj, bp 40°C (0.025 mm
Hg), nD20 1.4561. Found, %: C 21.09; H 3.24; Cl 47.11,
P 13.72. C4H8Cl3O2P. Calculated, %: C 21.29; H 3.54;
l 47.18; P 13.74.
Di(1-chloroehyl) chlorophosphate IVg. DMSO,
3.12 g (0.04 mol), was slowly added dropwise to the
solution of 9.02 g (0.01 mol) of crude di(1-chloroethyl)-
phosphorodichloridite Id in 15 mL of methylene
chloride. Vacuum distillation gave 4.1 g (42%) of
chlorophosphate IVg, bp 67–69°C (0.1 mm Hg).
2-Methyl-1-chloropropyl dichlorophosphate IVe.
Similar reaction of 51 g (0.206 mol) of 2-methyl-1-
chloropropyl phosphorodichloridite Ie with 16.09 g
(0.206 mol) of DMSO gave 28 g (52%) of dichloro-
phosphate IVe, bp 43°C (0.01 mm Hg). Found, %: C
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REACTION OF P(III) CHLORIDES WITH ALDEHYDES: III.
79
Found, %: C 19.76; H 3.26; Cl 43.94; P 12.85.
C4H8Cl3O3P. Calculated, %: C 19.87; H 3.31; Cl
44.10, P.12.84.
(0.093 mol) of methanol and 13.93 g (0.093 mol) of
N,N-diethylaniline in 100 mL of anhydrous diethyl
ether. The reaction mixture was stirred at that
temperature during 2.5 h. The precipitate formed was
filtered off, and 5.06 g (0.0116 mol) of tert-butyl
hypochlorite was added dropwise at –5 to –10°C to the
mixture obtained. Vacuum distillation gave 5.38 g
(53%) of phosphate IVk, bp 49–50°C (0.04 mm Hg),
nD20 1.4312, d420 1.1950. Found, %: C 33.05; H 6.34; Cl
15.98; P 13.93. C6H14ClO4P. Calculated, %: C 33.25;
H 6.47; Cl 16.40; P 14.30.
Di(2-methyl-1-chloropropyl)-2,2,2-trichloroethyl
phosphate IVi. Solution of 2.34 g (0.03 mol) of
DMSO in 8 mL of benzene was added dropwise to
solution of 13.85 g (0.03 mol) of crude phosphite Ii in
30 mL of benzene at 0–10°C. Vacuum distillation gave
5.32 g (37%) of phosphate IVi, bp 131°C (0.03 mm
Hg). Found, %: C 29.01; H 4.42; Cl 43.11; P 7.44.
C10H18Cl5O4P. Calculated, %: C 29.23; H 4.38; Cl
43.24; P 7.55.
Diethyl(2-methyl-1-chloropropyl) phosphate IVl.
Similar reaction of 3.64 g (0.079 mol) of ethanol,
11.82 g (0.079 mol) of N,N-diethylaniline, 8.3 g
(0.0396 mol) of phosphorodichloridite Ie, and 4.3 g
(0.039 mol) of tert-butyl hypochlorite gave 4.64 g
(48%) of phosphate IVl, bp 75–77°C (0.04 mm Hg),
nD20 1.4462, d420 1.1534. Found, %: C 38.96; H 7.27; Cl
14.18; P 12.13. C8H18ClO4P. Calculated, %: C 39.29;
H 7.36; Cl 14.49; P 12.67.
(2-Methyl-1-chloropropyl)bis(2,2,2-trichloroethyl)
phosphate IVf. Solution of 3.2 g (0.04 mol) of DMSO
in 5 mL of diethyl ether was added dropwise at 0–10°C
to a solution of 18.1 g (0.041 mol) of crude phosphite
If in 70 mL of diethyl ether. Vacuum distillation gave
7.9 g (43%) of phosphate IVf, bp 132–135°C
(0.02 mm Hg), nD20 1.5022, d420 1.2999. Found, %: C
21.13; H 2.58; Cl 54.87; P 6.67. C8H12Cl7O4P.
Calculated, %: C 21.26; H 2.65; Cl 55.03; P 6.17.
Phosphorus trichloroxide. 10 g (0.092 mol) of
tert-butyl hypochlorite was added dropwise to 4 g
(0.092 mol) of PCl3 at 10–15°C. Distillation of reaction
mixture gave 2 g of tert-butyl chloride, bp 50–53°C
(reported data 51–52°C [31]) and 2.53 g (57%) of
phosphorus trichloroxide, bp 103-105°C.
Di(1-chloroethyl)-2,2,2-trichloroethyl phosphate
IVh. Similar reaction of 28.19 g (0.08 mol) of crude
phosphite Ih and 6.5 g (0.08 mol) of DMSO gave
11.62 g (41%) of phosphate IVh, bp 119°C (0.03 mm
Hg). Found, %: C 20.23; H 2.79; Cl 49.97; P 8.67.
C6H10Cl5O4P. Calculated, %: C 20.31; H 2.82; Cl
50.07; P 8.74.
Ethyl dichlorophosphate. tert-Butyl hypochlorite,
3.8 g (0.035 mol), was added dropwise at 10–15°C to
4.25 g (0.029 mol) of ethyl phosphorodichloridite.
Distillation of the reaction mixture gave 1.63 g of tert-
butyl chloride (bp 49–50°C) and 0.9 g of ethyl
dichlorophosphate, bp 52–54°C (10 mm Hg), nD20
1.4445 (reported data bp 92°C (65 mm Hg) [32]).
1-Chloroethyl dichlorophosphate IVc. 12.47 g
(0.115 mol) of tert-butyl hypochlorite was added
dropwise at 0–2°C to solution of 20.84 g (0.115 mol)
of chloroethyl phosphorodichloridite Ic in 50 mL of
carbon tetrachloride. Vacuum distillation gave 6.13 g
of phosphate IVc, bp 30°C (0.04 mm Hg). nD20 1.4529,
d420 1.4858. Found, %: C 12.01; H 1.97; Cl 53.08; P
15.53. C2H4Cl3O2P. Calculated, %: C 12.15; H 2.02;
Cl 53.92; P 15.69.
Methyldi(1-chloroethyl) phosphate IVn. Chloro-
phosphate IVg, 6.25 g (0.027 mol), was added
dropwise to solution of 0.864 g (0.027 mol) of
methanol and 2.73 g (0.027 mol) of triethylamine in
diethyl ether. The reaction mixture was stirred during
2 h at room temperature, and triethylamine hydro-
chloride was filtered off. Vacuum distillation gave 3.1 g
(50%) of phosphate IVn, bp 83–84°C (0.1 mm Hg).
Found, %: C 25.31; H 4.60; Cl 29.81; P 13.18.
C5H11Cl2O4P. Calculated, %: C 25.31; H 4.64; Cl
29.96; P 13.08.
1-Chlorobutyl dichlorophosphate IVj. Similar
reaction of 9.84 g (0.047 mol) of phosphorodi-
chloridite Ij and 5.1 g (0.047 mol) of tert-butyl
hypochlorite gave 2.65 g (25%) of phosphate IVj, bp
40°C (0.025 mm Hg). Found, %: C 21.19; H 3.44; Cl
46.96; P 13.67. C4H8Cl3O2P. Calculated, %: C 21.29;
H 3.54; Cl 47.18; P 13.74.
Dimethyl(1-chloroethyl) phosphate IVo. 1-Chloro-
ethyl dichlorophosphate IVc, 4.68 g (0.024 mol), was
added dropwise at 0–3°C to a solution of 1.51 g
(0.047 mol) of methanol and 4.8 g (0.047 mol) of
triethylamine in 50 mL of diethyl ether. Reaction
Dimethyl(2-methyl-1-chloropropyl) phosphate
IVk. Solution of 9.76 g (0.0116 mol) of 2-methyl-1-
chloropropyl phosphorodichloridite Ie in diethyl ether
was added dropwise at –10°C to solution of 2.98 g
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80
GAZIZOV et al.
mixture was stirred during 1 h at that temperature, and
the obtained precipitate was filtered off. Distillation of
the filtrate in vacuum gave 1.58 g (35%) of phosphate
IVo, bp 73–75°C (10 mm Hg), nD20 1.4373, d420 1.2018.
the ratio of the δP 19 and 10 ppm signals was of 3 : 1;
in the spectrum of the second fraction [bp 100–104°C
(0.02 mm Hg)] those signals were observed in the 1 : 10
ratio. Thus, the main component of the second fraction
was the oxidation product IVa.
Reaction of (2-methyl-1-chloropropyl)pyrocate-
chol phosphite Im with phosphorus pentachloride.
a. Compound Im, 15.61 g (0.063 mol), was added
dropwise to a solution of 13.12 g (0.063 mol) of PCl5
in 50 mL of CH2Cl2 upon cooling with cold water.
Distillation of the reaction mixture gave 8.1 g (70%) of
pyrocatechol chlorophosphate VI, bp 82–83°C
Reaction of tris(1-chloroehyl)phosphite In with
phosphorus pentachloride. Acetaldehyde, 17.4 g
(0.396 mol), was slowly added dropwise to a mixture
of 12.0 g (0.088 mol) of phosphorus trichloride and
0.656 g (0.0011 mol) of N,N-diethylaniline at 0 to –3°C
upon vigorous intense stirring. The reaction mixture
was allowed to stand for 24 h at –1°C, and the volatile
products were removed upon cooling in high vacuum.
The residue, crude intermediate Ip, was dissolved in
15 mL of cold benzene, and that solution was added
dropwise to solution of 17.72 g (0.088 mol) of PCl5 in
60 mL of benzene. Reaction mixture was slowly
heated to 45°C. Distillation in vacuum gave 10.1 g
(47%) of di(1-chloroethyl) chlorophosphate Ig.
1
(0.03 mm Hg). H NMR spectrum (δ, ppm): 6.8 m
(C6H4); 31P NMR spectrum (δP, ppm): 19.
b. Solution of 39.2 g (0.187 mol) of PCl5 in 15 mL
of benzene was added dropwise to solution of 57.8 g
(0.234 mol) of compound Im in 120 mL of benzene
upon cooling with cold water. Distillation of the
reaction mixture in vacuum gave three fractions.
The first fraction contained pyrocatechol chloro-
phosphate (δP 19 ppm). According to 31P NMR data,
the second fraction consisted of compounds IVm and
V in the 1 : 3 ratio. In the third fraction, the same
compounds were found in 4 : 1 ratio. Distillation of the
third fraction with reflux condenser gave 22 g (36%)
of (2-methyl-1-chloropropyl)pyrocatechol phosphate
IVm, bp 104°C (0.02 mm Hg), nD20 1.0525, d420 1.3024.
Found, %: C 45.23; H 4.33; Cl 13.30; P 11.90.
C10H12ClO4P. Calculated, %: C 45.71; H 4.57; Cl
13.50; P 11.79.
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