Reactions of P(III) chlorides with aldehydes: I. Synthesis of primary intermediates of the reactions of aliphatic aldehydes with P(III) chlorides possessing electrophilic properties

Article abstract of DOI:10.1134/S1070363213120104

An approach to investigation of reactions of electrophilic P(III) chlorides with aliphatic aldehydes is developed. Its essence is the removal of HCl impurity from chloride and catalytic blocking of electrophilic center of the carbonyl group. For these pur

Full text of DOI:10.1134/S1070363213120104

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 12, pp. 2281–2292. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © M.B. Gazizov, R.A. Khairullin, R.F. Karimova, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83, No. 12, pp. 1996–2007.
Reactions of P(III) Chlorides with Aldehydes:
I. Synthesis of Primary Intermediates of the Reactions
of Aliphatic Aldehydes with P(III) Chlorides
Possessing Electrophilic Properties
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―An approach to investigation of reactions of electrophilic P(III) chlorides with aliphatic aldehydes
is developed. Its essence is the removal of HCl impurity from chloride and catalytic blocking of electrophilic
center of the carbonyl group. For these purposes nitrogen-containing organic bases and alkyl vinyl ethers are
used. Three types of primary intermediates with the nearest P(III) environment POCl2, O2PCl, and O3P are
synthesized. It is established that the stability of intermediates increases with the growing acceptor properties of
substituents at P(III) and donor properties of the aldehyde fragment.
DOI: 10.1134/S1070363213120104
>PCl + RCHO →>POCH(Cl)R
One of the reactions used in organophosphorus
chemistry for the synthesis of substances with C-P(IV)
bond is the interaction of P(III) chlorides I with
aldehydes II described for the first time in [1]. It was
established that phosphorus trichloride Ia vigorously
reacted with aldehydes II to give viscous oils. These
addition products due to the ambiguity of their
structure were called adducts.
V
In the case of phosphorus trichloride Ia the gradual
substitution of chlorine atom with 1-chloroalkoxyl
group and the formation of mono- VI, di- VII, and tri-
(1-chloroalkyl)phosphites VIII was suggested. These
substances undergo isomerization to P(IV) derivatives
IX [2].
PCl3 + RCHO ⇄ [Adduct].
PCl3 + RCHO → Cl2POCHClR
Ia
II
Ia
VI
If the adduct is subjected to pyrolysis it gives stable
1-chloroalkyl derivatives III [2–3]. Its hydrolysis
under mild conditions leads to 1-hydroxyalkanephos-
phonic acids IV [4–8].
RCHO
RCHO
ClP(OCHClR)2
VII
(RCHO)3P
|
Cl
VIII
P(O)CHClR
Δ
→ (RCHO)2P(O)CH(Cl)R
III
[Adduct]
|
HOH
Cl
IX
P(O)CH(OH)R
IV
Taking into account the influence of the nature of
substituents at P(III) in compounds I on the readiness
of the reaction proceeding it was concluded that PCl3
and P(III) dichlorides exhibited the electrophilic [11–
17] and monochlorophosphines the nucleophilic
reactivity [14, 18–20].
In contrast to [9, 10] the studies [2–5] showed that
P(III) chloride is an electrophile, and the coordination
of phosphorus atom in the primary process is retained.
Therefore the reaction products are 1-chloroalkyl P(III)
derivatives V.
2281

2282
GAZIZOV et al.
The reactivity of phosphoromonochloridites
component of adduct. They are formed evidently as a
result of isomerization of intermediate substances with
P(III) X.
depends on the nature of hydrocarbon substituents
bound with the oxygen atom. If this moiety is phenyl
(as in diphenyl chlorophosphite) or 1,2-phenylene (as
in catechol chlorophosphite) P(III) monochloride
exhibits electrophilic reactivity [21]. If it is an
unsubstituted alkyl group, phosphoromonochloridites
on different stages of the reaction exhibit nucleophilic
as well as electrophylic reactivity and form polymeric
products [22].
X(RCHClOCHRO)POCHROCHRCl
X
→ X(RCHClOCHRO)P(O)CHROCHRCl
XI
X = Et, Ph, Cl, RCHClOCHRO.
But compounds XI contain labile P(O)OCHRO·
CHRCl fragment. By treating with PCl5 they were
converted to stable P(IV) chlorides XII which were
isolated in the pure state: Et(Cl)P(O)CHROCHRCl
XIIa, Ph(Cl)P(O)CHROCHRCl XIIb, and Cl2P(O)·
CHROCHRCl XIIc.
Proceeding from the structure of P(IV) 1-chloro-
and 1-hydroxyderivatives III, IV it was suggested that
in the course of the formation of adduct one molecule
of aldehyde was consumed per each P–Cl bond. But
since the middle of nineteen seventies a series
investigations has shown that two molecules of
aldehyde are consumed per one P–Cl bond [11–14,
17–19, 21]. It has been shown [13, 17, 21] that in the
reactions of PCl3, ethyl- and phenyldichlorophosphines
with aliphatic aldehydes compound XI is the main
Summarizing the above data on the reactions of
P(III) chlorides having electrophilic properties with
aliphatic aldehydes under mild conditions (25–80°C)
the following general scheme can be suggested.
+
R1R2POCHR3Cl_
R1R2POCHClR3
R1R2PCl + R3CHO
ХIII
ХIV
R1R2POCHR3OC+HR3Cl_
+RCHO
R1R2POCHR3OCHClR3
R1R2P(O)CHR3OCHClR3
ХV
Х
ХI
The nucleophilic attack of the carbonyl group
oxygen on the electrophilic P(III) atom leads to the ion
pair XIII which converts to the addition product of
P(III) chloride to one molecule of aldehyde or in a
product of substitution of a chlorine atom on P(III) by
1-chloroalkoxy group XIV. The structure XIV is the
first intermediate of this reaction. It adds the next
aldehyde molecule to give new ion pair XV with two
fragments of aldehyde and then converts to compound
It must be emphasized here that catalytic effect of
HCl impurity in P(III) chlorides was found in the
reactions with many O-containing organic substances
like alkene oxides [23], carboxylic acids [24], acetals
[25], and aldehydes [20]. It proved that P(III) chloride
purified from HCl admixture by treating with alkyl
vinyl ethers did not react with aldehydes and acetals at
20°C. The reaction begins only by bringing HCl in the
reaction mixture by various ways [20]. Hence, the
problem of separation the stages of addition of the first
and the second aldehyde molecules to one P–Cl bond
can not be solved only by removing acidic admixtures
from P(III) chlorides.
X
containing 1-(1-chloroalkoxy)alkoxy group at
P(III). The product X is the second intermediate of the
reaction. When the nucleophilicity of P(III) is suf-
ficient it undergoes isomerization to P(IV) derivative XI.
Though the structure of primary intermediates XIV
is considered to be universally adopted, they were
neither isolated nor detected by spectral methods. It
was assumed that the second aldehyde molecule in the
presence of acidic admixtures adds very rapidly and
intermediates XIV hardly could be isolated. It was
therefore necessary to work up a quite new approach to
the investigation of these reactions with the purpose of
separating the stages of addition of the first and the
second aldehyde molecules to one P–Cl bond.
We also knew that P(III) chlorides, in particular,
catechol chlorophosphite Ib, reacted with aldehydes
activated by such nucleophiles as trialkyl phosphites
XVI and triethylamine XVIIa expending one molecule
of compound II per each P–Cl bond.
New C–X (X = P [26, 27], N [28, 29]) is formed,
and the coordination number of phosphorus atom
originally bound with chlorine does not change leading
to compounds XVIII, XIX.
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REACTIONS OF P(III) CHLORIDES WITH ALDEHYDES: I.
O
2283
_
+
[(R1O)2P(O)CHR2O]nPCl3 n
Cl Et3NCHROP
_
O
ХVIII
ХIХ
n = 1, 2, 3.
We suggested that nucleophiles XVI, XVIIa not
only activate the calbonyl group, but also protect the
electrophilic center from the addition of the second
aldehyde molecule.
precipitates during the reaction progress. At 20°C its
decomposition becomes noticeable especially under
continuous removing of the products of decomposition
from the reaction medium. If the salt XIX contacts
with excess triethyl phosphite for 30 days, compound
XX containing two phosphorus atoms is formed
according to the Birum reaction.
We have found [29, 30] that the reaction with
triethylamine is reversible. Under mild conditions
(–10°C) the salt XIX is comparatively stable and
O
O
>20oC
_10oC
+
_
P
Ib + MeCHO + Et3N
ХVII
OCHMeNEt3Cl
ХIХ
P(OEt)3
ХVI
O
O
OCHMeP(O)(OEt)2 + Et4NCl_
+
P
ХХ
Salt XIX was reported [28] to be transformed at
heating in a vacuum to vinylpyrocatechol phosphite,
but the temperature of the transformation was not
mentioned. We have found that while heating at 110–
120°C in a vacuum salt XIX completely decomposes
into starting substances, and initial chloride Ib is
formed in a good yield. Considering the reversibility of
the reaction in the case of amine XVIIa we suggested
that using it in a relatively low concentrations would
permit the synthesis of the primary intermediates XIV.
Due to that the essence of the approach we developed
was the removal of acidic impurities from the P(III)
chloride and the catalytic blocking of the electrophilic
center of the carbonyl group. Preliminary results we
reported recently [30–32]. This goal was achieved by
using compounds possessing basic and nucleophilic
properties like tertiary amines XVII and alkyl vinyl
ethers XXI.
We have developed three methods of synthesis of
primary intermediates using tertiary amines (method
a), alkyl vinyl ethers (method b), and transformation of
one primary intermediate into another (method c).
While treating P(III) chloride with tertiary amine
HCl admixture transforms in amine hydrochloride
XXII. Usually compounds I and XVII are mixed at
room temperature in 1.0 : 0.10–0.15 ratio and P(III)
chloride is distilled directly into the reaction flask [31].
Amine hydrochloride XXII remains in the still.
PCl HCl + B
PCl + B HCl
ХVII
ХХII
PCl HCl + CH2 CHOR
PCl + CH3CH(OR)Cl
ХХI
ХХIII
According to another procedure P(III) chloride and
alkyl vinyl ether are mixed in 1.0 : 1.0 ratio at 10°C. α-
Chloroether XXIII obtained and excess alkyl vinyl
ether are removed in a vacuum, and compound I is
distilled into the reaction flask [30]. It turned out that
alkyl vinyl ethers are convenient for purification of
high boiling P(III) chlorides, but they are unsuitable
for purification of PCl3. The latter vigorously reacts
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 12 2013

2284
GAZIZOV et al.
with alkyl vinyl ethers to give organophosphorus com-
pounds with P–C bond [33] and also promotes their
polymerization. Tertiary amines have appeared to be
more universal. They can be used for purification of
practically all P(III) chlorides including PCl3.
Regardless of the boiling point of P(III) chloride low
boiling trialkylamines and high boiling organic bases
like N,N-dialkylanilines can be used.
process was observed. In 31P NMR spectrum taken 2 h
after mixing the reagents three signals at δP 220, 178.1,
and 177.8 ppm were present. The intensity ratio of the
latter two was 3 : 1. Signals at 178.1 and 177.8 ppm
correspond to a phosphorus environment OPCl2 in
alkylphosphorodichloridites [34, 35]. Therefore it was
concluded that both these signals correspond to the
same intermediate VIa.
PCl3 + nRCHO ⇄ (RCHClO)nPCl3–n
We have synthesized primary intermediates which
by the character of nearest P(III) environment (OPCl2,
O2PCl, and O3P) were divided in three types. P(III)
atoms with the analogous environment are present in
previously mentioned compounds VI, VII, and VIII.
Their numbers are retained by us as general for three
types of intermediates.
I
II
VI–VIII
VI, n = 1, R = Me (a), n-Pr (b), i-Pr (c); VII, n = 2, R = Me
(a); VIII, n = 3, R = Me (a).
In 6 h after mixing of the reagents ratio PCl3: VIa
makes up 1.4 : 1 from the integral intensity of these
signals and further it doesn’t practically change. H
NMR spectra of the mixture recorded 5 h after the
beginning of the reaction show that compounds IIa,
XXIVa, and VIa are presented in 1 : 9 : 40 ratio.
1
RCHClOРCl2 R1CHClOP(OR2)Cl R1CHClOP(OR2)(OR3)
VI
VII
VIII
VII, R1 = Me, R2 = MeCHCl (a), R1 = i-Pr, R2 = CCl3CH2
(b); VI, R = Me (a), p-Pr (b), i-Pr (c), CCl3 (d); VII, VIII,
R1 = Me, R2 = R3 = MeCHCl (a), R1 = i-Pr, R2 = R3 =
After removing PCl3 and the insignificant
admixture of acetaldehyde in a vacuum of water-jet
pump, the residue was distilled in a vacuum from the
Arbuzov flask or from the flask equipped with the 10-
15 cm Vigreux column. A mixture containing com-
pounds VIa and XXIVa in 5 : 1 ratio was obtained. In
31P NMR spectrum of this mixture two signals at δP
178.1 and 177.8 ppm corresponding only to phos-
phorus atom in the intermediate VIa were observed.
13C NMR spectrum contained the signals at δC (ppm):
19.89 s (Me), 97.5 s (CH) belonging to XXIVa and at
24.88 s (Me), 86.06 d (2JPC 10.6 Hz, CH) attributed to
VIa.
CCl3CH2 (b), Ph (c), R1 = i-Pr, R2 = CCl3CH2, R3
=
i-PrCHCl (d), R1 = Me, R2 = CCl3CH2, R3 = MeCHCl (e),
R1 = i-Pr, R2 = R3 = Me (j), Et (k), R2 = R3 = 1,2-C6H4, R1 =
Me (g), i-Pr (f), n-Pr (h), t-Bu (i).
Intermediates with P–C bond proved to be unstable
and we failed yet to synthesize them.
With the purpose of preparing intermediate VI PCl3
was purified from the HCl impurity and was reacted
with aldehydes. But under these conditions no
formation of new phosphorus-containing products was
observed. In 31P NMR spectrum of the reaction mix-
ture only one signal at δP 220 ppm was observed cor-
responding to the phosphorus atom in compound Ia.
For the successful synthesis of compounds VIa-VIc
the best ratio of starting substances (PCl3, aldehyde,
and tertiary amine) is 1 : 1 : 0.03–0.05. Aldehyde is
slowly added dropwise under the intense stirring to a
mixture of purified PCl3 and amine at –5 to 0°C.
Compounds VIb,VIc were isolated in a pure state by
vacuum distillation. They are stable and can be stored
in a sealed ampule at room temperature for several
months. The structure of intermediates VI was
While performing the reaction between compounds
Ia and IIa in the presence of catalytic amounts of
tertiary amine the result of interaction crucially
depended on the order of mixing the reagents. The
addition of 3–4 drops of PCl3 to a mixture of aldehyde
and amine caused violent polymerization of compound
IIa and no formation of organophosphorus compounds
was observed. Addition of the rest amount of PCl3 did
not result in the temperature rise. After removing PCl3
in a vacuum paraldehyde XXIVa was obtained in a
high yield.
1
confirmed by their complete elemental analysis, H,
13C, and 31P NMR spectra (see the table), and chemical
transformations.
When the amount of aldehyde involved in the
reaction was increased further substitution of chlorine
atoms in PCl3 took place. While performing the
reaction of PCl3 with acetaldehyde in the presence of
2,6-dimethylpyridine in 1 : 2 : 0.01 ratio 31P NMR
At a slow addition of aldehyde IIa to a mixture of
PCl3 with the catalytic amount of tertiary amine like
triethylamine, N,N-dimethyl- and N,N-diethylanilines,
pyridine, and 2,6-diethylaniline a strongly exothermic
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 12 2013

REACTIONS OF P(III) CHLORIDES WITH ALDEHYDES: I.
1H, 13C, and 31P NMR data of primary intermediates R1R2POCHClR3
2285
δ, ppm (nJHH, nJPH и nJPC, Hz)
Comp.
no.
δP,
R1
Cl
R2
Cl
R3
mE
1H
Е1
Е2
Е3
Е4
Е5
ppm
CH3
–
6.38 d.q
(5.6, 13.9)
86.06 d (10.6)
6.35 d.t
1.81 d
–
–
178.1
177.7
VIa
24.88 s
13C
1H
Cl
Cl
Cl
Cl
p-Pr
–
–
2.1 d.t
(6.5, 7.5)
2.2 heptet
(3.8, 6.7)
36.87 s
1.55 sextet
(7.5, 7.5)
1.06 d, 1.08 d
(6.7)
0.94 t 180.42
VIb
VIc
(6.5, 15.0)
6.13 d.d
(7.5)
–
180.83
179.61
179.24
CH(CH3)2
1H
13C
1H
1H
13C
(3.8, 6.7)
94.4 d (10.0)
17.27 s,
16.63 s
Cl
Cl
Cl
CCl3
CH3
–
–
6.33 d (11.5)
–
–
–
–
184
VId
OCHClCH3
6.05–6.18 m
84.66 d,
1.83 d (6.4)
–
166.32
162.97
162.43
164.0
VIIa
27.66 s, 27.51 s
84.56 d (8.2)
6.14 d.d
Cl
CCl3CH2O
HC(CH3)2
CH3
1H
4.1 d
(5.0)
2.1 heptet
(4.0, 7.0)
0.9 d
(7.0)
–
–
VIIb
(4.0, 10.0)
161.0
OCHClCH OCHClCH3
1H
13C
–
6.00–6.15 m
1.81 d (5.6)
–
145.85
138.82
VIIIa
84.11–84.5 m 27.56–27.77 m
3
CCl3CH2O CCl3CH2O
HC(CH3)2
HC(CH3)2
1H
4.1 d
(5.0)
4.95 d.d
1.92–2.17 m
0.95 d
(6.3)
–
–
–
–
–
133.0
VIIIb
VIIIc
VIIId
VIIIe
VIIIf
(5.0, 9.0)
PhO
PhO
1H 6.90–7.15 m
5.6 d.d
1.93 d. гепt
0.9 d
(6.5)
138.0
141.0
(4.5, 9.0)
(4.5, 6.5)
CCl3CH2O OCHCl(CH3)2 HC(CH3)2
1H
1H
4.2 d (5.0)
4.1 d (5.0)
5.95–6.25 m
1.95–2.19 m
1.0 d
(6.5)
139.0
142.0
CCl3CH2O OCHClCH3
CH3
5.96–6.28 m
1.85 d (6.5)
–
138.0
141.0
CH(CH3)2
1H 6.70–7.05 m
5.5 d.d
(4.5, 9.0)
88.5 d (6.5)
1.93 d. hept
(4.5, 6.5)
33.5 s
0.9 d
(6.5)
133.0
133.1
133.0
O
O
13C
109.3 s
120.5 s
142.3 d
(6.5)
13.5 s
CH3
1H 6.85–7.15 m
5.4 d.q
(6.3, 7.5)
80.8 d (7.5)
1.37 d
(6.3)
–
–
–
VIIIg
O
O
13C
110.0 s,
120.5 s,
142.0 d
(6.3)
24.0 s
C(CH3)3
1H 6.75–7.10 m
5.3 d (9.0)
–
0.9 s
VIIIi
O
O
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2286
GAZIZOV et al.
spectrum of reaction mixture 26 h after mixing of
reagents (–5°C) contained three sets of signals: 220.0,
and 178.1, 177.8 (ratio of intensities of the latter two
was 3 : 1), and 163.3, 162.95, 162.43 ppm (3 : 2 : 1
ratio). As it was shown above, first three signals
correspond to phosphorus atom in PCl3 and
intermediate VIa. Chemical shifts of the third set of
signals correspond to a phosphorus environment
O2ClP(III) in dialkylphosphorochloridites [34, 35].
Therefore these three signals were attributed to
phosphorus atom in the intermediate VIIa. Integral
intensities of signals show that PCl3 : VIa : VIIa ratio
in the mixture is approximately makes up 1 : 8 : 11.
After careful evacuating volatile products at room
temperature and the residual pressure 0.02 mm into a
trap cooled with liquid nitrogen the 31P NMR spectrum
of the residue remained in the flask contained
practically only the set of signals corresponding to
24 h after mixing of reagents besides the signals of
phosphorus nuclei of the compounds VIa and VIIa
two new signals at δP 146.9 and 138.7 ppm were
observed in 1 : 5 ratio. These values of chemical shifts
correspond to a phosphorus environment O3P(III) in
trialkyl phosphites [34, 35]. Therefore they were
attributed to one more intermediate VIIIa, namely, to
tri(1-chloroethyl) phosphite. The ratio of compounds
VIa, VIIa, and VIIIa in the reaction mixture was
1 : 9 : 14. Thus intermediate VIIIa is the main
component of the mixture. New doublet at δ 1.81 ppm
(JHH 5.6 Hz) in the 1H NMR spectrum of a mixture was
attributed to the methyl group protons, and the signal
of methine group protons overlapped with the
multiplet of methine protons from compound VIIa at
δ 6.11 ppm. In the 13C NMR spectrum new multiplets
at δC 27.58–27.77 and δC 84.11–84.52 ppm were
found. They were attributed to the methyl and methine
group carbon atoms of compound VIIIa respectively.
1
compound VIIa. In the H NMR spectrum the protons
of methyl groups give a doublet at δ 1.83 ppm (JHH
6.4 Hz), and the methine group protons give a
multiplet at δ 6.1 ppm. It is shifted upfield as
compared to the methine proton signal in the
intermediate VIa (δ 6.38 ppm). 13C NMR spectrum
contains two upfield singlets at δC 27.66 and 27.51 ppm
belonging to nonequivalent carbon atoms of two
methyl groups and two downfield doublets at δC
84.66 ppm (2JPC 8.2 Hz) and 84.56 ppm (2JPC 5.3 Hz)
corresponding to methine carbon atoms. The structure
of intermediate VIIa is confirmed also by satisfactory
elemental analysis and its oxidation to the corres-
ponding phosphate. The mixture collected in the trap
according to NMR spectral data consists of PCl3,
trimer XXIVa, and intermediate VIa.
At the attempt to distil this mixture in a vacuum it
rather rapidly decomposes to give the intermediate
VIa, PCl3 and acetaldehyde. Note that the previously
suggested isomerization [2, 3] of compound VIIIa to
P(IV) derivative does not take place. Instead it decom-
poses while heating to give the starting products.
Hence, by the reaction of PCl3 with aldehydes in
the presence of catalytic amounts of tertiary amine three
types of primary intermediates VIa, VIIa, and VIIIa
were synthesized for the first time. They differ from
one another by the degree of substitution of chlorine
atoms in PCl3 with 1-chloroalkoxy group. The
formation of intermediates VI–VIII is a reversible
process. The accumulation of 1-chloroalkoxy groups at
P(III) atom decreases the stability. Intermediates VIIa
and VIIIa exist only in the cold. At room temperature
and above it, and at removing the decomposition
products in a vacuum they completely convert in
starting compounds. Intermediates VIa–VIc can be
distilled in a vacuum. They may be stored for a long
time in sealed ampules and decompose only at
prolonged heating in a vacuum.
At the attempts to distil compound VIIa in a
vacuum it gradually decomposes to give volatile
1
products. H and 31P NMR spectra of the decom-
position products (taken at –10°C) collected in the trap
cooled with liquid nitrogen show that they are
compounds Ia, IIa, and VIa. Special experiments
showed that at prolonged heating in a vacuum to 100°C
intermediate VIa completely decomposed to PCl3 and
aldehyde.
The reaction of P(III) chlorides with chloral must
be considered specially. Chloral is an aldehyde whose
carbonyl oxygen exhibits decreased nucleopilicity due
to the effect of three electron-acceptor chlorine atoms.
As known, P(III) chlorides exhibiting electrophilic
reactivity under the conditions of acidic catalysis do
not react with chloral [15, 16].
At further increase in the amount of aldehyde the
substitution of chlorine atoms at P(III) becomes non-
selective, and a series of products with various degree
of substitution of chlorine atoms with 1-chloroethoxy
group is formed. At performing the reaction between
compounds Ia, IIa, and XVII at 1 : 4 : 0.02 ratio at
–5°C in 31P NMR spectrum of reaction mixture taken
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 12 2013

REACTIONS OF P(III) CHLORIDES WITH ALDEHYDES: I.
2287
We suggested that chloral molecule activated with
tertiary amine would react at least with such active
electrophile as PCl3. It really occurred that under
considerably mild conditions (0 to –5°C) chloral reacts
with PCl3 in the presence of catalytic amount of
tertiary amine (1 : 1 : 0.03) to give primary inte-
rmediate VId.
phosphite. Compound VIIIi was isolated pure by
vacuum distillation (see the table). Other substances
were studied without purification after removing volatile
substances in a high vacuum (see the table).
Diphenyl posphorochloridite Ic reacts with
isobutyric aldehyde analogously.
·
B
(PhO)2PCl + Me2CHCHO
(PhO)2POCH(Cl)CHMe2
CCl3CHO + PCl3 ⇄ CCl3CHOPCl2
|
Ic
VIIIc
Cl
According to 31P NMR data the ratio of compounds
VIIIc (δP 130 ppm) and Ic (δP 156 ppm) after the
establishment of the equilibrium was 10 : 1. For the
confirmation of structure of the intermediate the
aldehyde was quickly removed from the ccoled
VId
Five hours after mixing of reagents 31P NMR
spectrum of reaction mixture contained three signals at
220, 184, and 164 ppm in 1 : 8 : 1 ratio. Intermediate
VId occurred to be the main reaction product, and the
signal with δP1184 ppm was attributed to its prosphorus
atom. In the H NMR spectrum only one doublet at
6.33 ppm (JPH 11.25 Hz) corresponding to methine
proton was observed. Another P(III) chlorides showing
electrophilic reactivity under the analogous conditions
did not show the signs of reaction with chloral.
1
reaction mixture in a high vacuum, and H NMR
spectrum of the residue was recorded (see the table).
By an example of the reactions of catechol
chlorophosphite we have established the character of
dependence of conversion of starting products and the
stability of the intermediates on the structure of
aldehyde. According to 31P NMR data at catechol
chlorophosphite: RCHO : alkyl vinyl ether ratio 1 : 2 : 1
the conversion of chlorophosphite was 58% when R =
Me, 65% when R = n-Pr, and 75% when R = i-Pr. At
the increase in the amount of aldehyde involved in the
reaction the conversion of catechol chlorophosphite
sharply increased. At 1 : 7 : 2 ratio of starting
substances the conversion of catechol chlorophosphite
reached 100% when R = i-Pr and t-Bu, and 90% when
R = Me, and n-Pr. Intermediate VIIIi was distilled
without decomposition. According to 31P NMR data
the catechol chlorophosphite content in distillate was
15% at R = i-Pr, 40% at R = n-Pr, and 50% at R = Me.
These data show that the stability of the intermediates
VIII increases with the increase in donor properties of
the aldehyde fragment.
Another method for preparing primary inter-
mediates is connected with the use of alkyl vinyl
ethers. Alkyl vinyl ethers were mixed at room
temperature with catechol chlorophosphite, and
isobutyric aldehyde was added to this mixture. Pre-
liminary purification of catechol chlorophosphite from
the HCl admixture was not carried out. It occurred that
in the 1H NMR spectrum of the distilled product VIIIf
multiplets at 3.9 and 1.0 ppm were observed. Their
intensity varied from the experiment to experiment.
These signals were attributed to the products of
polymerization of alkyl vinyl ethers.
O
O
POCHR
Cl
PCl + RCHO
O
O
Ib
It was important also to establish the character of
the effect of substituents at P(III) on the stability of
primary intermediates VI–VIII. The above data
concerning the two direct methods of synthesis of the
intermediates VI, VIIb, and VIIIf–VIIIi show that
introduction of more electropositive substituents like
1-chloroethoxy, phenoxy, or phenylene-1,2-dioxy
group instead of chlorine atoms on P(III) decreases the
stability of these compounds. As known, tris(2,2,2-
trichloroethyl)phosphite does not enter the Michaelis–
Arbuzov reaction even with such strong electrophiles
as α-chloroethers [36]. Evidently trichloroethoxy
VIII, R = i-Pr (f), Me (g), n-Pr (h), t-Bu (i).
With the purpose of removing these admixtures
catechol chlorophosphite after primary treatment with
alkyl vinyl esters was distilled into the reaction flask,
and then alkyl vinyl ethers and aldehyde were added.
In this way compound VIIIf was synthesized. After
distillation it did not contain admixtures except 15% of
starting catechol chlorophosphite. The improved
protocol was used for the synthesis of new
intermediates VIIIg–VIIIi from catechol chloro-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 12 2013

2288
GAZIZOV et al.
group is sufficiently strong acceptor of electrons, and
nucleophilicity of P(III) sharply decreases. We
suggested that introduction of 2,2,2-trichloroethoxy
groups to P(III) atom must lead to an increase in the
stability of the primary intermediate.
EtO(MeCHClO)PCl
Et(MeCHClO)PCl
VIIc
VIId
Hence, by introduction of several chlorine atoms
into the alkyl groups of dialkyl phosphorochloridites
we managed to direct the reaction towards the
formation of primary intermediates VIIIa, VIIIb
instead of the polymeric products.
Really, in the reaction of bis(2,2,2-trichloroethyl)
phosphorochloridite Id with aldehyde in presence of
alkyl vinyl ethers as a catalyst intermediate VIIIb was
obtained. It is stable at room temperature for a long time.
Analogous results were obtained also by replace-
ment of ethoxy group in ethyl phosphorodichloridite
by 2,2,2-trichloroethoxy one. At the reaction of 2,2,2-
trichloroethyl phosphorodichloridite Ie with the
twofold excess of isobutyraldehyde in the presence of
alkyl vinyl ethers the substitution of the first, and then
of the second chlorine atom with 1-chloroalkoxyl
group takes place. Hence, after 24 h of keeping the
reaction mixture at room temperature its 31P NMR
spectrum contains three signals at δP 164, 161
(intensity ratio 2 : 1) and at δP 179 ppm.
(CCl3CH2O)2PCl + i-PrCHO ⇄ (CCl3CH2O)2POCHPr-i
|
Cl
Id
VIIIb
Meanwhile, heating in a vacuum leads to its
decomposition with the liberation of aldehyde
molecule before reaching the boiling point. Therefore
compound VIIIb was identified as a crude product
after removing all volatile admixtures in a high
vacuum. Its spectral characteristics are presented in the
table. This substance was also synthesized by the third
indirect method by means of the reaction of
intermediate VIb with 2,2,2-trichloroethanol in the
presence of tertiary amine. Spectral characteristics of
compound VIIIb obtained by different methods are
identical. All the attempts to prepare primary inter-
mediates by direct method from ethyl phosphoro-
dichlorite and ethyldichlorophosphine failed. The
reaction mixture was a very viscous liquid, and in its
NMR spectra the signals belonging to P(III) atoms and
the protons of CH3CH·(Cl)OP(III) fragment were
absent. Evidently, primary intermediates contain-ing
EtO[MeCH(Cl)O]P(III) and Et[MeCH(Cl)O]P(III)
fragments are still less stable than compounds VIIa
and VIIIa. Another side of the problem is that P(III)
chlorides which can exhibit electrophilic as well as
nucleophilic properties in the reactions with the same
reagent, for example, nonsubstituted dialkyl phospho-
rochloridites, react with aldehydes to give polymeric
products [22]. The nucleophilicity of P(III) atom in bis-
(2,2,2-trichlo-roethyl)- Ic and di(1-chloroethyl) chloro-
phosphites VIIa is evidently decreased due to the
effect of two electron-acceptor 2,2,2-trichloroethyl or
1-chloroethyl groups. They exhibit only electro-philic
properties in the reactions with aldehydes leading to
the formation of intermediates VIIIb and VIIIa. At the
same time in ethyl (1-chloroethyl) phosphoro-
chloridite VIIc and (1-chloroethyl) ethylphosphono-
chloridite VIId the nucleophilicity of P(III) atom is
sufficiently high to react with aldehydes analogously
to nonsubstituted dialkyl phosphorochloridites.
CCl3CH2OPCl2 + Me2CHCHO
Ie
Cl
|
⇄ CCl3CH2OPOCHCHMe2
|
Cl
VIIb
Me2CHCHO
CCl3CH2OP(OCHCHMe2)2
|
Cl
VIIId
First two of them correspond to phosphorus envi-
ronment O2ClP(III) [34, 35], in dialkyl phosphoro-
chloridites. Therefore they were attributed to phos-
phorus atom in the intermediate VIIb. Third signal in
the spectrum belongs to the phosphorus atom of
starting dichlorophosphite Ie. From the integral
intensity of signals the ratio of compounds Ie and VIIb
is 1 : 1. After 6 days in 31P NMR spectrum of reaction
mixture weak signals at δP 164, 161, and 22 ppm and
intensive signals at δP 142 and 139 ppm (ratio 3 : 1)
were observed. First two signals of these mixtures are
attributed to phosphorus atom in compound VIIb, the
third signal, to P(IV) atom, and δP values of the last
two signals correspond to phosphorus environment
O3P(III) [34, 35] in trialkyl phosphites. Therefore they
were attributed to phosphorus atom in the intermediate
VIIId. Analogous intermediate VIIIe was synthesized
from acetaldehyde. Spectral characteristics of com-
pounds VIIId, VIIIe are listed in the table.
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REACTIONS OF P(III) CHLORIDES WITH ALDEHYDES: I.
2289
Finally, intermediates VIIIj, VIIIk containing two
nonsubstituted alkoxy groups on P(III) were prepared
by indirect method reacting compound VIc with the
corresponding alcohols in the presence of tertiary
amine. It turned out that they are stable in strongly
diluted ether solutions at 0 to –5°C. Their structure
was confirmed by NMR spectra and by oxidation to
the corresponding phosphates. At removing of solvent
or increasing the temperature to 20–25°C an exothermic
reaction leading to the formation of viscous liquid
takes place. In NMR spectra of the latter signals cor-
responding to Me2CHCH(Cl)OP(III) fragment were absent.
The above data also permit to come to the
conclusion that the stability of primary intermediates
increases with the increase in electron-acceptor
properties of substituents at P(III) and the donor
properties of aldehyde fragment.
R
+δ'
+δ
Nu
R
R
P
_δ
Cl
CH
OP
+δ
Nu
Cl_
O
Nu + CH
CH
O
ХХV
ХХVI
R
R
_δ
+δ
Nu
or
O
CH
Cl
Nu + ClCHOP
P
ХХVII
The mechanism of catalysis of the reaction of P(III)
chlorides with aldehydes with tertiary amines or alkyl
vinyl ethers we did not study specially. But it may be
suggested that the soft interaction of nucleophile with
carbonyl carbon atom increases nucleophilic properties
of the carbonyl oxygen. Carbonyl group is activated
and simultaneously its electrophilic center is protected
from the addition of the second aldehyde molecule.
The aldehyde molecule XXV activated with
nucleophile reacts with P(III) chlorides through the
charge separation XXVI or the synchronic cyclic
electron transfer XXVII to give the first intermediate
with the liberation of catalyst.
b. Treating with alkyl vinyl ethers. Catechol
chlorophosphite, 10 g (0.06 mol), was cooled to 10°C
and 4.13 g (0.06 mol) of ethyl vinyl ether was added.
α-Chloroether obtained and excess ethyl vinyl ether
were removed in a vacuum, and catechol chloro-
phosphite was distilled in a vacuum directly into the
reaction flask. Another alkyl vinyl ethers like vinyl
butyl and vinyl isobutyl ethers may be used.
Reactions of P(III) chlorides with aldehydes. a.
Reaction of purified PCl3 with acetaldehyde in the
absence of catalyst. Acetaldehyde, 3.2 g (0.073 mol),
was added dropwise under the intensive stirring to 10 g
(0.073 mol) of phosphorus trichloride twice treated
with N,N-dimethylaniline at –5°C. No increase in
temperature was observed. The mixture obtained was
kept for 27 h in the freezer. In 31P NMR spectrum only
one singlet at 220 ppm corresponding to PCl3 was
observed.
EXPERIMENTAL
NMR spectra were recorded on spectrometers 7.0 T
1
IBM/Bruker AF 300 (300 MHz H, 75.5 MHz 13C,
1
121.5 MHz 31P), Tesla BS-567A (100 MHz H), and
Bruker MSL-400 (162 MHz 31P). Chemical shifts of
hydrogen and carbon are given with respect to TMS,
and of phosphorus, with respect to 85% phosphoric
acid.
b. Reaction of PCl3 with aldehydes in the presence
of tertiary bases. Phosphorus trichloride, 7.55 g
(0.055 mol), was added dropwise under the intensive
stirring to a mixture of 7.26 g (0.168 mol) of acetal-
dehyde and 0.246 g (0.0017 mol) of N,N-diethylaniline
at –5 to 0°C. The addition of the first three drops of
PCl3 caused strong heat evolution and the temperature
of reaction mixture rose to 25°C. At the addition of the
rest amount of phosphorus trichloride at 0°C no
increase in temperature was observed. 1H NMR
spectrum, δ, ppm: 1.29 d (3JHH 5.1 Hz, 3H, Me), 4.94 q
Removing HCl impurity from P(III) chlorides. a.
Treating with tertiary amine. Commercial PCl3, 25.5 g
(0.186 mol), was mixed at room temperature with 3.5 g
(0.029 mol) of N,N-dimethylaniline, and PCl3 was
distilled directly into the reaction flask. For this
purpose another nitrogen-containing organic bases like
pyridine, 2,6-dimethylpyridine, and triethylamine can
be used.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 12 2013

2290
GAZIZOV et al.
wise at
(3JHH 5.1 Hz, 1H, CH). 13C NMR spectrum, δC, ppm:
19.89 s Me, 97.5 s CH (paraldehyde). 31P NMR
spectrum, δP, ppm: 220 (PCl3). PCl3 was removed in a
vacuum (120 mm) and the residue was distilled to give
4.1 g of paraldehyde.
–5°C to a mixture of 9.33 g (0.068 mol) of
PCl3 and 0.025 g (0.0017 mol) of N,N-diethylaniline.
The reac-tion mixture was kept for 26 h at –5°C, its 31P
NMR spectrum was taken, and volatile components
were distilled in high vacuum in a trap cooled with
liquid nitrogen. According to 31P, H, and 13C NMR
1
1-Chloro 2-methylpropyl phosphorodichloridite
VIc. To a mixture of 10 g (0.073 mol) of PCl3 and
0.139 g (0.0036 mol) of 2,6-dimethylpyridine 5.26 g
(0.073 mol) of isobutyraldehyde was added dropwise.
The reaction mixture was kept for 18 h and diluted
with 15 ml of anhydrous hexane. Insignificant amount
of precipitate was filtered off, the solvent was
removed, and the residue was distilled in a high
vacuum to give 8.17 g (53%) of product VIc, bp 30°C
(0.01 mm Hg), d420 1.3029. Found, %: C 22.74, H 3.81;
Cl 50.51; P 14.65. C4H8Cl3OP. Calculated, %: C
22.91; H 3.82; Cl 50.83; P 14.79. NMR spectral data
are listed in the table.
spectra (see the table) the residue is sufficiently pure
product VIIa. Found, %: Cl 47.85, P 13.34.
C4H8Cl3O2P. Calculated, %: Cl 47.23, P 13.74.
Crude compound VIIa, 3 g, was heated gradually
to 70°C at the residual pressure 0.01 mm. Progressive
increase in residual pressure to 0.1 mm took place, and
the distillation flask remained almost empty. In 31P
NMR spectrum of volatile compounds collected in the
nitrogen-cooled trap signals with δP 220 and 178.1,
177.9 ppm were observed at –10°C. They were
attributed to phosphorus atom in PCl3 and the
1
compound VIa respectively. In H NMR spectrum of
this preparation signals were present belonging to
acetaldehyde [δ 2.1 ppm, d (CH3CO); 9.7 ppm, q
(CHO)] and to compound VIa [δ 1.81 ppm, d.d (CH3);
6.38 ppm, d.q (PCH)]. Weak signals of trimer protons
were also observed.
1-Chlorobutyl phosphorodichloridite VIb. This
com-pound was obtained analogously from 19.53 g
(0.142 mol) of PCl3, 0.42 g (0.0028 mol) of N,N-
diethylaniline, and 10.24 g (0.142 mol) of butyral-
dehyde. Yield of product VIb 16.04 g (54%), bp 30–
32°C (0.02 mm Hg), nD20 1.4821, d420 1.2897. Found,
%: C 23.13, H 4.02, Cl 50.67, P 14.60. C4H8Cl3OP.
Calculated, %: C 22.91, H 3.82, Cl 50.83, P 14.29.
NMR spectral data are listed in the table.
Tri(1-chloroethyl) phosphite VIIIa. Acetaldehyde,
15.51 g (0.352 mol), was added dropwise with
intensive stirring at –5 to 0°C to a mixture of 12.12 g
(0.088 mol) of PCl3 and 0.43 g (0.0044 mol) of 2,6-
1
1-Chloroethyl phosphorodichloridite VIa. Vacuum
distillation of the reaction mixture prepared from 18.36 g
(0.134 mol) of PCl3, 0.4 g (0.0027 mol) of N,N-
diethylaniline, and 5.9 g (0.134 mol) of acetaldehyde
gave 12.8 g of a mixture of product VIa and paral-
dehyde XXVIIa (3:1 according to 1H NMR spectrum).
NMR spectral data are listed in the table. 3 g of this
mixture was heated at 20–90°C in a vacuum and
volatile products were collected in a trap cooled with
dimethylpyridine. After 24 h of keeping at –5°C H,
13C, and 31P NMR spectra of this mixture at the same
temperature were registered (see the table). Crude
product, 3 g, was gradually heated in a high vacuum at
the progressive increase in temperature from 23 to 80°C.
Volatile products were collected in a trap cooled with
liquid nitrogen. 31P NMR spectrum of a mixture from
1
the trap, δP, ppm: 220 (PCl3), 178.1, 177.8 (VIa). H
NMR spectrum, δ, ppm: IIa: 2.1 d (MeCO, 3JHH 3 Hz),
1
3
9.7 q (CH, JHH 3 Hz); paraldehyde: 1.29 d (CH3,3JHH
liquid nitrogen. H NMR spectrum of condensate, δ,
ppm: 2.1 d, 9.7 q, IIa; 1.29 d, 4.94 q, XVIIa. 31P NMR
spectrum, δP, ppm: 220, PCl3.
5.1 Hz), 4.9 q (CH, 3JHH 5.1 Hz ); VIa: 1.81 d, (Me,
JHH 5.6 Hz); 6.38 d.q (CH, 3JHH 5.6 Hz, 2JPH 13.0 Hz).
1,2,2,2-Tetrachloroethyl phosphorodichloridite VId.
Chloral, 17.38 g (0.118 mol), was added dropwise at
–5°C to a mixture of 16.2 g (0.118 mol) of PCl3 and
0.35 g (0.0024 mol) of N,N-diethylaniline. The reac-
tion mixture was stirred for 1 h at this temperature.
(1-Chloro-2-methylpropyl) diphenyl phosphite
VIIIc. Isobutyric aldehyde, 1.87 g (0.026 mol), was
added dropwise at 0–1°C to a mixture of 6.45 g
(0.026 mol) of diphenyl phosphorochloridite and 0.053 g
(0.00052 mol) of triethylamine. After keeping for four
days at room temperature an insignificant amount of
precipitate was filtered off. Volatile compounds were
removed in a high vacuum. In 31P NMR spectrum of
reaction mixture two signals at δP 130 and 156 ppm in
10 : 1 ratio (see the table) were observed.
1
Data of H and 31P NMR spectra of the crude product
VId after removing volatile components in a vacuum
are presented in the table.
Di(1-chloroethyl) phosphorochloridite VIIa.
Acetaldehyde, 5.52 g (0.1256 mol), was added drop-
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REACTIONS OF P(III) CHLORIDES WITH ALDEHYDES: I.
2291
Catechol (1-chloro-2-methylpropyl) phosphite
VIIIf. Catechol chlorophosphite, 17.79 g (0.10 mol), was
cooled to 10°C, and 14.7 g (0.2 mol) of ethyl vinyl
ether was added dropwise to it. Isobutyraldehyde,
50.47 g (0.7 mol), was added dropwise to a mixture
obtained. The resulting mixture was kept at room
temperature for three days. After that volatile products
were removed in a high vacuum to give 24.5 g of crude
product. Its 31P NMR spectrum contained one signal at
133 ppm (see the table), nD20 1.5220, d420 1.2459. The
conversion of catechol chlorophosphite was 100%. At
the distillation in high vacuum practically one fraction
was collected. Its 31P NMR spectrum contained two
signals at δP 174 and 133 ppm in 1 : 5.7 ratio. This
means that 15% of compounds VIIIf decomposes to
catechol chlorophosphite.
trichloroethyl) phosphorochloridite, 19 g (0.052 mol),
was cooled to 10°C and 7.5 g (0.104 mol) of ethyl
vinyl ether was added. Then 18.7 g (0.26 mol) of
isobutyraldehyde was added dropwise to this mixture.
After 5 days volatile substances were removed in a
vacuum, and 18.1 g of crude product was obtained. Its
31P NMR spectrum besides the intense signal at δP
138 ppm contained also weak signal at 165 ppm (see
the table).
b. 1-Chloro-2-methylpropyl phosphorodichloridite,
9.7 g (0.046 mol), was added dropwise at –2 to –4°C to
a solution of 13.89 g (0.093 mol) of triethylamine and
9.37 g (0.093 mol) of trichloroethanol in ether. After
stirring for 1 h at this temperature amine hydrochloride
was filtered off, and volatile compounds were removed
in a vacuum. 31P NMR spectrum of the residue
contained intensive signal at δP 138 ppm and weak
signals at 165 and 22 ppm. In the course of prolonged
keeping no change in the intensity of signals is
Catechol (1-chloro-2,2-dimethylpropyl) phosphite
VIIIi. Ethyl vinyl ether, 2.5 g (0.035 mol), was added
dropwise to 6.14 g (0.035 mol) of pyrocatechol
chlorophosphite cooled to 10°C, and then to this
mixture 6.06 g (0.07 mol) of trimethylacetaldehyde
was added dropwise. After 3 days volatile products
were removed in a vacuum. The distillation in a high
vacuum gave 6 g (77%) of product VIIIi, bp 74–75°C
(0.02 mm Hg), nD20 1.5168, d420 1.2159. Found, %: C
50.52; H 5.29; Cl 13.85; P 11.61. C11H14ClO3P.
Calculated, %: C 50.67; H 5.37; Cl 13.60; P 11.88.
1
observed. H NMR spectra of compounds obtained by
different methods are identical.
Di(1-chloroethyl) (2,2,2-trichloroethyl) phosphite
VIIIe. 2,2,2-Trichloroethyl phosphorodichloridite,
29.8 g (0.119 mol), was cooled to 10°C and 17.2 g
(0.24 mol) of ethyl vinyl ether was added to it. After
that 36.7 g (0.83 mol) of acetaldehyde was added
dropwise to the mixture obtained. After 5 days volatile
substances were removed in a vacuum. In 31P NMR
spectrum of reaction mixture signals at δP 141 and 138,
163, and 22 ppm were present. First two of them
correspond to P(III) atom in compound VIIIe. Total
integral intensity of the first two signals relates to the
intensities of the second and third signals as 8 : 1 : 2.
Catechol (1-chlorobutyl) phosphite VIIIh. Ethyl
vinyl ether, 4.3 g (0.06 mol), was added drop-wise to
5 g (0.03 mol) of catechol chlorophosphite cooled to
10°C, and 15.14 g (0.21 mol) of butyraldehyde was
added dropwise to this mixture. After 3 days two
signals at δP 174 and 133 ppm in 1 : 9 ratio were
observed in 31P NMR spectrum. Thus the conversion
of catechol chlorophosphite was 90%.
1
The description of H NMR spectrum of compound
VIIIe is presented in the table.
Catechol (1-chloroethyl) phosphite VIIIg. Ethyl
vinyl ether, 4.3 g (0.06 mol) was added dropwise to 5 g
(0.03 mol) of catechol chlorophosphite as in the
previous experiments, and then 9.25 g (0.21 mol) of
acetaldehyde was added dropwise to this mixture. Two
signals at δP 174 and 133 ppm in 1 : 9 ratio were
observed in 31P NMR spectrum. Thus the conversion
of catechol chlorophosphite was 90%. After distillation
of reaction mixture practically one fraction was
obtained. Its 31P NMR spectrum contained the same
two signals at 174 and 133 ppm in 1 : 1 ratio indicating
about 40% decomposition of compound VIIIg.
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