Synthesis and reactivity of substituted α-carbonylphosphonites and their derivatives

Article abstract of DOI:10.1002/hc.21024

Convenient methods for the synthesis of functionalized organophosphorus compounds containing carbonyl groups as well as di- or trialkoxymethyl fragments attached to phosphorus, and their derivatives, starting from the available derivatives of trivalent phosphorus acids, are proposed, and some properties of the new functionalized organophosphorus compounds are presented. So, the alkylation and acylation reaction of (dialkoxymethyl) phosphonites and their analogs have been studied. It is found that the Arbuzov rearrangement of these compounds was accompanied by the phosphorus-carbon bond cleavage with unique retention of the three-coordinate phosphorus.

Full text of DOI:10.1002/hc.21024

Heteroatom Chemistry
Volume 00, Number 0, 2012
Synthesis and Reactivity of Substituted
α-Carbonylphosphonites and Their Derivatives
Andrey A. Prishchenko, Mikhail V. Livantsov, Olga P. Novikova,
Ludmila I. Livantsova, and Valery S. Petrosyan
Department of Chemistry, M. V. Lomonosov Moscow State University, Moscow, 119991 Russia
Received 19 September 2011; revised 12 January 2012, 19 March 2012
recent years; rather convenient methods of synthesis
ABSTRACT: Convenient methods for the synthe-
of these compounds have been proposed, and their
sis of functionalized organophosphorus compounds
properties have been studied in detail [1–6]. Vari-
containing carbonyl groups as well as di- or tri-
ous biological activities of these compounds were
alkoxymethyl fragments attached to phosphorus, and
found [2], and the most promising results were ob-
their derivatives, starting from the available deriva-
tained for trisodium phosphonoformate (foscarnet
tives of trivalent phosphorus acids, are proposed, and
sodium) and its derivatives as potential prodrugs
some properties of the new functionalized organophos-
for human acquired immunodeficiency syndrome
phorus compounds are presented. So, the alkylation
(AIDS) chemotherapy [7]. However, the correspond-
and acylation reaction of (dialkoxymethyl) phospho-
ing compounds of tricoordinated phosphorus, which
nites and their analogs have been studied. It is found
are the key substances for the synthesis of this type
that the Arbuzov rearrangement of these compounds
of compound, are not available and are almost un-
was accompanied by the phosphorus–carbon bond
known (cf. [4]). The present paper is devoted to the
cleavage with unique retention of the three-coordinate
synthesis and study of the reactivity of functional-
ꢀ
C
phosphorus. 2012 Wiley Periodicals, Inc. Heteroatom
ized phosphonites and their analogs with di- and tri-
Chem 00:1–21, 2012; View this article online at wileyon-
alkoxymethyl or carbonyl fragments, which possess
linelibrary.com. DOI 10.1002/hc.21024
promising useful properties.
RESULTS AND DISCUSSION
INTRODUCTION
Previously unknown esters of (dialkoxymethyl)
The functionalized organophosphorus compounds
phosphonous acid containing a trivalent phos-
containing in the α-position to phosphorus the car-
phorus atom and a formate group, are of great
bonyl groups or their derivatives such as di- and
interest as a basis for the synthesis of new types
trialkoxymethyl fragments are of great interest in
of organophosphorus compounds with three-,
both theoretical investigations and for practical ap-
four-, and five-coordinated phosphorus. For the
plications. These compounds with tetracoordinated
synthesis of (dialkoxymethyl)phosphines and
phosphorus have been intensively investigated in
their derivatives, we conducted a detailed study
of dialkoxymethylation of various PH acids and
their derivatives with trialkyl orthoformates under
various conditions (cf. [8]). So, the reaction of
Dedicated to Professor Ivan F. Lutsenko (1912–1993).
Correspondence to: Andrey A. Prishchenko; e-mail:
hypophosphorus acid with trialkyl orthoformates
in the ratio 1:2 in the presence of p-toluenesulfonic
acid as a catalyst proceeds via alkoxyphosphines
oxides A and leads to unstable phosphonites
aprishchenko@yandex.ru
Contract grant sponsor: Russian Foundation for Basic Re-
search.
Contract grant numbers: 11-03-00402 and 12-03-00003.
2012 Wiley Periodicals, Inc.
c
ꢀ
1

2
Prishchenko et al.
B (cf. [9,10]), which are used to synthesize silicon-containing (dialkoxymethyl)phosphonites 1–4. The corre-
sponding reaction of phosphonites B with an excess of bis(trimethylsilyl)amine may be carried out without
their isolation from the reaction mixture ((Eq. (1)):
RO
RO
(Me3Si)2NH
– NH3, – NH
HC(OR)3, Cat
ROH, HCOOR
HC(OR)3, Cat
PCH(OR)2
H2POH
O
H2POR
PCH(OR)2
Cat
−
−
ROH
3
H
Me3SiO
O
O
B
1–4
A
R = Me (1), Et (2), Pr (3), Bu (4)
Cat = 4-MeC6H4SO3H
(1)
It was found that the reaction of hypophosphorus acid with an excess of trialkyl orthoformate in the presence
of boron trifluoride etherate as a catalyst is a multistage process, the final result of which is determined by the
conditions of the reaction. Boron trifluoride etherate significantly accelerates the formation of intermediates
A and also makes possible a second esterification stage, that is, the formation of dialkoxyphosphines C, which
react rapidly with a third molecule of orthoformate to form (dialkoxymethyl)phosphonites 5–8. It should be
noted that phosphonites 5–8 may be obtained with good yields only if the catalyst is subsequently removed
using diethylamine. If this is not done, one observes a further reaction of these phosphonites with an excess
of orthoformate, which leads to phosphinates 9 and 10 (Eq. (2))
HC(OR)3
1. HC(OR)3, Cat 2. Et2NH
HC(OR)3, Cat
H2POH
O
H2POR
(RO)2PH
− ROH, HCOOR
− Et NH Cat
2
− ROH,
− ROH, HCOOR
O
C
A
HC(OR)3, Cat
(RO)2PCH(OR)2
ROP[CH(OR)2]2
− ROR
O
5–8
9,10
R = Me (5), Et (6,9), Pr (7,10), Bu (8)
Cat = Et2O BF3
(2)
The formation of phosphonite 8 and phosphine 11 was studied in detail using the reactions of dibutoxyphos-
phine or dibutylphosphine with trialkyl orthoformates. So, dibutoxyphosphine as well as dibutylphosphine
react slowly with orthoformates even at 20◦C; the rate of the reaction is significantly dependent on electronic
and steric effects of the substituents on the phosphorus atom. According to 31P NMR data, in 24 h at 20◦C,
30% of starting dibutoxyphosphine reacts, whereas 60% of the more nucleophilic dibutylphosphine reacts,
yet under the same conditions. Note that the scheme of this reaction is similar to the Arbuzov reaction. So,
the electrophilic carbon atom of orthoformate attacks the trivalent phosphorus atom, and the decomposition
of intermediate D leads to (dialkoxymethyl)phosphonite 8 or phosphine 11 in high yield (Eq. (3))
+
−
X2PH + HC(OR)3
X2PCH(OR)2 OR
X2PCH(OR)2
−ROH
H
8,11
D
X = BuO (8), Bu (11); R = Bu (8), Et (11)
(3)
Also, it was found that the rate of the given reaction increases under conditions of activation of orthoformates
by boron trifluoride etherate as a catalyst due to formation of significantly more electrophilic carboxonium
complex E (Eq. (4); cf. [11])
+
+
BF3
Et2O
X2PH
−
−
HC(OR)3
HC(OR)2 ROBF3
X2PCH(OR)2 ROBF3
X2PCH(OR)2
− Et2O
− ROH, − BF 3
H
E
8,11,12
X = BuO (8), Bu (11), i-Pr (12)
R = Bu (8), Et (11,12)
(4)
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Synthesis and Reactivity of Substituted α-Carbonylphosphonites and Their Derivatives
3
Note that in the presence of a catalyst, the formation of dialkoxymethyl derivatives of trivalent phosphorus
takes place at 20◦C in 1.5 h with a yield of up to 90%. An increase in the volume of the substituents on the
phosphorus atom in starting diisopropylphosphine decreases the yield of the corresponding phosphine 12 to
30% (in 24 h), whereas di-tert-butylphosphine does not react at all. Also, the general method of synthesis of
di- and (trialkoxymethyl)phosphines is realized by us via the interaction of lithium dialkylphosphides with
dialkoxy- and trialkoxy-substituted carbonium tetrafluoroborates, which are specially prepared as described
in [12,13]. Really, this reaction proceeds quickly even under cooling to −30◦C to give the corresponding
phosphines 12–15 with bulky substituents at phosphorus and alkoxy groups (Eq. (5))
+
−
X2PCH(OR)2
(RO)2CH BF4
X2PLi
+
− LiBF4
12,13
+
−
X2PC(OR)3
(RO)3C BF4
X2PLi
+
− LiBF
4
14,15
X = i-Pr (12), t- Bu (13,15), Bu (14)
R = Et (12,13,15), i-Pr (14)
(5)
It should be noted that dialkyl(trialkoxymethyl)phosphines 16 and 17 without bulky substituents are easily
transformed by distillation into bisphosphines 18 and 19 and tetraalkyl orthocarbonates (Eq. (6)). These
intermediates 16 and 17 were registered only by 31P NMR spectroscopy in the mixtures before distillation
2 (RO)+3C BF4
+
−
2 X2PC(OR)3
(X2P)2C(OR)2
2 X2PLi
−
LiBF4
−
C(OR)4
16,17
18,19
X = R = Pr (16):
X = Pr (18), Bu (19); R = Pr (18,19)
−
13.37; X = Bu, R = Pr (17):
− 12.0
P
P
(6)
The self-condensation of (dialkoxymethyl)phosphines was never observed, but the similar transformation
takes place by the interaction of corresponding dialkylphosphines with trialkyl orthoacetates in the presence
of boron trifluoride etherate as a catalyst under 20◦C (Eq. (7)). The intermediate phosphines 20–22 were
registered by NMR spectroscopy in the reaction mixtures, and bisphosphines 23–25 were obtained via
distillation with good yields (Eq. (7))
2 MeC(OR)3, Et2O BF3
2 X2PC(OR)2Me
(X2P)2C(OR)Me
2 X2PH
− MeC(OR)3
− ROH
23–25
20–22
X= Pr (20,21,23,24), Bu (22,25)
R = Et (20,22,23,25), Bu (21,24)
In 13C, 31P NMR fragment PC for
In 31P NMR for 21: δP − 20.20; for22: δP − 19.39.
1
δ
20:
105.86 d, JPC 9.8; δP − 25.44.
C
(7)
Note the corresponding phosphonite 26 was prepared similarly in high yield, and its self-condensation into
phosphonite F was not observed (Eq. (8))
2 MeC(OR)3, Et2O BF3
2 (RO)2PC(OR)2Me
[(RO)2P]2C(OR)Me
2 (RO)2PH
− ROH
− MeC(OR)3
26
F
R = Bu
(8)
Previously unavailable (trialkoxymethyl)phosphonates 27–31 were prepared using the similar methods. So,
sodium dialkyl phosphites smoothly react with trialkoxycarbonium tetrafluoroborates to give phosphonates
Heteroatom Chemistry DOI 10.1002/hc

4
Prishchenko et al.
27–31, which are also prepared from tetraalkyl pyrophosphites and tetraalkyl orthocarbonates in the presence
of boron trifluoride etherate as a catalyst with good yields (Eq. (9))
−
(RO)3C+ BF4
C(OR)4, BF3
Et2O
(XO)2PC(OR)3
O
(XO)2POP(OX)2
(XO)2PONa
− NaBF
4
− (XO) POR
2
27-31
X = Et (27), Pr (28), Bu (29,30), i-Pr (31)
R = Et (27,30,31), Pr (28), Bu (29)
(9)
In contrast to (trialkoxymethyl)phosphines, phosphonates 27–31 are not transformed into the self-
condensation products. Yet, it should be noted that these phosphonates 27–31 may be obtained with good
yields only if the catalyst is completely removed using an excess of sodium dialkyl phosphites. If it is not
done, during the distillation, we observed the decomposition of phosphonates 27–29 via intermediates G
into corresponding trialkyl phosphites and dialkyl carbonates (see the section Experimental) (Eq. (10))
+
Et2O
BF3
(RO)3P + (RO)2C=O
(RO)2P-C(OR)2
27–29
− BF
− Et2O
3
- O
O
F3B
R
G
R = Et, Pr, Bu
(10)
We have found that the unusual lability of the phosphorus–carbon bond was the characteristic property
of functionalized organophosphorus compounds with di- and trialkoxymethyl fragments as well as with
carbonyl groups at phosphorus. This unique property of the investigated compounds was successfully used
by us for the numerous synthetic purposes. So, the reaction of dibutyl(diethoxymethyl)phosphine 11 with
gaseous hydrogen chloride takes place with breakage of the P C bond in the intermediate quasiphosphonium
compound H with the formation of dibutylphosphine and unstable chloro(diethoxy)methane (Eq. (11))
+
HCl
-
Bu2PCH(OEt)2 Cl
EtCl + HCOOEt
Bu2PH + ClCH(OEt)2
Bu2PCH(OEt)2
H
H
11
(11)
A similar reaction takes place using water in the presence of catalytic quantity of hydrochloric acid and leads
to dibutylphosphine, ethyl formate, and ethanol (Eq. (12))
+
H2O
HCl
Bu2PCH(OEt)2 Cl−
EtOH + HCOOEt
Bu2PH + HOCH(OEt)2
Bu2PCH(OEt)2
− HCl
H
H
11
(12)
The scheme of this reaction assumed irreversible cleavage of the P C bond in the intermediate quasiphos-
phonium compound H by water; the attack of the external nucleophile (water) takes place at the most
electrophilic central carbon atom of the dialkoxymethyl group. This reaction does not take place in the ab-
sence of a catalyst. In both cases, the alternative formation of expected aldehyde I was not realized. Evidently,
aldehyde I is not stable and decomposes to dibutylphosphine and carbon monoxide (Eq. (13))
HCl
Bu2PCH(OEt)2
Bu2PCH
Bu2PH + CO
− EtCl, − EtOH
O
I
(13)
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Synthesis and Reactivity of Substituted α-Carbonylphosphonites and Their Derivatives
5
Another proof of the schemes presented above is the result of reaction of dibutoxy- and dibutyl
(dialkoxymethyl)phosphines 8 and 11 with iodobenzene dichloride, which takes place easily at low temper-
ature. In the last case, quasiphosphonium compound J was observed by 31P NMR at −30◦C and decomposed
on increasing the temperature to chlorophosphine, alkyl formate, and alkyl chloride (Eq. (14))
+
PhICl2
− PhI
-
X2PCH(OR)2 Cl
RCl + HCOOR
X2PCl + ClCH(OR)2
X2PCH(OR)2
Cl
J
8,11
R = Et, X = BuO (8), Bu (11); X = Bu (J), for J: P 30.2.
(14)
Thus, the breakage of the P C bond in the quasiphosphonium compound J takes place with an attack of a
chloride anion on the electrophilic central carbon atom of the dialkoxymethyl group and is (for phosphonium
J, X = BuO) more favorable than formation of a phosphoryl group as a result of the usual dealkylation reac-
tion. For using unstable chloro(diethoxy)methane for synthetic purposes, the reaction of some dichlorophos-
phines with an excess of triethyl orthoformate was carried out by us. The first step of these reactions is an
exchange of chloro and ethoxy groups and formation of the phosphonites and chloro(diethoxy)methane as
intermediates. So, dichloro(chloromethyl)phosphine and bis(dichlorophosphino)methane easily react with
an excess of triethyl orthoformate in diethyl ether solutions via phosphonites K and L as intermediates,
which were completely transformed with a large excess of chloro(diethoxy)methane into phosphinate 32 or
bisphosphinate 33 (cf. [2,14]; Eq. (15))
CH2Cl
2 ClCH(OEt)2
2 HC(OEt)3
Cl2PCH2Cl
(EtO)2PCH2Cl
EtOP
O
– 2 ClCH(OEt)2
– 2 EtCl, - HCOOEt
CH(OEt)2
K
32
EtO
4 ClCH(OEt)2
4 HC(OEt)3
P CH2
(Cl2P)2CH2
[(EtO)2P]2CH2
(EtO)2CH
– 4 ClCH(OEt)2
– 4 EtCl, - 2 HCOOEt
2
O
L
33
(15)
Much less active in this reaction is dichloro(dichloromethyl)phosphine, which even with the first triethyl or-
thoformate equivalent forms phosphonite 34 at 0◦C, whereas an excess of orthoformate leads to phosphonite
35 and phosphinate 36 in the ratio 1:1.5 (Eq. (16)). Note that carrying out this reaction in the presence of
boron trifluoride etherate as a catalyst, which favors the decomposition of chloro(diethoxy)methane, leads
to the formation of only phosphonite 35 with a high yield (Eq. (16))
EtO
Cl
HC(OEt)3
HC(OEt)3
ClCH(OEt)2
Cl2PCHCl2
PCHCl2
(EtO)2PCHCl2
– EtCl, − HCOOEt
– ClCH(OEt)2
− 2 EtCl
34
35
CHCl2
EtOP
CH(OEt)2
O
36
(16)
Dichloro(trichloromethyl)phosphine reacts with an excess of triethyl orthoformate only under heating at
130◦C in the presence of catalyst (zinc chloride) to give only trichloromethylphosphonite 37. Unstable
chloro(diethoxy)methane formed in this reaction does not enter into a rearrangement with phosphonite
37 due to the low nucleophilicity of tricoordinated phosphorus, related to the electronic and steric effects of
the trichloromethyl group (Eq. (17))
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Prishchenko et al.
2 HC(OEt)3, ZnCl2
Cl2PCCl3
(EtO)2PCCl3
– 2 EtCl, − 2 HCOOEt
37
(17)
It should be noted that in none of the investigated examples of the Arbuzov reaction of chlorosub-
stituted methylphosphonites was breakage of the P C bond observed, distinct from (dialkoxymethyl)
phosphonites. The presence of a labile P C bond in (dialkoxymethyl)phosphonites makes it extremely inter-
esting to study the Arbuzov reaction for these compounds. So, the reaction of (dialkoxymethyl)phosphonites
6 and 8 with methyl iodide, allyl iodide, and also with iodomethyl methyl ether under moderate conditions
(boiling in a diethyl ether solution), in addition to the usual regrouping products—phosphinates 38–41 of
asymmetrical structure, formed phosphinates 9 and 42–46 of symmetrical structure; the concentration of
which in the reaction mixtures according to 31P NMR data is 10%–20% (Eq. (18))
CH(OR)2
X
+
XI
(RO)2PCH(OR)2 I−
ROP
O
(RO)2PCH(OR)2
– RI
X
38–41
M
6,8
(RO)2PCH(OR)2
– RI
XI
– RI
(RO)2PX + ICH(OR)2
ROP[CH(OR)2]2
O
ROPX2
O
N
42–45
9,46
R = Et (6,9,38,40,41), Bu (8,39,43,46)
X = Me (38,39,42,43), CH2=CHCH2 (40,44), MeOCH2 (41,45)
In 31P NMR spectra, P for compounds; 42: 48.7; 43: 49.5; 44: 44.7; 45: 41.1
(18)
The unusual direction of the Arbuzov reaction is doubtless related to the breakage of the P C bond on the
attack of the iodide anion at the electrophilic central atom of the dialkoxymethyl group in quasiphosphonium
compound M. The phosphonites N formed in the course of the reaction are easily rearranged by the starting
alkyl iodides, which lead to phosphinates 42–45, whereas the iodo(diethoxy)methane rapidly reacts with the
starting phosphonites 6 and 8 with formation of phosphinates 9 and 46. The chloromethyl methyl ether
reacts with phosphonite 6 under more severe conditions (100◦C). The concentration of products 9 and 45
formed due to the breakage of the P C bond increases to 60%. This is apparently due to the smaller volume
of the chloride anion, which makes an attack on the central carbon atom preferential. The breakage of the
P C bond becomes the single direction of the reaction of phosphonites 6 and 8 with alkyl chloroformates;
and previously unknown alkoxycarbonylphosphonites 47–49 were obtained with high yields. The reaction
takes place smoothly on boiling of the mixture in diethyl ether; it is necessary to use 2 equiv of the starting
phosphonites 6 and 8 (Eq. (19))
+
6,8
ClCOOX
-
(RO)2PCH(OR)2 Cl
(RO)2PCOOX + ClCH(OR)2
9,46
6,8
– RCl
COOX
47–49
B
R = Et (6,47,48), Bu (49)
X = Me (47,49), Bu (48)
(19)
It is interesting to note that a further rearrangement of phosphonites 47–49 by alkyl chloroformates is
impossible under the moderate conditions of this reaction due to the low nucleophilicity of the three-
coordinated phosphorus attached to the alkoxycarbonyl group. The reaction of phosphonite 47 with methyl
chloroformate takes place only on heating of the mixture to 90◦C in the absence of a solvent (Eq. (20))
Heteroatom Chemistry DOI 10.1002/hc

Synthesis and Reactivity of Substituted α-Carbonylphosphonites and Their Derivatives
7
ClCOOMe
(EtO)2PCOOMe
47
EtOP(COOMe)2
– EtCl
O
50
(20)
The reaction of dibutyl(diethoxymethyl)phosphine 11 with methyl chloroformate under analogous condi-
tions leads to dibutyl(methoxycarbonyl)phosphine 51. In this case, unstable chloro(diethoxy)methane cannot
compete with methyl chloroformate and decomposes by the usual scheme (Eq. (21))
+
ClCOOMe
–
Bu2PCH(OEt)2 Cl
Bu2PCOOMe + EtCl + HCOOEt
Bu2PCH(OEt)2
COOMe
11
51
(21)
In distinction from (dialkoxymethyl)phosphonites 5–8, the silicon-containing (dialkoxymethyl)phosphonites
1–3 react with alkyl chloroformates under mild conditions by the usual path of the Arbuzov rearrangement.
Actually, the decomposition of phosphonium salt O in which the most electrophilic center is the silicon atom
is accompanied by formation of chlorotrimethylsilane and phosphinates 52–55 (Eq. (22))
CH(OR)2
+
RO
RO
ClCOOX
-
ROP
O
PCH(OR)2 Cl
PCH(OR)2
COOX
– Me SiCl
Me3SiO
Me3SiO
3
COOR
1–3
O
52–55
R = Me (1,52), Et (2,53,54), Pr (55)
X = Me (51,53,55), Bu (52,54)
(22)
Note (dichloromethyl)phosphonite 35 also reacts with methyl chloroformate under heating to 100◦C in the
presence of zinc chloride as a catalyst, yielding phosphinate 56 by the usual scheme (Eq. (23))
CHCl2
ClCOOMe, ZnCl2
(EtO)2PCHCl2
EtOP
O
– EtCl
COOMe
35
56
(23)
It should be noted that the oxidation of (dialkoxymethyl)phosphonites or (dialkoxymethyl)phosphines, even
under moderate conditions, takes place nonuniformly with formation of a mixture of compounds, which are
the products of the breakage of the P C bond. On the contrary, the addition of sulfur to these compounds
takes place smoothly and leads to the corresponding thio derivatives 57–61 (Eq. (24))
S
X2PCH(OR)2
X2PCH(OR)2
S
6,11
57,58
RO
RO
S
PCH(OR)2
S
PCH(OR)2
Me3SiO
Me3SiO
1–3
59–61
(24)
The unique lability of the P C bond in (dialkoxymethyl)phosphonites 5–8 under conditions of the Arbu-
zov reaction may doubtless be widely used for synthetic purposes. So, carbon tetrachloride easily cleaves
the P C bond in phosphonite 6 with formation of trichloromethylphosphonite 37 and phosphinate 9.
Heteroatom Chemistry DOI 10.1002/hc

8
Prishchenko et al.
Trichloromethylphosphonite 37 does not react under the conditions of the reaction either with the start-
ing carbon tetrachloride or with the chloro(diethoxy)methane which is formed, which is rapidly bonded by
the starting phosphonite to give phosphinate 9 as usual (Eq. (25))
CCl4
2 (EtO)2PCH(OEt)2
(EtO)2PCCl3
+
EtOP[CH(OEt)2]2
– EtCl
O
6
37
9
(25)
The most interesting results are obtained in the reaction of (diethoxymethyl)phosphonite 6 with acyl chlo-
rides. This interaction proceeds under mild conditions, and only the P C bond cleavage takes place with
formation of yellow–greenish-colored α-carbonylphosphonites 62–64 and phosphinate 9 (Eq. (26))
XCOCl
2 (RO)2PCH(OR)2
(RO)2PC(O)X + ROP[CH(OR)2]2
O
– RCl
6
62–64
9
R = Et ; X = t-Bu (62), i-Pr (63), Me (64)
(26)
α-Carbonylphosphonite 62 is a stable compound due to bulky substituent at the carbonyl group; in contrast,
phosphonite 63 is slowly dimerized at 20◦C, and its dimerization was completed in 4 days to form adduct
65 with high yield. The most reactive phosphonite 64 is easily transformed into adduct 66 by distillation,
and its dimerization proceeded in 60% for 1 h under 0◦C (Eq. (27)). Evidently, the dimerization of α-
carbonylphosphonites proceeds because of the unique lability of the P C bonds of these compounds (cf.
Eq. (32))
X
X
(RO)2PCOP(OR)2
2 (RO)2PC O
C(O)X
63,64
65,66
R = Et ; X = i-Pr (63,65), Me (64,66)
(27)
On the contrary, silicon-containing phosphonite 2 reacts with pivaloyl chloride under the same conditions
via the usual scheme of the Arbuzov rearrangement to yield α-carbonylphosphinate 67, but not phosphonite
68 (Eq. (28); cf. Eq. (22)).
CH(OR)2
ROP
C(O)Bu-t
– Me3SiCl
RO
t-BuCOCl
O
PCH(OR)2
67
Me3SiO
2
RO
PC(O)Bu-t
– ClCH(OR)2
Me3SiO
R =Et
68
(28)
The interaction of α-carbonylphosphonites 47 and 62 with methyl iodide proceeds only under boiling of the
reaction mixture in acetonitrile via the classic Arbuzov reaction to yield phosphinates 69 and 70 (Eq. (29))
+
RO
Me
MeI
(RO)2PC(O)X I-
PC(O)X
(RO)2PC(O)X
– RI
O
Me
47,62
69,70
R = Et ; X = MeO (47,69), t-Bu (62,70)
(29)
Yet, the most striking is the lability of the P C bond in α-carbonylphosphonites. Thus, the reaction of
pivaloylphosphonite 62 with an excess of methyl chloroformate leads to bis(methoxycarbonyl)phosphinate
Heteroatom Chemistry DOI 10.1002/hc

Synthesis and Reactivity of Substituted α-Carbonylphosphonites and Their Derivatives
9
50, that is, it proceeds with the rupture of the P C bond via the formation of intermediate phosphonite 47
and pivaloyl chloride (Eq. (30))
C(O)X
+
ClCOOMe
ClCOOMe
– RCl
-
(RO)2PC(O)X
(RO)2P
Cl
(RO)2PCOOMe
– XC(O)Cl
COOMe
62
47
ROP(COOMe)2
O
50
R = Et ; X = t-Bu.
(30)
The P C bond lability is also observed in the unsuccessful attempt to synthesize phosphonium salt P from
phosphine 51 and an excess of methyl iodide. The mixing of the reagents in acetonitrile is accompanied by
rapid formation of carbon dioxide to give the stable phosphonium salt 71. The decay of intermediate salt
P proceeds evidently via an attack of the iodide anion on the methoxy group to give carbon dioxide and
methyldibutylphosphine, which readily reacts with methyl iodide with formation of crystalline compound
71 (Eq. (31))
+
+
+
MeI
Bu2PCOO-
Me2Bu2P I-
Bu2PCOOMe I -
MeI
Bu2PMe
Bu2PCOOMe
– MeI
– CO2
Me
Me
51
P
71
(31)
The unique reactivity of α-carbonylphosphonites made it possible to use these compounds as new
organophosphorus synthons for the development of a selective method of the C C bond formation. Under
mild conditions, α-carbonylphosphonites can be easily added to the carbonyl group of a number of aldehydes,
ketones, and α-carbonylphosphonates forming functionally substituted phosphites of various structures. Ev-
idently, the addition begins with the tricoordinated phosphorus attack at the carbonyl group and the bipolar
intermediate stabilization is accompanied by the rupture of the P C bond and the acylium-cation migration
(Eq. (32))
+
-
C-OP(OR)2
(RO)2PC(O)X + C=O
C-OP(OR)2
C(O)X
C(O)X
X = Alk, AlkO
(32)
So, the interaction of α-carbonylphosphonites with aromatic aldehydes and α-carbonylphos-phonates pro-
ceeds according to the scheme (Eq. (32)) under mild condition to form the functionalized phosphites 72–76
with high yields (Eq. (33))
+
-
XYC=O
XYCOP(OEt)2
(EtO)2PC(O)R
XYCOP(OEt)2
C(O)R
C(O)R
62,63
72–76
R = i-Pr (63,72), t-Bu (62, 73-76)
X = H (72-74), i-Pr (75), Me (76)
Y = Ph (72),
(73),
(74), (EtO)2P(O) (75), (i-PrO)2P(O) (76)
N
O
(33)
Heteroatom Chemistry DOI 10.1002/hc

10 Prishchenko et al.
The most reactive hexafluoroacetone reacts with α-carbonylphosphonites 47, 62, and 63 in dilute ether
solutions under cooling to −70◦C. The first step of this reaction is the formation of functionalized phosphites
77–79 with high yields, and the further interaction of these phosphites with an excess of hexafluoroacetone
proceeds similarly to the reaction with triethyl phosphite described in [15], yielding the corresponding
functionalized phosphoranes 80–82 (Eq. (34))
OC(CF3)2CX
O
O
(CF3)2C
(CF3)2C
(CF3)2C=O
2 (CF3)2C=O
P(OEt)2
O
(EtO)2PCX
O
(EtO)2POC(CF3)2CX
O
47,62,63
77–79
80–82
X = i-Pr (63,77,80), t-Bu (62,78,81), MeOOC (47,79,82)
(34)
In contrast to α-carbonylphosphonites under the same conditions, (diethoxymethyl)phosphonite 6 reacts
with hexafluoroacetone similarly to triethyl phosphite to give phosphorane 83 (cf. [15]; Eq. (35))
CH(OR)2
O
O
(CF3)2C
(CF3)2C
2 (CF3)2C=O
P(OR)2
(RO)2PCH(OR)2
6
83
R = Et.
(35)
The similar interaction proceeds between phosphonite 6 and diacetyl (2,3-butanedione) under refluxing in
diethyl ether to give phosphoranes 84 and 85, depending on the ratio of starting reagents (cf. [16,17]; Eq. (36))
CH(OR)2
P(OR)2
CH(OR)2
P(OR)2
O
O
MeCO(Me)C
MeCO(Me)C
O
O
MeC
MeC
MeCOCOMe
MeCOCOMe
(RO)2PCH(OR)2
6
84
85
R = Et
(36)
It is interesting that much less reactive than hexafluoroacetone, diacetyl reacts with α-carbonylphosphonite
47 under the refluxing in methylene chloride forming phosphorane 86 with good yield (Eq. (37))
COOMe
O
O
MeC
MeC
MeCOCOMe
P(OEt)2
(EtO)2PCOOMe
47
86
(37)
The silicon-containing phosphonite 2 reacts with carbonyl compounds via the usual addition of POSi frag-
ment to the carbonyl group (cf. [18]), yielding adducts 87–89 (Eq. (38))
EtO
CH(OEt)2
CH(OEt)2
RCHO
MeCOCOMe
PCH(OEt)2
EtOP
O
EtOP
O
OC=COSiMe3
Me3SiO
CHR(OSiMe3)
Me
Me
87,88
2
89
R = Pr (87), Ph (88)
(38)
Heteroatom Chemistry DOI 10.1002/hc

Synthesis and Reactivity of Substituted α-Carbonylphosphonites and Their Derivatives 11
α-Carbonylphosphonites with POSi fragments are extremely interesting compounds for comparison of their
reactivity with the investigated reactivity of α-carbonylphosphonites 62 and 63. The compounds 68 and 90
were specially prepared via the reaction of pivaloyl chloride with trimethylsiloxyphosphines Q and R [19] in
the ratio 1:1 under mild conditions in the presence of triethylamine (Eq. (39); cf. Eq. (28)).
RO
Me3SiO
Q,R
RO
t-BuC(O)Cl, Et3N
– Et 3N HCl
PH
PC(O)Bu-t
Me3SiO
68,90
R = Et (68), Me3Si (90)
(39)
Also, if the ratio of the starting compounds is changed into 1:2, it is possible to give bis(α-carbonyl)
phosphinates 91 and 92 via the classic Arbuzov rearrangement (Eq. (40); cf. Eqs. (22) and (28))
RO
t-BuC(O)Cl
ROP[C(O)Bu-t]2
O
PC(O)Bu-t
– Me SiCl
3
Me3SiO
68,90
91,92
R = Et (91), Me3Si (92)
(40)
Also, bis(trimethylsiloxy)phosphine is easily added to α-carbonylphosphonites 62, 68, and 90, yielding bis-
phosphonites 93–95 with high yields (Eq. (41))
Bu-t
XO
YO
XO
YO
OSiMe3
H
(Me3SiO)2PH
PC(O)Bu-t
P-C-P
O
OSiMe3
62,68,90
93–95
X = Y= Et (62,93), Me3Si (90,95)
X = Et, Y= Me3Si (68,94)
(41)
Note that the bisphosphonite 95 is formed as a by-product in 35% yield even in an equimolar ratio of starting
reagents in the reaction described by Eq. (39). So, the reactions of silicon-containing α-carbonylphosphonite
proceed without splitting the P C bond. Much less nucleophilic diethyl trimethylsilyl phosphite is slowly
added to α-carbonylphosphonite 62 under heating at 100◦C to give adduct 96 (Eq. (42)).
Bu-t
(EtO)2PCP(O)(OEt)2
(EtO)2PC(O)Bu-t + (EtO)2POSiMe3
OSiMe3
62
96
(42)
For comparison, pivaloyl phosphonate 97 with a more reactive carbonyl group, which was prepared as
described in [20,21], and diethyl trimethylsilyl phosphite already at 20◦C gives bisphosphonate 98 with a
high yield; however, this compound is converted by distillation into starting reagents (cf. [3,5]; Eq. (43))
Heteroatom Chemistry DOI 10.1002/hc

12 Prishchenko et al.
20°C, (EtO)2POSiMe3
100°C, - (EtO)2POSiMe3
Bu-t
[(EtO)2P]2 C
O
(EtO)2P(O)C(O)Bu-t
OSiMe3
97
98
(43)
The similar interaction of bis(α-carbonyl)phosphinate 91 with an excess of diethyl trimethylsilyl phosphite
proceeds under the same conditions via splitting the P C bond in adduct S to give phosphonite 68 and
phosphonate 97, but not the expected compound T with a PCPCP fragment (Eq. (44))
Bu-t
EtOP
O
C
P(O)(OEt)2
OSiMe3
2
T
(EtO)2POSiMe3
EtOP[C(O)Bu-t]2
O
C
Bu-t
t-Bu(O)
°
EtO
20 C
EtOP
O
CP(O)(OEt)2
O
PC(O)Bu-t + (EtO)2PC(O)Bu-t
91
Me3SiO
O
68
97
Me3Si
S
(44)
The oxidation of α-carbonylphosphonites even under mild conditions gives only the mixtures of compounds;
in contrast, the addition of sulfur of these phosphonites proceeds smoothly, yielding the corresponding thio
derivatives 99–103 (Eq. (45))
XO
YO
S
XO
YO
PC(O)R
PC(O)R
S
99–103
X = Y = Et (99-101); X = Et, Y= Me3Si (102); X = Y= Me3Si (103)
R = MeO (99), BuO (100), t-Bu (101-103)
(45)
We found that among the α-carbonyl-phosphonites, the N,N-substituted α-carbamoyl phosphonites 104–
107 possessed the most stable P C bond. These phosphonites 104–107 are obtained by us via the slow
interaction of available carbamoyl chlorides (cf. [22,23]) with an excess of bis(trimethylsiloxy)phosphine
and triethylamine at 20◦C for 2 days with good yields (Eq. (46))
Et3N
(Me3SiO)2PC(O)NR2
(Me3SiO)2PH + ClC(O)NR2
Et3N HCl
104–107
NR2 = NMe2 (104), NEt2 (105),
N
(106),
N
O (107)
(46)
α-Carbamoyl phosphonites are the key substances for preparing various organophosphorus compounds
with carbamoyl groups. So, phosphonite 104 easily adds sulfur and propionaldehyde as well as reacts with
(chloromethyl)dimethylamine to give the corresponding thiophosphonate 108 and α-carbamoyl phosphi-
nates 109 and 110 with good yields (Eq. (47))
Heteroatom Chemistry DOI 10.1002/hc

Synthesis and Reactivity of Substituted α-Carbonylphosphonites and Their Derivatives 13
C(O)NMe2
CH2NMe2
ClCH2NMe2
– Me3SiCl
S
Me3SiOP
O
(Me3SiO)2PC(O)NMe2
S
104
108
110
EtCHO
C(O)NMe2
Me3SiOP
O
CH(OSiMe3)Et
109
(47)
Also, the phosphonites 105–107 smoothly add sulfur, yielding the corresponding thiophosphonates 111–113
with high yields (Eq. (48))
S
(Me3SiO)2PC(O)NR2
(Me3SiO)2PC(O)NR2
S
105–107
111–113
NR2 = NEt2 (105,111),
(106,112),
N
N
O (107,113).
(48)
Thus, the investigations of the properties of dialkoxy-, trialkoxymethyl-, and α-carbonylphosphonites revealed
a unique reactivity of these compounds in various transformations connected with a high lability of the
P C bond at the stage of quasiphosphonium compound formation. So, these functionalized phosphonites
interact with the classical reagents of organophosphorus chemistry in a new direction via the P C bond
rupture and retention of tricoordinated phosphorus. Recently, these perspective synthons were used by us in
the successful synthesis of new substituted aminomethylphosphonites and aminomethylenebisphosphonites
[24,25].
1
The structures of compounds 1–113 were confirmed by the H, 13C, 19F, 29Si, and 31P NMR spectra,
which show characteristic signals of the central P C or PC(O) fragments by the tri-, tetra-, or pentacoordi-
nated phosphorus (see Tables 1–4). According to the NMR spectra, several compounds are mixtures of the
stereoisomers. Their ratio was determined from the 1H NMR and 31P spectra. The elemental analysis data of
synthesized compounds are summarized in Table 5.
EXPERIMENTAL
The 1H, 13C, 19F, 29Si, and 31P NMR spectra were registered on a Bruker Avance-400 spectrometer in CDCl3 or
C6D6 (1–113) against TMS (1H, 13C, and 29Si), CF3COOD (19F), and 85% H3PO4 in D2O (31P). All reactions were
performed under dry argon in anhydrous solvents. Starting crystalline hypophosphorous acid was prepared
according to the procedure described in [8].
O-Methyl O-trimethylsilyl(dimethoxymethyl)phosphonite (1)
p-Toluenesulfonic acid, 1.8 g, was added by stirring to the mixture of 6.6 g hypophosphorous acid and 25.5 g
of trimethyl orthoformate. The mixture was stirred for 3 h at 20◦C and was kept in vacuum (1 mmHg) under
30–35◦C, then this mixture was added dropwise to 19.4 g of bis(trimethylsilyl)amine and was refluxed until
the formation of ammonia was finished. Pentane (100 mL) was added to the mixture, the precipitate was
separated, the solvent was removed, and the residue was distilled to yield 7.6 g of phosphites 1.
Phosphonites 2–4 were prepared similarly.
Heteroatom Chemistry DOI 10.1002/hc

14 Prishchenko et al.
TABLE 1 Yields, Products Constants, and NMR Spectral Data (δ, ppm; J, Hz) for the PC1Hn Fragments of Compounds 1–113a
Compound
Yield (%)
Bp (◦C) (p, mmHg), mp (◦C)
nD20
δ C1Hd
2JPH
δ(C1)d
1JPC
δ , sb
H
P
c
1
34
54
60
57
25
62
60
53
29
21
87
61
52
59
57
59
61
51
49
60
88
60
68
74
78
72
91
39 (1)
49 (1)
83 (1)
106(1)
36 (1)
65 (1)
4.13
4.38
4.37
4.53
4.52
4.75
4.80
4.39
4.65
4.67
4.82
5.01
4.97
–
–
–
–
–
–
–
–
–
1.0
1.0
1.1
1.1
1.0
1.1
1.2
1.2
9.1
9.2
1.4
2.3
11.2
–
–
–
–
–
–
–
–
–
108.09
107.96
107.88
107.90
107.23
106.83
106.59
106.48
99.68
9.9
10.0
10.2
10.1
10.9
10.3
10.6
10.8
138.2
137.5
2.0
3.1
15.9
4.9
11.0
26.8
27.8
147.90
146.32
146.64
146.41
160.63
157.34
157.08
157.06
28.02
28.60
−38.34
−7.22
20.16
−6.59
40.39
−11.14
−9.69
−13.23
−11.25
−9.29
163.6
8.10
2
1.4242
1.4375
3
4
1.4445
c
5
6
1.4300
1.4420
1.4400
1.4851
1.4385
7
89 (1)
8
108 (1)
104 (1)
129 (1)
86 (2)
72 (2)
67 (1)
9
10
11
12
13
14
15
18
19
23
24
25
26
27
28
29
30
31
32
99.03
1.4453
106.12
106.38
106.73
121.35
120.72
109.49d
109.71d
78.96d
78.81d
79.27d
105.79
111.62
111.77
111.76
111.82
111.66
99.49
c
c
c
c
c
c
c
c
c
c
93 (1)
83 (1)
124 (1)
136 (0.5)
109 (1)
131 (1)
133 (1)
119 (1)
85 (1)
112 (1)
135 (1)
111 (1)
83 (1)
28.1
27.8
27.8
15.4
1.4252
1.4335
1.4390
1.4295
1.4220
1.4504
259.7
260.6
260.1
259.8
258.9
152.0
90.3
–
–
–
–
–
–
–
–
8.36
8.24
8.54
7.15
93 (1)
4.88
3.62f
4.96
4.88
5.82f
5.40f
4.98
5.78f
–
4.45
1.11f
4.47
1.12f
4.53
2.52f
4.63
3.78f
4.57
–
8.2
7.3
9.6
9.6
6.2
1.0
10.1
3.4
–
7.0
14.1
7.1
14.0
8.0
17.3
8.5
15.5
10.1
–
33.11
32.29
33e
81
178 (1)
1.4531
101.97
101.95
74.83
81.07
101.6
154.4e
153.9e
63.5
35.67
35.42
150.22
149.10
26.30
–
c
34
35
36
70
35
57
39 (1)
42 (1)
102 (1)
c
19.6
1.4612
153.9
126.8
82.1
153.5
94.2
151.8
32.6
150.9
91.6
141.0
89.7
137.8
35.3
35.1
35.0
74.42
c
37
38
70
87
54 (1)
75 (1)
100.11
101.09
16.42
100.96
16.14
100.23
34.37
99.72
138.34
42.52
1.4345
39
40
41
81
77
55
125 (1)
87 (1)
79 (1)
1.4396
1.4475
1.4375
42.23
39.12
35.11
62.52
99.28
46
47
48
49
50
51
52
53
54
55
56
90
93
90
89
85
85
77
84
82
80
61
155 (1)
40 (1)
62 (1)
68 (1)
102 (1)
57 (1)
122 (1)
102 (1)
130 (1)
122 (1)
103 (1)
1.4427
28.26
132.44
134.74
135.10
−6.01
−17.39
15.40
14.42
14.30
13.06
11.54
c
177.30
177.15
176.94
167.19
174.11
169.12
168.26
168.86
168.03
166.87
61.69
c
c
–
–
–
–
–
–
1.4447
3.90f
3.86f
4.68
4.70
4.82
4.88
–
197.8
28.6
c
1.4482
1.4422
1.4420
1.4412
1.4702
10.2
10.1
10.1
10.0
–
2.3
10.8
11.0
13.3
13.2
13.0
–
171.8
171.2
171.3
170.9
202.2
100.2
178.9
68.9
173.3
173.1
173.5
57.4
6.02f
4.47
4.60
4.40
4.52
4.58
–
57
58
59
60
61
62
63
64
67
80
89
89
78
80
95
94
28
55
72 (1)
114 (1)
71 (1)
66 (0.5)
110 (1)
42 (1)
39 (1)
33 (1)
109 (2)
1.4602
1.4863
1.4614
1.4527
107.52
83.94
81.08
49.55
71.40
70.33
70.29
148.41
143.94
140.65
15.31
105.30
104.28
103.98
227.50f
1.4544
c
c
c
–
–
–
9.2
228.45f
44.4
–
144.7
81.8
a
a
1.4402
4.67
99.22
218.78f
(Continued)
Heteroatom Chemistry DOI 10.1002/hc

Synthesis and Reactivity of Substituted α-Carbonylphosphonites and Their Derivatives 15
TABLE 1 Continued
Compound
Yield (%)
Bp (◦C) (p, mmHg), mp (◦C)
nD20
δ C1Hd
2JPH
δ(C1)d
1JPC
δ , sb
H
P
c
68
69
71
64
45 (1)
68 (1)
1.13f
1.65g
< 1
16.2
228.41f
12.82
61.1
102.6
175.8
92.8
136.75
27.22
1.4361
170.68f
12.84
70
72
59 (1)
1.4368
1.52g
14.5
32.99
219.92f
108.11
107.82
171.16
99.35
91.6
84f
85f
86
90
34
63
69
85 (1)
129 (1)
95 (2)
1.4428
1.4480
1.4491
1.4390
4.73
4.62
14.2
14.0
–
9.1
–
9.2
–
9.0
9.1
7.2
11.2
5.9
8.1
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
279.9
270.3
372.9
133.1
107.4
134.2
109.9
137.3
106.8
138.6
111.1
200.2
208.1
66.2
−42.64
−45.71
−49.26
36.60
1.75f
4.91
m
s
87e
113 (1)
69.94f
97.84
4.85
m
35.97
31.78
31.15
69.55f
100.03
72.93
88e
67
140 (1)
1.4825
5.41
4.85f
5.31
4.77f
4.67
4.87
1.24f
1.25f
1.29f
–
98.91
72.86
98.79
99.27
89e,f
51
117.2 (1)
1.4461
27.59
27.66
131.33
9.18
c
90
25
81
79
90
86
89
87
89
83
53
52
57
61
75
64
63 (1)
108 (1)
92 (1), 43
102 (8)
75 (1)
93 (2)
74 (1)
75 (1)
75 (1)
72 (1)
90 (1)
s
s
s
229.63
217.57
218.70
215.29
168.11
167.75
212.54
212.68
213.11
178.49
178.09
176.94
177.46
167.76
169.24
71.88f
168.54
72.53f
169.46
57.19f
167.32
166.12
166.57
91
1.4442
77.1
82.6
92
0.01
−2.5
97
1.4312
1.4680
1.4632
1.4645
1.4567
148.5
226.4
226.1
102.09
113.90
116.8
44.1
44.5
43.2
45.4
195.2
146.4
127.6
143.6
140.3
152.7
126.8
194.0
196.0
196.3
99
–
–
–
–
60.06
58.23
62.23
50.14
40.98
124.96
124.37
124.42
124.27
41.78
19.25
100
101
102
103
104f
105f
106
107f
108f
109e
1.4486
1.28f
–
s
c
c
c
c
c
c
–
–
–
–
–
m
–
m
–
m
–
–
112 (1)
104 (1)
108 (1)
110 (1)
19.63
19.65
c
110
69
90 (1)
c
c
c
111f
112
113
78
83
81
122(1)
120 (1)
130 (1)
42.64
42.42
40.88
–
aSome of the synthesized compounds are presented in Tables 2–4. All signals of alkyl, aryl, and trimethylsilyl groups are in the standard area.
Phosphonite 64 was rapidly dimerized; therefore, only the 31P NMR spectrum datum was presented.
1
bData of 31P–{ H} spectra.
cBecause of the ease of hydrolysis and oxidation, the refractive index of these compounds was not measured.
dt, fragment P2C1C2H3, δ (C2) for compounds: 23, 19.05 t, 2JPC 10.5; 24, 19.03 t, 2JPC 10.8;25, 19.17 t, 2JPC 10.2;26, 17.32 d, 2JPC 3.3.
eThese compounds are the mixtures of two stereoisomers; their ratio for compounds: 33, 55:45; 33, 55:45; 87, 60:40; 88, 70:30; 89, 55:45; 109,
65:35; for compound 33, fragment PCH2P in the NMR spectra, the first isomer: δ(HA) 2.87, δ(HB) 2.34, 2J(HA HB) 15.6,2J(PXHA) = 2J(PYHA)
14.7, 2J(PXHB) 15.0, 2J(PYHB) 17.2; δC25.09 t, 1JPC 78.7; the second isomer: δH 2.60 t, 2JPH 16.1; δC 25.07 t, 1JPC 77.5; in 13C NMR δ(C1) d d,
3JPC 19.3 and 18.2.
f Fragments for compounds: 32, PCH2Cl; 34–36, PCHCl2; 40, PCH2C, d d, 3JHH 7.0; 41, PCH2O; 50 and 51, OMe, s; 56, PCHCl2; 62, for PC1(O)
2
3
2
2
C2C3: δ(C2) 46.83 d, JPC 20.8, δ(C3) 26.10 d, JPC 3.7; 63, for PC1(O) C2: δ(C2) 39.93 d, JPC 23.3; 67, for C1(O) C2C3: δ(C2) 46.92 d, JPC
42.1, δ(C3) 24.74 s; 68, for C1(O) C2C3: δ(C2) 46.43 d, JPC 22.1, δ(C3) 26.15 d, JPC 4.9; δC(Me3Si) 1.73 d, JPC 2.4; 69, C1(O)OMe: δC(Me)
2
3
3
51.62 d, JPC 3.6; 70, C1(O) C2C3: δ(C2) 46.60 d, JPC 43.9; δ(C3) 25.12 s; 84, for MeC CMe, δH1.63 s, δC(C ) 129.61 d, JPC 2.2, δC(Me)
3
2
2
10.72 d, 3JPC 9.5; 85, for MeC(O)C(Me) C(Me)C(O)Me, δH2.27 m, δC(C ) 84.74 d, 2JPC 4.0, δC(C O) 207.42 d, 3JPC 4.3; 86, for MeC CMe,
2
3
δC(C ) 130.71 d, JPC 2.2, δC(Me) 10.41 d, JPC 10.30; 87, CHOSi, the signals of protons are overlapping; 88, CHOSi; 89, for MeC CMe,
δH1.57 s, δC(C C) 135.20 d, 2JPC 1.8 and 128.50 s, δC(Me) 10.78 s and 11.09 s; 90, CMe3: δC(Me) 26.14 d, 3JPC 4.7, δC(C) 46.27 d, 2JPC 22.1,
for SiMe3δH 0.29 s, δC(Me) 1.48 d,3JPC 2.3, δSi 18.32 d, 2JPSi 4.9; 91, CMe3, δC(Me) 25.19 s, , δC(C) 47.29 d, 2JPC 44.1; 92, CMe3, δC(Me) 25.54
2
2
s and δC(C) 47.21 d, JPC 44.9, SiMe3, δH 0.26 s, δC(Me) 1.08 s; 103, CMe3, δC(Me) 27.32 s, δC(C) 45.96 d, JPC 57.7; 104, for Me2N, δH 2.66
d, 4JPH0.8 and 2.87 d, 4JPH2.3, δC 34.37 s and 35.62 d, 3JPC 21.6; for Me3Si, δH 0.30 s, δC1.65 d, 3JPC 2.1; 105, for CH2N, δC39.47 s and 40.60
3
3
3
3
d, JPC 22.3; 106, for CH2N, δC 42.11 s and 45.94 d, JPC 20.9; 107, for CH2N, δC41.92 s and 45.42 d, JPC 20.5, for CH2O, δC 60.74 d, JPC
3
6.0; 108, for Me2N, δH 2.62 s and 3.12 s, δC 35.07 d, JPC 4.6 and 37.55 s; for Me3Si, δH 0.36 s, δC1.20 s. 109, CHOSi, the signals of protons
are overlapping; 110, CH2N, in 1H NMR spectra–m ABX, for Me2NCH2, δH 2.31 s, δC47.61 d, JPC 10.2, for Me2NC(O), δH 2.63 s and 3.27 s,
3
3
3
3
δC34.78 d, JPC 3.9 and 36.32 s; 111, for CH2N, δC39.74 d, JPC 5.9 and 42.03 s; 112, for CH2N, δC 43.04 d, JPC 4.2 and 47.46 s; 113, for
CH2N, δC 42.44 d, 3JPC 4.4 and 47.23 s, for CH2O, δC66.38 s.
gPMe.
Heteroatom Chemistry DOI 10.1002/hc

16 Prishchenko et al.
TABLE 2 Yields, Products Constants, and NMR Spectral Data (δ, ppm; J, Hz) for the P1OC1HC2(O) and P1OC1(P2)C2(O)
Fragments of Functionalized Phosphites 65, 66, and 72–76a
Yield
Compound (%) (p, mmHg)
Bp (◦C)
δ(H)
δ(C1)
d d
nD20
C1Hd 3JPH
1JPC 2JPC δ(C2)d nJPC
δ(P1)
δ(P2)
3JPP
b
b
65
66
72
73
74
75
76
72
73
67
76
77
65
75
124 (1)
104 (1)
118 (1)
137 (2)
104 (1)
134 (1)
128 (1)
–
–
97.81
89.14
76.73
71.47
65.36
23.9 2.5 211.83 <1 131.12 174.51 101.4
1.85c 12.1
14.5
<1
205.20 3.7 133.30 165.64
31.1
–
–
1.4895 5.62
1.4917 5.92
1.4727 6.03
1.4610
1.4500
9.0
9.1
9.0
–
–
–
–
6.2 208.93 <1 135.09
4.1 207.56 2.3 135.51
5.9 206.31 2.2 134.91
–
–
–
–
–
–
94.72 146.1
86.95 157.5 5.2 212.43 2.6 133.75
<1
212.37 2.1 134.57
16.23
14.10
<1
5.9
–
1
aAll signals of alkyl, aryl, and trimethylsilyl groups are in the standard area. Data of the 31P–{ H} spectra are presented.
bBecause of the ease of hydrolysis and oxidation, the refractive index of these compounds was not measured.
cFragment PCCH3; in the 1H NMR spectrum for C(O)CH3: 2.36 s.
TABLE 3 Yields, Products Constants, and NMR Spectral Data (δ, ppm; J, Hz) for the POC1(CF3)C2(O) Fragments of Com-
pounds 77–83a
Yield
(%)
Bp (◦C)
20
nD
Compound
(p, mmHg)
δ( C1)m
δ(C2)s
δ(C3)q
1JFC
δ
F
δ
P
4JPF
77
78
79
80
88
90
81
75
41 (1)
52 (1)
39 (1)
73 (1)
1.3875
1.3970
1.3785
1.3675
83.67
84.62
80.38
202.29
202.04
162.04
199.34
–
127.39
121.67
121.47
121.32
121.67
121.31
121.55
121.34
121.46
121.74
288.7
290.4
289.1
292.9
286.9
280.4
290.7
290.4
302.1
293.8
−69.17 d
−67.86 d
−71.87 d
−67.31 s
−66.89 s
−65.51 s
−66.81 s
−70.36 s
−66.75 s
−72.04 s
133.80 sp
140.94 sp
137.09 sp
−57.62 s
24.4
44.2
14.3
–
82.21
86.05b
82.26
81
80
78
96
96 (1)
90 (1)
66 (1)
1.3750
1.3630
1.3770
201.35c
–
−57.94 s
−58.57 s
−39.40 s
–
–
–
87.52b
81.34
82
161.77
–
82.38b
108.05c
83d
–
aAll signals of alkyl and trimethylsilyl groups are in the standard area. Data of the 31P–{ H} spectra are presented. Sp = septet.
1
bCyclic fragment.
cd, for 81, 3JPC7.5, for 83, 1JPC 274.7.
dFragment PCH, δH 4.55 d, 2JPH 13; for cyclic fragment OCCO, δC 81.85 m.
the low-boiling substances were removed, and the
residue was distilled in a vacuum to obtain 17 g of
phosphinate 9.
O,O-Dimethyl(dimethoxymethyl)phosphonite
(5)
A mixture of 6.6 g of hypophosphorous acid and
38.2 g of trimethyl orthoformate was stirred for 0.5
h at 20◦C, then boron trifluoride etherate, 0.2 g, was
added under stirring. The mixture was stirred for 3
h, and a solution of 15 g of diethylamine in 150 mL of
pentane was added. The precipitate was separated,
the solvent was removed, and the residue was dis-
tilled to yield 4.2 g of phosphonite 5.
Phosphinate 10 was prepared similarly.
O,O-Dibutyl(dibutoxymethyl)phosphonite (8)
The mixture of 8.1 g of dibutoxyphosphine and 13.5 g
of tributyl orthoformate was stirred for 0.5 h at 20◦C,
then a boron trifluoride etherate, 0.2 g, was added
under stirring. The mixture was stirred for 1.5 h at
20◦C, and then distilled in a vacuum to obtain 13 g
of phosphonite 8.
Phosphonites 6–8 were prepared similarly.
O-Ethyl Bis(diethoxymethyl)phosphinate (9)
A mixture of 13.2 g of hypophosphorous acid and
8.9 g of triethyl orthoformate was stirred for 0.5 h
at 20◦C, and boron trifluoride etherate, 0.2 g, was
added. The mixture was kept at 20◦C for 1 day; then
Phosphines 11 and 12, bisphosphines 23–25,
and phosphonite 26 were prepared similarly. For
phosphine12, the reaction period is 24 h and the
yield is 30%.
Heteroatom Chemistry DOI 10.1002/hc

Synthesis and Reactivity of Substituted α-Carbonylphosphonites and Their Derivatives 17
Diisopropyl(diethoxymethyl)phosphine (12)
P
J
A solution of lithium diisopropylphosphide, which
was obtained from 9.5 g of diisopropylphosphine in
100 mL of tetrahydrofuran and 57 mL of 1.4 M of
butyllithium solution in pentane, was added under
stirring and cooling at −30◦C to the suspension of di-
ethoxycarbonium tetrafluoroborate, which was pre-
pared from 11.8 g of triethyl orthoformate and 15.1 g
of boron trifluoride etherate in 100 mL of diethyl
ether. The mixture was stirred at −30◦C for 0.5 h,
then the solvents were removed, and was added to
150 mL of hexane. The precipitate was separated, the
solvent was removed, and the residue was distilled
in a vacuum to obtain 10.7 g of phosphine 12.
d
b
(P
J
a
d
b
(P
C
P
J
J
C
P
J
Phosphines 13–15, bisphosphines 18 and 19,
and phosphonates 27–31 were prepared similarly.
d
d
d
)
d
(C
t
O,O-Diethyl(triethoxymethyl)phosphonate (27)
C
A solution of 0.1 g of boron trifluoride etherate in
5 mL of diethyl ether was added to the solution of
6.8 g of tetraethyl pyrophosphite and 5 g of tetraethyl
orthocarbonate in 10 mL of ether. This mixture was
kept under 20◦C until the signal of pyrophosphite in
31P NMR spectrum (δP 128) disappeared, and then
a solution of sodium diethyl phosphite, which was
prepared from 1 g of diethyl phosphite and 0.2 g of
sodium, was added. The precipitate was separated,
the solvent was removed, and the residue was dis-
tilled in a vacuum to obtain 6 g of phosphonate 27,
yielding 80%.
P
J
C
P
J
)
d
(C
C
P
J
J
J
Phosphonates 28–31 were synthesized similarly,
yields for phosphonates: 28 (62%), 29 (64%), 30
(62%), and 31 (67%).
C
P
J
t
)
d
(C
Decomposition of O,O-Diethyl(triethoxymethyl)
phosphonate (27)
c
The mixture of 11.2 g phosphonate 27 and 0.3 g of
boron trifluorite etherate was heated under a vac-
uum of 60 mmHg with distillation of low-boiling
products, which were distilled under 750 mmHg
to obtain 3.1 g of diethyl carbonate, yield 67%, bp
125◦C, n2D0 1.3830, and 4.9 g of triethyl phosphite,
yield 75%, bp 156◦C, nD20 1.4130, δP 138.21.
Ratio
C)
(
C)
(pm
(
p
B
t
mgH)
,
The decomposition of phosphonates 28 and 29
proceeds similarly under vacuum 8 mmHg to ob-
tain for 28: tripropyl phosphite, yield 68%, bp 80◦C
(8 mmHg), n2D0 1.4280, δP 137.11, and dipropyl car-
bonate, yield 70%, bp 48◦C (8 mmHg), nD20 1.4030;
for 29: tributyl phosphite, yield 71%, bp 122◦C (8
mmHg), n2D0 1.4320, δP 136.12, and dibutyl carbonate,
yield 74%, bp 86◦C (8 mmHg), nD20 1.4125. n2D0 These
p
(
d
l
e
()%
Yi
d
a
b
c
d
Heteroatom Chemistry DOI 10.1002/hc

18 Prishchenko et al.
TABLE 5 Elemental Analyses Data of Compounds 1–113a
Calculated (%)
Found (%)
Compound
Empirical Formula
Formula Weight
C
H
C
H
1
C7H19O4PSi
C10H25O4PSi
C13H31O4PSi
226.28
268.37
310.45
352.53
168.13
224.24
280.34
336.45
298.32
368.45
248.35
220.29
248.35
334.48
292.40
364.49
420.60
306.41
334.46
362.52
350.48
354.42
424.56
244.66
404.38
195.41
205.02
279.10
210.21
294.37
236.25
240.24
438.59
180.14
222.22
236.25
210.12
204.25
254.22
254.22
296.30
296.30
235.00
256.30
280.41
258.34
300.43
342.51
206.22
192.20
164.15
394.40
328.29
280.30
250.35
166.11
192.19
298.32
37.16
44.76
50.30
54.51
35.72
48.21
55.70
60.69
48.31
55.42
62.87
59.97
62.87
64.64
61.62
62.63
65.68
62.72
64.64
66.26
61.69
54.22
59.41
39.27
44.55
18.43
29.28
34.42
45.71
57.12
50.84
45.00
60.25
40.01
48.64
50.84
34.30
58.80
42.52
42.52
48.64
48.64
25.56
42.18
55.68
32.54
39.98
45.59
52.27
49.99
43.90
49.99
43.90
51.42
47.98
36.15
50.00
60.39
8.46
9.39
10.07
10.58
7.79
37.54
44.44
50.78
54.29
35.55
48.26
55.49
60.44
48.57
55.20
62.70
60.29
63.01
64.48
61.87
62.71
65.41
62.58
64.71
66.55
61.42
54.38
59.90
39.56
44.68
18.61
29.09
34.26
45.49
56.96
51.05
45.35
60.04
39.86
48.45
50.49
34.03
58.65
42.27
42.30
48.46
48.37
25.19
41.94
55.48
32.84
39.73
46.02
52.42
49.75
43.72
49.61
43.94
51.70
47.59
35.90
49.95
60.27
8.47
9.54
10.27
10.45
7.68
2
3
4
C16H37O4PSi
5
C5H13O4P
C9H21O4P
C13H29O4P
C17H37O4P
C12H27O6P
C17H37O6P
C13H29O2P
6
9.44
9.51
7
10.43
11.08
9.12
10.27
11.32
8.95
8
9
10
11
12
13
14
15
18
19
23
24
25
26
28
29
32
33
34
35
36
38
39
40
41
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
72
10.12
11.77
11.44
11.77
11.75
11.38
11.59
11.98
11.84
12.05
12.33
11.22
9.95
10.68
7.42
8.48
3.09
5.41
6.14
9.11
10.62
8.96
8.81
10.80
7.27
8.62
8.96
5.28
10.36
7.53
7.53
8.51
8.51
3.86
8.26
10.42
7.41
8.39
9.12
9.18
8.92
7.98
10.09
11.74
11.58
11.69
11.69
11.29
11.48
11.79
11.95
12.21
12.41
11.03
10.10
10.86
7.51
8.55
3.06
5.31
6.01
9.02
10.73
8.79
8.75
10.71
7.10
8.51
8.90
5.10
10.19
7.41
7.45
8.39
8.40
3.75
8.12
10.50
7.37
8.52
9.29
9.29
8.78
7.83
8.86
C11H25O2P
C13H29O2P
C18H39O3P
C
15H33O3P
C19H42O2P2
23H50O2P2
C
C16H36OP2
C18H40OP2
C
C
20H44OP2
18H39O4P
C16H35O6P
C21H45O6P
C8H18ClO4P
C15H34O8P2
C3H6Cl3OP
C5H11Cl2O2P
C8H17Cl2O4P
C8H19O4P
C14H31O4P
C10H21O4P
C9H21O5P
C22H47O6P
C6H13O4P
C9H19O4P
C10H21O4P
C6H11O6P
C10H21O2P
C9H19O6P
C9H19O6P
C12H25O6P
C12H25O6P
C5H9Cl2O4P
C9H21O4PS
C13H29O2PS
C7H19O4PSSi
C10H25O4PSSi
C13H31O4PSSi
C9H19O3P
C8H17O3P
C6H13O3P
C16H34O6P2
8.92
7.98
8.99
9.26
6.67
8.92
7.77
C
C
12H26O6P2
12H25O5P
7.89
8.87
9.21
6.84
8.96
7.69
C10H23O3PSi
C5H11O4P
C8H17O3P
C15H23O4P
(Continued)
Heteroatom Chemistry DOI 10.1002/hc

Synthesis and Reactivity of Substituted α-Carbonylphosphonites and Their Derivatives 19
TABLE 5 Continued
Calculated (%)
Found (%)
Compound
Empirical Formula
Formula Weight
C
H
C
H
73
74
75
C15H24NO4P
C14H23O5P
C17H36O7P
313.33
302.31
414.42
414.42
358.23
372.26
346.18
690.30
704.32
678.24
556.31
310.33
396.43
266.23
340.47
374.49
354.46
294.48
262.29
306.41
416.58
460.71
504.84
416.49
432.51
212.20
254.28
238.28
282.41
326.54
281.43
309.49
321.50
323.48
313.50
339.51
266.35
341.56
353.57
355.54
57.50
55.62
49.27
49.27
36.88
38.72
31.23
29.58
30.70
26.56
32.39
50.32
51.51
45.12
49.39
54.52
47.44
44.87
54.95
50.96
43.25
41.72
40.44
46.14
44.43
33.96
42.51
45.37
42.53
40.47
38.41
42.69
44.83
40.84
34.48
42.45
40.59
38.68
40.76
37.16
7.72
7.67
8.76
8.76
4.78
5.14
3.79
2.48
2.72
1.93
3.81
8.77
8.39
7.19
9.77
8.34
8.82
9.24
8.84
8.88
9.19
9.17
9.18
9.20
8.86
6.18
7.53
8.04
8.21
8.34
8.60
9.12
8.78
8.10
7.72
8.91
8.70
8.26
7.98
7.37
57.35
55.76
49.53
49.43
36.61
38.58
31.47
29.73
30.73
26.71
32.04
50.03
51.38
44.70
49.79
54.26
47.61
45.01
54.82
50.78
43.43
41.49
40.29
45.92
44.34
34.27
42.35
45.83
41.79
40.21
38.47
42.41
44.55
40.73
34.52
42.07
40.02
38.49
40.52
36.98
7.64
7.58
8.56
8.97
4.69
5.08
3.96
2.38
2.59
2.07
3.70
8.59
8.30
7.28
9.67
8.47
8.92
9.30
8.69
8.80
9.27
9.27
9.03
8.95
9.07
6.33
7.42
8.33
8.44
8.29
8.53
8.95
8.88
8.02
7.48
9.06
8.74
8.15
7.83
7.29
76
C
17H36O7P2
2
77
C11H17F6O4P
C12H19F6O4P
C9H13F6O5P
C17H17F18O6P
78
79
80
81
C18H19F18O6P
82
C15H13F18O7P
C15H21F 12O6P
C13H27O6P
C17H33O8P
C10H19O6P
C14H33O5PSi
C17H31O5PSi
83
84
85
86
87
88
89
C
14H31O6PSi
C11H27O3PSi2
12H23O4P
C13H27O4PSi
C15H38O5P2Si2
90
91
C
92
93
94
C16H42O5P2Si3
C17H46O5P2Si4
C16H38O6P2Si
C16H38O7P2Si
C6H13O4PS
C9H19O4PS
C9H19O3PS
95
96
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
C
C
10H23O3PSSi
11H27O3PSSi2
C9H24NO3PSi2
C11H28NO3PSi2
C12H28NO3PSi2
C11H26NO4PSi2
C9H24NO3PSi2
C12H30NO4PSi2
C9H23N2O3PSi2
C11H28NO3PSSi2
C
C
12H28NO3PSSi2
11H26NO4PSSi2
aCompounds 16, 17, and 20–22 were observed only as intermediates. Compounds 27, 30, 31, 37, 71, and 97 are described in [29], [30], [28],
[20], [21], and their constants are in agreement with the reported values.
product constants concur with those described in
[26] and [27].
The same results were obtained from the reac-
tion of phosphine 11 with an excess of water in the
presence of hydrochloric acid as a catalyst.
Interaction of Dibutyl(diethoxymethyl)
phosphine 11 with Hydrogen Chloride
Interaction of O,O-Dibutyl(dibutoxymethyl)
phosphonite 8 with Iodobenzene Dichloride
Dry hydrogen chloride was bubbled through a so-
lution of 7.6 g of phosphine 11 in 20 mL of ether
cooled to 0◦C for 1 h. Then, a solution of 4 g of tri-
ethylamine in 5 mL of ether was added to the mix-
ture. The precipitate was separated, the solvent was
removed, and the residue was distilled to obtain 3.2 g
of dibutylphosphine, yield 71%, bp 60◦C (12 mmHg),
δP−70.9, 1 JPH191.
Iodobenzene dichloride, 4.3 g, was added with stir-
ring and cooling at −60◦C to a solution of 5.3 g of
phosphonite 8 in 20 mL of ether. The mixture was
stirred for 1 h, then the solvent was removed, and
the residue was distilled to give 2.5 g of iodoben-
zene, yield 78%, bp 62◦C (8 mmHg), nD20 1.6210,
Heteroatom Chemistry DOI 10.1002/hc

20 Prishchenko et al.
and 2 g of dibutyl chlorophosphite, yield 61%, bp
90◦C (8 mmHg), nD20 1.4455, δP 166.30. Similarly,
dibutylchlorophosphine was obtained from phos-
phine 11, yield 64%, bp 96 C (11 mmHg), n2D0 1.4745,
δP 114.7.
then the solvent was removed, and the residue was
distilled to obtain 8.2 g of thiophosohonate 57.
Compounds 58–61, 99–103, and 108 were ob-
tained similarly.
Diethyl Phenyl(isobutyryl)methyl phosphite (72)
O-Ethylchloromethyl(diethoxymethyl)
phosphinate (32)
A solution of 3.9 g benzaldehyde in 5 mL of methyl-
ene chloride was added under stirring to a solution
of 6.2 g of phosphonite 63 in 20 mL of methylene
chloride. The mixture was refluxed for 6 h, then the
solvent was removed, and the residue was distilled
to give 6.5 g of phosphite 72.
A solution of 7.6 g of dichloro(chloromethyl)
phosphine in 20 mL of ether was added under stir-
ring and cooled at 0◦C to a solution of 14.8 g of tri-
ethyl orthoformate in 10 mL of ether. The solvent
was removed, and the residue was distilled to obtain
11.2 g of phosphinate 32.
Compounds 73–76, 84–89, 93–95, 109, and 110
were obtained similarly.
Compounds 33–37 were obtained similarly.
O-Ethyl(diethoxymethyl)methylphosphinate
(38)
Diethyl 1,1-Bis(trifluoromethyl)-3-methyl-2-
A solution of 3.1 g of methyl iodide in 5 mL of diethyl
ether was added under stirring to a solution of 4.9 g
of phosphonite 6 in 15 mL of ether. The mixture was
refluxed for 3 h, the solvent was removed, and the
residue was distilled to give 4 g of phosphinate 38.
Compounds 37, 39–49, 51–55, 62–70, 91, 92,
and 97 were prepared similarly.
oxobutyl phosphite (77)
The gaseous hexafluoroacetone, 3 g, was bubbled
through a solution of 3.5 g of phosphonite 63 in
20 mL of diethyl ether under stirring and cooling to
−70◦C. The mixture was stirred at −70◦C for 0.5 h,
then its temperature was slowly raised to 20◦C, the
solvent was removed, and the residue was distilled
to obtain 5.7 g of phosphite 77.
Compounds 78–83 were synthesized by the same
procedure.
O-Ethyl Bis(methoxycarbonyl)phosphinate (50)
The mixture of 2.9 g of phosphonite 47 and 1.6 g of
methoxycarbonyl chloride was heated at 80–90◦C for
1 h, then distilled to give 2.6 g of phosphinate 50.
Compounds 56 and 96 were prepared similarly.
O-Ethyl O-Trimethylsilyl Pivaloylphosphonite
(68)
A solution of 4.5 g of pivaloyl chloride in 10 mL of
ether was added under stirring to a solution of 6.2 g
of ethoxy(trimethylsiloxy)phosphine and 3.8 g of tri-
ethylamine in 150 mL of diethyl ether. The mixture
was kept at 20◦C for 24 h, then 150 mL of pentane
was added to the mixture, triethylamine hydrochlo-
ride was filtered off, the solvents were removed, and
the residue was distilled to obtain 6.6 g of phospho-
nite 68.
Dimethyldibutylphosphonium Iodide (71)
Methyl iodide, 7.1 g, was added dropwise
with stirring to the solution of dibutyl
(methoxycarbonyl)phosphine 51, 5 g, in 10 mL
of acetonitrile at 10◦C. Spontaneous heating of
the mixture and formation of carbon dioxide were
observed. The solvent was removed, and the residue
was crystallized from a mixture of chloroform and
diethyl ether to give 6.9 g of compound 71, yield
93%, mp 168–169◦C. In 1H, 31P NMR, fragment
PCH3: δH 2.20 d, 2 JPH 14; δP 30.1.
Compounds 90–92 and 104–107 were obtained
similarly.
The constants of compound 71 coincide with the
data from [28].
O,O,O,O-Tetraethyl 2,2-dimethyl-1-
trimethylsiloxypropylidenebisphosphonate (98)
The mixture of 7 g of diethyl trimethylsilyl phosphite
and 6.7 g of phosphonate 97 was kept at 20◦C for
2 days. The crystals were washed with pentane and
exposed to a vacuum of 1 mmHg for 0.5 h to obtain
12.3 g of bisphosphonate 98.
O,O-Diethyl(diethoxymethyl)thiophosphonate
(57)
The mixture of 7.6 g of phosphonite 6, 1.5 g of sulfur,
and 10 mL of diethyl ether was refluxed for 0.5 h,
Heteroatom Chemistry DOI 10.1002/hc

Synthesis and Reactivity of Substituted α-Carbonylphosphonites and Their Derivatives 21
[15] Gambaryan, N. P.; Cheburkov, Yu. A.; Knunyants,
I. L. Izv AN SSSR Ser Khim 1964, 1526–1528 (in
Russian).
[16] Ramirez, F.; Desai, N. B. J Am Chem Soc 1960, 82,
2652–2653.
[17] Ramirez, F.; Ramanathan, N.; Desai, N. B. J Am
Chem Soc 1962, 84, 1317–1318.
Under similar conditions, the interaction of 3.9 g
of phosphinate 91 and 7.3 g of diethyl trimethylsi-
lyl phosphite forms via distillation 4.3 g of starting
phosphite, 2.5 g of phosphonite 68, yield 69%, and
2.4 g of phosphonate 97, yield 75%.
[18] Prishchenko, A. A.; Livantsov, M. V.; Novikova, O. P.;
Livantsova, L. I.; Petrosyan, V. S. Heteroatom Chem
2008, 19, 418–428.
[19] Prishchenko, A. A.; Livantsov, M. V.; Novikova, O. P.;
Livantsova, L. I.; Petrosyan, V. S. Heteroatom Chem
2012, 23, 138–145.
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Heteroatom Chemistry DOI 10.1002/hc