Synthesis and properties of phosphabetaine structures: III. Phosphabetaines derived from tertiary phosphines and α,β-unsaturated carboxylic acids. Synthesis, structure, and chemical properties

Article abstract of DOI:10.1023/A:1015487416152

Methods of synthesis of acylate phosphabetaines by reactions of triphenylphosphine with methacrylic, cinnamic, and p-methoxycinnamic acids are developed. The phosphabetaine form is proposed to exist in equilibrium with the (σ⁵-oxaphospholane form. The features of methylation of the phosphabetaines are discussed.

Full text of DOI:10.1023/A:1015487416152

Russian Journal of General Chemistry, Vol. 72, No. 3, 2002, pp. 384 389. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 3, 2002,
pp. 412 418.
Original Russian Text Copyright
2002 by Galkin, Bakhtiyarova, Polezhaeva, Galkina, Cherkasov, Krivolapov, Gubaidullin, Litvinov.
Synthesis and Properties of Phosphabetaine Structures:
III.1 Phosphabetaines Derived from Tertiary Phosphines
and , -Unsaturated Carboxylic Acids. Synthesis, Structure,
and Chemical Properties
V. I. Galkin, Yu. V. Bakhtiyarova, N. A. Polezhaeva, I. V. Galkina,
R. A. Cherkasov, D. B. Krivolapov, A. T. Gubaidullin, and I. A. Litvinov
Kazan State University, Kazan, Tatarstan, Russia
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Received October 9, 2000
Abstract Methods of synthesis of acylate phosphabetaines by reactions of triphenylphosphine with metha-
crylic, cinnamic, and p-methoxycinnamic acids are developed. The phosphabetaine form is proposed to exist
in equilibrium with the 5-oxaphospholane form. The features of methylation of the phosphabetaines are
discussed.
Earlier [1, 2] we developed a method of synthesis
of phosphabetaine I (R1, R2 = H) by reaction of tri-
phenylphosphine with acrylic acid and showed that a
necessary condition for stabilization of the acylate
phosphabetaine is the presence in its crystal lattice of
a proton donor (water, chloroform, excess acrylic acid,
etc.)
forms showed that in the gas phase the cyclic form is
thermodynamically preferred [4].
O
R1
C
O
Ph3P
Ph3P=C CHCOOH
R2
I
R1
R2
II
III
In the present work, with the aim to extend the
range of , -unsaturated carboxylic acids capable of
forming acylate phosphabeines, we reacted triphenyl-
phosphine with methacrylic, cinnamic, and methoxy-
cinnamic acids.
We also did not rule out formation of form III, in
view of the published data [5, 6], according to which
5-oxaphospholanes can be considered latent ylides
capable of entering the Wittig reaction.
R1
The reactions of triphenylphosphines with metha-
crylic, cinnamic, and p-methoxycinnamic acids in
chloroform smoothly occur at room temperature, and,
according to 31P NMR data, give rise to phosphonium
compounds: The signal of triphenylphosphine com-
pletely disappears and signals characteristic of phos-
phabetaines (( 22 25 ppm) appear. The IR spectra
show well-defiPned carboxylate absorption bands at
+
Ph3P + R1CH=C COOH
R2
Ph3P CH CH COO ,
R2
I
R1 = H, Ph, p-MeOC6H4; R2 = H, Me.
Therewith, we supposed that aryl or methyl sub-
stituents R1 and R2 in the acylate moiety of phos-
phabetaines I would both stabilize the zwitter-ionic
structure of betaines I and favor their isomerization
into 5-phosphacyclanes II. It is well known that the
latter are stabilized by ring substituents [3].
1
1600 cm . The product of the reaction of triphenyl-
phosphine with methacrylic acid, betaine I (R1 = H,
R2 = Me), was isolated as crystals. Moreover, the 31P
NMR spectra of the products of the reactions of tri-
phenylphosphine with cinnamic and p-methoxy-
cinnamic acids detect, along with betaines and in
comparable quantities, phosphorane derivatives at
20.0 and 16.20 ppm, respectively. This resulPt
strongly suggest formation of phosphoranes II, which
we did not observed earlier in the reaction of tri-
Moreover, our quantum-chemical calculations of
the energy of formation of the dipolar I and cyclic II
1
For communication II, see [1].
1070-3632/02/7203-0384$27.00 2002 MAIK Nauka/Interperiodica

SYNTHESIS AND PROPERTIES OF PHOSPHABETAINE STRUCTURES: III.
385
O2
C13
C14
O1
C3
C15
C12
C2
C11
C10
C18
C17a
C1
C19
P1
C16
C4
C21
Cl2
C23
C22
C24
C5
C27
Cl5
C26
C35
C25
C6
C9
Cl3
Cl4
C7
C8
Fig. 1. Molecular structure of (2-carboxy-1-phenylethyl)triphenylphosphonium chloride (VI).
phenylphosphine with acrylic acid [1, 2]. Further
evidence for phosphorane formation in the reactions
studied is provided by the fact that treatment of the
reaction mixture containing a cynnamic acid derived
betaine and its phosphorane isomer with hydrochloric
acid gives rise to (2-carboxy-1-phenylethyl)triphenyl-
phosphonium chloride (VI) as a single product. Thus,
the signal in the phosphorane region can firmly be
assigned to 5-phosphacyclane V.
solvents contained no hydrogen chloride, it remains
to suggest that phosphabetaine IV formed by the re-
action of triphenylphosphine with cinnamic acid has,
for the sake of stabilization, to decompose chloroform
to hydrogen chloride and dichlorocarbene. Note that
chloroform is also present in the crystal of phos-
phonium salt VI (Fig. 1).
+
Ph3P + PhCH=CH COOH
[Ph3P CHCHCOOH]
Ph
O
Ph
Ph
O
Ph3P
+
+
Ph3P CHCH2COO
Ph3P CHCH2COO
IV
IV
Ph
V
+
CHCl3
CCl2
[Ph3P CHCHCOOH]Cl .
+
HCl
Ph
[Ph3P CHCHCOOH]Cl
VI
Ph
The asymmetric part of the unit cell contains one
independent ion part of [(2-carboxy-1-phenylethyl)tri-
phenylphosphonium chloride (VI)] and one solvation
chloroform molecule. The phosphorus atom has a
usual, distorted tetrahedral coordination, and its bond
VI
It is interesting that salt VI was isolated after
prolonged standing of a dilute chloroform solution of
betaine IV. We could grow relatively stable and well-
formed crystals satisfactory for X-ray diffraction lengths and angles (Table 1) are values characteristic
analysis.
of phosphonium salts [7]. These results nicely agree
with those we obtained earlier with betaine I (R = H)
[2]. The bond lengths and angles in the benzene rings,
too, are normal values (Table 1). The conformation of
the P1C1C2C3 fragment is transoid [torsion angle
(P1C1C2C3) 174.1(3) ] and that of the C1C2C3O2
According to X-ray diffraction data, compound VI
is actually a phosphonium salt formed by HCl addi-
tion to phosphabetaine VI (Fig. 1).
Since thoroughly purified starting materials and
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 3 2002

386
GALKIN et al.
Table 1. Bond lengths (d, ) and bond ( , deg) and torsion angles ( , deg) in structure VI
Bond
d
Bond
d
Bond
d
Bond
d
Cl3 C35
Cl4 C35
Cl5 C35
P1 C1
1.723(7)
1.693(7)
1.647(8)
1.837(4)
1.788(4)
1.799(5)
1.791(5)
1.214(5)
1.304(5)
C8 C9
1.389(6)
1.401(6)
1.384(6)
1.372(8)
1.365(8)
1.378(7)
1.390(7)
1.390(6)
1.363(6)
O2 H2
0.85(5)
C17 C18
C18 C19
C19 C20
C4 C5
1.369(8)
1.338(8)
1.359(7)
1.399(7)
1.389(6)
1.362(6)
1.379(8)
1.338(9)
1.382(8)
C10 C11
C10 C15
C11 C12
C12 C13
C13 C14
C14 C15
C16 C17
C16 C21
C1 C2
1.521(6)
1.515(7)
1.504(6)
1.363(8)
1.362(8)
1.389(7)
1.394(6)
1.404(9)
1.331(8)
C1 C22
C2 C3
P1 C4
C6 C7
C4 C9
P1 C10
P1 C16
O1 C3
O2 C3
C7 C8
C5 C6
C20 C21
C22 C27
C23 C24
C24 C25
C22 C23
C25 C26
C26 C27
Bond angle
Bond angle
Bond angle
Bond angle
C1P1C4
109.9(2)
108.9(2)
111.1(2)
108.3(2)
111.0(2)
107.5(2)
106.(3)
111.5(3)
111.9(3)
113.6(4)
112.7(4)
120.1(4)
122.6(4)
C4C5C6
120.0(5)
121.0(5)
120.1(4)
120.5(5)
119.5(5)
118.4(3)
122.4(3)
119.2(4)
119.5(4)
121.3(5)
120.9(4)
121.3(4)
119.0(5)
O2C3C2
117.3(4)
119.8(3)
121.3(4)
118.9(4)
118.3(3)
123.5(3)
118.1(4)
119.1(5)
122.9(5)
118.6(5)
120.2(5)
109.9(4)
100.(4)
C22C23C24
C23C24C25
C24C25C26
C25C26C27
C22C27C26
C13C14C15
C10C15C14
C12C13C14
Cl4C35Cl5
Cl4C35H35
Cl5C35H35
Cl3C35Cl5
118.3(5)
122.3(6)
119.3(6)
121.9(5)
119.2(5)
119.8(5)
120.3(4)
119.9(5)
109.9(4)
99.(3)
C1P1C10
C1P1C16
C4P1C10
C4P1C16
C10P1C16
C3O2H2
P1C1C2
C5C6C7
P1C4C5
C6C7C8
P1C4C9
C7C8C9
C5C4C9
C4C9C8
P1C16C17
P1C16C21
C17C16C21
C16C17C18
C17C18C19
C18C19C20
C19C20C21
Cl3C35Cl4
Cl3C35H35
P1C10C11
P1C10C15
C11C10C15
C10C11C12
C11C12C13
C16C21C20
C1C22C23
C23C22C27
P1C1C22
C2C1C22
C1C2C3
O1C3O2
O1C3C2
124.(3)
113.3(4)
Torsion angle
Torsion angle
Torsion angle
Torsion angle
a
C4P1C1C2
C4P1C1C22
C10P1C1C2
C10P1C1C22
C16P1C1C2
C16P1C1C22
C1P1C4C5
C1P1C4C9
C10P1C4C5
C10P1C4C9
C16P1C4C5
179.8(3) C22C1C2C3
51.8(4) P1C1C22C23
61.3(4) P1C1C22C27
170.3(3) C2C1C22C23
56.9(4) C2C1C22C27
71.5(4) C1C2C3O1
113.9(4) C1C2C3O2
67.5(4) P1C4C5C6
4.9(4) P1C4C9C8
58.4(5) C16P1C4C9
88.1(5) C1P1C10C11
94.6(5) C1P1C10C15
39.2(6) C4P1C10C11
138.1(4) C4P1C10C15
19.2(6) C16P1C10C11
162.8(4) C16P1C10C15
178.7(4) C1P1C16C17
178.6(4) C1P1C16C21
176.9(4) C4P1C16C17
177.5(4)
55.9(4) P1C16C17 C18
161.8(3) P1C16C21C20
21.4(4) C1C22C23C24
78.7(4) C1C22C27C26
98.1(4) C4P1C16C21
41.3(4) C10P1C16C17
141.9(4) C10P1C16C21
74.8(4) H2O2C3O1
178.5(4)
177.1(4)
175.3(5)
177.6(5)
14.6(5)
44.3(4)
132.9(4)
178(4)
108.1(4) H2O2C3C2
162.5(4) P1C1C2C3
0.5(4)
174.1(3)
173.7(4) P1C10C11C12
122.7(4) P1C10C15C14
fragment is close to eclipsed [ 19.2(6) ], which is,
too, nicely consistent with what have been found in
betaine I (R = H). It is interesting to note that the
P1C1C2C3 fragment in similar phosphonium has an
orthogonal conformation [2]. The fact that the car-
bonyl fragment preserves its conformation may be
associated with intra- and intermolecular interactions
in the crystal. As already mentioned, betaine struc-
tures are stabilized by H bonding with proton donors,
which distinguish them from phosphonium salts
[1, 2, 4]. However, in the crystal of compound VI we
found a solvation molecule of chloroform, which
takes part in intermolecular interactions like C H Cl
(Fig. 2). The tendency of HCl molecule to exist in
crystal as an ion pair and the ability of chloride anion
to H-bond formation is well known [8]. In the crystal
of compound VI, the intermolecular H bond C35
H35 Cl2 has the following parameters: d(C35 H35)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 3 2002

SYNTHESIS AND PROPERTIES OF PHOSPHABETAINE STRUCTURES: III.
387
1.05(7), d(H35 Cl2) 2.38(7), d(C35 Cl2) 3.384(7)
,
and C35H35Cl2 159(5) . Moreover, we found a
classical H bond between the cation and anion:
O2 H2 Cl2 [x, 1 + y, z] d(O2 H2) 0.86(5),
d(H2 Cl2) 2.12(5), d(O2 Cl2) 2.970(4) , and
O2H2Cl2 171(5) .
Thus, we obtained evidence to show that betain IV
undergoes facile hydrochlorination and that 5-oxa-
phospholane V can convert to phosphonium chloride
VI. At the same time, it should be stressed that all our
attempts to isolate and identify cyclic phosphoranes
from the reaction mixtures failed. Some assumptions
as to the reasons for this failure we will present later.
We also failed to react betaine IV with benzaldehyde
and thus cannot postulate the betain phosphorane
phosphorus ylide equilibrium.
Interesting and unexpected results were obtained
in alkylation of the newly synthesized betaines with
methyl iodide.
Fig. 2. Intermolecular interactions in the crystal of
phosphonium chloride VI.
Whereas phosphabetaine VII obtained from tri-
phenylphosphine and methacrylic acid reacts with
methyl iodide by a scheme we established earlier
[1, 2] with the acrylate derivative, giving methyl ester
VIII, the reactions of phosphabetaines IV and IX
synthesized from cinnamic acids with methyl iodide
involve P C bond cleavage and result in formation of
methyltriphenylphosphonium iodide. The structure of
+
Bu3P + CH2=CH COOH
[Bu3P CH2CH2COOH]
+
+
CH3I
Bu3P CH2CH2COO
[Bu3P CH2CH2COOCH3]I
XI
XII
possible reasons may lie in the fact that aryl substi-
tuents better stabilize the phosphonium center than
alkyls.
1
the latter was proved by H and 31P NMR and IR
spectroscopy and by independent synthesis.
+
+
EXPERIMENTAL
Ph3P CH2CHCOO + CH3I
[Ph3P CH2CH2COOCH3]I
CH3
CH3
The IR spectra were obtained on a Specord M-80
spectrometer in the range 700 3600 cm 1 in thin films
VII
VIII
Ar
1
and mineral oil between KBr plates. The H and 31P
+
+
Ph3P CHCH2COO + CH3I
[Ph3PCH3]I
NMR spectra were obtained in CDCl3 on a Varian
Unity-300 spectrometer at 300 MHz (1H), internal
reference HMDS, and at 121.64 MHz (31P), external
reference H3PO4.
IV, IX
X
Ph3P + CH3I
Ar = Ph (IV), p-MeOC6H4 (IX).
X-ray diffraction study. Crystals of compound
VI, [C27H24O2P1]+Cl CNCl3, triclinic. At 20 C, a
Aiming at extending the range of phosphabetaines
obtained by phosphine addition to , -unsaturated
carboxylic acids, we turned to aliphatic tertiary phos-
phines. However, contrary to expectations, tributyl-
phosphine proved less rather than more reactive than
triphenylphosphine toward unsaturated carboxylic
acids. We could only isolate and firmly identify the
adduct of tributylphosphine with acrylic acid (com-
pound XI) and its alkylation product XII as oily
liquids not crystallizing upon prolonged standing.
9.869(1), b 9.999(2), c 14.258(2)
;
81.45(1),
85.446(9),
82.11(1) ; V 1375.6(4) 3, Z 2, dcalc
1.37 g/cm3, space group P-1. The unit cell parameters
and the intensities of 5920 reflections, 3005 of which
had I
3 , were measured on an Enraf Nonius
CAD-4 automatic four-circle diffractometer ( MoK
radiation, graphite monochromator, /2 scanning,
29 ). No intensity decay of three reference reflec-
tions was observed during measurements. Absorption
1
was not included ( Mo 5.1 sm ). The structure was
Such a different reactivity of aromatic and aliphatic
phosphines is difficult to understand. One of the
solved by the direct method by the SIR program [9]
and refined first isotropically and then anisotropically.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 3 2002

388
GALKIN et al.
Table 2. Atomic coordinates in structure I, equivalent isotropic thermal parameters of non-hydrogen atoms B =
3
4/33
(aiaj)B(i,j) ( 2) and isotropic thermal parameters of hydrogen atoms Biso
(
)
2
i = 1 j= 1
Atom
x
y
z
B
Atom
x
y
z
B
Cl2
Cl3
Cl4
Cl5
P1
0.4578(1) 0.2503(1) 0.2428(1)
0.1263(2) 0.3606(2) 0.1449(2)
0.1951(3) 0.1487(3) 0.0056(2) 18.1(1)
0.3355(4) 0.4040(3) 0.0022(3) 22.2(1)
4.75(3)
9.22(6)
C24
C25
C26
C27
C35
H1
0.1621(6) 0.0540(6) 0.1954(4)
0.2843(5) 0.0169(6) 0.2371(5)
0.2917(5) 0.0506(6) 0.3120(4)
0.1756(5) 0.0779(5) 0.3500(4)
0.2568(7) 0.2963(7) 0.0719(5)
6.4(1)
6.2(2)
5.5(1)
4.1(1)
7.1(2)
2.5(8)
7(1)
2.5(8)
5(1)
8(1)
0.1410(1) 0.2252(1)
0.29625(8) 2.60(2)
O1
0.0557(3) 0.1894(3) 0.4602(2)
0.2294(3) 0.2290(3) 0.3873(3)
0.0810(4) 0.0635(4) 0.3503(3)
0.1956(4) 0.0550(4) 0.3504(4)
0.1536(5) 0.1862(4) 0.4031(3)
0.0033(4) 0.3614(4) 0.2981(3)
0.0089(5) 0.4644(5) 0.3538(3)
0.0945(5) 0.5698(5) 0.3540(4)
0.2041(5) 0.5775(5) 0.3000(4)
0.2122(5) 0.4783(5) 0.2455(4)
0.1087(4) 0.3692(5) 0.2436(3)
0.2744(4) 0.2600(4) 0.3647(3)
0.3615(5) 0.3545(5) 0.3227(4)
0.4598(5) 0.3878(5) 0.3749(4)
0.4758(5) 0.3290(5) 0.4667(4)
0.3906(5) 0.2363(5) 0.5093(4)
0.2893(5) 0.2020(5) 0.4582(3)
0.2125(4) 0.2150(4) 0.1777(3)
0.3417(5) 0.1420(6) 0.1656(4)
0.3993(6) 0.1358(7) 0.0755(4)
0.3387(5) 0.2008(6) 0.0021(3)
0.2128(6) 0.2733(6) 0.0087(4)
0.1496(5) 0.2798(5) 0.0988(3)
0.0472(4) 0.0392(4) 0.3069(3)
0.0396(6) 0.0257(5) 0.2276(4)
4.40(8)
4.50(8)
3.0(1)
3.5(1)
3.2(1)
2.73(9)
3.5(1)
4.7(1)
4.8(1)
4.5(1)
3.6(1)
2.79(9)
3.8(1)
4.8(1)
4.7(1)
4.4(1)
3.5(1)
3.1(1)
4.6(1)
6.3(2)
4.9(1)
5.2(1)
4.2(1)
3.3(1)
5.0(1)
0.060(3)
0.294(5)
0.075(3)
0.087(4)
0.278(5)
0.280(4)
0.119(3)
0.351(4)
0.508(5)
0.569(6)
0.401(3)
0.225(4)
0.377(4)
0.541(4)
0.382(4)
0.165(4)
0.061(5)
0.061(5)
0.140(5)
0.365(5)
0.371(4)
0.182(4)
0.306(6)
0.221(4)
0.271(4)
0.082(3)
0.276(5)
0.454(3)
0.643(4)
0.659(5)
0.479(4)
0.297(3)
0.391(4)
0.443(5)
0.351(6)
0.190(3)
0.146(4)
0.091(4)
0.893(4)
0.205(4)
0.320(4)
0.339(5)
0.040(5)
0.096(5)
0.046(5)
0.067(4)
0.118(4)
0.256(6)
0.067(4)
0.972(4)
0.423(3)
0.347(4)
0.394(3)
0.386(3)
0.301(4)
0.217(3)
0.203(2)
0.260(3)
0.337(3)
0.508(4)
0.569(2)
0.484(3)
0.210(3)
0.929(3)
0.050(3)
0.040(3)
0.101(4)
0.189(4)
0.142(3)
0.218(4)
0.348(3)
0.407(3)
0.122(5)
0.278(3)
0.381(3)
O2
H2
C1
H5
C2
H6
C3
H7
C4
H8
4(1)
C5
H9
2.5(8)
3.5(9)
6(1)
9(2)
2.2(8)
4(1)
5(1)
3.5(9)
5(1)
5(1)
7(1)
8(1)
6(1)
7(1)
6(1)
4(1)
11(2)
5(1)
5(1)
C6
H11
H12
H13
H14
H15
H17
H18
H19
H20
H21
H23
H24
H25
H26
H27
H35
H221
H222
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
Hydrogen atoms were revealed by difference synthesis
and refined isotropically in the final stage. The final
divergence factors were R 0.046 and RW 0.082, on
of chloroform. The reaction mixture was left to stand
for 1 week at room temperature, and the solvent was
then removed in a vacuum. The residue was treated
with absolute diethyl ether, the precipitate that formed
was filtered off, washed with diethyl ether, and dried
in a vacuum to obtain compound VII as colorless
1996 reflections with F2
3 .
All calculations were performed on AlphaStation
200 using the MolEN program package [10]. Mole-
cular drawings and analysis of intermolecular contacts
were perfomed using the PLATON program [8]. The
atomic coordinates are listed in Table 2.
crystals, mp 175 182 C. IR spectrum:
(CO)
1
1605 cm . 31P NMR spectrum:
18.2 ppm.
P
Betaine VII was alkylated with methyl iodide
according to the procedure in [1] to obtain phospho-
Synthesis and alkylation of 3-(triphenylphos-
phonio)propanoate (I) have been described in [1].
nium salt VIII, mp 115 C. IR spectrum: (CO)
1
1700 cm . 31P NMR spectrum:
22.4 ppm.
P
Reaction of triphenylphosphine with metha-
crylic acid. A solution of 0.81 g methacrylic acid in
5 ml of chloroform was added dropwise with stirring
to a solution of 2.4 g of triphenylphosphine in 7 ml
Reaction of triphenylphosphine with cinnamic
acid. Cinnamic acid, 2.12 g, was thoroughly mixed
with a solution of 3.47 g of triphenylphosphine in 5 ml
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 3 2002

SYNTHESIS AND PROPERTIES OF PHOSPHABETAINE STRUCTURES: III.
of chloroform, and the mixture was left to stand for
389
ACKNOWLEDGMENTS
1 week at room temperature, treated with 1 ml with
diethyl ether, and then left to stand for 1 week at
10 C. Well-formed crystals dropped, which, according
to X-day diffraction data, phosphonium salt VI
containing one solvation chloroform molecule, mp
The work was financially supported by the Russian
Foundation for Basic Research (project no. 99-03-
32880) and the Universitety Rossii fundamental’-
nye issledovaniya
Scientific and Engineering
1
68 C. IR spectrum: (CO) 1705 cm . 31P NMR
Program (project no. 05.01.18).
spectrum:
18 ppm.
P
REFERENCES
The reaction of triphenylphosphine with p-meth-
oxycinnamic acid was performed in a similar way.
1. Galkin, V.I., Bakhtiyarova, Yu.V., Polezhaeva, N.A.,
Cherkasov, R.A., Krivolapov, D.B., Gubaidullin, A.T.,
and Litvinov, I.A., Zh. Obshch. Khim., 2002, vol. 72,
no. 3, pp. 404 411.
Methyltriphenylphosphonium iodide (X). a. A
solution of 1.12 g of cinnamic acid in 5 ml of chloro-
form was added with stirring to a solution of 1.97 g
of triphenylphosphine in 5 ml of chloroform. The re-
action mixture was left to stand for 1 day, and the
solvent was removed in a vacuum. According to spec-
tral data, the reaction product was betaine IV. Without
isolation, it was treated with 1.07 g, and the resulting
mixture was left to stand for an additional 1 day, after
which the solvent was removed in a vacuum, and the
residue was treated with diethyl ether. The precipitate
that formed was filtered off, washed with diethyl ether,
and dried in a vacuum to isolate compound X as
yellow crystals, mp 190 195 C. 31P NMR specrum:
52.8 ppm. The 1H NMR spectrum showed a
2. Galkin, V.I., Bakhtiyarova, Yu.V., Polezhaeva, N.A.,
Shaikhutdinov, R.A., Klochkov, V.V., and Cherka-
sov, R.A., Zh. Obshch. Khim., 1998, vol. 68, no. 7,
pp. 1104 1108.
3. Cherkasov, R.A. and Polezhaeva, N.A., Usp. Khim.,
1985, vol. 54, no. 11, pp. 1899 1939.
4. Cherkasov, R.A., Bakhtiyarova, Yu.V., Galkin, V.I.,
and Polezhaeva, N.A., Abstracts of Papers, XII Int.
Conf. on Chemistry of Phosphorus Compounds, Kiev,
1999, p. 17.
dPoublet of methyl protons at
7.08 Hz).
3.14 ppm (J2PH
5. Cherkasov, R.A. and Pudovik, M.A., Usp. Khim.,
1994, vol. 63, no. 12, pp. 1087 1113.
b. A solution of methyl iodide, 1.16 g, was added
to a solution of 2.1 g of triphenylphosphine in 7 ml
of chloroform. The reaction mixture was left to stand
for 1 day and treated as described in experiment a to
obtain a compound coincident in melting point and
NMR and IR spectra with that obtained in experiment
a.
6. Maryanoff, B.E. and Reits, A.B., Chem. Rev., 1989,
vol. 89, no. 4, pp. 900 905.
7. Naumov, V.A. and Vilkov, L.V., Molekulyarnye
struktury fosfororganicheskikh soedinenii (Molecular
Structures of Organophosphorus Compounds),
Moscow: Nauka, 1986.
8. Fujwara, F.U. and Martin, J.S., J. Am. Chem. Soc.,
vol. 96, no. 25, pp. 2625 2631; Iogansen, A.V.,
Vodorodnaya svyaz’ (Hydrogen Bond), Moscow:
Nauka, 1981, p. 118.
Reaction of tributylphosphine with acrylic acid.
Acrylic acid, 0.41 g, was added dropwise with stirring
to a solution of 1.12 g of tributylphosphine in 5 ml of
chloroform. Strong heat release was observed. The
reaction mixture was left to stand for 1 day, and the
solvent was removed in a vacuum to obtain betaine
9. Altomare, A., Cascarano, G., Giacovazzo, C., and
Viterbo, D., Acta Crystallogr., Sect. A, 1991, vol. 47,
no. 3, pp. 744 748.
XI as an oily substance, n2D0 1.4751. IR spectrum:
1
(CO) 1600 cm . 31P NMR spectrum:
23 ppm.
10. Straver, H. and Schierbeek, A.J., MolEN. Structure
Determination System, Nonius, B.V., 1994, nos. 1
and 2.
P
Compound XI was alkylated by the above-des-
cribed procedure to give phosphonium salt XII as a
1
tarry substance. IR spectrum: (CO) 1730 cm . 31P
11. Spek, A.L., Acta Crystallogr., Sect. A, 1990, vol. 46,
NMR spectrum:
23.4 ppm.
no. 1, pp. 34 40.
P
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 3 2002