Furoyl phosphonates

Article abstract of DOI:10.1134/S107036321605011X

A series of furoyl phosphonates bearing methyl, methoxymethyl, and diethoxyphosphorylmethyl groups in the furan ring have been synthesized via the Arbuzov reaction from the corresponding acid chlorides. NMR spectral parameters of the prepared compounds were studied. The values of coupling constants between the phosphorus nuclei and the carbon nuclei of the furan ring have been examined with relation to the location of the acylphosphoryl group in the furan ring, the nature of second substituent, and location of the latter with respect to the phosphorus-containing substituent in the furan ring. The substitution in position 4 of the furan ring of 3-furoyl phosphonates has been shown to strongly decrease the value of the coupling constant between the phosphorus nucleus and the C² atom of the heterocycle. The interaction between the phosphorus nuclei has not been detected in the spectra of the compounds containing both diethoxyphosphorylmethyl and acylphosphonate fragments.

Full text of DOI:10.1134/S107036321605011X

ISSN 1070-3632, Russian Journal of General Chemistry, 2016, Vol. 86, No. 5, pp. 1046–1053. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © L.M. Pevzner, 2016, published in Zhurnal Obshchei Khimii, 2016, Vol. 86, No. 5, pp. 782–790.
Furoyl Phosphonates
L. M. Pevzner
St. Petersburg State Institute of Technology (Technical University), Moskovskii pr. 26, St. Petersburg, 190013 Russia
e-mail: pevzner_lm@list.ru
Received October 1, 2015
Abstract—A series of furoyl phosphonates bearing methyl, methoxymethyl, and diethoxyphosphorylmethyl
groups in the furan ring have been synthesized via the Arbuzov reaction from the corresponding acid chlorides.
NMR spectral parameters of the prepared compounds were studied. The values of coupling constants between
the phosphorus nuclei and the carbon nuclei of the furan ring have been examined with relation to the location
of the acylphosphoryl group in the furan ring, the nature of second substituent, and location of the latter with
respect to the phosphorus-containing substituent in the furan ring. The substitution in position 4 of the furan
ring of 3-furoyl phosphonates has been shown to strongly decrease the value of the coupling constant between
the phosphorus nucleus and the C2 atom of the heterocycle. The interaction between the phosphorus nuclei has
not been detected in the spectra of the compounds containing both diethoxyphosphorylmethyl and
acylphosphonate fragments.
Keywords: acyl phosphonate, furoyl chloride, the Arbuzov reaction, spin-spin coupling constant
DOI: 10.1134/S107036321605011X
R1
Acyl phosphonates have been extensively studied
[1,2] as available compounds capable of wide range of
chemical transformations. At the same time, first furan
derivatives of class have been synthesized quite
recently [3]. Since then, no attempts to utilize furoyl
phosphonates in organic synthesis have been reported.
R1
PO(OEt)2
P(OEt)3
R2
R2
COCl
O
O
O
3a, 3b
1a, 1b
O
R2
COCl
R1
R2
R3
In this work we have proposed the methods of
preparation of furoyl phosphonates containing the
substituents allowing their further functionalization.
For instance, methyl and methoxymethyl groups have
been chosen in view of the pathway to halomethyl
compounds, alkoxycarbonyl group can be used in a
wide range of transformations as well, and diethoxy-
phosphorylmethyl group is a CH-acidic center.
P(OEt)3
PO(OEt)2
R1
R3
O
O
2a_2c
4a_4c
R1 = CH3, R2 = H (1a, 3a); R1 = H, R2 = CH3 (1b, 3b);
R1 = CH3, R2 = R3 = H (2a, 4a); R1 = R3 = H, R2 = CH3
(2b, 4b); R1 = R2 = H, R3 = CH3 (2c, 4c).
Phosphorylation of acid chlorides of methylfuran-2-
(1a, 1b) and 3-carboxylic acids (2a–2c) was carried
out in benzene in the presence of slight excess of
triethyl phosphite. The reaction was complete in 2–3 h
and led to formation of the corresponding phosphonate
3a, 3b and 4a–4c. Diethyl ethanephosphonate was
found as the only side product. Reduction of the
carbonyl group and formation of 1,1-bis(phosphonates)
characteristic of the reaction with trimethyl phosphite
[3] were not observed.
The phosphonates 3a, 3b and 4a–4c were colorless
high-boiling oils gradually turning yellow when ex-
posed to light. Structure of the compounds was
elucidated using NMR spectroscopy data. 31P NMR
spectra of compounds 3a, 3b and 4a–4c contained
signals of the phosphorus nuclei in the range of –1.2 to
–3.1 ppm. The 13C signal of the carbonyl carbon atom
in the 2-furoyl derivatives was a doublet around
182 ppm (1JPC = ≈180 Hz). In the case of the 3-furoyl
compounds, the doublet of the carbonyl carbon atom
1046

1047
FUROYL PHOSPHONATES
was located at 192–194 ppm, its 1JPC coupling constant
being the same.
under conditions of majority of transformations involv-
ing carbonyl group of acyl phosphonate. In view of
that, we studied the synthesis of isomeric methoxy-
methyl derivatives of 2- and 3-furoyl phosphonates.
The corresponding acid chlorides 7a–7f prepared from
available alkyl halomethylfuroates (the scheme of
preparation of compound 7a given below exemplifies
the procedure) were chosen as the starting compounds.
In order to investigate the possibility of func-
tionalization of the prepared phosphonate at the methyl
group, we attempted the bromination of compound 4a
with N-bromosuccinimide initiated with azobisiso-
butyronitrile. The reaction was carried out in carbon
tetrachloride.
NaOMe
O
O
KI
O
O
ClCH2
COOEt
O
COOMe
PO(OEt)2
Br
NBS
4a
SOCl2
KOH
O
7a
5
COOH
O
The bromination occurred selectively at the methyl
group. H NMR spectrum of the product 5 contained
Addition of 5 mol % of potassium iodide as catalyst
allowed smooth substitution even in the case of rela-
tively inert ethyl 4-chloromethyl-3-furoate. Synthesis
of the acid chlorides was never accompanied by
cleavage of the ether bond in the methoxymethyl fragment.
1
the signal of bromomethyl group protons at 4.71 ppm.
13C signal of the corresponding carbon atom was
observed at 21.15 ppm. The 31P signal of phosphorus
atom shifted downfield from –1.76 ppm (compound 4)
to –2.84 ppm.
Phosphorylation of the corresponding acid
chlorides 7a–7f was carried out similarly to that of
compounds 1 and 2. The Arbuzov reaction occurred
within 2–3 h to yield furoyl phosphonates 8a–8f. Their
spectral parameters were close to those of the methyl
derivatives 3 and 4.
The synthesized bromide readily eliminated
hydrogen bromide on cooling. When treated with the
solution of urotropine in chloroform at room tem-
perature, it formed urotropine hydrobromide within
10 min after mixing the reagents. Hence, formation of
the 2-bromomethyl derivative of 3-furoyl phosphonate
was reliably registered by spectral methods, but its
application in further transformations was limited due
to hydrogen bromide elimination followed by forma-
tion of the polymer.
R2
R3
P(OEt)3
7a_7f
R4
R1
O
8a_8f
R1 = C(O)P(O)(OEt)2, R2 = R3 = H, R4 = CH2OCH3 (8а);
R1 = C(O)P(O)(OEt)2, R2 = H, R3 = CH2OCH3, R4 = Me (8b);
R1 = C(O)P(O)(OEt)2, R2 = CH2OCH3, R3 = R4 = H (8c);
R1 = CH2OCH3, R2 = C(O)P(O)(OEt)2, R3 = R4 = H (8d);
R1 = R4 = H, R2 = C(O)P(O)(OEt)2, R3 = CH2OCH3 (8e);
R1 = R3 = H, R2 = CH2OCH3, R4 = C(O)P(O)(OEt)2 (8f).
In view of that, we attempted phosphorylation of 2-
chloromethyl-3-furoyl chloride. The reaction was
carried out in benzene in the presence of slight excess
of triethyl phosphite. The process was not selective
even at room temperature. A complex set of products
was formed, as reflected in the presence of 11 signals
of phosphorus nuclei over –13.24 to 20.03 ppm in the
31P NMR spectrum of the reaction mixture. The
presence of phosphonate signals was especially sur-
prising, since substitution of chlorine in ethyl 2-chloro-
methyl-3-furoate under conditions of the Arbuzov
reaction required heating to 165–170°C.
The ester group is another moiety convenient for
further transformations and inert under the conditions
of phosphorylation. The available 4-(ethoxycarbonyl)-
3-furoyl chloride 9 is of special interest among the
alkoxycarbonyl derivatives of furoyl chlorides: it
potentially opens the way to preparation of the phos-
phorylated analogs of 3-functionalyzed furans, found
in natural compounds. The acid chloride 9 was phos-
phorylated via the Arbuzov reaction similarly to the
above-described compounds, to afford the acyl phos-
phonate 9a. The obtained compound was stabile below
Hence, introduction and necessary transformations
of the acylphosphoryl group should precede any other
functionalization of the furan ring. Methoxymethyl
group is convenient in this instance, since it can be
easily converted into bromomethyl one upon treatment
with triphenylphosphine dibromide, being fairly inert
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1048
PEVZNER
80°C but was decomposed below its boiling point
when heated in vacuum.
obtained bis(phosphonates) 11a–11f were highly viscous
syrups decomposing on heating in vacuum.
R2
R3
O
COCl
EtOOC
EtOOC
P(OEt)3
PO(OEt)2
10a_10f
P(OEt)3
R4
R1
O
11a_11f
O
9a
O
9
R1 = C(O)P(O)(OEt)2, R2 = R3 = H, R4 = CH2P(O)(OEt)2
(11а); R1 = C(O)P(O)(OEt)2, R2 = H, R3 = CH2P(O)(OEt)2,
R4 = Me (11b); R1 = C(O)P(O)(OEt)2, R2 = CH2P(O)(OEt)2,
R3 = R4 = H (11c); R1 = CH2P(O)(OEt)2, R2 = C(O)P(O)(OEt)2,
R3 = R4 = H (11d); R1 = R4 = H, R2 = C(O)P(O)(OEt)2,
R3 = CH2P(O)(OEt)2 (11e); R1 = R3 = H, R2 = CH2P(O)(OEt)2,
R4 = C(O)P(O)(OEt)2 (11f).
Analysis of the spectral data revealed that for the
studied furoyl phosphonates the 31P chemical shift
ranged between –1.9 and –3.6 ppm. It was independent
of the location of the phosphorus-containing fragment
in the furan ring and the presence of the other
substituents. On the contrary, the value of the coupling
constant between the phosphorus and the carbonyl
carbon atom depended on the substitution pattern of
the furan ring, being of 184–188 Hz in 2-furoyl phos-
phonates and decreases to 181–183 Hz in the case of
the 3-furoyl derivatives. When position 4 of the furan
ring was occupied by methyl or methoxymethyl group
(as in the case of compounds 4b and 8e), the 1JPC value
was down to 178.3 Hz and 180.4 Hz, respectively. The
The 31P chemical shifts of the acyl phosphonate
group (from –2.1 to –3.6 ppm) and of the methane-
phosphonate one (23.7–25.6 ppm for β-substituted
furans and 20.5–21.6 ppm for α-substituted ones) in
compounds 11a–11f coincided with the values for
compounds containing a single phosphorus atom. The
coupling between the phosphorus atoms was never
observed in the 31P NMR spectra. The value of the
coupling constant between the phosphorus atom and
the C2 carbon atom of the furan ring in compound 11c
(2JPC = 58.9 Hz) was lower than that observed for
2-furoyl phosphonates and bis(phosphonates) 11a, 11b
(2JPC = 90 Hz).
2
change of the JPC value (the interaction between the
phosphorus atom and the adjacent carbon atom of the
furan ring) revealed certain specific features as well. In
the case of furoyl phosphonates, it was several times
higher than the coupling constant typical of
furylmethane phosphonates. On top of that, its value
depended on the location of the acyl phosphonate
The effects of location of the acylphosphonate frag-
ment and the nature of second substituent on the JPC
3
2
group in the furan ring. In 2-furoyl phosphonates, JPC
constant of the coupling between the acyl phosphorus
atom and the carbon atoms of the furan ring can be
exemplified by the series of compounds 3a, 8c, 11c;
4a, 8d, 11d; and 4b, 8e, 11e, 9a. For compounds 3a,
ranged between 89 and 91 Hz if position 3 of the furan
ring is not occupied. In the presence of methyl (3a) or
2
the methoxymethyl (8c) group JPC value decreased to
60.1 Hz and 60.6 Hz, respectively. In 3-furoyl phos-
8c, and 11c, the 3JP(C )
value somewhat increased in the
3
2
phonates, the JPC value was 68–70 Hz, except for the
2
CH3 < CH2OCH3 < CH2PO(OEt)2 substituent series,
being close to 9 Hz. In that case, the transfer of the
interaction was opposite to the direction of the
electronic density polarization in the furan ring
2-methoxymethyl derivative 8d exhibiting the JPC
value as high as 86.5 Hz.
We have earlier applied the NMR spectroscopy
method to study the interaction of the phosphorus
nuclei of diethoxyphosphorylmethyl groups located at
various positions of the furan ring [4,5]. In the present
work, phosphorylation of the corresponding (diethoxy-
phosphorylmethyl)furoyl chlorides 10a–10f afforded
the bis(phosphonates) 11a–11f, and the influence of
two different phosphorus atoms on the parameters of
the 13C and 31P NMR spectra was examined.
induced by the oxygen atom. For compounds 4a, 8d,
3
and 11d, two coupling types with constants JP(C )
4
and
3JP(C )
were possible. The former one was not revealed,
2
meaning that the magnetic interaction in the direction
perpendicular to the direction of polarization of the
electronic density was absent. The value of the second
constant was independent of the nature of the sub-
stituent in the position 2, being close to 15 Hz at the
average. That reflected the transfer of the magnetic
interaction codirectional with the polarization of hetero-
cycle. Hence, transfer of the magnetic interaction
Phosphorylation of the phosphorus-containing acid
chlorides 10a–10f was carried out with triethyl phos-
phite via the Arbuzov reaction as described above. The
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 5 2016

1049
FUROYL PHOSPHONATES
between the phosphorus and carbon nuclei in the latter
case was more efficient.
furoyl phosphonates. The method was applicable for
the wide range of compounds bearing different substi-
tuents in the furan ring. It was established that mag-
netic interactions between the phosphorus atom and
carbon atoms of the furan ring in diethoxyphosphoryl-
methyl derivatives of furoyl phosphonates differed
significantly from that operative in bis(di-ethoxy-
phosphorylmethyl)furans. The presence of the acyl
phosphonate group significantly altered the generally
observed values of the JPC coupling constants. Magnetic
interaction between phosphorus nuclei of the
phosphonomethyl and acyl phosphonate groups was
not revealed in the spectra.
The situation was more complicated for the series
of compounds 4b, 8e, 11e, 9a. In that case, the spin-
spin coupling constants 3JP(C )
4
and 3JP(C )
were observed
2
on top of the increase in the electron-accepting
properties of the substituent located in position 4 of the
heterocycle [CH3 < CH2OCH3 < CH2PO(OEt)2 <
3
COOEt]. The JP(C )
4
value was only slightly varied,
being of 10.5 Hz on the average. The so high value has
been never observed previously for phosphonomethyl
3
derivatives. The JP(C )
2
value for compounds 4b, 8e,
11e ranged between 3.7 and 3.9 Hz, being much lower
3
than has been earlier observed. The JP(C ) value was
2
EXPERIMENTAL
decreased to 2.8 Hz with the appearance of ethoxy-
carbonyl group in the structure; that was probably
characteristic exclusively for acyl phosphonates, since
such effect has not been observed for phosphono-
methyl compounds.
1H, 13C, and 31P NMR spectra were registered using
1
a Bruker DPX-400 spectrometer (400.13 MHz H,
161.97 MHz 31P, 100.16 MHz 13C) in CDCl3.
Methyl methoxymethylfuroates (general procedure).
30 mmol of ethyl chloromethyl- or bromomethyl-
furoate dissolved in 30 mL of toluene and 1.5 mmol of
finely crumbled potassium iodide were added to a
solution of sodium methylate prepared via dissolution
of 36 mmol of sodium in 20 mL of methanol. The
reaction mixture was refluxed with stirring during
10 h. After cooling, the precipitate was filtered off, the
solvent was removed on a rotary evaporator, and the
residue distilled in vacuum.
The changes of the 2JPC and 3JPC coupling constants
between the phosphorus atom of the phosphonomethyl
group and the carbon atoms of the furan ring could be
followed using bis(phosphonates) 11c–11e. In the case
2
3
of the phosphonate 11c, JPC
3
and JPC
2
coupling
constants exhibited the usual values of 9.3 and 9.8 Hz,
3
respectively, whereas the coupling constant JPC
not observed. In the case of phosphonate 11d, 2JPC
3JPC
4
was
and
2
3
were as large as 14.7 Hz and 7.4 Hz, respectively.
Comparison of the listed values showed that the
relationship between the coupling constant value and
the orientation of the P–C magnetic interaction with
respect to the direction of electronic density polariza-
tion in the furan ring earlier established for the phos-
phonomethyl derivatives [4, 5] was observed in
Methyl 5-methoxymethyl-2-furoate. Yield 66%,
colorless oil, bp 94–96°С (1 mmHg). Н NMR spec-
1
trum, δ, ppm: 3.28 s (3Н, СН3О), 3.77 s (3Н, СН3ООС),
4.34 s (2Н, ОСН2-furan), 6.34 d (1Н, Н4-furan, JHH
3.4 Hz), 7.03 d (1Н, Н3-furan, JHH = 3.4 Hz).
=
Methyl 5-methyl-4-methoxymethyl-2-furoate. Yield
53%, colorless oil, bp 92°C (1 mmHg). 1Н NMR spec-
trum, δ, ppm: 2.32 s (3Н, СН3-furan), 3.28 s (3Н,
СН3О), 3.81 s (3Н, СН3ООС), 4.21 s (2Н, ОСН2-
furan), 7.03 s (1Н, Н3-furan).
presence of the acyl phosphonate substituent as well.
2
For the phosphonate 11e, the JPC
4
constant value was
3
typical (9.8 Hz), and the coupling constant JPC
smaller than usual (7.8 Hz). The JPC
5
was
3
3
coupling
constant was unexpectedly high (5.9 Hz). Probably, in
such compounds the P3 phosphorus atom of the
acylphosphonate group efficiently interacted with the
C4 carbon atom (cf. the series of compounds 4b, 8e,
11e, 9a), and also the magnetic interaction of the P4
phosphonomethyl phosphorus atom with the C5 carbon
atom of the furan ring was significantly enhanced in
presence of the acylphosphonate moiety.
Methyl 3-methoxymethyl-2-furoate. Yield 66%,
1
colorless oil, bp 79–80°С (1 mmHg). Н NMR spec-
trum, δ, ppm: 3.35 s (3Н, СН3О), 3.84 s (3Н, СН3ООС),
4.62 s (2Н, ОСН2-furan), 6.57 br.s (1Н, Н4-furan),
7.45 br.s (1Н, Н5-furan).
Methyl 2-methoxymethyl-3-furoate. Yield 46%,
1
colorless oil, bp 76°С (1 mmHg). Н NMR spectrum,
In summary, it was shown that phosphorylation of
furoyl chlorides with triethyl phosphite under condi-
tions of the Arbuzov reaction led to formation of
δ, ppm: 3.38 s (3Н, СН3О), 3.83 s (3Н, СН3ООС),
4.72 s (2Н, ОСН2-furan), 6.68 br.s (1Н, Н4-furan),
7.35 br.s (1Н, Н5-furan).
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1050
PEVZNER
Methyl 4-methoxymethyl-3-furoate. Yield 64%,
colorless oil, bp 67°С (1 mmHg). Н NMR spectrum,
δ, ppm: 3.41 s (3Н, СН3О), 3.80 s (3Н, СН3ООС),
4.54 s (2Н, ОСН2-furan), 7.41 br.s (1Н, Н5-furan),
7.95 d (1Н, Н2-furan, JHH = 1.6 Hz).
5-Methyl-4-methoxymethyl-2-furoyl
chloride.
Yield 45%, colorless oil with bp 106°С (1 mmHg). 1Н
NMR spectrum, δ, ppm: 2.42 s (3Н, СН3-furan), 3.37 s
(3Н, СН3О), 4.29 s (2Н, ОСН2-furan), 7.46 s (1Н, Н3-
furan). 13С NMR spectrum, δС, ppm: 12.60 (СН3-
furan), 58.14 (СН3О), 65.07 (ОСН2-furan), 121.13 С4-
furan), 127.15 (С3-furan), 143.74 (С2-furan), 151.99
(С5-furan), 159.41 (С=О).
1
Methyl 5-methoxymethyl-3-furoate. Yield 70%,
1
colorless oil, bp 87°С (1 mmHg). Н NMR spectrum,
δ, ppm: 3.34 s (3Н, СН3О), 3.81 s (3Н, СН3ООС),
4.37 s (2Н, ОСН2-furan), 6.15 s (1Н, Н4-furan), 7.97 s
(1Н, Н2-furan).
3-Methoxymethyl-2-furoyl chloride. Yield. 73%,
colorless oil with bp 69–70°С (1 mmHg). Н NMR
1
spectrum, δ, ppm: 3.43 s (3Н, СН3О), 4.65 s (2Н,
ОСН2-furan), 6.78 br.s (1Н, Н4-furan), 7.66 br.s (1Н,
Н5-furan). 13С NMR spectrum, δС, ppm: 58.84 (СН3О),
66.28 (ОСН2-furan), 114.22 (С4-furan), 138.02 (С3-
furan), 148.38 (С2-furan), 147.91 (С5-furan), 156.43
(С=О).
Methoxymethylfuroic acids (general procedure).
30 mmol of methyl methoxymethylfuroate was added
to a solution of 40 mmol of potassium hydroxide in a
mixture of 5 mL of water and 40 mL of ethanol. The
obtained mixture was refluxed with stirring during 7 h
and then evaporated to dryness on a rotary evaporator.
The residue was dissolved in the minimum amount of
water and acidified with concentrated hydrochloric
acid to pH 2–3. The formed precipitate was filtered off
and dried in air to constant mass.
2-Methoxymethyl-3-furoyl chloride. Yield 67%,
1
colorless oil with bp 68–69°С (1 mmHg). Н NMR
spectrum, δ, ppm: 3.40 s (3Н, СН3О), 4.68 s (2Н,
ОСН2-furan), 6.81 d (1Н, Н4-furan, JHH = 2.0 Hz),
7.43 d (1Н, Н5-furan, JHH = 2.0 Hz). 13С NMR spec-
trum, δС, ppm: 58.84 (СН3О), 64.92 (ОСН2-furan),
112.61 (С4-furan), 128.67 (С3-furan), 142.73 (С5-
furan), 159.14 (С2-furan), 161.66 (С=О).
5-Methoxymethyl-2-furoic acid. Yield 71%, color-
less crystals with mp 69–70°С.
5-Мethyl-4-methoxymethyl-2-furoic acid. Yield
99%, colorless crystals with mp 82°C.
4-Methoxymethyl-3-furoyl chloride. Yield 86%,
1
3-Methoxymethyl-2-furoic acid. Yield 93%, color-
less crystals with mp 146°С.
colorless oil with bp 68°С (1 mmHg). Н NMR spec-
trum, δ, ppm: 3.45 s (3Н, СН3О), 4.51 s (2Н, ОСН2-
furan), 7.51 s (1Н, Н5-furan), 8.23 s (1Н, Н2-furan).
13С NMR spectrum, δС, ppm: 58.81 (СН3О), 65.20
(ОСН2-furan), 122.70, 122.91 (С3,4-furan), 143.29 (С2-
furan), 154.05 (С5-furan), 159.22 (С=О).
2-Methoxymethyl-3-furoic acid. Yield 72%, color-
less crystals with mp 792°С.
4-Methoxymethyl-3-furoic acid. Yield 90%, color-
less crystals with mp 135°С.
5-Methoxymethyl-3-furoyl chloride. Yield 75%,
colorless oil with bp 90°С (1 mmHg). 1Н NMR
spectrum, δ, ppm: 3.37 s (3Н, СН3О), 4.39 s (2Н,
ОСН2-furan), 6.69 s (1Н, Н4-furan), 8.17 s (1Н, Н2-
furan). 13С NMR spectrum, δС, ppm: 58.16 (СН3О), 65.83
(ОСН2-furan), 108.58 (С4-furan), 124.83 (С3-furan),
151.90 (С2-furan), 154.81 (С5-furan), 159.67 (С=О).
5-Methoxymethyl-3-furoic acid. Yield 96%, color-
less crystals with mp 94°С.
Methoxymethylfuroyl chlorides (general proce-
dure). 45 mmol of thionyl chloride and 5 drops of
DMF were added to a suspension of 30 mmol of me-
thoxymethylfuroic acid in 40 mL of benzene. The ob-
tained mixture was refluxed with stirring during 8 h.
The target product was isolated via vacuum distillation.
Synthesis of diethyl methyl- and methoxy-
methylfuroyl phosphonates (general procedure). A
solution of 20 mmol of methylfuroyl or methoxy-
methylfuroyl chloride in 10 mL of benzene was added
to a solution of 30 mmol of triethyl phosphite in 20 mL
of benzene. Heat evolution was observed, and tem-
perature of the reaction mixture reached 28–35°C.
After spontaneous cooling to room temperature, the
formed mixture was heated with stirring at 70°C
during 3 h and then distilled in vacuum.
5-Methoxymethyl-2-furoyl chloride. Yield 75%,
colorless oil with bp 92°С (1 mmHg). 1Н NMR
spectrum, δ, ppm: 3.42 s (3Н, СН3О), 4.48 s (2Н,
ОСН2-furan), 6.56 d (1Н, Н4-furan, JHH = 3.6 Hz),
7.47 d (1Н, Н3-furan, JHH = 3.6 Hz). 13С NMR
spectrum, δС, ppm: 58.80 (СН3О), 66.53 (ОСН2-
furan), 111.70 (С4-furan), 125.67 (С3-furan), 145.53
(С2-furan), 155.27 (С5-furan), 160.39 (С=О).
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FUROYL PHOSPHONATES
Diethyl 3-methyl-2-furoyl phosphonate (3a).
Yield 73%. Colorless oil with bp 146–147°C (2 mmHg).
1Н NMR spectrum, δ, ppm: 1.37 t (6Н, СН3-phos-
phonate, JHH = 7.0 Hz), 2.39 s (3Н, СН3-furan), 4.29
d.q (4Н, СН2ОР, JHH = 7.0 Hz, JРH = 14.4 Hz), 6.42
br.s (1Н, Н4-furan), 7.58 br.s (1Н, Н5-furan). 13С NMR
spectrum, δС, ppm: 11.78 (СН3-furan), 16.36 d (СН3-
NMR spectrum, δ, ppm: 1.33 t (6Н, СН3-phosphonate,
JHH = 7.0 Hz), 2.29 s (3Н, СН3-furan), 4.15–4.23 m
(4Н, СН2ОР), 6.37 s (1Н, Н4-furan), 8.54 s (1Н, Н2-
furan). 13С NMR spectrum, δС3, ppm: 13.19 (СН3-furan),
16.29 d (СН3-phosphonate, JPC = 5.6 Hz), 63.89 d
2
3
(СН2ОР, JPC = 6.8 Hz), 103.11 d (С4-furan, JPC
=
2
8.3 Hz), 128.35 d (С3-furan, JPC = 69.0 Hz), 152.19
(С5-furan), 154.64 (С2-furan, 3JPC = 3.8 Hz), 192.90 d
3
2
phosphonate, JPC = 5.8 Hz), 63.92 d (СН2ОР, JPC
=
4
7.0 Hz), 116.22 d (С4-furan, JPC = 2.8 Hz), 134.83 d
(С=О, JPC = 180.1 Hz). ). 31P NMR spectrum, δP,
1
3
(С3-furan, JPC = 8.6 Hz), 147.42 d (С5-furan), 148.73
ppm: –2.69.
2
1
d (С2-furan, JPC = 60.1 Hz), 186.49 d (С=О, JPC
=
184.0 Hz). 31P NMR spectrum, δP, ppm: –1.30.
Diethyl 5-methoxymethyl-2-furoyl phosphonate
(8a). Yield 65%. Colorless oil with bp 164–165°С
Diethyl 5-methyl-2-furoyl phosphonate (3b).
Yield 73%. Colorless oil with bp 146–147°С (2 mmHg).
1Н NMR spectrum, δ, ppm: 1.18 t (6Н, СН3-phos-
phonate, JHH = 7.2 Hz), 2.25 s (3Н, СН3-furan), 4.03–
1
(1 mmHg). Н NMR spectrum, δ, ppm: 1.25 t (6Н,
СН3-phosphonate, JHH = 7.2 Hz), 3.29 s (3Н, СН3О),
4.15 d. q (4Н, СН2ОР, JHH = 7.2 Hz, JРH = 14.4 Hz),
4.38 s (2Н, О–СН2-furan), 6.45 d (1Н, Н4-furan, JHH
=
4.10 m (4Н, СН2ОР), 6.12 d (1Н, Н4-furan, JHH
=
3.6 Hz), 7.76 d (1Н, Н3-furan, JHH = 3.6 Hz). 13С NMR
3.6 Hz), 7.67 d (1Н, Н3-furan, JHH = 3.6 Hz). 13С NMR
spectrum, δС, ppm: 13.99 (СН3-furan), 16.14 d (СН3-
3
spectrum, δС, ppm: 16.12 d (СН3-phosphonate, JPC
=
=
2
5.6 Hz), 58.63 (СН3О), 64.08 d (СН2ОР, JPC
3
2
phosphonate, JPC = 5.6 Hz), 63.88 d (СН2ОР, JPC
=
6.8 Hz), 66.45 (ОСН2-furan), 111.39 (С4-furan),
126.57 (С3-furan), 151.63 d (С2-furan, 2JPC = 89.9 Hz),
6.8 Hz), 110.19 (С4-furan), 127.94 (С3-furan), 151.12
d (С2-furan, 2JPC = 90.8 Hz), 161.38 (С5-furan), 183.20
1
159.80 (С5-furan), 184.48 d (С=О, JPC = 188.4 Hz).
1
d (С=О, JPC = 187.5 Hz). 31P NMR spectrum, δP,
31P NMR spectrum, δP, ppm: –2.67.
ppm: –2.23.
Diethyl 4-methoxymethyl-5-methyl-2-furoyl phos-
Diethyl 2-methyl-3-furoyl phosphonate (4а). Yield
70%. Colorless oil with bp 132–133°С (1 mmHg). Н
1
phonate (8b). Yield 72%. Colorless oil with bp 183–
1
184°С (1 mmHg). Н NMR spectrum, δ, ppm: 1.24 t
NMR spectrum, δ, ppm: 1.30 t (6Н, СН3-phosphonate,
JHH = 7.2 Hz), 2.54 d (3Н, СН3-furan, JРH = 1.2 Hz),
4.18 d. q (4Н, СН2ОР, JHH = 7.2 Hz, JРH = 14.0 Hz),
6.07 br.s (1Н, Н4-furan), 7.21 br.s (1Н, Н5-furan). 13С
NMR spectrum, δС, ppm: 14.61 (СН3-furan), 16.27 d
(6Н, СН3-phosphonate, JHH = 7.2 Hz), 2.30 s (3Н,
СН3-furan), 3.22 s (3Н, СН3О), 4.07–4.15 m (4Н,
СН2ОР), 4.16 s (2Н, О–СН2-furan), 7.76 s (1Н, Н3-
furan). 13С NMR spectrum, δС, ppm: 13.41 (СН3-furan),
3
3
16.19 d (СН3-phosphonate, JPC = 5.6 Hz), 57.92
(СН3-phosphonate, JPC = 5.7 Hz), 63.68 d (СН2ОР,
2
2JPC = 7.1 Hz), 111.01 (С4-furan), 120.36 d (С3-furan,
2JPC = 68.8 Hz), 140.82 (С5-furan), 161.52 d (С2-furan,
(СН3О), 63.98 d (СН2ОР, JPC = 6.7 Hz), 65.02
(ОСН2-furan), 120.92 (С4-furan), 128.29 (С3-furan),
150.18 d (С2-furan, 2JPC = 90.8 Hz), 159.21 (С5-furan),
1
3JPC = 15.0 Hz), 193.82 d (С=О, JPC = 181.5 Hz). 31P
1
183.34 d (С=О, JPC = 187.6 Hz). 31P NMR spectrum,
NMR spectrum, δP, ppm: –1.76.
δP, ppm: –2.34.
Diethyl 4-methyl-3-furoyl phosphonate (4b).
Yield 59%. Colorless oil with bp 121°С (1 mmHg). 1Н
NMR spectrum, δ, ppm: 1.33 t (6Н, СН3-phosphonate,
JHH = 7.2 Hz), 2.16 s (3Н, СН3-furan), 4.16–4.26 m
(4Н, СН2ОР), 7.20 br.s (1Н, Н5-furan), 8.70 br.d (1Н,
Diethyl 3-methoxymethyl-2-furoyl phosphonate
(8с). Yield 59%. Colorless oil with bp 155–156°С
1
(1 mmHg). Н NMR spectrum, δ, ppm: 1.29 br.s (6Н,
СН3-phosphonate), 3.32 s (3Н, СН3О), 4.19–4.23 m
(4Н, СН2ОР), 4.59 s (2Н, О–СН2-furan), 6.67 br.s
Н2-furan, JРH = 1.2 Hz). 13С NMR spectrum, δС, ppm:
3
(1Н, Н4-furan), 7.59 br.s (1Н, Н5-furan). 13С NMR
9.23 (СН3-furan), 16.28 d (СН3-phosphonate, JPC
=
5.5 Hz), 63.90 d (СН2ОР, 2JPC = 7.0 Hz), 119.86 d (С4-
3
spectrum, δС, ppm: 16.00 d (СН3-phosphonate, JPC
6.3 Hz), 16.28 d (СН3-phosphonate, JPC = 5.6 Hz),
=
3
2
furan, JPC = 10.7 Hz), 126.06 d (С3-furan, JPC
=
=
3
69.0 Hz), 141.31 (С5-furan), 154.96 d (С2-furan, 3JPC
2
58.66 (СН3О), 63.99 d (СН2ОР, JPC = 6.9 Hz), 66.40
3.8 Hz), 194.12 d (С=О, JPC = 178.Hz). 31P NMR
1
(ОСН2-furan), 113.62 (С4-furan), 136.97 d (С3-furan,
3JPC = 9.0 Hz), 147.89 (С5-furan), 147.30 d (С2-furan,
spectrum, δP, ppm: –3.15.
2JPC = 60.6 Hz), 186.71 d (С=О, JPC = 186.1 Hz. 31P
1
Diethyl 5-methyl-3-furoyl phosphonate (4c).
Yield 87%. Colorless oil with bp 129°С (1 mmHg). 1Н
NMR spectrum, δP, ppm: –1.93.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 5 2016

1052
PEVZNER
Diethyl 2-methoxymethyl-3-furoyl phosphonate
Brown oil, 6.9 g, was obtained. Its major component
was phosphonate 5. Н NMR spectrum, δ, ppm: 1.32 t
1
(8d). Yield 75%. Colorless oil with bp 163°С
1
(1 mmHg). Н NMR spectrum, δ, ppm: 1.28 t (6Н,
(6Н, СН3-phosphonate, JHH = 7.2 Hz), 4.20 d. q (4Н,
СН2ОР, JHH = 7.2 Hz, JРH = 14.8 Hz), 4.71 s (2Н,
СН2Вr), 7.15 d (1Н, Н4-furan, JHH = 2.0 Hz), 7.40 d
(1Н, Н5-furan, JHH = 2.0 Hz). 13С NMR spectrum, δС,
ppm: 16.30 d (СН3-phosphonate, 3JPC = 5.7 Hz), 21.15
(СН2Вr), 64.12 d (СН2ОР, 2JPC = 7.1 Hz), 111.83 (С4-
СН3-phosphonate, JHH = 7.0 Hz), 3.32 s (3Н, СН3О),
4.15 d.q (4Н, СН2ОР, JHH = 7.0 Hz, JРH = 14.0 Hz),
4.63 s (2Н, О–СН2-fran), 7.11 br.s (1Н, Н4-furan),
7.36 br.s (1Н, Н5-furan). 13С NMR spectrum, δС, ppm:
3
16.26 d (СН3-phosphonate, JPC = 5.4 Hz), 58.68
2
2
(СН3О), 63.39 d (СН2ОР, JPC = 7.0 Hz), 65.54
furan), 121.39 d (С3-furan, JPC = 68.7 Hz), 143.09
(ОСН2-furan), 111.15 (С4-furan), 122.06 d (С3-furan,
2JPC = 86.5 Hz), 142.63 (С5-furan), 158.75 d (С2-furan,
(С5-furan), 156.65 d (С2-furan, 3JPC = 14.9 Hz), 194.37
1
d (С=О, JPC = 185.0 Hz). 31P NMR spectrum, δP,
3JPC = 15.2 Hz), 194.36 d (С=О, JPC = 183.7 Hz). 31P
ppm: –2.84.
1
NMR spectrum, δP, ppm: –2.36.
Synthesis of furoyl phosphonates 9a and 11a–11f
(general procedure). A solution of 20 mmol of acid
chloride in 10 mL of benzene was added to a solution
of 30 mmol of triethyl phosphite in 20 mL of benzene.
Stirring of the reagents caused spontaneous heating of
the reaction mixture to 28–35°C. After complete heat
evolution, the formed mixture was heated with stirring
at 70°C during 3 h. The volatile products were re-
moved on a rotary evaporator, and the fraction with bp
30–60°C (1 mmHg) was further distilled off. The
residual substance was the target product.
Diethyl 4-methoxymethyl-3-furoyl phosphonate
(8е). Yield 73%. Colorless oil with bp 151°С
1
(1 mmHg). Н NMR spectrum, δ, ppm: 1.29 t (6Н,
СН3-phosphonate, JHH = 7.0 Hz), 3.34 s (3Н, СН3О),
4.13–4.17 m (4Н, СН2ОР), 4.63 s (2Н, О–СН2-furan),
7.38 s (1Н, Н5-furan), 8.68 s (1Н, Н2-furan). 13С NMR
3
spectrum, δС, ppm: 16.21 d (СН3-phosphonate, JPC
=
5.Hz), 58.64 (СН3О), 63.99 d (СН2ОР, 2JPC = 6.9 Hz),
65.97 (ОСН2-furan), 122.40 d (С4-furan, 3JPC = 11.1 Hz),
124.96 d (С3-furan, 2JPC = 70.1 Hz), 141.96 (С5-furan),
3
154.96 d (С2-furan, JPC = 3.8 Hz), 193.83 d (С=О,
Diethyl 4-(ethoxycarbonyl)-3-furoyl phosphonate
1JPC = 180.4 Hz). 31P NMR spectrum, δP, ppm: –3.44.
1
(9a). Yield 68%. Yellow oil. Н NMR spectrum, δ,
Diethyl 5-methoxymethyl-3-furoyl phosphonate
ppm: 1.29 t (6Н, СН3-phosphonate, JHH = 7.0 Hz),
1.32 t (3Н, СН3-ester, JHH = 7.0 Hz), 4.16–4.23 m (4Н,
СН2ОР), 4.27 q (2Н, СН92°С, JHH = 7.0 Hz), 7.94 s
(1Н, Н5-furan), 8.68 s (1Н, Н2-furan). 13С NMR
spectrum, δС, ppm: 14.03 (СН3-ester), 16.21 d (СН3-
(8f). Yield 75%. Colorless oil with bp 156–158°С
1
(1 mmHg). Н NMR spectrum, δ, ppm: 1.21 t (6Н,
СН3-phosphonate, JHH = 7.0 Hz), 3.20 s (3Н, СН3О),
4.05–4.11 m (4Н, СН2ОР), 4.25 s (2Н, ОСН2-furan),
6.59 s (1Н, Н4-furan), 8.53 s (1Н, Н2-furan). 13С NMR
phosphonate, JPC = 5.6 Hz), 61.13 (СН2О-ester),
3
3
2
spectrum, δС, ppm: 16.15 d (СН3-phosphonate, JPC
=
=
64.30 d (СН2ОР, JPC = 7.1 Hz), 117.84 d (С4-furan,
2
2
5.4 Hz), 57.91 (СН3О), 63.88 d (СН2ОР, JPC
3JPC = 10.3 Hz), 125.01 d (С3-furan, JPC = 74.6 Hz),
6.8 Hz), 65.67 (ОСН2-furan), 106.44 d (С4-furan,
148.86 (С5-furan), 153.82 d (С2-furan, 3JPC = 2.8 Hz),
3JPC = 7.9 Hz), 127.78 d (С3-furan, JPC = 70.0 Hz),
192.28 d (С=О, JPC = 184.6 Hz). 31P NMR spectrum,
2
1
153.06 (С2-furan), 153.91 (С5-furan), 192.90 d (С=О,
1JPC = 181.6 Hz). 31P NMR spectrum, δP, ppm: –3.10.
δP, ppm: –3.48.
Diethyl 5-(diethoxyphosphorylmethyl)-2-furoyl
phosphonate (11a). Yield 95%. Light brown syrup. 1Н
NMR spectrum, δ, ppm: 1.22 t (6Н, СН3-phosphonate,
JHH = 7.2 Hz), 1.27 t (6Н, СН3-acyl phosphonate,
Diethyl 2-bromomethyl-3-furoyl phosphonate (5).
4.5 g of N-bromosuccinimide and 0.2 g of azobisiso-
butyronitrile were added to a solution of 5.6 g of
furoylphosphonate 4a in 100 mL of carbon tetra-
chloride. The reaction mixture was heated until the
beginning of vigorous reaction, and after completion of
heat evolution it was refluxed with stirring until dis-
appearance of N-bromosuccinimide crystals. After
that, the formed mixture was left overnight for
crystallization. On the next day the precipitate was
filtered off, the solvent was removed from the filtrate
on a rotary evaporator, and the residue was incubated
in vacuum (1 mmHg) during 1 h at room temperature.
JHH = 7.2 Hz), 3.27 d (2Н, СН2Р, JPН = 22.0 Hz), 4.00–
4.08 m (4Н, СН2ОР-phosphonate), 4.13–4.21 m (4Н,
СН2ОР-acyl phosphonate), 6.41 d (1Н, Н4-furan, JHH
=
3.6 Hz), 7.73 d (1Н, Н3-furan, JHH = 3.6 Hz). 13С NMR
3
spectrum, δС, ppm: 16.24 d (СН3-phosphonates, JPC
=
1
4.4 Hz), 27.23 d (СН2Р, JPC = 141.0 Hz), 62.67 d
2
2
(СН2ОР, JPC = 6.4 Hz), 64.09 d (СН2ОР-acyl, JPC
=
6.8 Hz), 111.94 d (С4-furan, JPC = 6.0 Hz), 127.36
3
(С3-furan), 151.52 d (С2-furan, 2JPC = 90.8 Hz), 154.79
d (С5-furan, JPC = 8.3 Hz), 183.88 d (С=О, JPC
=
2
1
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 5 2016

1053
FUROYL PHOSPHONATES
188.6 Hz). 31P NMR spectrum, δP, ppm: 20.54 (Р5),
–2.67 (Р2).
Diethyl 4-(diethoxyphosphorylmethyl)-3-furoyl
phosphonate (11е). Yield 73%. Dark yellow syrup. 1Н
NMR spectrum, δ, ppm: 1.11 t (6Н, СН3-phosphonate,
JHH = 7.0 Hz), 1.21 t (6Н, СН3-acyl phosphonate,
Diethyl 4-(diethoxyphosphorylmethyl)-5-methyl-
2-furoyl phosphonate (11b). Yield 83%. Brown
1
JHH = 7.0 Hz), 3.21 d (2Н, СН2Р, JPН = 21.2 Hz), 3.87–
syrup. Н NMR spectrum, δ, ppm: 1.01–1.12 m (12Н,
3.94 m (4Н, СН2ОР-phosphonate), 4.04–4.12 m (4Н,
СН2ОР-acyl phosphonate), 7.39 s (1Н, Н5-furan), 8.63
s (1Н, Н2-furan). 13С NMR spectrum, δС, ppm: 16.16 d
СН3-phosphonate), 2.14 s (3Н, СН3-furan), 2.66 d
(2Н, СН2Р, JPН = 20.4 Hz), 3.83 br.s (4Н, СН2ОР),
3.97 br.s (4Н, СН2ОР-acyl phosphonate), 7.56 s (1Н,
Н3-furan). 13С NMR spectrum, δС, ppm: 12.16 (СН3-
furan), 16.08 br.s (СН3-phosphonate), 22.81 d (СН2Р,
1JPC = 148.2 Hz), 62.02 br.s (СН2ОР-phosphonate),
63.78 br.s (СН2ОР-acyl phosphonate), 114.27 d (С4-
furan, 2JPC = 9.3 Hz), 128.59 (С3-furan), 149.87 d (С2-
3
(СН3-phosphonates, JPC = 5.5 Hz), 20.75 d (СН2Р,
1JPC = 141.5 Hz), 61.96 d (СН2ОР-phosphonate, 2JPC
=
=
2
6.4 Hz), 63.88 d (СН2ОР-acyl phosphonate, JPC
2
3
6.8 Hz), 114.44 t (С4-furan, JPC= JPC = 11.Hz),
124.95 d. d (С3-furan, JPC = 70.1 Hz, JPC = 5.9 Hz),
2
3
141.16 (С5-furan, JPC = 7.8 Hz), 154.70 d (С2-furan,
3
2
3
furan, JPC = 90.3 Hz), 158.76 d (С5-furan, JPC
=
3JPC = 3.9 Hz), 194.83 d (С=О, JPC = 180.6 Hz). 31P
1
9.2 Hz), 183.14 d (С=О, JPC = 187.8 Hz). 31P NMR
1
NMR spectrum, δP, ppm: 25.55 (Р4), –3.62 (Р3).
spectrum, δP, ppm: 24.84 (Р4), –2.42 (Р2).
Diethyl 5-(diethoxyphosphorylmethyl)-3-furoyl
phosphonate (11f). Yield 85%. Light brown syrup. 1Н
NMR spectrum, δ, ppm: 1.28 t (6Н, СН3-phosphonate,
JHH = 7.2 Hz), 1.33 t (6Н, СН3-acyl phosphonate,
Diethyl 3-(diethoxyphosphorylmethyl)-2-furoyl
phosphonate (11с). Yield 87%. Brown syrup. Н
1
NMR spectrum, δ, ppm: 1.04–1.16 br.s (12Н, СН3-
phosphonate), 3.32 d (2Н, СН2Р, JPН = 22.4 Hz), 3.85–
4.10 m (8Н, СН2ОР), 6.54 br.s (1Н, Н4-furan), 7.48
br.s (1Н, Н5-furan). 13С NMR spectrum, δС, ppm:
JHH = 7.2 Hz), 3.21 d (2Н, СН2Р, JPН = 20.2 Hz), 4.04–
4.10 m (4Н, СН2ОР-phosphonate), 4.16–4.24 m (4Н,
СН2ОР-acyl phosphonate), 6.63 d (1Н, Н4-furan, JPН
=
3
15.89 d (СН3-phosphonate, JPC = 5.5 Hz), 16.16 d
3.6 Hz), 8.60 s (1Н, Н2-furan). 13С NMR spectrum, δС,
ppm: 16.29–16.34 br.s (СН3-phosphonates), 26.50 d
3
(СН3-acyl phosphonate, JPC = 5.0 Hz, 23.45 d (СН2Р,
1JPC = 138.9 Hz), 62.16 d (СН2ОР-phosphonate, 2JPC
=
=
=
1
2
(СН2Р, JPC = 143.0 Hz), 62.52 d (СН2ОР-phos-
6.5 Hz), 63.85 d (СН2ОР-acyl phosphonate, JPC
2
2
6.8 Hz), 115.76 (С4-furan), 128.32 t (С3-furan, JPC
phonate, JPC = 6.4 Hz), 64.02 d (СН2ОР-acyl phos-
2
2
phonate, JPC = 6.8 Hz), 106.44 t (С4-furan, JPC
=
3JPC = 9.3 Hz), 147.56 (С5-furan), 148.40 d. d (С2-
3JPC = 7.8 Hz), 128.42 d (С3-furan, JPC = 69.3 Hz),
2
2
3
furan, JPC = 58.5 Hz, JPC = 9.8 Hz), 186.87 d (С=О,
1JPC = 186.8 Hz). 31P NMR spectrum, δP, ppm: 23.73
(Р3), –2.16 (Р2).
152.66 (С2-furan), 148.69 d (С5-furan, JPC = 9.2 Hz),
2
192.88 d (С=О, JPC = 181.5 Hz). 31P NMR spectrum,
1
δP, ppm: 25.55 (Р5), –3.62 (Р3).
Diethyl 2-(diethoxyphosphorylmethyl)-3-furoyl
phosphonate (11d). Yield 69%. Yellow syrup. 1Н NMR
ACKNOWLEGMENTS
spectrum, δ, ppm: 1.25 t (6Н, СН3-phosphonate, JHH
7.0 Hz), 1.35 t (6Н, СН3-acyl phosphonate, JHH
=
=
The work was carried out within the frames of basic
part of State Project of the Ministry of Education and
Science.
7.2 Hz), 3.73 d (2Н, СН2Р, JPН = 22.8 Hz), 4.07 d. q
(4Н, СН2ОР-phosphonate, JHH = 7.0 Hz, JРH = 14.8 Hz),
4.22 d. q (4Н, СН2ОР-acyl phosphonate, JHH = 7.2 Hz,
JРH = 14.6 Hz), 7.18 d (1Н, Н4-furan, JPН = 2.0 Hz),
7.36 d. d (1Н, Н5-furan, JHH = 2.0 Hz, JРH = 2.0 Hz).
13С NMR spectrum, δС, ppm: 16.24 d (СН3-phos-
REFERENCES
1. Savignac, F. and Iorga, B., Modern Phosphonate
Chemistry, CRC Press, 2003, p. 435.
2. McKenna, C.E. and Kashemirov, B.A., in New Aspects
in Phosphorus Chemistry, Maioral, J.-P., Ed., vol. 220,
Springer, 2003, p. 201.
3. Griffiths, D.V., Al-Jeboori, M.J., Cheong, Y-K.,
Duncanson, P., and Harris, J.E., Org. Bioor. Chem.,
2008, vol. 6, p. 577. DOI: 10.1039/b717130g .
3
phonate, JPC = 6.2 Hz), 16.32 d (СН3-acyl phos-
3
1
phonate, JPC = 6.0 Hz), 27.15 d (СН2Р, JPC
=
=
=
2
137.5 Hz), 62.52 d (СН2ОР-phosphonate, JPC
2
6.9 Hz), 63.89 d (СН2ОР-acyl phosphonate, JPC
7.0 Hz), 111.44 (С4-furan), 121.44 d. d (С3-furan,
2JPC = 86.5 Hz, JP3C = 7.4 Hz), 142.24 (С5-furan),
3
4. Pevzner, L.M., Russ. J. Gen. Chem., 2015, vol. 85,
no. 2, p. 428. DOI 10.1134/S1070363215020139.
5. Pevzner, L.M., Russ. J. Gen. Chem., 2015, vol. 85,
158.75 t (С2-furan, JPC = JPC = 4.7 Hz), 194.03 d
3
(С=О, JPC = 183.6 Hz). 31P NMR spectrum, δP, ppm:
1
20.59 (Р2), –2.23 (Р3).
no. 7, p. 1650. DOI 10.1134/S1070363215070130.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 5 2016