Synthesis of substituted fulvenes with inden-2-ylphosphonic acid fragments

Article abstract of DOI:10.1007/s11172-017-1882-9

We have developed preparative methods for the synthesis of substituted fulvenes including inden-2-ylphosphonic acid fragments, as well as aromatic and heterocyclic substituents, based on bis(trimethylsilyl)inden-2-ylphosphonate and substituted azomethines

Full text of DOI:10.1007/s11172-017-1882-9

Russian Chemical Bulletin, International Edition, Vol. 66, No. 7, pp. 1261—1264, July, 2017
1261
Synthesis of substituted fulvenes with indenꢀ2ꢀylphosphonic acid fragments
A. A. Prishchenko, M. V. Livantsov, O. P. Novikova, L. I. Livantsova, and V. S. Petrosyan
M. V. Lomonosov Moscow State University, Department of Chemistry,
Build. 3, 1 Leninskie Gory, 119991 Moscow, Russian Federation.
Eꢀmail: aprishchenko@yandex.ru
We have developed preparative methods for the synthesis of substituted fulvenes includꢀ
ing indenꢀ2ꢀylphosphonic acid fragments, as well as aromatic and heterocyclic substituents,
based on bis(trimethylsilyl)indenꢀ2ꢀylphosphonate and substituted azomethines in the presꢀ
ence of sodium hydride as an efficient initiator of the reaction. Subsequent treatment of the
phosphonates with methanolic solution of sodium methoxide furnished waterꢀsoluble disodium
salts of the corresponding phosphonic acids.
Key words: organophosphorus fulvenes, bis(trimethylsilyl)indenꢀ2ꢀylphosphonate, subꢀ
stituted azomethines, sodium hydride, disodium salts.
Fulvenes are an important class of crossꢀconjugatꢀ
ed alkenes with unique electronic, spectroscopic, and
chemical properties. Substituted fulvenes are convenient
synthons for the preparation of metallocene catalysts1
and are used in materials science and molecular elecꢀ
tronics,3 and as key intermediate products in the synꢀ
and heterocyclic fragments based on trimethylsilyl esters
of tervalent phosphorus acids.1
2—14
In the present work, we study the reaction of esters 2
of available indenꢀ2ꢀylphosphonic acid 1, the synthesis
of which has been described earlier,1 with substituted
azomethines, which leads to new fulvenes 3 bearing aroꢀ
,2
5
4
,5
16
thesis of biologically active compounds.
Some fulꢀ
matic and heterocyclic substituents. The starting esters
venes have been isolated from natural objects and
found to possess antibacterial activity, for example,
fulvoplumierin, which was later synthesized in several
steps.6
2a,b were obtained in high yields by the reaction of inꢀ
denꢀ2ꢀylphosphonic acid 1 with triethylorthoformate or
bis(trimethylsilyl)amine, respectively (Scheme 1).
,7
We have found that the stirring the mixture of phosꢀ
phonate 2b with azomethines in diethyl ether in the presꢀ
ence of sodium hydride as the reaction initiator is accomꢀ
panied by the evolution of methylamine and leads to the
formation of good yields of fulvenes 3a—d (Scheme 2).
Note that the reaction of phosphonate 2a under similar
conditions leads mainly to polymeric products, that can
be apparently explained by the higher stability of triꢀ
methylsilylꢀcontaining fulvenes formed in the reaction
process. The reaction scheme includes the formation
of an intermediate adduct as a result of the baseꢀcataꢀ
lyzed addition of the phosphorusꢀsubstituted indene as
a CHꢀacid at the double bond of the azomethine with
subsequent elimination of methylamine (see Scheme 2).
There are known methods for the synthesis of some
fulvenes based on the condensation of aldehydes and keꢀ
tones with substituted cyclopentadienes in the presence
of basic catalysts, however, this was accompanied by the
formation of a considerable amount of resinꢀlike polyꢀ
mers.8 At the same time, stable 6ꢀdimethylaminofulꢀ
vene was obtained in high yield based on cyclopentadiene
,9
1
0
and dimethylformamide. There is also known an origiꢀ
nal method for obtaining fulvenes, which involves radical
cyclization of substituted oꢀphenylenediynes in the presꢀ
1
1
ence of tributylstannane. Recently, we have developed
convenient methods for the synthesis of some organoꢀ
phosphorus compounds with different functional groups
Scheme 1
Reaction conditions: 100—125 °C.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1261—1264, July, 2017.
066ꢀ5285/17/6607ꢀ1261 © 2017 Springer Science+Business Media, Inc.
1

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Russ. Chem. Bull., Int. Ed., Vol. 66, No. 7, July, 2017
Prishchenko et al.
It is obvious that an increased CHꢀacidity of ester 2b is
related to the influence of the electronꢀwithdrawing phosꢀ
phorusꢀcontaining group.
Treatment of both phosphonate 2b and phosphonates
3a—d with a dilute solution of sodium methoxide in methꢀ
anol gave stable waterꢀsoluble disodium salts 4 and 5,
respectively (Scheme 5), which are hygroscopic white (4)
and lemonꢀyellow (5) crystals.
Scheme 2
Scheme 5
X = Ph (3a), 4ꢀMeO—C H4 (3b),
(3c),
(3d)
6
Reaction conditions: Et O, 25 °C.
2
X = Ph (a), 4ꢀMeO—C H4 (b),
(c),
(d)
6
The first step of the suggested reaction scheme inꢀ
cludes the metallation of CHꢀacid 2b with sodium
hydride, the addition of sodium intermediate 2c at the
double bond of the azomethine with the formation of
intermediate 2d, which then disintegrates to the target
fulvenes 3a—d and sodium Nꢀmethylamide (Scheme 3).
Reaction conditions: Et O, 10 °C.
2
In conclusion, based on the readily available starting
compounds we have developed original methods for the
synthesis of new stable phosphorusꢀsubstituted fulvenes
including aromatic and heterocyclic fragments together
with the indenꢀ2ꢀylphosphonic acid moieties. The new
compounds are convenient synthons for the preparation
of various functionalized organophosphorus compounds
and are interesting as biologically active compounds and
promising polydentate ligands.
Scheme 3
Experimental
1H, 13C{ H}, and P{ H} NMR spectra were recorded on
1
31
1
a Bruker Avance 400 spectrometer (400, 100, and 162 Hz, reꢀ
1
13
1
spectively), using Me Si ( H, C{ H}) and 85% H PO in D O
(
4
3
4
2
3
1
1
P{ H}) as references. All the reactions were carried out unꢀ
der dry argon in anhydrous solvents. The starting indenꢀ2ꢀylꢀ
phosphonic acid was obtained according to the known method.13
Disodium salts 4 and 5 undergo decomposition upon heating
higher 100 °C and do not have sharp melting points.
Reaction conditions: Et O, 25 °C.
2
O,OꢀDiethyl 1Hꢀindenꢀ2ꢀylphosphonate (2a). A mixture of
triethylorthoformate (101 g, 0.68 mol) and 1Hꢀindenꢀ2ꢀylphosꢀ
phonic acid (1) (33.3 g, 0.17 mol) (obtained according to the
Then, sodium Nꢀmethylamide successfully catalyzed
this reaction with the formation of substituted fulvenes
a—d and elimination of methylamine (Scheme 4).
3
3
method described in the literature ) was refluxed for 2 h and
then distilled to obtain ester 2a (34.7 g, 81%), b.p. 144 °C
(
1 Torr). Found (%): C, 61.74; H, 6.68. C13H17O P. Calculatꢀ
3
Scheme 4
1
ed (%): C, 61.90; H, 6.79. H NMR (CDCl ), δ: 1.2 (t, 6 H,
2
3
3
Me, JH,H = 7.2 Hz); 3.50 (s, 2 H, C(1)H ); 4.00—4.10
2
(
m, 4 H, 2 OCH ); 7.20—7.40 (m, 4 H, 4 CaromH); 7.50 (d, 1 H,
2
3
13
1
C(3)H, J
3
= 10.4 Hz). C{ H} NMR (CDCl ), δ: 1.2 (t, Me,
P,H
3
2
JP,C = 6.2 Hz); 39.6 (d, C(1), J
= 14.0 Hz); 61.3 (d, OCH2,
P,C
2J
= 5.5 Hz); 122.3 (s, Carom); 123.5 (s, Carom); 126.3
P,C
(s, Carom); 126.6 (s, Carom); 133.1 (d, C(2), 1JP,C = 198.9 Hz);
Reaction conditions: Et O, 25 °C.
2

Organophosphorus fulvenes with indenyl moieties
Russ. Chem. Bull., Int. Ed., Vol. 66, No. 7, July, 2017
1263
2
1
1
42.1 (d, C(3a), 3J = 21.1 Hz); 144.6 (d, C(3), J = 13.9 Hz);
O,OꢀBis(trimethylsilyl) [1ꢀ(pyridinꢀ3ꢀylmethylene)ꢀ1Hꢀinꢀ
denꢀ2ꢀyl]phosphonate (3d). The yield was 72%, b.p. 200 °C
P,C
3
P,C
31
1
44.8 (d, C(7a), JP,C = 11.9 Hz). P{ H} NMR (CDCl ),
3
δ: 17.7 (s).
O,OꢀBis(trimethylsilyl) 1Hꢀindenꢀ2ꢀylphosphonate (2b).
A mixture of bis(trimethylsilyl)amine (100 g, 0.62 mol) and
Hꢀindenꢀ2ꢀylphosphonic acid 1 (43 g, 0.22 mol) (obtained
according to the method described in the work ) was refluxed
until ammonia ceased to evolve, then distilled to obtained ester
(1 Torr), m.p. 65 °C. Found (%): C, 58.62; H, 6.52.
1
C21H28NO PSi . Calculated (%): C, 58.71; H, 6.57. H NMR
3
2
(CDCl ), δ: 0.45 (s, 18 H, 2 Me Si); 7.05—7.86 (m, 8 H,
3
3
3
1
4 CaromH, 4 CPyH); 8.66 (d, 1 H, C(3)H, J
(s, 1 H, C(8)H). C{ H} NMR (CDCl ), δ: 1.1 (s, 2 Me Si);
= 9.7 Hz); 8.78
P,H
3
13
1
3 3
122.2 (s, Carom); 123.7 (s, CPy); 127.4 (s, Carom); 128.6 (s, Carom);
1
2
b (66.4 g, 89%), b.p. 149 °C (1 Torr), m.p. 52 °C. Found (%):
132.1 (s, Carom); 132.7 (s, C ); 133.3 (d, C(2), J = 208.2 Hz);
Py P,C
2
C, 52.76; H, 7.26. C15H25O PSi . Calculated (%): C, 52.91;
135.9 (d, C(1), J = 12.3 Hz); 136.8 (s, C(8)); 141.3 (d, C(3a),
3
2
P,C
1
4
3
3
H, 7.40. H NMR (CDCl ), δ: 0.21 (d, 18 H, 2 Me Si, J =
P,H
JP,C = 15.9 Hz); 141.9 (d, C(7a), JP,C= 20.9 Hz); 142.7
3
3
2
=
4.8 Hz); 3.50 (s, 2 H, C(1)H ); 7.10—7.40 (m, 5 H, C H ).
(d, C(3), JP,C = 12.5 Hz); 149.1 (s, CPyN); 149.5 (s, CPyN).
P{ H} NMR (CDCl ), δ: –3.3 (s).
2
9
7
1
3
1
31
1
C{ H} NMR (CDCl ), δ: 0.60 (s, 2 Me Si); 39.6 (d, C(1),
3
3
3
2JP,C = 15.2 Hz); 122.2 (s, Carom); 123.6 (s, Carom); 126.3
1HꢀIndenꢀ2ꢀylphosphonic acid disodium salt (4). A solution
1
(
2
s, 2 Carom); 137.3 (d, C(2), J
JP,C = 14.7 Hz); 142.5 (d, C(3a), JP,C = 21.3 Hz); 144.6 (d,
= 208.2 Hz); 141.9 (d, C(3),
3
of phosphonate 2b (3.4 g, 0.01 mol) in diethyl ether (5 mL) was
added to a solution of sodium methoxide (1.1 g, 0.02 mol) in
methanol (30 mL) with stirring at 10 °C. The reaction mixture
was brought to reflux, the solvent was removed, the residue was
allowed to stand in vacuo (1 Torr) for 1 h. The yield of salt 4b
P,C
3
31
1
C(7a), J
= 12.3 Hz). P{ H} NMR (CDCl ), δ: –1.1 (s).
3
P,C
O,OꢀBis(trimethylsilyl) (1ꢀbenzylideneꢀ1Hꢀindenꢀ2ꢀyl)phosꢀ
phonate (3a). NꢀBenzylideneꢀNꢀmethylamine (1.6 g, 0.013 mol)
and sodium hydride (0.1 g, 0.004 mol) were added to a solution
of phosphonate 2b (4.5 g, 0.013 mol) in diethyl ether (10 mL)
with stirring. After 2 h, the solvent was removed and the resiꢀ
due was distilled to obtain phosphonate 3a (4.3 g, 75%), b.p.
was 2.3 g (96%). Found (%): C, 44.91; H, 3.03. C H Na O P.
9
7
2
3
1
Calculated (%): C, 45.02; H, 2.94. H NMR (D O), δ: 3.65 (s, 2 H,
2
C(1)H ); 7.20—7.50 (m, 4 H, 4 C
JP,H = 7.6 Hz). C{ H} NMR (D O), δ: 40.7 (d, C(1), J
H); 7.58 (d, 1 H, C(3)H,
arom
2
3
13
1
2
=
P,C
2
2
12 °C (2 Torr), m.p. 74 °C. Found (%): C, 61.56; H, 6.71.
= 11.9 Hz); 121.8 (s, Carom); 124.1 (s, Carom); 125.4 (s, Carom);
1
); 135.9 (d, C(3), 2JP,C = 10.7 Hz); 144.6
C22H29O PSi . Calculated (%): C, 61.65; H, 6.82. H NMR
126.6 (s, C
(d, C(3a), J
3
2
arom
3
3
(
CDCl ), δ: 0.43 (s, 18 H, 2 Me Si); 6.80—7.60 (m, 9 H,
= 18.9 Hz); 145.6 (d, C(7a), JP,C= 10.7 Hz);
3
3
P,C
3
1
31
1
5
CPhH); 7.52 (d, 1 H, C(3)H, JP,H = 6.8 Hz); 7.97 (s, 1 H,
147.1 (d, C(2), J = 176.2 Hz). P{ H} NMR (D O), δ: 10.7 (s).
P,C 2
1
3
1
C(8)H). C{ H} NMR (CDCl ), δ: 1.9 (s, 2 Me Si); 122.5
Salt 5a—d were obtained similarly.
3
3
(
(
(
s, Carom); 123.6 (s, Carom); 127.0 (s, Carom); 128.3 (s, CPh); 128.5
s, CPh); 129.1 (s, CPh); 129.2 (s, CPh); 136.5 (s, Carom); 135.9
1ꢀBenzylideneꢀ1Hꢀindenꢀ2ꢀylphosphonic acid disodium salt
(5a). The yield was 97%. Found (%): C, 58.43; H, 3.41.
d, C(2), 1JP,C = 208.3 Hz); 136.3 (d, C(1),
2
J
= 14.9 Hz);
C16H11Na O P. Calculated (%): C, 58.55; H, 3.38. H NMR
1
P,C
2
3
3
3
1
1
36.8 (d, C(8), J = 6.1 Hz); 139.1 (d, C(3a), J = 16.0 Hz);
41.9 (d, C(3), J = 12.3 Hz); 141.7 (d, C(7a), J = 18.4 Hz).
(D O), δ: 6.75—7.55 (m, 9 H, 4 CaromH, 5 CPhH); 7.64 (d, 1 H,
2
P,C
P,C
2
3
3
13
1
C(3)H, JP,H = 7.2 Hz); 7.89 (s, 1 H, C(8)H). C{ H} NMR
P,C
P,C
3
1
1
P{ H} NMR (CDCl ), δ: –2.9 (s).
(D O), δ: 121.9 (s, Carom); 123.7 (s, Carom); 127.1 (s, Carom);
3
2
Phosphonates 3b—d were obtained similarly.
O,OꢀBis(trimethylsilyl) [1ꢀ(4ꢀmethoxybenzylidene)ꢀ1Hꢀinꢀ
denꢀ2ꢀyl]phosphonate (3b). The yield was 78%, b.p. 210 °C
1.5 Torr), m.p. 89 °C. Found (%): C, 60.06; H, 6.69.
128.1 (s, CPh); 128.4 (s, CPh); 129.2 (s, CPh); 129.4 (s, CPh);
2
136.1 (d, C(1), J
JP,C = 9.8 Hz); 137.4 (s, C
= 8.4 Hz); 136.4 (s, C(8)); 136.7 (d, C(3),
P,C
2
3
); 140.0 (d, C(3a), J = 12.1 Hz);
arom
P,C
1
3
(
143.2 (d, C(2), J = 174.4 Hz); 143.6 (d, C(7a), J = 20.4 Hz).
P,C
P,C
1
31
1
C23H31O PSi . Calculated (%): C, 60.23; H, 6.81. H NMR
P{ H} NMR (D O), δ: 7.8 (s).
4
2
2
(
(
=
0
(
1
(
1
1
1
CDCl ), δ: 0.29 (s, 18 H, 2 Me Si); 3.84 (s, 3 H, MeO); 6.81—7.60
1ꢀ(4ꢀMethoxybenzylidene)ꢀ1Hꢀindenꢀ2ꢀylphosphonic acid
disodium salt (5b). The yield was 97%. Found (%): C, 56.89;
H, 3.74. C17H13Na O P. Calculated (%): C, 57.00; H, 3.66.
3
3
3
m, 8 H, 4 CaromH, 4 C
8.4 Hz); 7.83 (s, 1 H, C(8)H). C{ H} NMR (CDCl ), δ:
H); 7.64 (d, 1 H, C(3)H, JP,H =
C H
6
4
1
3
1
3
2
4
1
.03 (s, 2 Me Si); 55.2 (s, MeO); 60.0 (s, C
O); 113.8
H NMR (D O), δ: 3.78 (s, 3 H, MeO); 6.80—7.40 (m, 4 H,
3
C H
2
6
4
3
s, 2 C
); 122.3 (s, Carom); 123.4 (s, Carom); 126.7 (s, Carom);
4 CaromH); 6.99 (d, 2 H, 2 C
(d, 1 H, C(3)H, JP,H = 8.0 Hz); 7.55 (d, 2 H, 2 C
JH,H = 8.4 Hz); 7.93 (s, 1 H, C(8)H). C{ H} NMR (D O), δ:
H, JH,H = 8.4 Hz); 7.45
C H
C H
6
4
6
4
3
27.8 (s, Carom); 128.7 (s, C
); 131.0 (s, 2 C
); 135.3
= 14.8 Hz);
H,
C H
4
C H
C H
6
4
6
4
6
d, C(2), 1JP,C = 206.2 Hz); 136.1 (d, C(1),
2
J
3
13
1
P,C
2
3
36.5 (s, Carom); 137.1 (s, C(8)); 138.9 (d, C(3a), J = 17.0 Hz);
55.5 (s, MeO); 114.1 (s, 2 C
(s, Carom); 125.3 (s, Carom); 128.0 (s, Carom); 130.0 (s, C
); 121.6 (s, Carom); 123.1
C H
4
P,C
6
2
3
40.9 (d, C(3), J = 11.9 Hz); 141.6 (d, C(7a), J = 12.1 Hz);
);
C H
4
P,C
P,C
6
3
1
1
); 135.7 (d, C(3), 2J
60.0 (s, CO). P{ H} NMR (CDCl ), δ: –2.6 (s).
131.2 (s, 2 C
= 9.5 Hz); 136.0
3
C H
P,C
6
4
2
O,OꢀBis(trimethylsilyl) [1ꢀ(furanꢀ2ꢀylmethylene)ꢀ1Hꢀindenꢀ
ꢀyl]phosphonate (3c). The yield was 74%, b.p. 210 °C (2 Torr),
(d, C(1), JP,C = 8.3 Hz); 137.1 (s, C(8)); 139.8 (d, C(3a),
3
1
2
JP,C = 12.8 Hz); 143.3 (d, C(2), JP,C = 172.9 Hz); 143.6
3
31
1
m.p. 61 °C. Found (%): C, 57.23; H, 6.42. C20H27O PSi . Calꢀ
culated (%): C, 57.39; H, 6.50. H NMR (CDCl ), δ: 0.42 (s, 18 H,
(d, C(7a), J
= 16.0 Hz); 159.1 (s, C
O). P{ H} NMR
C H
4
4
2
P,C
6
1
(D O), δ: 8.1 (s).
2
3
2
Me Si); 6.57—7.60 (m, 7 H, 4 CaromH, 3 CHetH); 7.70 (s, 1 H,
1ꢀ(Furanꢀ2ꢀylmethylene)ꢀ1Hꢀindenꢀ2ꢀylphosphonic acid diꢀ
sodium salt (5c). The yield was 95%. Found (%): C, 52.64;
3
3
13
1
C(8)H); 8.70 (d, 1 H, C(3)H, JP,H = 7.6 Hz). C{ H} NMR
(
1
(
1
1
1
CDCl ), δ: 0.9 (s, 2 Me Si); 112.8 (s, CHet); 118.4 (s, CHet);
20.9 (s, Carom); 122.3 (s, Carom); 124.9 (s, Carom); 127.2
H, 2.91. C H Na O P. Calculated (%): C, 52.85; H, 2.85.
3
3
14 9 2 4
1
H NMR (D O), δ: 6.63—7.67 (m, 7 H, 4 C
H, 3 CHetH);
arom
2
1
3
s, Carom); 127.8 (s, C(8)); 133.8 (d, C(2),
J
= 205.6 Hz);
7.75 (s, 1 H, C(8)H); 8.63 (d, 1 H, C(3)H, JP,H = 7.2 Hz).
P,C
3
2
13
1
34.9 (d, C(3a), J = 16.4 Hz); 135.5 (d, C(1), J = 15.6 Hz);
40.6 (d, C(3), J = 12.3 Hz); 141.4 (d, C(7a), J = 21.7 Hz);
44.9 (s, CHetHO); 151.7 (s, CHetO). P{ H} NMR (CDCl ),
C{ H} NMR (D O), δ: 113.2 (s, CHet); 118.4 (s, CHet); 121.3
P,C
P,C
2
2
3
(s, Carom); 121.8 (s, Carom); 124.7 (s, Carom); 126.1 (s, Carom);
P,C
P,C
3
1
1
2
128.3 (s, C(8)); 135.5 (d, C(1), J
= 8.1 Hz); 135.8 (d, C(3),
3
P,C
2
3
δ: –2.2 (s).
JP,C = 11.4 Hz); 136.5 (d, C(3a), JP,C = 12.1 Hz); 143.5

1
264
Russ. Chem. Bull., Int. Ed., Vol. 66, No. 7, July, 2017
Prishchenko et al.
d, C(7a), 3JP,C = 17.4 Hz); 143.9 (d, C(2), J
1
= 173.3 Hz);
P,C
4. J. Vicente, J. Abad, J. GilꢀRubio, Organometallics, 1995,
14, 2677.
(
1
3
1
1
45.5 (s, CHetHO); 152.2 (s, CHetO). P{ H} NMR (D O),
2
δ: 8.3 (s).
5. A. Korte, J. Legros, C. Bolm, Synlett, 2004, 13, 2397.
6. D. J. Bertelli, J. H. Crabtree, Tetrahedron, 1968, 24, 2079.
7. G. Buechi, J. A. Carlson, J. Am. Chem. Soc., 1968, 90, 5336.
8. N. Coskun, I. Erden, Tetrahedron, 2011, 67, 8607.
9. E. D. Bergman, Chem. Rev., 1968, 68, 41.
1
ꢀ(Pyridineꢀ3ꢀylmethylidene)ꢀ1Hꢀindenꢀ2ꢀylphosphonic acid
disodium salt (5d). The yield was 98%. Found (%): C, 54.59;
H, 3.04. C15H10NNa O P. Calculated (%): C, 54.73; H, 3.06.
2
3
1
H NMR (D O), δ: 7.10—7.90 (m, 8 H, 4 CaromH, 4 CPyH);
2
3
8
.61 (d, 1 H, C(3)H, JP,H = 9.2 Hz); 8.82 (s, 1 H, C(8)H).
C{ H} NMR (D O), δ: 122.1 (s, Carom); 123.8 (s, 2 CPy);
10. K. Hafner, K. H. Voеpel, G. Ploss, C. Koеnig, Org. Syn.,
1967, 47, 52.
1
3
1
2
1
27.3 (s, Carom); 128.9 (s, Carom); 132.0 (s, Carom); 133.0
11. S. W. Peabody, B. Breiner, S. V. Kovalenko, S. Patil, I. V.
Alabugin, Org. Biomol. Chem., 2005, 3, 218.
2
(
(
s, CPy); 136.0 (d, C(1), J
d, C(3), J
= 7.2 Hz); 137.3 (s, C(8)); 137.8
P,C
2
3
= 11.6 Hz); 142.9 (d, C(3a), J
= 11.8 Hz);
P,C
12. A. A. Prishchenko, M. V. Livantsov, O. P. Novikova, L. I.
Livantsova, V. S. Petrosyan, Russ. Chem. Bull., 2016, 65, 228.
13. A. A. Prishchenko, M. V. Livantsov, O. P. Novikova, L. I.
Livantsova, V. S. Petrosyan, Russ. Chem. Bull., 2016, 65, 1846.
14. A. A. Prishchenko, R. S. Alekseyev, M. V. Livantsov, O. P.
Novikova, L. I. Livantsova, V. I. Terenin, V. S. Petrosyan,
Russ. Chem. Bull., 2017, 66, 342.
P,C
1
3
1
1
43.3 (d, C(2), J = 175.5 Hz); 144.1 (d, C(7a), J = 16.8 Hz);
P,C P.C
3
1
1
49.7 (s, CPyN); 150.0 (s, CPyN). P{ H} NMR (D O), δ: 7.3 (s).
2
This work was financially supported by the Russian
Foundation for Basic Research (Project Nos 15ꢀ03ꢀ00002
and 17ꢀ03ꢀ00169).
1
1
5. E. D. Bergmann, A. Bondi, Chem. Ber., 1930, 63, 1158.
6. A. A. Prishchenko, M. V. Livantsov, O. P. Novikova,
Ya. N. Koval´, D. P. Krut´ko, Russ. J. Gen. Chem., 2004,
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