Effect of electronic nature of substituents in arylacetylene on the rate of reaction with 2,2,2-trichloroareno-1,3,2-dioxaphosphols

Full text of DOI:10.1134/S1070363213050253

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 5, pp. 1010–1012. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © A.S. Aniskin, A.V. Nemtarev, D.S. Baranov, V.F. Mironov, S.F. Vasilevskii, 2013, published in Zhurnal Obshchei Khimii, 2013,
Vol. 83, No. 5, pp. 876–878.
LETTERS
TO THE EDITOR
Effect of Electronic Nature of Substituents
in Arylacetylene on the Rate of Reaction
with 2,2,2-Trichloroareno-1,3,2-dioxaphosphols
A. S. Aniskina, A. V. Nemtareva, D. S. Baranovb, V. F. Mironova, and S. F. Vasilevskiib
a Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Centre,
Russian Academy of Sciences, ul. Arbuzova, 8, Kazan, Tatarstan, 420088 Russia
e-mail: nemtarev@iopc.ru
b Institute of Chemical Kinetics and Combustion, Russian Academy of Sciences, Novosibirsk, Russia
Received November 19, 2012
DOI: 10.1134/S1070363213050253
Reaction of 2,2,2-trihaloareno-1,3,2-dioxaphosphols
with the terminal acetylenes is a convenient method for
the synthesis of benzo-1,2-oxaphosphorine-2-oxide
derivatives [1]. Formation of the latter is a multi-step
process. So far a number of regularities of influence of
the phosphorus center nature on a result of the reaction
is known [2]. However, there is no information on the
effect of the nature of substituents in arylacetylene on
synthetic result as well as on the reaction rate. To
estimate the effect of the electronic properties of the
substituent in arylacetylene we investigated the reac-
tion of benzodioxaphosphols I, II with arylacetylenes
III, IV, containing in the p-position strong +М-donor
like a methoxy group, or a strong М-acceptor such as
nitro group.
31P, 13C). Thus, the introduction of the strong +М-
donors as well as the strong –М-acceptors into aryl-
acetylene does not prevent the formation of benzo-
oxaphosphorine derivatives.
In order to estimate the reaction rate we investigated
the competitive reactions of benzodioxaphosphols I
and II with pairs phenylacetylene–compound III and
phenylacetylene–compound IV. The reaction progress
was monitored by 1H NMR. It was found that from the
first pair 4-methoxyphenylacetylene III reacts pre-
dominantly (over 75%) and from the second pair,
exclusively phenylacetylene. Thus, the rate deter-
mining stage of the reaction is very sensitive to the
electronic nature of the aryl substituent. The reaction
rate increases as the donor nature of the substituent
enhances. Apparently, this stage is the donor-acceptor
interaction of phosphol as a Lewis acid with aryl-
acetylene as a Lewis base.
Both phosphoranes I, II react easily with acetylenes
III, IV to produce after hydrolysis of the reaction
mixture the benzooxaphosphorine derivatives V–VIII
in high yields. The structure of the isolated compounds
was identified by spectroscopic methods (IR, 1H NMR,
The NMR spectra were registered on an Avance-
400 spectrometer [400.0 (1H), 162.0 (31P), 100.6 MHz
(1) YC6H4
(III, IV),
O
X
O
O
hexene, CH2Cl2
P
OH
PCl3
(2) H2O
Cl
O
X
C6H4Y
V_VIII
I, II
X = H (I), Me (II); Y = 4-MeO (III), 4-NO2 (IV); X = H, Y = 4-MeO (V), 4-NO2 (VI); X = Me, Y = 4-MeO (VII), 4-NO2
(VIII).
1010

EFFECT OF ELECTRONIC NATURE OF SUBSTITUENTS
1011
1
1
(13C)] in DMSO-d6 (unless otherwise indicated)
relative to internal TMS or HMDS, or external Н3РО4.
The IR spectra were recorded on a Bruker Vector-22
instrument for suspensions in mineral oil. Phos-
phoranes I, II were prepared according to [3]. The
reaction with arylacetylenes was carried out in СН2Cl2
under argon atmosphere followed by hydrolysis under
conditions similar to the reaction of compound I with
phenylacetylene [4].
(С3, JPC 167.6, JHC 164.7), 148.80 m (s) (С4), 123.38
d. d. d. (d) (С4а, 3JPC 16.5, 3JHC 8.1, 3JHC 8.0), 127.68 d.
d (s) (С5, JHC 165.8, JHC 5.1), 127.68 d. d. d (s) (C6,
1
3
3JHC 11.4, JHC 3.6, JHC 3.6), 131.29 d. d (s) (С7, JHC
2
2
1
170.2, JHC 5.9), 121.82 d. d (d) (C8, JHC 168.0, JPC
3
1
3
6.6), 150.49 d. d. d. d (d) (C8a, JPC 7.3, JHC 8.4, JHC
2
3
3
8.4, 2JHC 3.7), 144.71 d. t. d (d) (С9, 3JPC 18.7, 3JHC 7.3,
3JHC 7.3), 124.38 d. d (s) (С10, JHC 170.6, JHC 4.0),
130.36 d. d (s) (С11, 1JHC 166.5, 2JHC 6.6), 148.16 m (s)
(С12, 3JHC 9.2). 31Р NMR spectrum: δР 3.3 ppm (d, 2JPH
16.7 Hz). Found, %: С 48.20; Н 2.93; Cl 11.40; N
4.28; Р 8.97. С14Н9ClNO5P. Calculated, %: С 49.80; Н
2.69; Cl 11.40; N 4.15; Р 9.17.
1
2
2-Hydroxy-4-(4-methoxyphenyl)-6-chlorobenzyl-
[e]-1,2-oxaphosphorine-2-oxide (V). Yield 73%,
mp 272°C. IR spectrum, ν, cm–1: 441, 449, 537, 565,
585, 641, 721, 776, 801, 829, 886, 908, 960, 1014,
1112, 1151, 1178, 1221, 1247, 1294, 1337, 1377,
1463, 1510, 1551, 1574, 1606, 1667, 2330, 2359,
2675, 2724, 2854, 2923, 2954, 3435. 1Н NMR
spectrum (DMSO-d6:СDCl3 = 1:4), δН, ppm (J, Hz):
2-Hydroxy-7-methyl-4-(4-methoxyphenyl)-6-
chlorobenzo[e]-1,2-oxaphosphorine-2-oxide (VII).
Yield 84%, mp 286°C. IR spectrum, ν, cm–1: 2550 br,
2290 br (РОН), 1611, 1595, 1539, 1510, 1483, 1460,
1376, 1337, 1302, 1294, 1248, 1179, 1166, 1128,
1033, 1014, 922, 890, 883, 860, 853, 820, 801, 782,
748, 739, 722, 666, 631, 584, 553, 535, 521, 484, 463,
2
3.58 s (3Н, C13H), 6.07 d (1H, C3H, JPH 17.8), 6.93 d
(2H, C11H, AA'-part of AA'XX'-system), 7.09 d (1H,
C5H, 4JHH 2.2), 7.10 d (1H, C8H, 3JHH 8.3), 7.22 m (2H,
C10H, XX'-part of AA'XX'-system), 7.26 d. d. d (1H,
1
3
4
5
C7H, JHH 8.3, JHH 2.2, JPH 1.6). 13С–{1H} NMR
444, 415. Н NMR spectrum, δН, ppm (J, Hz): 2.36 s
(3H, CH3), 3.83 s (3H, CH3О), 6.22 d (1H, C3H, JPH
2
spectrum, (DMSO-d6:СDCl3 = 1:4), δС, ppm (J, Hz):
17.8), 7.08 s (Н5), 7.32 br. s (Н8), 7.06 m (2H, C11H,
114.80 d. d (d) (С3, JPC 171.7, JHC 163.2), 151.18 m
(d) (С4, 2JPC 1.5), 123.38 d. d. d (d) (С4а, 3JPC 16.1, 3JHC
5.5, 3JHC 7.7), 127.86 d. d (s) (С5, 1JHC 166.2, 3JHC 5.5),
1
1
3
АА'-part of АА'ХХ'-system, JHН 8.8), 7.32 m (2H,
C10H, ХХ'-part of АА'ХХ'-system, JHН 8.8). 13С–{1H}
3
3
2
2
127.47 d d d (s) (C6, JHC 11.4, JHC 4.0, JHC 4.0),
NMR spectrum, δС, ppm (J, Hz): 19.91 q. d (s) (CH3,
1JНC 128.6, JНС 4.6), 55.74 q (s) (СН3О, JНC 144.5),
3
1
129.94 d d (s) (С7, JHC 169.1, JHC 5.9), 120.42 d. d
1
3
115.76 d. d (d) (С3, JPC 169.4, JHC 163.5), 150.78 m
(d) (С4, 2JPC 1.5), 122.04 d. d. d (d) (С4а, 3JPC 16.5, 3JНC
8.8, 3JНC 5.8), 128.30 d (s) (С5, 1JHC 164.6), 127.82 d. q
(s) (C6, 2JHС 5.6, 3JHC 5.0), 139.22 d. q (s) (С7, 3JHC 6.3,
1
1
(d) (C8, 1JHC 166.2, 3JPC 7.4), 149.76 d. d. d. d (d) (C8a,
2JPC 7.3, JHC 10.2, JHC 10.2, JHC 4.0), 129.91 d t (d)
3
3
2
(С9, JPC 18.7, JHC 7.7), 129.26 d. d (s) (С10, JHC
3
3
1
159.2, JHC 7.7), 113.74 d d (s) (С11, JHC 160.3, JHC
2
1
2
4.4), 159.77 m (s) (С12), 54.91 q (s) (С13, JHC 171.5).
1
2JHC 6.3), 122.23 d. d. q (d) (C8, JHC 164.3, JPC 7.0,
1
3
31Р NMR spectrum, (DMSO-d6): δР 4.7 ppm (d, JPH
2
3JHC 5.6), 150.31 d. d. d (d) (C8а, JPC 7.0, JHC 7.0,
2
3
2JHC 3.4), 130.53 d. t. d (d) (С9, JPC 18.7, JHC 7.8,
3
3
17.6 Hz). Found, %: С 54.98; Н 4.30; Cl 10.87; Р 9.54.
С15Н12ClO4P. Calculated, %: С 55.83; Н 3.75; Cl
10.99; Р 9.60.
3JHC 6.4), 130.18 d. d (s) (С10, JHC 159.5, JHC 7.4),
114.70 d. d (s) (С11, 1JHC 160.5, 2JHC 4.7), 160.35 m (s)
(С12). 31Р NMR spectrum: δР 3.0 ppm (d, 2JPH 17.5 Hz).
Found, %: С 56.79; Н 4.87; Cl 10.34; Р 9.05.
С16Н14ClO4P. Calculated, %: С 57.06; Н 4.19; Cl 10.53;
Р 9.20.
1
2
2-Hydroxy-4-(4-nitrophenyl)-6-chlorobenzo[e]-
1,2-oxaphosphorine-2-oxide (VI). Yield 92%, mp
321°C (decomp.). IR spectrum, ν, cm–1: 3435, 2346,
2029, 1976, 1959, 1655, 1638, 1616, 1588, 1572,
1537, 1445, 1394, 1343, 1313, 1243, 1197, 1181,
1166, 1119, 1076, 1006, 966, 929, 880, 862, 820, 761,
748, 701, 668, 629, 601, 588, 570, 537, 511, 434. 1Н
NMR spectrum, δН, ppm (J, Hz): 6.53 d (1H, C3H, 2JPH
2-Hydroxy-7-methyl-4-(4-nitrophenyl)-6-chloro-
benzo[e]-1,2-oxaphosphorine-2-oxide (VIII). Yield
90%, mp 324°C (decomp.). IR spectrum, ν, cm–1:
2500–2604 br. s, 2306 br (РОН), 1602, 1587, 1516,
1484, 1462, 1376, 1353, 1339, 1312, 1259, 1249,
1190, 1168, 1130, 1109, 1038, 1015, 926, 890, 869,
854, 809, 752, 734, 700, 612, 565, 530, 524, 464, 438.
1Н NMR spectrum, δН, ppm (J, Hz): 2.35 s (3H, CH3),
4
16.4), 6.97 d (1H, C5H, JHH 2.6), 7.34 d (1H, C8H,
3JHH 8.7), 7.52 d. d. d (1H, C7H, 3JHH 8.7, 4JHH 2.6, 5JPH
1.4), 7.68 m (2H, C10H, AA'-part of AA'XX'-system),
8.33 m (2H, C11H, XX'-part of AA'XX'-system). 13С–
{1H} NMR spectrum, δС, ppm (J, Hz): 119.70 d. d (d)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 5 2013

1012
ANISKIN et al.
6.4 d (1H, C3H, 2JPH 16.6), 6.94 s (Н5), 7.33 br. s (Н8),
ACKNOWLEDGMENTS
1
7.66 m (2H, C10H, АА'-part of АА'ХХ'-system, JHН
This work was supported by the Russian
Foundation for Basic Research (grant no. 12-03-
90703-mob_st, 10-03-00525).
7.6), 8.32 m (2H, C11H, ХХ'-part of АА'ХХ'-system,
3JHН 7.6). 13С–{1H} NMR spectrum, δС, ppm (J, Hz):
1
3
19.59 q. d (s) (CH3, JНC 128.7, JНС 4.2), 118.15 d. d
(d) (С3, JPC 168.0, JHC 164.6), 148.57 m (br. s) (С4),
1
1
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3
1
120.82 m (d) (С4а, JPC 16.5), 127.54 d (s) (С5, JHC
3
3
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2
3
3
3
1JHC 164.7, JPC 6.6, JНC 3.4), 149.87 d. d. d (d) (C8а,
2JPC 7.0, JHC 9.6, JHC 3.8), 144.45 d. t (d) (С9, JPC
3
2
3
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3
1
2
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3
2
t. t (s) (С12, JHC 9.5, JHC 3.5). 31Р NMR spectrum: δР
2.5 ppm (d, 2JPH 15.6 Hz). Found, %: С 50.95; Н 3.67;
Cl 9.87; N 4.01; Р 9.07. С15Н11ClNO5P. Calculated, %:
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 5 2013