Reactions of 3,5-di(tert-butyl)-1,2-benzoquinone with terminal acetylenes in the presence of phosphorus trichloride. ipso-Substitution of the tert-butyl group

Article abstract of DOI:10.1007/s11172-007-0292-9

The reactions of 3,5-di(tert-butyl)-1,2-benzoquinone with aryl-and alkylacetylenes in the presence of phosphorus trichloride afford 4-aryl(alkyl)-8-tert-butyl-2,6-dichloro-2-oxo-2H-benzo[e][1,2]oxaphosphinines as the major ipso-substitution products of th

Full text of DOI:10.1007/s11172-007-0292-9

Russian Chemical Bulletin, International Edition, Vol. 56, No. 9, pp. 1900—1910, September, 2007
1900
Reactions of 3,5ꢀdi(tertꢀbutyl)ꢀ1,2ꢀbenzoquinone
with terminal acetylenes in the presence of phosphorus trichloride.
ipsoꢀSubstitution of the tertꢀbutyl group*
V. F. Mironov,aꢀ A. V. Bogdanov,a A. V. Nemtarev,a A. A. Shtyrlina,a E. N. Varaksina,a
V. K. Cherkasov,b A. B. Dobrynin,a D. B. Krivolapov,a R. Z. Musin,a I. A. Litvinov,a and A. I. Konovalova
aA. E. Arbuzov Institute of Organic and Physical Chemistry,
Kazan Research Center of the Russian Academy of Sciences,
8 ul. Akad. Arbuzova, 420088 Kazan, Russian Federation.
Fax: +7 (843) 273 2253. Eꢀmail: mironov@iopc.knc.ru
bG. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences,
49 ul. Tropinina, 603950 Nizhny Novgorod, Russian Federation.
Fax: +7 (831) 262 7497. Eꢀmail: cherkasov@iomc.ras.ru
The reactions of 3,5ꢀdi(tertꢀbutyl)ꢀ1,2ꢀbenzoquinone with arylꢀ and alkylacetylenes in the
presence of phosphorus trichloride afford 4ꢀaryl(alkyl)ꢀ8ꢀtertꢀbutylꢀ2,6ꢀdichloroꢀ2ꢀoxoꢀ2Hꢀ
benzo[e][1,2]oxaphosphinines as the major ipsoꢀsubstitution products of the tertꢀbutyl group by
the chlorine atom. 4ꢀAryl(alkyl)ꢀ6,8ꢀdi(tertꢀbutyl)ꢀ2,5ꢀdichloroꢀ2ꢀoxoꢀ and 4ꢀaryl(alkyl)ꢀ6ꢀ
tertꢀbutylꢀ2,8ꢀdichloroꢀ2ꢀoxoꢀ2Hꢀbenzo[e][1,2]oxaphosphinines were obtained as the minor
products. The structures of the stable representatives of this series were confirmed by Xꢀray
diffraction.
Key words: alkynes, 1,2ꢀbenzoquinones, phosphorus trichloride, 4,6ꢀdi(tertꢀbutyl)ꢀ2,2,2ꢀ
trichlorobenzoꢀ1,3,2ꢀdioxaphosphole, ipsoꢀsubstitution, 2Hꢀbenzo[e][1,2]oxaphosphinine
Pꢀoxides, organophosphorus compounds, Xꢀray diffraction study.
The reactions of 2,2,2ꢀtrihalobenzoꢀ1,3,2ꢀdioxaꢀ
rivatives, other products. On the whole, the results of
the reactions in the orthoꢀquinone—phosphorus triꢀ
halide—arylacetylene system differ from those of the reꢀ
actions of 2,2,2ꢀtrihalobenzoꢀ1,3,2ꢀdioxaphospholes with
arylacetylenes.
phospholes with arylacetylenes are known to give 2ꢀoxoꢀ
benzo[e][1,2]oxaphosphinines or phosphacoumarin deꢀ
rivatives,1—3 which are phosphorusꢀcontaining analogs of
natural heterocycles (coumarins and αꢀchromenes) posꢀ
sessing diverse biological activities.4 Recently, alternative
approaches to the synthesis of phosphacoumarins and reꢀ
lated phosphaisocoumarin derivatives have been develꢀ
oped. However, these procedures involve many steps and
are based on the use of difficultly accessible starting comꢀ
pounds.5—7 The resulting compounds inhibit protein tyroꢀ
sine phosphatases and exhibit anticancer activity.6,7
A more convenient approach to the synthesis of 2ꢀoxoꢀ
benzo[e][1,2]oxaphosphinine derivatives is based on the
reaction in a threeꢀcomponent system consisting of
phenanthrenequinone, or tetrachloroꢀ1,2ꢀbenzoquinone,
or, alternatively, 3,6ꢀdi(tertꢀbutyl)ꢀ1,2ꢀbenzoquinone,
arylacetylene, and phosphorus trihalide.8—15 The reacꢀ
tion pathway was found to strongly depend on the strucꢀ
ture of the starting quinone. Thus, the reactions often
afford, along with 2ꢀoxobenzo[e][1,2]oxaphosphinine deꢀ
Results and Discussion
The aim of the present study was to reveal the characꢀ
teristic features of the reactions in the threeꢀcomponent
3,5ꢀdi(tertꢀbutyl)ꢀ1,2ꢀbenzoquinone (1)—monosubstiꢀ
tuted acetylene—phosphorus trichloride system. Unlike
orthoꢀquinones used earlier, compound 1 is unsymmetriꢀ
cal and contains bulky substituents in different positions
with respect to the carbonyl groups. It appeared that
the reaction of phosphorus trichloride with a mixture
of quinone 1 and arylacetylene follows two pathways
(Scheme 1) to form the ipsoꢀsubstitution products of the
tertꢀbutyl group, 2 and 4, and benzophosphinines 3 conꢀ
taining the chlorine atom at position 5 of the heterocyclic
system. This is the difference between the reaction in the
system under consideration and the earlier studied reacꢀ
tion of 3,5ꢀdi(tertꢀbutyl)ꢀ2,2,2ꢀtrichlorobenzoꢀ1,3,2ꢀ
dioxaphosphole (5) with phenylacetylene,2 which gives
* Dedicated to Academician G. A. Abakumov on the occasion
of his 70th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1836—1845, September, 2007.
1066ꢀ5285/07/5609ꢀ1900 © 2007 Springer Science+Business Media, Inc.

Benzo[e][1,2]oxaphosphinines
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 9, September, 2007
1901
compound 2a as the major prodꢀ
uct. In this case, phosphinines
2a—4a are present in the reacꢀ
The aminolysis of compound 2a with tertꢀbutylamine
afforded tertꢀbutylamide 6. The hydrolysis of compound
2a followed by the treatment of intermediate 8ꢀtertꢀbutylꢀ
6ꢀchloroꢀ2ꢀhydroxyꢀ2ꢀoxoꢀ4ꢀphenylꢀ2Hꢀbenzo[e]ꢀ
[1,2]oxaphosphinine with tertꢀbutylamine produced amꢀ
monium salt 7. The alcoholysis of compound 2a with
ethanol and methanol afforded esters 8 and 9. The hydroꢀ
lysis of phosphinine 2b gave cyclic phosphonic acid 10.
The structures of benzophosphinines 6—10 were estabꢀ
lished by spectroscopic methods. In all cases, the cyclic
nature of the compounds is retained.
The structures of esters 8 and 9 were additionally conꢀ
firmed by Xꢀray diffraction. The molecular structures and
the atomic numbering schemes for esters 8 and 9 are
presented in Figs 1 and 2, respectively. These figures give
also selected geometric parameters of the molecules (bond
lengths and bond angles).
tion mixture in
a ratio of
72 : 21 : 7. The reaction with the
use of 4ꢀchlorophenylacetylene
produces these compounds in approximately the same
ratio, whereas the reaction with 2ꢀchlorophenylacetylene
affords compound 2c as the major product (>90%).
Scheme 1
X = H (a), 4ꢀCl (b), 2ꢀCl (c)
The major portion of compounds 2a,b can be sepaꢀ
rated after the storage of a mixture of the reaction prodꢀ
ucts in vacuo (0.1 Torr, 120 °C) followed by the treatment
of the glassy residue with dry hexane. These compounds
R = Me (8), Et (9)
are characterized by a doublet at δP 16.5—17.0 (2JPCH
=
In molecules 8 and 9, the heterocycle adopts a disꢀ
torted (unsymmetrical) boat conformation with the
planar (within 0.01(2) and 0.01(2) Å in molecule 8
and within 0.015(5) and 0.004(1) Å in molecule 9)
O(1)C(8a)C(4a)C(4) and P(2)C(3)C(4)C(4a) fragments.
The dihedral angle between these fragments is 17(2) and
19.3(3)° in 8 and 9, respectively. The P(2) and C(3) atoms
deviate from the O(1)C(8a)C(4a)C(4) plane by 0.743(6)
and 0.31(2) Å, respectively, in 8 and by –0.755(1) and
–0.334(5) Å in 9. The O(1) and C(8a) atoms deviate
from the P(2)C(3)C(4)C(4a) plane by –0.68(2) and
–0.35(2) Å (8) and by 0.677(3) and 0.360(5) Å (9), reꢀ
spectively. Therefore, these atoms deviate in the same
direction, but the deviations are different in the
magnitude, resulting in a distorted boat conformaꢀ
tion. The phosphoryl group is in an equatorial position
24—25 Hz) in the 31P NMR spectra (CDCl3). An analoꢀ
gous doublet is observed in the 1H NMR spectra (CDCl3,
2
δ 6.2—6.3, JPCH = 24—25 Hz). An analysis of the
1H NMR spectra showed also that only one tertꢀbutyl
group is present in the molecules of these compounds.
The ipsoꢀsubstitution of the second tertꢀbutyl group was
established based on the 13C—{1H} NMR data. Thus, the
spectrum of phosphinine 2b shows only two signals at
high field assigned to the carbon atoms of the C(CH3)3
fragment with the corresponding multiplicities. The comꢀ
plex appearance of the multiplet for the C(8) atom conꢀ
firms the presence of the tertꢀbutyl substituent at this
atom. The multiplicity of the signal for the C(6) atom
(a doublet of doublets) is consistent with the
C(7)HC(6)(Cl)C(5)H structure.

1902
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 9, September, 2007
Mironov et al.
O(3) atom deviates from the O(1)C(8a)C(4a)C(4) and
P(2)C(3)C(4)C(4a) planes by 2.25(2) and 1.48(2) Å in 8
and by –1.476(4) and –2.259(4) Å in 9). The exocyclic
O(3)—P(2) bond length (1.53(1) Å (8) and 1.558(4) Å (9))
is smaller than the endocyclic O(1)—P(2) bond length
(1.61(1) Å (8) and 1.586(4) Å (9)), which is associꢀ
ated with the anomeric effect of the alkoxy substituent.
The endocyclic angle at the phosphorus atom,
O(1)—P(2)—C(3), is 103.3(8)° in 8 and 101.7(2)° in 9.
The phenyl substituent at the C(4) atom is twisted with
respect to the plane of the phenylene fragment by 42(3)°
in 8 and –55.6(7)° in 9.
Acid 11 and amide 12 were obtained from minor prodꢀ
ucts 3a and 3b after the treatment of the latter with water
or isopropylamine, correspondingly, followed by the fracꢀ
tional crystallization. The structures of 11 and 12 were
established by spectroscopic methods.
C(9)
O(3)
P(2)
O(2)
O(1)
C(11)
C(3)
C(4)
C(17)
C(12)
C(13)
C(10)
C(4a)
C(8a)
C(16)
C(18)
C(8)
C(7)
C(5)
C(15)
Cl(6)
C(14)
C(19)
C(6)
Fig. 1. Molecular geometry of compound 8 in the crystal strucꢀ
ture. Selected bond lengths/Å: P(2)—O(1), 1.61(1); P(2)—O(2),
1.49(2); P(2)—O(3), 1.53(1); P(2)—C(3), 1.73(2); O(1)—C(8a),
1.39(2); C(3)—C(4), 1.33(3); C(4)—C(4a), 1.49(2). Seꢀ
lected bond angles/deg: O(1)—P(2)—O(2), 110.0(8);
O(1)—P(2)—O(3), 105.4(8); O(1)—P(2)—C(3), 103.3(8);
O(2)—P(2)—O(3), 113.6(9); O(2)—P(2)—C(3), 118.7(9);
O(3)—P(2)—C(3), 104.6(9).
C(20)
C(19)
Cl(6)
C(16)
C(7)
C(6)
C(17)
C(18)
The reaction of quinone 1 with phosphorus trichloride
in the presence of 2ꢀchlorophenylacetylene followed by
the treatment of intermediate 2c with tertꢀbutylamine proꢀ
duced a stable mixture of diastereomeric amides 13
and 13´ in a ratio of 2 : 1. The diastereomerism in this
compound is associated with the presence of the chiral
phosphorus atom and the atropoisomerism with respect
to the C(4)—C(9) bond.
C(8)
C(8a)
C(5)
C(4a)
C(4)
C(15)
O(1)
C(11)
C(12)
P(2)
C(14)
O(2)
C(10)
C(3)
C(13)
O(3)
C(9)
Fig. 2. Molecular geometry of compound 9 in the crystal strucꢀ
ture. Selected bond lengths/Å: Cl(6)—C(6), 1.733(5);
P(2)—O(1), 1.587(3); P(2)—O(2), 1.459(4); P(2)—O(3),
1.556(3); P(2)—C(3), 1.737(4); O(1)—C(8a), 1.395(5);
O(3)—C(9), 1.431(7); C(3)—C(4), 1.342(6); C(4)—C(4a),
1.478(7); C(4)—C(11), 1.497(5); C(4a)—C(5), 1.396(6);
C(4a)—C(8a), 1.398(5); C(5)—C(6), 1.368(7); C(6)—C(7),
1.386(5); C(7)—C(8), 1.374(6); C(8)—C(8a), 1.408(6). Seꢀ
lected bond angles/deg: O(1)—P(2)—O(2), 112.0(2);
O(1)—P(2)—O(3), 103.3(2); O(1)—P(2)—C(3), 101.7(2);
O(2)—P(2)—O(3), 114.9(2); O(2)—P(2)—C(3), 117.5(2);
O(3)—P(2)—C(3), 105.9(2); P(2)—O(1)—C(8a), 122.8(2);
P(2)—O(3)—C(9), 125.6(4).
Aliphatic alkynes, viz., hexꢀ1ꢀyne and heptꢀ1ꢀyne, can
also be involved in the reactions with quinone 1 and phosꢀ
phorus trichloride (Scheme 2). The reactions proceed unꢀ
der mild conditions to give exclusively compounds of
the benzophosphinine nature. These compounds are
(the O(2) atom deviates from the O(1)C(8a)C(4a)C(4)
and P(2)C(3)C(4)C(4a) planes by 0.37(2) and
–0.72(2) Å in 8 and by 0.701(5) and –0.394(5) Å in 9).
The alkoxy substituent occupies an axial position (the
characterized by doublets at δP 18.5—19.1 (2JPCH
=
24.1—27.3 Hz) in the 31P NMR spectra. An analysis of
1
the H, 13C, and 13C—{1H} NMR spectra of the reaction

Benzo[e][1,2]oxaphosphinines
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 9, September, 2007
1903
Scheme 2
R = H (a), Me (b)
mixtures, which were dried in vacuo to remove the solvent
and 2ꢀchloroalkꢀ1ꢀene (the latter was formed as a result
of the addition of HCl that was evolved to an excess of the
starting acetylene), showed that the reaction produces
phosphinines 14—16. The percentage of these compounds
in the reaction mixture was 55, 28, and 17% (for R = H)
and 57, 27, and 16% (for R = Me), respectively.
with arylꢀ and alkylacetylenes in the presence of PCl3
resulted in the formation of 2Hꢀbenzo[e][1,2]oxaphosꢀ
phinine derivatives, with the ipsoꢀsubstitution of the
tertꢀbutyl group in the para position with respect to the
endocyclic oxygen atom predominating. The formation
of benzo[e][1,2]phosphinines containing the chlorine
atom at positions 5 and 8 of the heterocyclic system is
a new unusual reaction pathway.
In the 13C—{1H} NMR spectra, these reaction prodꢀ
ucts are characterized by doublets of C(3), C(4a), C(8),
C(8a), and C(9). Based on the multiplicities of these sigꢀ
nals in the 13C NMR spectra, these products were unamꢀ
biguously identified as phosphinines 14—16. Unlike the
reactions of arylacetylenes, the latter reactions are less
selective and afford the ipsoꢀsubstitution products of eiꢀ
ther of the two tertꢀbutyl groups. The same compounds
were prepared by the reactions of phosphole 5 with hexyne
and heptyne. These reactions also yield phosphinine 14 as
the major product. Its percentage in the reaction mixture
was 70% (14a) and 62% (14b). 1,2ꢀOxaphosphinines 15
and 16 are formed as byꢀproducts in approximately equal
amounts (15%) in the reactions with hexyne and in 24
and 14% yields in the reactions with heptyne. Compounds
17 and 18 were isolated after the hydrolysis of the mixꢀ
ture. Their structures were established by 1H and 13C NMR
spectroscopy.
Experimental
The NMR spectra were recorded on Bruker Avanceꢀ600
(600 MHz for 1H, 150.9 MHz for 13C, and 242.8 MHz for 31P),
Bruker MSLꢀ400 (400 MHz for 1H and 100.6 MHz for 13C), and
Bruker CXPꢀ100 (36.48 MHz for 31P) instruments. The IR specꢀ
tra were measured on a Bruker Vectorꢀ22 instrument in Nujol
mulls. The mass spectra were obtained on a TRACE MS Finnigan
MAT instrument; the ionizing electron energy was 70 eV; the
ion source temperature was 200 °C. The evaporator tube was
heated in the programmed mode from 35 to 150 °C with a step of
35 deg min–1. The mass spectrometric data were processed with
the use of the Xcalibur program.
Quinone 1 was supplied by V. K. Cherkasov (G. A. Razuvaev
Institute of Organometallic Chemistry of the Russian Academy
of Sciences). Compound 5 was synthesized according to a known
procedure.16 All arylꢀ and alkylacetylenes were synthesized and
purified according to procedures described earlier.17 Freshly disꢀ
tilled phosphorus trichloride was used.
Reaction of 3,5ꢀdi(tertꢀbutyl)ꢀ1,2ꢀbenzoquinone (1) with
phenylacetylene in the presence of phosphorus trichloride. A soꢀ
lution of phosphorus trichloride (0.8 mL, 0.0079 mol) in CH2Cl2
(1 mL) was added dropwise with stirring to a mixture of quinone 1
(1.5 g, 0.0068 mol), CH2Cl2 (20 mL), and phenylacetylene
(1.1 mL, 0.01 mol) under argon. The reaction mixture was kept
for 9 h. Then the solvent and excess phosphorus trichloride were
removed by distillation. The residue was dried in vacuo (120 °C,
0.1 Torr). A mixture of 8ꢀtertꢀbutylꢀ2,6ꢀdichloroꢀ4ꢀphenylꢀ2ꢀ
oxoꢀ2Hꢀbenzo[e][1,2]oxaphosphinine (2a) (72%), 6,8ꢀdi(tertꢀ
butyl)ꢀ2,5ꢀdichloroꢀ4ꢀphenylꢀ2ꢀoxoꢀ2Hꢀbenzo[e][1,2]oxaphosꢀ
phinine (3a) (21%), and 6ꢀtertꢀbutylꢀ2,8ꢀdichloroꢀ2ꢀoxoꢀ4ꢀ
phenylꢀ2Hꢀbenzo[e][1,2]oxaphosphinine (4a) (7%) was obꢀ
tained as a glassy yellowish substance. 31P NMR (CDCl3,
R = H (a), Me (b)
To summarize, the involvement of unsymmetrical
3,5ꢀdi(tertꢀbutyl)ꢀ1,2ꢀbenzoquinone (1) in the reactions
2
242.8 MHz), δ: 17.14 (d, JPCH(3) = 24.6 Hz) (2a); 17.89 (d,

1904
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 9, September, 2007
Mironov et al.
2
2
2
2JPCH = 25.4 Hz) (3a); 18.51 (d, JPCH(3) = 27.8 Hz) (4a). The
reaction mixture was treated with hexane (10 mL) under argon.
The white precipitate of oxaphosphinine 2a that formed was
filtered off. The yield was 1.36 g (60%), m.p. 195—197 °C (cf. lit.
data2: m.p. 196 °C). The mass spectrum of compound 2a, m/z:
370, 368, 366 (C16H1735Cl2O2P) [M]•+, 351 [M – CH3], 353
[M – CH]. The spectroscopic parameter of this compound are
consistent with those described earlier.2 The precipitate of comꢀ
pound 2a was separated, and the filtrate was concentrated
in vacuo (0.1 Torr). The glassy mixture consisting of phosphinines
2a (14%), 3a (71%), and 4a (15%) was characterized by spectroꢀ
scopic method. 1H NMR of compound 3a (CDCl3, 600 MHz),
5.7 Hz); 128.34 (dd [s], C(6), JHCC(6) = 4.5 Hz, JHCC(6)
=
4.5 Hz); 128.78 (dd [s], C(7), 1JHC(7) = 164.5, 3JHC(5)CC(7) = 7.2);
141.97 (m [d], C(8), JPOCC(8) = 6.2 Hz); 149.08 (ddd [d],
C(8a), 2JPOC(8a) = 8.7 Hz, 3JHCCC(8a) = 9.0—9.2 Hz, 3JHCCC(8a)
9.0—9.2 Hz); 139.31 (dtd [d], C(9), JPCCC(9) = 18.2 Hz,
3JHC(11)CC(9) = 7.5 Hz, JHC(3)CC(9) = 6.5 Hz); 128.30 (ddd [s],
3
=
3
3
1
3
C(10), JHC(10) = 158.5 Hz, JHCCC(10) = 5.6—6.0 Hz,
3JHCCC(10) = 5.6—6.0 Hz); 128.79 (dd [s], C(11), JHC(11)
=
=
1
159.6 Hz, 3JHCCC(11) = 6.0 Hz); 128.92 (dt [s], C(12), 1JHC(12)
3
161.3 Hz, JHC(10)CC(12) = 7.4 Hz); 35.33 (m [s], C(13)); 30.0
(qm [s], C(14), 1JHC(14) = 126.5 Hz, 3JHCCC(14) = 4.7 Hz); 51.70
(m [d], C(15), JPNC(15) = 1.8 Hz); 32.02 (qm [d], C(16),
2
5
δ: 7.67 (d, H(7), JPOCCCH(7) = 1.7 Hz); 7.49—7.51 and
7.37—7.39 (both m, C6H5); 6.49 (d, H(3), JPCH(3) = 26.6 Hz);
1.47 and 1.53 (both s, H(14), H(16)). 1H NMR of compound 4a
1JHC(16) = 126.2 Hz, 3JPNCC(16) = 4.3 Hz, 3JHCCC(16) = 2.3 Hz).
tertꢀButylammonium 8ꢀtertꢀbutylꢀ6ꢀchloroꢀ2ꢀoxoꢀ4ꢀphenylꢀ
2Hꢀbenzo[e][1,2]oxaphosphininꢀ2ꢀoate (7) was prepared by
hydrolysis of compound 2a (0.3 mmol) followed by mixing with
tertꢀbutylamine (0.03 mL, 0.3 mmol) in CH2Cl2, the removal of
the solvent, washing of the precipitate that formed with diethyl
ether, and drying in air. The yield was 0.09 g (69%), m.p.
218—219 °C. Found (%): C, 63.57; H, 6.94; N, 3.41; P, 7.39.
2
4
(CDCl3, 600 MHz), δ: 7.58 (dd, H(7), JH(5)CCCH(7) = 2.4 Hz,
5JPOCCCH(7) = 1.8 Hz); 7.11 (d, H(5), JH(7)CCCH(5) = 2.4 Hz);
4
7.49—7.51 and 7.37—7.39 (both m, C6H5); 6.49 (d, H(3),
2JPCH(3) = 26.6 Hz); 1.45 (s, H(14)). 13C NMR of compound 4a
1
(CDCl3, 150.9 MHz), δ:* 119.75 (dd [d], C(3), JPC(3)
=
=
161.6 Hz, 1JHC(3) = 171.9 Hz); 157.76 (dt [s], C(4), 2JHC(3)C(4)
C22H29ClNO3P. Calculated (%): C, 62.63; H, 6.88; N, 3.32;
3
3.7 Hz, JHC(10)CC(4) = 3.6 Hz); 123.65 (dd [d], C(4a),
3JPCCC(4a) = 18.4 Hz, JHC(3)CC(4a) = 8.1 Hz); 131.86 (dd [s],
C(5), JHC(7)CC(5) = 12.0 Hz, JPOCCC(5) = 1.5 Hz); 144.31
(m [s], C(6)); 128.62 (d [s], C(7), JHC(7) = 158.8 Hz); 137.65
(m [d], C(8), JPOCC(8) = 6.5 Hz); 148.16 (dd [d], C(8a),
2JPOC(8a) = 10.9 Hz, JHCCC(8a) = 11.6 Hz); 140.80 (dtd [d],
C(9), JPCCC(9) = 20.5 Hz, JHCCC(9) = 7.2 Hz, JHC(3)CC(9)
6.2 Hz); 128.29 (br.dm [br.s], C(10), JHC(10) = 161.0 Hz);
128.60 (br.dm [br.s], C(11), 1JHC(11) = 161.4 Hz); 129.05 (dt [s],
P, 7.35. 1H NMR (CDCl3, 600 MHz), δ: 6.28 (br.d, H(3),
2JPCH(3) = 18.5 Hz); 6.90 (d, H(5), 4JH(7)CCCH(5) = 2.5 Hz); 7.22
(br.d, H(7), 4JH(5)CCCH(7) = 2.5 Hz); 7.29—7.31 and 7.43—7.45
3
3
4
1
(both m, C6H5); 1.46 (s, H(14)); 1.33 (br.s, H(16)); 8.49 (br.s,
N+H3). 31P NMR (CDCl3, 36.48 MHz), δ: 1.7 (d, JPCH(3)
=
3
2
18.3 Hz). 13C NMR (CDCl3, 150.9 MHz), δ: 121.15 (dd [d],
3
3
3
3
1
1
=
C(3), JPC(3) = 166.4 Hz, JHC(3) = 160.0 Hz); 149.07 (m [s],
1
3
C(4)); 125.53 (dd [d], C(4a), JPCCC(4a) = 15.3 Hz,
3JHC(3)CC(4a) = 8.3 Hz); 125.48 (dd [s], C(5), 1JHC(5) = 165.7 Hz,
1
2
C(12), JHC(12) = 161.2 Hz, JHCC(12) = 7.3 Hz); 35.33 (m [s],
3JHC(7)CC(5) = 5.7 Hz); 126.35 (dd [s], C(6), 2JHC(7)C(6) = 4.5 Hz,
3
2
1
C(13), JHCCC(13) = 3.8 Hz, JHCC(13) = 3.7—3.8 Hz);
2JHC(5)C(6)
=
4.5 Hz); 128.13 (dd [s], C(7), JHC(7)
=
1
3
3
29.86 (q.sept [s], C(14), JH3C(14) = 126.5 Hz, JHCCC(14)
=
=
163.0—164.0 Hz, JHC(5)CC(7) = 6.4 Hz); 141.42 (m [d], C(8),
3JPOCC(8) = 5.1 Hz); 150.74 (ddd [d], C(8a), 2JPOC(8a) = 8.7 Hz,
3JHCCC(8a) = 8.5—8.7 Hz, JHCCC(8a) = 8.5—8.7 Hz); 140.29
(m [d], C(9), JPCCC(9) = 17.5 Hz); 128.56 (ddd [s], C(10),
1JHC(10) = 159.0 Hz, 3JHCCC(10) = 7.0 Hz, 3JHCCC(10) = 7.0 Hz);
128.48 (dd [s], C(11), 1JHC(11) = 160.3 Hz, 3JHCCC(11) = 5.4 Hz);
128.13 (dt [s], C(12), JHC(12) = 161.0 Hz, JHC(10)CC(12)
7.2 Hz); 35.32 (m [s], C(13)); 30.20 (qm [s], C(14), JHC(14)
126.3 Hz, JHCCC(14) = 4.7 Hz); 51.61 (m [s], C(15)); 27.90
(br.q [s], C(16), 1JHC(16) = 127.1 Hz).
8ꢀtertꢀButylꢀ6ꢀchloroꢀ2ꢀmethoxyꢀ2ꢀoxoꢀ4ꢀphenylꢀ2Hꢀbenꢀ
zo[e][1,2]oxaphosphinine (8). Anhydrous MeOH (2 mL) was
added to phosphinine 2a (0.4 g), and the reaction mixture was
stirred. The reaction was accompanied by vigorous evolution of
HCl. After heating at 65 °C for 30 min, the reaction mixture was
cooled and kept for 10 h. The precipitate of phosphinine 8 was
filtered off and washed with diethyl ether. The yield was 0.38 g
(90%), m.p. 175 °C. Found (%): C, 63.01; H, 5.76; P, 8.49.
C19H20ClO3P. Calculated (%): C, 62.90; H, 5.52; P, 8.55.
MS, m/z: 364, 362 (C19H2035ClO3P) [M]•+, 347 [M – CH3],
327 [M – Cl], 297 [M – Cl – OCH3], 241 [M – Cl –
OCH3 – C4H8], 56 [C4H8]. IR, ν/cm–1: 1595, 1553, 1419,
1335, 1279, 1254, 1214, 1148, 1045, 923, 879, 865, 823, 792,
2
4.7 Hz); 36.78 (m [s], C(15), JHCCC(15) = 3.8 Hz, JHCC(15)
1
3
3.8 Hz); 29.92 (q.sept [s], C(16), JHC(16) = 126.5 Hz,
3JHCCC(16) = 4.7 Hz).
3
2ꢀtertꢀButylaminoꢀ8ꢀtertꢀbutylꢀ6ꢀchloroꢀ2ꢀoxoꢀ4ꢀphenylꢀ
2Hꢀbenzo[e][1,2]oxaphosphinine (6). tertꢀButylamine (0.6 mL,
0.006 mol) was added to a solution of phosphinine 2a (1.0 g,
0.003 mol) in CH2Cl2 (10 mL). The reaction mixture was kept
for 10 h. Then the solvent was removed in vacuo (12 Torr) until a
cottonꢀlike white substance was obtained. The latter was treated
with diethyl ether (10 mL). The white precipitate of tertꢀbutylꢀ
ammonium chloride was filtered off, and the ethereal filtrate
was concentrated until compound 6 was obtained as a white
precipitate. The yield was 0.9 g (75%), m.p. 165—167 °C.
Found (%): C, 65.17; H, 6.77; N, 3.37; P, 7.55. C22H27ClNO2P.
Calculated (%): C, 65.42; H, 6.69; N, 3.47; P, 7.68. 1H NMR
(CDCl3, 600 MHz), δ: 6.17 (d, H(3), JPCH(3) = 19.1 Hz);
7.00 (d, H(5), JH(7)CCCH(5) = 2.5 Hz); 7.34 (dd, H(7),
4JH(7)CCCH(5) = 2.5 Hz, JPOCCCH(7) = 1.5 Hz); 7.29, 7.31, and
7.43 (all m, C6H5); 3.56 (d, PNH, JPNH = 6.1 Hz); 1.52
(s, H(14)); 1.29 (s, H(16)). 31P NMR (CDCl3, 36.48 MHz), δ:
6.9 (dd, 2JPCH(3) = 19.2 Hz, 2JPNH = 6.2 Hz). 13C NMR (CDCl3,
1
3
=
=
1
3
2
4
5
2
1
150.9 MHz), δ: 117.51 (dd [d], C(3), JPC(3) = 158.0 Hz,
1JHC(3) = 163.0 Hz); 153.31 (m [d], C(4), JPCC(4) = 1.7 Hz);
754, 701, 637, 559, 538. H NMR (CDCl3, 600 MHz), δ: 6.12
(d, H(3), JPCH(3) = 18.6 Hz); 7.03 (d, H(5), JH(7)CCCH(5)
2.5 Hz); 7.38 (dd, H(7), JH(5)CCCH(7) = 2.5 Hz, JPOCCCH(7)
2
1
3
3
2
4
123.99 (dd [d], C(4a), JPCCC(4a) = 15.3 Hz, JHC(3)CC(4a)
8.3 Hz); 116.99 (dd [s], C(5), 1JHC(5) = 167.3 Hz, 3JHC(7)CC(5)
=
=
=
=
4
5
1.6 Hz); 7.32—7.33 and 7.46 (both m, C6H5); 1.50 (s, H(17));
3
* Hereinafter, the multiplicities of the signals in the
13C—{1H} NMR spectra are given in brackets.
3.88 (POCH3, JPOCH = 11.8 Hz). 31P—{1H} NMR (CDCl3,
36.48 MHz), δ: 10.2. 13C NMR (CDCl3, 150.9 MHz), δ: 111.70

Benzo[e][1,2]oxaphosphinines
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 9, September, 2007
1905
1
1
(dd [d], C(3), JPC(3) = 175.0 Hz, JHC(3) = 166.3 Hz); 156.75
4ꢀchlorophenylacetylene (0.92 g), and a solution of phosphorus
trichloride (0.8 mL) in CH2Cl2 (1 mL). As described above, the
reaction mixture was kept over a period of time. The solvent and
excess phosphorus trichloride were removed. The residue was
dried in vacuo (120 °C, 0.1 Torr) and treated with hexane.
The white precipitate of 8ꢀtertꢀbutylꢀ2,6ꢀdichloroꢀ4ꢀ(4ꢀchloroꢀ
phenyl)ꢀ2ꢀoxoꢀ2Hꢀbenzo[e][1,2]oxaphosphinine (2b) was filtered
off. The yield was 1.2 g (65%). 31P NMR (CDCl3, 36.48 MHz),
3
(m [s], C(4)); 123.73 (dd [d], C(4a), JPCCC(4a) = 15.7 Hz,
3JHC(3)CC(4a) = 8.3 Hz); 127.21 (ddd [s], C(5), JHC(5)
=
1
167.8 Hz, 3JHC(7)CC(5) = 5.7 Hz, 4JHC(3)CCC(5) = 0.9 Hz); 128.54
(dd [s], C(6), 2JHC(5)C(6) = 4.5 Hz, 2JHC(7)C(6) = 4.5 Hz); 129.45
(dd [s], C(7), 1JHC(7) = 164.6 Hz, 3JHC(5)CC(7) = 6.2 Hz); 141.88
3
(m [d], C(8), JPOCC(8) = 6.1 Hz); 149.20 (ddd [d], C(8a),
2JPOC(8a) = 8.7 Hz, 3JHCCC(8a) = 10.0 Hz, 3JHCCC(8a) = 10.0 Hz);
1
2
2
53.69 (qd [d], C(9), JHC(9) = 148.4 Hz, JPOC(9) = 6.6 Hz);
δ: 16.50 (d, JPCH = 24.4 Hz). 1H NMR (CDCl3, 400 MHz), δ:
3
3
138.79 (dtd [d], C(10), JPCCC(10) = 19.8 Hz, JHC(12)CC(10)
7.5 Hz, 3JHC(3)CC(10) = 6.2 Hz); 128.43 (dm [s], C(11), 1JHC(11)
160.4 Hz, 3JHCCC(11) = 6.3—7.0 Hz, 3JHCCC(11) = 6.3—7.0 Hz);
128.90 (br.dd [s], C(12), JHC(12) = 162.2 Hz, JHCCC(12)
5.5—6.0 Hz); 129.41 (dt [s], C(13), JHC(13) = 161.0 Hz,
3JHC(11)CC(13) = 7.7 Hz); 35.49 (m [s], C(16), JHC(17)C(16)
=
=
6.34 (d, H(3), 2JPCH(3) = 24.4 Hz); 7.00 (d, H(5), 4JH(7)CCCH(5)
=
4
2.5 Hz); 7.45 (d, H(7), JH(5)CCCH(7) = 2.5 Hz); 7.29 and 7.46
(both m, AA´BB´ system, H(10), H(11), 3JHCCH = 8.5 Hz); 1.48
(s, H(14)). 13C NMR (CDCl3, 150.9 MHz), δ: 115.62 (dd [d],
1
3
=
1
1
1
C(3), JPC(3) = 156.0 Hz, JHC(3) = 172.1 Hz); 155.69 (m [d],
2
=
C(4), 2JPCC(4) = 2.2 Hz, 2JHC(3)C(4) = 3.0—3.2 Hz, 3JHC(5)CC(4)
=
1
3
3.8 Hz); 29.88 (q.sept [s], C(17), JHC(17) = 126.6 Hz,
3JHCCC(17) = 4.8 Hz).
3.5—4.0 Hz); 124.58 (dd [d], C(4a), JPCCC(4a) = 15.8 Hz,
3JHC(3)CC(4a) = 8.1—8.2 Hz); 126.20 (dd [s], C(5), JHC(5)
=
=
=
1
8ꢀtertꢀButylꢀ6ꢀchloroꢀ2ꢀethoxyꢀ2ꢀoxoꢀ4ꢀphenylꢀ2Hꢀbenꢀ
zo[e][1,2]oxaphosphinine (9). The reaction of phosphinine 2a
(1 g) with ethanol was carried out analogously. The yield of
compound 9 was 0.9 g (87%), m.p. 140 °C. Found (%): C, 63.82;
H, 6.07; P, 8.37. C20H22ClO3P. Calculated (%): C, 63.75;
H, 5.84; P, 8.23. MS, m/z: 378, 376 (C20H2235ClO3P) [M]•+
361 [M – CH3], 341 [M – Cl], 333 [M – C3H7]. IR, ν/cm–1
1596, 1556, 1421, 1337, 1276, 1253, 1213, 1150, 1043, 955, 920,
867, 822, 803, 760, 720, 700, 638, 585, 560, 539. 1H NMR
(CDCl3, 600 MHz), δ: 6.11 (d, H(3), JPCH(3) = 18.5 Hz);
166.1 Hz, 3JHC(7)CC(5) = 5.7 Hz); 127.23 (dd [s], C(6), 2JHCC(6)
2
1
4.6 Hz, JHCC(6) = 4.6 Hz); 128.47 (dd [s], C(7), JHC(7)
3
164.4 Hz, JHC(5)CC(7) = 5.8 Hz); 142.18 (m [d], C(8),
3JPOCC(8) = 6.0 Hz); 149.62 (ddd [d], C(8a), 2JPOC(8a) = 8.1 Hz,
3JHCCC(8a) = 8.4 Hz, JHCCC(8a) = 9.6 Hz); 137.83 (ddt [d],
3
,
:
C(9), 3JPCCC(9) = 18.9 Hz, 3JHC(11)CC(9) = 7.6 Hz, 3JHC(3)CC(9)
=
=
6.1 Hz); 130.59 (dd [s], C(10), 1JHC(10) = 162.5 Hz, 3JHCCC(10)
1
6.2—6.3 Hz); 129.28 (two ddd [s], C(11), JHC(11) = 163.8 Hz,
3JHCCC(11) = 4.4 Hz, JHC(10)C(11) = 3.6 Hz); 134.38 (tt [s],
C(12), JHC(10)CC(12) = 10.8 Hz, JHC(10)CC(12) = 3.3 Hz);
35.55 (m [s], C(13), JHC(7)CC(13) = 7.4 Hz, JHC(14)C(13) =
3.8 Hz); 29.94 (q.sept [s], C(14), JHC(14) = 126.7 Hz,
3JHCCC(14) = 4.7 Hz).
2
2
3
3
4
3
2
7.01 (d, H(5), JH(7)CCCH(5) = 2.6 Hz); 7.37 (dd, H(7),
4JH(5)CCCH(7) = 2.6 Hz, JPOCCCH(7) = 1.5 Hz); 4.26—4.29
5
1
(POC(9)HAHB, 2JH
= 10.6—11.0 Hz, 3JPHA = 10.0—10.2 Hz,
H
A
B
3JPH = 9.6—10.0 Hz, 3JH
= 7.1 Hz); 1.38 (t, C(10)HX,
The filtrate obtained after the isolation of compound 2b was
concentrated in vacuo (100 °C, 0.2 Torr). 6,8ꢀDi(tertꢀbutyl)ꢀ
2,5ꢀdichloroꢀ4ꢀ(4ꢀchlorophenyl)ꢀ2ꢀoxoꢀ2Hꢀbenzo[e][1,2]oxaꢀ
phosphinine (3b) was obtained as a glassy compound (~90%).
H
X
B
3JHH = 7.1); 7.29—7.31 and 7.43—7.44 (both m, C6H5); 1.49
X
1
(s, H(18)). H NMR (acetoneꢀd6, 600 MHz), δ: 6.31 (d, H(3),
2JPCH(3) = 18.2 Hz); 7.02 (d, H(5), 4JH(7)CCCH(5) = 2.6 Hz); 7.46
4
5
2
(dd, H(7), JH(5)CCCH(7) = 2.6 Hz, JPOCCCH(7) = 1.7 Hz);
7.42—7.44 and 7.53—7.54 (both m, C6H5); 1.51 (s, H(14));
4.23—4.27 (m, AB part of an ABMX3 system, POC(9)HAHB,
31P NMR (CDCl3, 36.48 MHz), δ: 17.3 (d, JPCH = 26.6 Hz).
2
1H NMR (CDCl3, 400 MHz), δ: 6.34 (d, H(3), JPCH(3)
=
24.4 Hz); 7.00 (d, H(5), 4JH(7)CCCH(5) = 2.5 Hz); 7.45 (d, H(7),
4JH(5)CCCH(7) = 2.5 Hz); 7.29 and 7.46 (both m, AA´BB´ system,
H(10), H(11), 3JHCCH = 8.5 Hz); 1.48 (s, H(14)).
2JH B = 10.2 Hz, 3JPOCH = 7.3 Hz, 3JPOCH = 7.3 Hz, 3JH
=
H
H
7.0 AHz); 1.36 (t, C(10)HXA, JHH = 7.0 HzB). 31P—{1H} NMR
X
3
X
(CDCl3, 36.48 MHz), δ: 7.5. 13C NMR (CDCl3, 150.9 MHz),
8ꢀtertꢀButylꢀ6ꢀchloroꢀ4ꢀ(4ꢀchlorophenyl)ꢀ2ꢀhydroxyꢀ2ꢀoxoꢀ
2Hꢀbenzo[e][1,2]oxaphosphinine (10). Compound 2b (1.5 g) was
dissolved in wet diethyl ether and kept in air. After evaporation
of the solvent, compound 10 was obtained as a white powder in
quantitative yield, m.p. 125 °C. Found (%): C, 56.25; H, 4.73;
Cl, 18.74; P, 7.98. C18H17Cl2O3P. Calculated (%): C, 56.40;
H, 4.44; Cl, 18.54; P, 8.09. MS, m/z: 382 [M]•+
(C18H1735Cl2O3P). IR, ν/cm–1: 3300—3400, 2740, 2370—2250,
1670—1770, 1598, 1555, 1422, 1335, 1257, 1217, 1148, 1125,
1091, 1013, 932, 865, 834, 806, 770, 734, 718, 685, 600, 566,
520, 485, 454. 31P NMR (DMSOꢀd6, 36.48 MHz), δ: 2.9
δ: 112.51 (dd [d], C(3), 1JPC(3) = 174.7 Hz, 1JHC(3) = 165.9 Hz);
2
156.01 (m [d], C(4), JPCC(4) = 1.5 Hz); 123.70 (dd [d], C(4a),
3JPCCC(4a) = 15.6 Hz, JHC(3)CC(4a) = 8.4 Hz); 127.09 (dd [s],
3
1
3
C(5), JHC(5) = 167.3 Hz, JHC(7)CC(5) = 5.7 Hz); 127.84 (s,
C(6), overlap with the component of the signal of C(12)); 129.25
(dd [s], C(7), 1JHC(7) = 164.3 Hz, 3JHC(5)CC(7) = 5.5 Hz); 141.77
3
(m [d], C(8), JPOCC(8) = 6.8 Hz); 149.17 (ddd [d], C(8a),
2JPOC(8a) = 8.9 Hz, JHCCC(8a) = 8.9 Hz, JHCCC(8a) = 8.9 Hz);
3
3
1
2
63.59 (tdq [d], C(9), JHC(9) = 148.2 Hz, JPOC(9) = 6.6 Hz,
2JHCC(9) = 4.4 Hz); 16.62 (qdt [d], C(10), JHC(10) = 127.4 Hz,
1
3JPOCC(10) = 5.9 Hz, 2JHCC(10) = 2.4 Hz); 138.82 (dtd [d], C(11),
(d, 2JPCH = 16.6 Hz). H NMR (DMSOꢀd6, 600 MHz), δ: 6.38
1
3JPCCC(9) = 19.4 Hz, JHC(13)CC(11) = 7.4 Hz, JHC(3)CC(11)
=
=
(d, H(3), JPCH(3) = 17.8 Hz); 6.86 (d, H(5), JH(7)CCCH(5) =
3
3
2
4
6.2 Hz); 128.37 (ddd [s], C(12), 1JHC(12) = 159.0 Hz, 3JHCCC(12)
2.5 Hz); 7.36 (br.m, H(7)); 7.38 and 7.54 (both m,
3
3
5.8—6.0 Hz, JHCCC(12) = 5.8—6.0 Hz); 128.82 (dd [s],
C(13), 1JHC(13) = 160.5 Hz, 3JHCCC(13) = 6.0 Hz); 129.27 (dt [s],
AA´BB´ system, H(10), H(11), JHCCH = 8.5 Hz); 1.44
(s, H(14)). 13C NMR (DMSOꢀd6, 150.9 MHz), δ: 118.11 (dd [d],
1
3
1
1
C(14), JHC(14) = 162.0 Hz, JHC(12)CC(14) = 7.1 Hz); 35.39
(m [s], C(17)); 29.83 (qm [s], C(18), JHC(18) = 126.1 Hz,
3JHCCC(18) = 4.6 Hz).
Reaction of quinone 1 with 4ꢀchlorophenylacetylene in the
presence of phosphorus trichloride. The reaction was carried out
analogously with the use of quinone 1 (1 g), CH2Cl2 (20 mL),
C(3), JPC(3) = 169.4 Hz, JHC(3) = 164.0 Hz); 150.58 (m [d],
1
2
2
3
C(4), JPCC(4) = 1.5 Hz, JHC(3)C(4) = 3.5 Hz, JHC(5)CC(4) =
3
3.5—4.0 Hz); 123.53 (br.dd [d], C(4a), JPCCC(4a) = 17.2 Hz,
3JHC(3)CC(4a) = 8.5 Hz); 127.54 (ddd [d], C(5), JHC(5)
=
168.3 Hz, JHC(7)CC(5) = 5.9 Hz, JPOCCC(5) = 1.7 Hz); 130.23
(ddd [d], C(6), JPOCCCC(6) = 1.7 Hz, JHCC(6) = 4.4 Hz,
1
3
4
5
2

1906
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 9, September, 2007
Mironov et al.
1
2JHCC(6) = 5.7 Hz); 130.80 (dd [s], C(7), JHC(7) = 165.4 Hz,
with the use of quinone 1 (1 g). The reaction mixture was dried
at 110 °C (0.8 Torr). A mixture of diastereomers of 8ꢀtertꢀbutylꢀ
2,6ꢀdichloroꢀ4ꢀ(2ꢀchlorophenyl)ꢀ2ꢀoxoꢀ2Hꢀbenzo[e][1,2]oxaꢀ
phosphinine (2c) (~90%) and 6,8ꢀdi(tertꢀbutyl)ꢀ2,5ꢀdichloroꢀ4ꢀ
(2ꢀchlorophenyl)ꢀ2ꢀoxoꢀ2Hꢀbenzo[e][1,2]oxaphosphinine (3c)
3JHC(5)CC(7) = 5.9 Hz); 143.06 (m [d], C(8), 3JPOCC(8) = 7.2 Hz,
4JHC(5)CCC(8) = 1.5 Hz, 2JHC2(7)C(8) = 3.2 Hz, 3JHCCC(8) = 4.2 Hz);
3
148.92 (ddd [d], C(8a), JPOC(8a) = 11.3 Hz, JHCCC(8a)
=
10.4—10.5 Hz, 3JHCCC(8a) = 8.6—8.7 Hz); 136.06 (dtd [d], C(9),
3JPCCC(9) = 21.3 Hz, JHC(11)CC(9) = 7.8 Hz, JHC(3)CC(9)
=
=
(~10%) was obtained as a glassy lightꢀyellow substance. 31P NMR
3
3
6.1 Hz); 130.59 (dd [s], C(10), 1JHC(10) = 162.5 Hz, 3JHCCC(10)
(CDCl3, 36.48 MHz), δ: 15.3 and 15.4 (two d, JPCH(3)
=
=
2
1
2
6.2—6.3 Hz); 129.28 (two ddd [s], C(11), JHC(11) = 163.8 Hz,
23.6—24.0 Hz) (2c); 16.6 and 16.7 (two d, JPCH(3)
3JHCCC(11) = 4.4 Hz, JHC(10)C(11) = 3.6 Hz); 134.38 (tt [s],
24.0—25.0 Hz) (3c). The mixture was dissolved in CH2Cl2
(6 mL), and tertꢀbutylamine (0.96 mL) was added with stirring.
After 2 h, the solvent was removed in vacuo (12 Torr), and the
viscous residue was washed with water and extracted with diꢀ
ethyl ether. The ethereal extract was concentrated, and the resiꢀ
due was triturated with wet acetone. The precipitate that formed
was filtered off, washed with acetone, and dried. A 2 : 1 mixture
of diastereomers of 2ꢀtertꢀbutylaminoꢀ8ꢀtertꢀbutylꢀ6ꢀchloroꢀ
4ꢀ(2ꢀchlorophenyl)ꢀ2ꢀoxoꢀ2Hꢀbenzo[e][1,2]oxaphosphinine
(13 and 13´) was obtained in a yield of 1.3 g (72%), m.p. 110 °C.
Found (%): C, 60.03; H, 6.11; Cl, 16.13; N, 3.09; P, 7.14.
C22H26Cl2NO2P. Calculated (%): C, 60.27; H, 5.94; Cl, 16.21;
2
3
3
C(12), JHC(10)CC(12) = 10.8 Hz, JHC(11)C(12) = 3.3 Hz);
35.44 (d.dec [s], C(13), JHC(7)CC(13) = 7.5 Hz, JHC(14)C(13)
3.7 Hz); 29.94 (q.sept [s], C(14), JHC(14) = 126.5 Hz,
3JHC(14)CC(14) = 4.7 Hz).
3
2
=
1
6,8ꢀDi(tertꢀbutyl)ꢀ5ꢀchloroꢀ4ꢀ(4ꢀchlorophenyl)ꢀ2ꢀisoꢀ
propylaminoꢀ2ꢀoxoꢀ2Hꢀbenzo[e][1,2]oxaphosphinine (12). Comꢀ
pound 3b (0.6 g, 1.3 mmol) was dissolved in hexane (10 mL).
Then isopropylamine (0.7 mL) was added dropwise under arꢀ
gon. The precipitate that formed was filtered off, washed with
hexane and water (pH 8), and dried. Compound 12 was obꢀ
tained in a yield of 0.14 g, m.p. 214 °C. Found (%): C, 62.43;
H, 6.74; Cl, 14.86; N, 3.05; P, 6.29. C22H27ClNO3P. Calcuꢀ
lated (%): C, 62.50; H, 6.67; Cl, 14.79; N, 2.92; P, 6.46. MS,
m/z: 483, 481, 479 (C25H3235Cl2NO2P) [M]•+, 466 [M – CH],
464 [M – CH3], 423 [M – C4H8], 422 [M – C4H9],
N, 3.20; P, 7.08. MS, m/z: 437 (C22H2635Cl2NO2P) [M]•+
,
424 [M – CH], 422 [M – CH3], 381 [M – C4H8], 365
[M – C4H9NH]. Diastereomer 13. 31P NMR (DMSOꢀd6,
2
36.48 MHz), δ: –2.8 (d, JPCH = 18.5 Hz). 1H NMR
421 [M – NHC3H7], 57 [C4H9], 58 [NHC3H7]. IR, ν/cm–1
3153, 2618, 1584, 1554, 1485, 1464, 1368, 1339, 1228, 1169,
:
(CDCl3—DMSOꢀd6 (1 : 1), 600 MHz), δ: 6.10 (d, H(3),
2JPCH(3) = 18.5 Hz); 6.54 (d, H(5), 4JH(7)CCCH(5) = 2.3 Hz); 7.24
1140, 1073, 1013, 949, 919, 872, 833, 799, 746, 548, 487, 419.
(br.s, H(7)); 1.43 (s, H(8)); 7.41 (br.m, H(11), 3JH(12)CCH(11)
=
31P NMR (DMSOꢀd6, 36.48 MHz), δ: 9.7 (ddd, JH(3)CP
=
7.3 Hz, JH(14)CCCH(12)
=
1.6 Hz); 7.36 (m, H(12),
2
4
20.5 Hz, JHNP = 10.1 Hz, JHCNP = 10.6 Hz). 1H NMR
(CDCl3—DMSOꢀd6 (1 : 1), 600 MHz), δ: 6.47 (d, H(3),
2JPCH(3) = 21.3 Hz); 7.55 (s, H(7)); 7.23 (br.s, H(10)); 7.38
3JH(12)CCH(11) = 7.3 Hz, JH(12)CCCH(14) = 1.8 Hz); 7.37 (m,
2
3
4
3
4
H(13), JH(14)CCH(13) = 7.0—7.1 Hz, JH(11)CCCH(13) = 1.6 Hz);
3
4
7.28 (br.m, H(14), JH(14)CCH(13) = 7.0 Hz, JH(14)CCCH(12)
=
3
2
(br.m, H(11), JH(10)CCH(11) = 8.3 Hz); 1.46 (s, H(14)); 1.41
(s, H(16)); 5.53 (br.dd, NH, JPNH = 10.0 Hz, JHCNH
10.0 Hz); 3.39 (m, H(17)); 1.13 and 1.15 (both d, H(18), H(19),
3JH(17)CCH(18) = 6.5 Hz, JH(17)CCH(19) = 6.6 Hz). 13C NMR
(CDCl3—DMSOꢀd6 (1 : 1), 150.9 MHz), δ: 122.50 (dd [d],
C(3), JPC(3) = 161.0 Hz, JHC(3) = 163.7 Hz); 151.08 (dt [s],
C(4), 2JHC(3)C(4) = 4.2 Hz, 3JHC(10)CC(4) = 4.2—4.3 Hz); 123.08
1.8 Hz); 4.64 (d, NH, JPNH = 6.8 Hz); 1.22 (s, H(16)).
2
3
=
13C NMR (CDCl3—DMSOꢀd6 (1 : 1), 150.9 MHz), δ: 119.55
1
1
(dd [d], C(3), JPC(3) = 154.2 Hz, JHC(3) = 163.4 Hz); 150.29
3
2
(m [br.s], C(4), JPC(3)C(4) = 2.1 Hz); 122.92 (dd [d], C(4a),
3
3JPCCC(4a) = 15.0 Hz, JHC3(3)CC(4a) = 8.0 Hz); 125.51 (dd [s],
1
1
1
C(5), JHC(5) = 166.1 Hz, JHCCC(5) = 6.0 Hz); 127.66 (dd [s],
2
2
C(6), JHCC(6) = 4.7 Hz, JHCC(6) = 4.7 Hz); 130.48 (dd [s],
C(7), 1JHC(7) = 164.1 Hz, 3JHC(5)CC(7) = 8.1 Hz); 141.89 (m [d],
3
3
(ddd [d], C(4a), JPCCC(4a) = 15.2 Hz, JHC(3)CC(4a) = 8.9 Hz,
4JHCCCC = 1.0 Hz); 129.75 (dd [s], C(5), 3JHC(7)CC(5) = 12.3 Hz,
4JPOCCC(5) = 1.8 Hz); 141.19 (m [s], C(6)); 126.43 (d [s], C(7),
3
2
C(8), JPOCC(8) = 6.0 Hz, JH(7)CC(8) = 2.3—2.6 Hz); 148.64
2
3
(ddd [d], C(8a), JPOC(8a) = 8.9 Hz, JHCCC(8a) = 9.3 Hz,
3JHCCC(8a) = 9.3 Hz); 137.54 (ddt [d], C(9), 3JPCCC(9) = 18.3 Hz,
3
1JHC(7) = 156.9 Hz); 139.78 (m [d], C(8), JPOCC(8) = 4.8 Hz);
148.74 (dd [d], C(8a), 2JPOC(8a) = 8.4 Hz, 3JHCCC(8a) = 12.0 Hz);
3JHC(3)CC(9) = 6.8—7.0 Hz, JHCCC(9) = 7.3—7.4 Hz); 132.28
3
3
3
3
3
140.59 (ddt [d], C(9), JPCCC(9) = 18.0 Hz, JHCCC(9)
7.5—7.7 Hz, JHC(3)CC(9) = 6.9 Hz); 127.57 (dd [s], C(10),
1JHC(10) = 161.9 Hz, 3JHCCC(10) = 8.0 Hz); 128.13 (br.dm [br.s],
166.9 Hz); 132.46 (tt [s], C(12),
3JHC(10)CC(12) = 10.8 Hz, JHCC(12) = 3.5 Hz); 34.64 (m [s],
C(13), JHCCC(13) = 7.0 Hz, JHCC(13) = 3.6—3.7 Hz);
29.26 (q.sept [s], C(14), JHC(14) = 126.5 Hz, JHCCC(14)
=
(br.dd [s], C(10), JHCCC(10) = 9.9—10.0 Hz, JHCCC(10) =
3
1
9.9—10.0 Hz); 129.91 (ddd [s], C(11), JHC(11) = 166.7 Hz,
3JHCCC(11) = 5.8—6.0 Hz, JHCC(11) = 1.5 Hz); 128.53 (dd [s],
2
1
1
3
C(11), JHC(11)
=
C(12), JHC(12) = 164.2 Hz, JHC(14)CC(12) = 5.8 Hz); 127.71
2
1
3
(dd [s], C(13), JHC(13) = 164.1 Hz, JHC(11)CC(13) = 7.8 Hz);
3
2
1
3
130.74 (br.dd [br.s], C(14), JHC(14) = 162.9 Hz, JHCCC(14) =
1
3
=
7.8 Hz); 35.28 (m [s], C(15), 2JHCC(15) = 3.6 Hz); 29.96 (qm [s],
C(16), 1JHC(16) = 126.5 Hz, 3JHCCC(16) = 4.5 Hz); 51.52 (m [d],
3
4.7—4.8 Hz); 35.95 (m [s], C(15), JHCCC(15) = 7.0 Hz,
2JHCC(15) = 3.6—3.7 Hz); 29.48 (q.sept [s], C(16), JHC(16)
1
2
1
=
C(17), JPNC(17) = 1.8 Hz); 31.93 (qm [d], C(18), JHC(18)
126.8 Hz, 3JPNCC(18) = 4.5 Hz, 3JHCCC(18) = 4.4 Hz, 3JHNCC(18)
=
=
3
126.4 Hz, JHCCC(16) = 4.7—4.8 Hz); 42.58 (d.sept [s], C(17),
1JHC(17) = 147.3 Hz, JHCC(17) = 4.6 Hz); 24.93 and 24.58
2.4 Hz). Diastereomer 13´. 1H NMR (CDCl3—DMSOꢀd6 (1 : 1),
600 MHz), δ: 6.07 (d, H(3), 2JPCH(3) = 17.7 Hz); 6.56 (d, H(5),
4JH(7)CCCH(5) = 2.2 Hz); 7.24 (br.s, H(7)); 1.43 (s, H(8)); 7.45
2
(two qm [two d], C(18), C(19), 1JHC(18),C(19) = 125.0—126.0 Hz,
3JPNCC(18) = 3.8 Hz, JPNCC(19) = 5.4 Hz). The signals
3
3
of the carbons and protons were interpreted using the
1H—13C HETCOR experiment.
Reaction of quinone 1 with 2ꢀchlorophenylacetylene in the
presence of phosphorus trichloride. The reaction was carried out
as described above for the reaction of 4ꢀchlorophenylacetylene
(br.d, H(11), JH(12)CCH(11) = 7.8 Hz); 7.36 (m, overlap with
H(12) and H(13)); 7.32 (br.dd, H(13), 3JH(14)CCH(13) = 7.4 Hz);
3
2
7.14 (d, H(14), JH(14)CCH(13) = 7.4 Hz); 4.61 (d, NH, JPNH =
7.8 Hz); 1.24 (s, H(16)). 13C NMR (CDCl3—DMSOꢀd6 (1 : 1),
150.9 MHz), δ: 119.62 (dd [d], C(3), JPC(3) = 154.5 Hz,
1

Benzo[e][1,2]oxaphosphinines
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 9, September, 2007
1907
1JHC(3) = 163.5 Hz); 149.30 (m [br.s], C(4), 2JPC(3)C(4) = 2.1 Hz);
3JHH(12) = 7.3 Hz); 1.46 and 1.58 (both s, H(15) and H(17)).
13C NMR (CDCl3), δ: 118.12 (ddt [d], C(3), 1JPC(3) = 162.8 Hz,
1JHC(3) = 169.7 Hz, 3JHC(9)CC(3) = 5.7 Hz); 161.07 (m [s], C(4));
124.92 (m [d], C(4a), 3JPCCC(4a) = 19.2 Hz); 130.46 (d [s], C(5),
3JHC(7)CC(5) = 7.2 Hz); 143.90 (m [s], C(6)); 128.05 (d [s], C(7),
1JHC(7) = 158.9 Hz); 137.91 (m [d], C(8), 3JPOC(8a)C(8) = 6.6 Hz);
3
3
122.68 (dd [d], C(4a), JPCCC(4a) = 15.3 Hz, JHC(3)CC(4a)
=
1
7.9—8.0 Hz); 125.78 (dd [s], C(5), JH2C(5) = 165.8 Hz,
3JHCCC(5) = 6.0 Hz); 127.47 (dd [s], C(6), JHCC(6) = 4.4 Hz,
1
2JHCC(6) = 4.4 Hz); 130.32 (dd [s], C(7), JHC(7) = 164.3 Hz,
3JHC(5)CC(7) = 8.4 Hz); 141.69 (m [d], C(8), 3JPOCC(8) = 5.9 Hz,
2
3
2
2JH(7)CC(8) = 2.3—2.6 Hz); 149.00 (ddd [d], C(8a), JPOC(8a)
=
147.24 (dd [d], C(8a), JHC(7)CC(8a) = 11.3 Hz, JPOC(8a)
=
=
3
3
1
9.2 Hz, JHCCC(8a) = 8.6—9.0 Hz, JHCCC(8a) = 8.6—9.0 Hz);
11.4 Hz); 38.37 (tdm [s], C(9), JHC(9) = 129.8 Hz, 3JPCCC(9)
3
3
137.65 (m [d], C(9), JPCCC(9) = 18.0 Hz); 132.43 (br.dd [s],
C(10), JHCCC(10) = 9.9—10.0 Hz, JHCCC(10) = 9.9—10.0 Hz);
130.07 (dd [s], C(11), 1JHC(11) = 166.8 Hz, 3JHCCC(11) = 7.8 Hz);
128.55 (dd [s], C(12), JHC(12) = 164.0 Hz, JHC(14)CC(12)
5.5 Hz); 127.43 (dd [s], C(13), JHC(13)
3JHC(11)CC(13) = 8.0 Hz); 129.95 (br.dd [br.s], C(14), JHC(14)
161.7 Hz, 3JHCCC(14) = 8.0 Hz); 35.28 (m [s], C(15), 2JHCC(15)
3.6 Hz); 29.95 (qm [s], C(16), 1JHC(16) = 126.5 Hz, 3JHCCC(16)
4.5 Hz); 51.52 (m [d], C(17), 2JPNC(17) = 1.9 Hz); 32.01 (qm [d],
C(18), JHC(18) = 127.0 Hz, JPNCC18) = 4.5 Hz, JHCCC(18)
4.4 Hz, 3JHNCC(18) = 2.4 Hz).
18.6 Hz, JHC(3)CC(9) = 6.3 Hz); 30.08 (tm [s], C(10)); 22.28
3
3
1
3
(tm [s], C(11), JHC(11) = 125.3 Hz, JHCCC(11) = 3.2—3.5 Hz,
2JHCC(11) = 3.2—3.5 Hz); 13.80 (qm [s], C(12), JHC(12)
125.0 Hz, JHC(10)CC(12) = 3.9—4.1 Hz, JHC(11)C(12)
=
=
1
1
3
3
2
=
1
=
164.0 Hz,
1
3.9—4.1 Hz); 35.43 (m [s], C(14)); 29.96 (q.sept [s], C(15),
=
=
=
1JHC(15) = 126.6 Hz, 3JHCCC(15) = 4.6 Hz); 37.02 (m [s], C(16));
1
3
31.16 (q.sept [s], C(17), JHC(17) = 126.0 Hz, JHCCC(17)
=
4.6 Hz).
4ꢀButylꢀ6ꢀtertꢀbutylꢀ2,8ꢀdichloroꢀ2ꢀoxoꢀ2Hꢀbenzo[e]ꢀ
[1,2]oxaphosphinine (16a). 1H NMR (CDCl3), δ: 6.31 (d, H(3),
2JPCH(3) = 24.0 Hz); 7.52 and 7.58 (both br.s, H(5) and H(7));
2.70 and 2.82 (both m, AB part of an ABX2 system, C(9)H2);
1.00 (t, H(12), 3JHCCH(12) = 7.3 Hz); 1.37 (s, H(16)). 13C NMR
1
3
3
=
Reaction of dioxaphosphole 5 with hexꢀ1ꢀyne. A mixture of
phosphole 5 (4.5 g, 0.0126 mol), CH2Cl2 (5 mL), and hexꢀ1ꢀyne
(2.2 mL, 1.57 g, 0.019 mol) was kept at 10—20 °C for 12 h. Then
the reaction mixture was dried in vacuo (130 °C, 12 Torr) to
remove the solvent, excess alkyne, and 2ꢀchlorohexꢀ1ꢀene. The
glassy lightꢀbrown residue, a mixture of phosphinines 14a—16a,
was obtained. 31P NMR (CDCl3, 242.8 MHz), δ: 18.09 (d,
(CDCl3), δ: 113.28 (ddt [d], C(3), 1JPC(3) = 157.4 Hz, 1JHC(3)
=
3
169.6 Hz, JHC(9)CC(3) = 6.0 Hz); 157.06 (m [s], C(4)); 121.76
3
(m [d], C(4a), JPCCC(4a) = 18.3 Hz); 121.81 (dd. [s], C(5),
1JHC(5) = 158.0 Hz, 3JHC(7)CC(5) = 7.2 Hz); 148.30 (m [s], C(6));
129.94 (dd [s], C(7), 1JHC(7) = 163.7 Hz, 3JHC(5)CC(7) = 7.2 Hz);
124.25 (ddd [d], C(8), 3JPOCC(8) = 8.4 Hz, 2JHC(7)C(8) = 4.2 Hz,
2
2JPCH = 24.0 Hz) (14a, 70%); 18.84 (d, JPCH = 27.2 Hz)
(15a, 15%); 19.35 (d, 2JPCH = 24.2 Hz) (16a, 15%).
4JHC(5)CCC(8) = 1.3 Hz); 144.52 (ddd [d], C(8a), 3JHC(7)CC(8a)
=
3
2
4ꢀButylꢀ8ꢀtertꢀbutylꢀ2,6ꢀdichloroꢀ2ꢀoxoꢀ2Hꢀbenzo[e]ꢀ
[1,2]oxaphosphinine (14a). MS, m/z: 350, 348, 346
(C16H2135Cl2O2P) [M]•+, 331 [M – CH3], 311 [M – Cl], 289
[M – C4H9], 57 [C4H9]. 13C NMR (CDCl3), δ: 113.28 (ddt [d],
8.7 Hz, JHC(5)CC(8a) = 8.7 Hz, JPOC(8a) = 9.0 Hz); 34.69
3
1
(tdm [s], C(9), JPCCC(9) = 19.8 Hz, JHC(9) = 128.0 Hz); 30.08
(tm [s], C(10)); 22.28 (tm [s], C(11), JHC(11) = 125.3 Hz,
3JHCCC(11) = 3.2—3.5 Hz, JHCC(11) = 3.2—3.6 Hz); 13.80
(qm [s], C(12), JHC(12) = 125.0 Hz, JHCC(12) = 3.9—4.1 Hz,
3JHCCC(12) = 3.9—4.1 Hz).
1
2
1
1
3
1
2
C(3), JPC(3) = 157.4 Hz, JHC(3) = 169.6 Hz, JHC(9)CC(3)
=
6.0 Hz); 156.82 (m [s], C(4)); 123.09 (ddtd [d], C(4a),
3
3
3JPCCC(4a) = 18.0 Hz, JHC(3)CC(4a) = 7.8 Hz, JHC(9)CC(4a)
=
=
=
=
=
4ꢀButylꢀ8ꢀtertꢀbutylꢀ6ꢀchloroꢀ2ꢀhydroxyꢀ2ꢀoxoꢀ2Hꢀbenꢀ
zo[e][1,2]oxaphosphinine (17a). A glassy substance (a mixture
of compounds 14a—16a) was treated with water in diethyl ether.
1,2ꢀOxaphosphinine 17a that precipitated was filtered off
and dried in vacuo. The yield was 0.88 g (21%) (unoptimized),
m.p. 164—166 °C. Found (%): C, 58.22; H, 6.81; P, 9.72.
2
1
3.1 Hz, JHC(5)C(4a) = 0.9 Hz); 124.37 (dd. [s], C(5), JHC(5)
165.8 Hz, 3JHC(7)CC(5) = 5.4 Hz); 130.02 (dd [s], C(6), 2JHCC(6)
4.8 Hz, JHCC(6) = 4.4 Hz); 129.89 (dd [s], C(7), JHC(7)
165.4 Hz, 3JHC(5)CC(7) = 5.8 Hz); 142.53 (d [d], C(8), 3JPOCC(8)
7.4 Hz); 148.52 (ddd [d], C(8a), JHC(5)CC(8a) = 10.4 Hz,
3JHC(7)CC(8a) = 10.4 Hz, JPOC(8a) = 11.4 Hz); 35.04 (tdm [d],
C(9), JPCCC(9) = 19.8 Hz, JHC(9) = 127.8 Hz, JHC(3)CC(9)
5.6—6.0 Hz, JHC(11)CC(9) = 3.9—4.0 Hz, JHC(10)C(9)
3.9—4.0 Hz); 30.08 (tm [s], C(10), JHC(10) = 126.6 Hz,
3JHCCC(10) = 3.9—4.2 Hz, JHCC(10) = 3.9—4.2 Hz); 22.28
(tm [s], C(11), JHC(11) = 125.3 Hz, JHCCC(11) = 3.2—3.5 Hz,
2JHCC(11) = 3.2—3.5 Hz); 13.80 (qm [s], C(12), JHC(12)
125.1 Hz, JHCCC(12) = 3.9—4.1 Hz, JHCC(12) = 3.9—4.1 Hz);
35.43 (m [s], C(13)); 29.83 (q.sept [s], C(15), JHC(15)
126.7 Hz, JHCCC(15) = 4.6 Hz). H NMR (CDCl3), δ: 6.33 (d,
2
1
3
2
C16H22ClO3P. Calculated (%): C, 58.45; H, 6.70; P, 9.44. IR,
3
1
3
=
=
ν/cm–1: 471, 492, 537, 582, 612, 648, 728, 747, 772, 822,
881, 891, 912, 952, 1001, 1016, 1052, 1072, 1110, 1135, 1176,
1206, 1236, 1271, 1319, 1377, 1428, 1462, 1561, 1597, 1667,
2330, 2670, 2725, 2854, 2925, 3469. 31P NMR (DMSOꢀd6,
3
2
1
2
1
3
2
36.48 MHz), δ: 7.1 (d, JPCH(3) = 18.4 Hz). 1H NMR
1
2
=
(DMSOꢀd6), δ: 6.15 (d, H(3), JPCH(3) = 18.3 Hz); 7.31 (br.s,
3
2
4
H(5)); 7.51 (d, H(7), JHC(5)CCH(7) = 2.4 Hz); 2.62 (br.t, H(9),
1
=
3JHCCH(9) = 7.6 Hz); 1.46 (m, H(10)); 1.34 (m, H(11)); 0.89
3
1
3
(t, H(12), JHH(12) = 7.3 Hz); 1.38 (s, H(14)). 13C NMR
2
1
H(3), JPCH(3) = 24.1 Hz); 7.47 and 7.49 (both d, H(7), H(5),
(DMSOꢀd6), δ: 114.13 (ddt [d], C(3), JPC(3) = 171.4 Hz,
4JH(5)CCCH(7) = 1.7 Hz); 2.73 (m, AB part of an ABX2 system,
H(9)); 1.66 (m, H(10)); 1.49 (m, H(11)); 0.99 (t, H(12),
3JHCCH(12) = 7.3 Hz); 1.48 (s, H(15)).
1JHC(3) = 162.5 Hz, 3JHC(9)CC(3) = 5.6 Hz); 151.46 (m [s], C(4));
3
3
123.79 (ddt [d], C(4a), JPCCC(4a) = 15.8 Hz, JHC(3)CC(4a)
=
3
8.3 Hz, JHC(9)CC(4a) = 3.2—3.5 Hz); 123.74 (dd [s], C(5),
1JHC(5) = 165.3 Hz, 3JHC(7)CC(5) = 5.8 Hz); 126.90 (dd [s], C(6),
2JHC(5)C(6) = 4.9—5.0 Hz, JHC(7)C(6) = 4.9—5.0 Hz); 127.47
(dd [s], C(7), JHC(7) = 165.2 Hz, JHC(5)CC(7) = 5.8 Hz);
141.11 (dm [d], C(8), JPOCC(8) = 5.6 Hz); 148.81 (ddd [d],
4ꢀButylꢀ6,8ꢀdi(tertꢀbutyl)ꢀ2,5ꢀdichloroꢀ2ꢀoxoꢀ2Hꢀ
benzo[e][1,2]oxaphosphinine (15a). MS, m/z: 406, 404, 402
2
(C20H2935Cl2O2P) [M]•+, 387 [M – CH3], 367 [M – Cl], 345
1
3
2
3
[M – C4H9]. 1H NMR (CDCl3), δ: 6.48 (d, H(3), JPCH(3)
=
3
3
27.3 Hz); 7.62 (s, H(7)); 2.85 and 3.22 (both br.ddd, C(9)HAHX,
C(8a), JHC(7)CC(8a) = 8.9—9.1 Hz, JHC(5)CC(8a) = 9.0 Hz,
2JH = 14.8 Hz, 3JH = 5.3 Hz, 3JH
= 9.9 Hz,
2JPOC(8a) = 8.1 Hz); 33.89 (tdm [s], C(9), JHC(9) = 127.9 Hz,
1
HX
H(10)
A
H(10)
A
3JH
= 5.3 Hz, 3JH
= 9.0 Hz); A0.89 (t, H(12),
3JPCCC(9) = 17.8 Hz); 29.77 (m [s], C(10)); 21.67 (m [s], C(11),
H(10)
H(10)
X
X

1908
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 9, September, 2007
Mironov et al.
1
1
3
1JHC(11) = 127.8 Hz); 13.64 (qt [s], C(12), JHC(12) = 124.8 Hz,
27.50 (tm [s], C(11), JHC(11) = 127.1 Hz, JHCCC(11)
=
2
2
3JHCCC(12) = 3.9 Hz, JHCC(12) = 3.9 Hz).
3.6—3.9 Hz, JHCC(11) = 3.6—3.9 Hz); 22.28 (tm [s], C(12),
1JHC(12) = 125.9 Hz, JHCCC(12) = 4.1—4.2 Hz, JHCC(12)
4.1—4.2 Hz); 13.84 (qm [s], C(13), JHC(13) = 124.9 Hz,
3JHCCC(13) = 3.4—3.9 Hz, JHCC(13) = 3.4—3.9 Hz); 35.30
3
2
4ꢀButylꢀ6ꢀtertꢀbutylꢀ8ꢀchloroꢀ2ꢀhydroxyꢀ2ꢀoxoꢀ2Hꢀbenꢀ
zo[e][1,2]oxaphosphinine (18a) was obtained by crystallization
of the reaction mixture from hexane after the partial separation
of compound 17a. The yield was 0.1 g (2.4%), m.p. 174—176 °C.
Found (%): C, 58.37; H, 7.09; P, 9.51. C16H22ClO3P. Calcuꢀ
lated (%): C, 58.45; H, 6.70; P, 9.44. 31P NMR (DMSOꢀd6,
=
1
2
1
(m [s], C(14)); 29.77 (q.sept [s], C(15), JHC(15) = 126.8 Hz,
3JHCCC(15) = 4.7 Hz).
6,8ꢀDi(tertꢀbutyl)ꢀ2,5ꢀdichloroꢀ2ꢀoxoꢀ4ꢀpentylꢀ2Hꢀbenꢀ
zo[e][1,2]oxaphosphinine (15b). H NMR (CDCl3), δ: 6.40 (d,
36.48 MHz), δ: 7.0 (d, JPC2H(3) = 18.2 Hz). 1H NMR
2
1
2
(DMSOꢀd6), δ: 6.21 (d, H(3), JPCH(3) = 18.0 Hz); 7.53 (br.s,
H(3), JPCH(3) = 27.3 Hz); 7.54 (br.s, H(7)); 2.74 (br.ddd,
4
H(5)); 7.47 (d, H(7), JHC(5)CCH(7) = 2.0 Hz); 2.69 (br.m,
C(9)HA, 2JH
= 15.3 Hz, 3JH
= 6.2 Hz, 3JH
=
=
H
H(10)
H(10)
= 15.3 Hz, 3JH
H H(10)
A
X
A
A
C(9)H2, 3JHCCH(9) = 7.4 Hz); 1.48 (m, H(10)); 1.37 (m, H(11));
0.90 (t, C(12)H3, 3JHH(12) = 7.2 Hz); 1.28 (s, H(14)). 13C NMR
9.1 Hz); 3.16 (br.ddd, C(9)HX, 2JH
9.5—10.0 Hz, 3JH H(10) = 16.1—16.8XHAz); 1.19—1.20 (mX, H(11),
A
1
(DMSOꢀd6), δ: 114.13 (ddt [d], C(3), JPC(3) = 171.4 Hz,
H(12)); 0.77 (t, H(13), 3JHH(13) = 7.2 Hz); 1.46 and 1.58 (both s,
H(15), H(17)). 13C NMR (CDCl3), δ: 118.07 (ddt [d], C(3),
1JHC(3) = 162.5 Hz, 3JHC(9)CC(3) = 5.6 Hz); 151.81 (m [s], C(4));
3
1
3
122.39 (m [d], C(4a), JPCCC(4a) = 17.3 Hz); 121.64 (dd [s],
C(5), 1JHC(5) = 158.2 Hz, 3JHC(7)CC(5) = 7.5 Hz); 146.14 (m [s],
C(6)); 127.73 (dd [s], C(7), JHC(7) = 163.7 Hz, JHC(5)CC(7)
8.1 Hz); 122.31 (dd [d], C(8), 3JPOCC(8) = 7.1 Hz, JHC(7)C(8)
1JPC(3) = 162.8 Hz, JHC(3) = 169.1 Hz, JHC(9)CC(3) = 5.6 Hz);
161.05 (m [s], C(4)); 124.84 (m [d], C(4a), 3JPCCC(4a) = 19.2 Hz);
130.43 (d [s], C(5), 3JHC(7)CC(5) = 7.2 Hz); 143.85 (m [s], C(6));
1
3
=
=
2
1
128.00 (d [s], C(7), JHC(7) = 159.1 Hz); 137.88 (m [d], C(8),
3JPOC(8a)C(8) = 6.6 Hz); 147.19 (dd [d], C(8a), JHC(7)CC(8a)
11.6 Hz, JPOC(8a) = 10.8 Hz); 38.62 (tdm [s], C(9), JHC(9)
129.2 Hz, JPCCC(9) = 18.6 Hz); 29.90 (tm [s], C(10)); 28.86
(tm [s], C(11), JHC(11) = 126.2 Hz); 22.19 (tm [s], C(12),
1JHC(12) = 124.9 Hz); 13.84 (qm [s], C(13), 1JHC(13) = 125.0 Hz);
35.38 (m [s], C(14)); 29.89 (q.sept [s], C(15), JHC(15)
3
3
5.9 Hz); 144.59 (ddd [d], C(8a), JHC(7)CC(8a) = 9.0 Hz,
3JHC(5)CC(8a) = 9.0 Hz, 2JPOC(8a) = 6.8 Hz); 33.66 (tdm [s], C(9),
1JHC(9) = 128.0 Hz, 3JPCCC(9) = 17.8 Hz); 29.94 (tdm [s], C(10),
1JHC(10) = 127.0 Hz); 21.67 (m [s], C(11), 1JHC(11) = 127.8 Hz);
13.64 (qm [s], C(12), 1JHC(12) = 124.8 Hz, 3JHCCC(12) = 3.9 Hz,
3JHCC(12) = 3.9 Hz).
Reaction of quinone 1 with hexꢀ1ꢀyne in the presence of phosꢀ
phorus trichloride. The reaction was carried out analogously to
the reaction with phenylacetylene. A mixture of compounds
14a—16a was obtained; the percentage of these compounds in
the mixture was 55, 28, and 17%, respectively. The mixture
was treated analogously to that obtained in the reaction of
phosphole 5 with hexꢀ1ꢀyne. Hydroxyphosphinine 17a was isoꢀ
lated in 22% yield.
Reaction of dioxaphosphole 5 with heptꢀ1ꢀyne. A mixture of
phosphole 5 (4.5 g, 0.0126 mol), CH2Cl2 (12 mL), and heptꢀ1ꢀ
yne (2.5 mL, 1.81 g, 0.0189 mol) was kept at 10—20 °C for 12 h.
Then the reaction mixture was dried in vacuo (130 °C, 12 Torr)
to remove the solvent, excess alkyne, and 2ꢀchloroheptꢀ1ꢀene.
A glassy lightꢀbrown mixture of phosphinines 14b—16b was obꢀ
tained. 31P NMR, δ: 17.3 (d, 2JPCH = 24.2 Hz) (14b, 62%); 17.8
=
=
2
1
3
1
1
=
3
126.6 Hz, JHCCC(15) = 4.8 Hz); 36.97 (m [s], C(16)); 30.03
(q.sept [s], C(17), 1JHC(17) = 126.3 Hz, 3JHCCC(17) = 4.8 Hz).
6ꢀtertꢀButylꢀ2,8ꢀdichloroꢀ2ꢀoxoꢀ4ꢀpentylꢀ2Hꢀbenzo[e]ꢀ
[1,2]oxaphosphinine (16b). 1H NMR (CDCl3), δ: 6.24 (d, H(3),
2JPCH(3) = 23.7 Hz); 7.44 (H(5), JH(7)CCCH(5) = 2.1 Hz); 7.50
4
4
5
(dd, H(7), JH(5)CCCH(7) = 2.1 Hz, JPOCCCH(7) = 1.4 Hz); 2.63
(m, C(9)H2, AB part of the ABX2 system); 0.86 (t, H(13),
3JHCC(13) = 7.2 Hz); 1.29 (s, H(17)). 13C NMR (CDCl3), δ:
113.19 (ddt [d], C(3), JPC(3) = 157.4 Hz, JHC(3) = 169.0 Hz,
3JHC(9)CC(3) = 5.4 Hz); 157.04 (m [s], C(4)); 121.72 (m [d],
1
1
3
1
C(4a), JPC3 CC(4a) = 18.0 Hz); 121.73 (dd [s], C(5), JHC(5)
=
158.2 Hz, JHC(7)CC(5) = 7.5 Hz); 148.25 (m [s], C(6)); 129.89
(dd [s], C(7), 1JHC(7) = 163.7 Hz, 3JHC(5)CC(7) = 7.5 Hz); 124.23
3
(m [d], C(8), JPOCC(8) = 7.8 Hz); 144.48 (ddd [d], C(8a),
3
2
3JHC(7)CC(8a) = 9.0 Hz, JHC(5)CC(8a) = 9.0 Hz, JPOC(8a)
=
=
=
2
2
3
1
(d, JPCH = 27.3 Hz) (15b, 24%); 18.7 (d, JPCH = 24.2 Hz)
10.2 Hz); 34.95 (tdm [s], C(9), JPCCC(9) = 19.2 Hz, JHC(9)
130.7 Hz); 30.03 (tm [s], C(10)); 27.70 (tm [s], C(11), 1JHC(11)
(16b, 14%).
3
2
8ꢀtertꢀButylꢀ2,6ꢀdichloroꢀ4ꢀpentylꢀ2ꢀoxoꢀ2Hꢀbenzo[e]ꢀ
[1,2]oxaphosphinine (14b). 1H NMR (CDCl3), δ: 6.25 (d, H(3),
126.8 Hz, JHCCC(11) = 4.1—4.7 Hz, JHCC(11) = 4.1—4.7 Hz);
22.3 (tm [s], C(12), 1JHC(12) = 124.9 Hz, 2JHCC(12) = 3.4—3.9 Hz,
2JPCH(3) = 24.0 Hz); 7.39 (dd, H(7), JH(5)CCCH(7) = 2.1 Hz,
3JHCCC(12) = 3.4—3.9 Hz); 13.80 (qm [s], C(13), JHC(13)
=
4
1
5JPOCCCH(7) = 1.4 Hz); 7.40 (d, H(5), JH(5)CCCH(7) = 2.1 Hz);
125.0 Hz).
4
2.63 (m, AB part of an ABX2 system, H(9), 2JH
B = 11.5 Hz,
6ꢀtertꢀButylꢀ8ꢀchloroꢀ2ꢀhydroxyꢀ2ꢀoxoꢀ4ꢀpentylꢀ2Hꢀbenꢀ
zo[e][1,2]oxaphosphinine (18b). A glassy substance (a mixture
of compounds 14b—16b) was treated with water in diethyl ether.
1,2ꢀOxaphosphinine 18b that precipitated was filtered off and
dried in vacuo. The yield was 0.26 g (6%) (unoptimized),
m.p. 185—186 °C. Found (%): C, 59.17; H, 7.33; P, 8.79.
CH
A
3
2JH
= 7.4 Hz); 1.66 (m, H(10), JH(9)CCH(10) = 7.4 Hz,
CH
X
3JH(11)CCH(10) = 7.0—7.4 Hz); 1.33—1.34 (m, H(11), H(12));
0.86 (t, H(13), 3JH(12)CCH(13) = 7.0 Hz); 1.48 (H(15)). 13C NMR
(CDCl3), δ: 113.19 (ddt [d], C(3), 1JPC(3) = 157.4 Hz, 1JHC(3)
=
3
169.0 Hz, JHC(9)CC(3) = 5.7 Hz); 156.80 (m [s], C(4)); 123.04
3
3
(ddtd [d], C(4a), JPCCC(4a) = 18.0 Hz, JHC(3)CC(4a) = 8.0 Hz,
C17H24ClO3P. Calculated (%): C, 59.56; H, 7.01; P, 9.05. MS,
3JHC(9)CC(4a) = 3.1 Hz, JHC(5)C(4a) = 0.9 Hz); 124.30 (dd [s],
m/z: 344, 342 (C17H2435ClO3P) [M]•+, 327 [M – CH3], 286
[M – C4H8], 271 [M – C5H11]. IR, ν/cm–1: 431, 494, 537, 586,
613, 68, 725, 737, 789, 822, 853, 881, 908, 953, 1000, 1011,
1034, 1069, 1134, 1176, 1209, 1271, 1280, 1302, 1333, 1377,
2
C(5), 1JHC(5) = 166.1 Hz, 3JHC(7)CC(5) = 5.8 Hz); 129.98 (dd [s],
2
2
C(6), JHCC(6) = 4.5—4.8 Hz, JHCC(6) = 4.5—4.8 Hz); 129.85
(dd [s], C(7), 1JHC(7) = 165.4 Hz, 3JHC(5)CC(7) = 5.9 Hz); 142.50
3
(d [d], C(8), JPOCC(8) = 7.2 Hz); 148.47 (ddd [d], C(8a),
1426, 1460, 1560, 1596, 1659, 2284, 2670, 2723, 2854, 2924,
3JHC(5)CC(8a) = 10.2—10.5 Hz, JHC(7)CC(8a) = 10.2—10.5 Hz,
3437. 31P NMR (DMSOꢀd6, 36.48 MHz), δ: 6.5 (d, JPCH(3)
=
=
=
3
2
2JPOC(8a) = 11.4 Hz); 35.24 (tdm [d], C(9), 3JPCCC(9) = 20.4 Hz,
1JHC(9) = 127.4 Hz); 31.23 (tm [s], C(10), 1JHC(10) = 123.9 Hz);
18.4 Hz). 1H NMR (DMSOꢀd6), δ: 6.22 (d, H(3), JPCH(3)
2
4
18.2 Hz); 7.48 (br.s, H(5)); 7.55 (d, H(7), JHC(5)CCH(7)

Benzo[e][1,2]oxaphosphinines
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 9, September, 2007
1909
2.0 Hz); 2.69 (br.m, H(9), 3JHCCH(9) = 7.7 Hz); 1.51 (m, H(10),
3JHCCH(10) = 7.3—7.7 Hz); 1.31—1.32 (m, H(11), H(12)); 0.86
Crystals of comp–ound 9 (C20H22ClO3P) are colorless, triꢀ
clinic, space group Р1, at 20 °C a = 8.745(1) Å, b = 9.751(2) Å,
c = 12.857(2) Å, α = 93.71(2)°, β = 107.04(2)°, γ = 113.26(2)°,
V = 942.4(3) Å3, dcalc = 1.33 g cm–3, Z = 2. The unit cell
parameters and the intensities of 3799 reflections, of which
2051 reflections were with I ≥ 2σ, were measured at 20 °C
(λ(CuKα) radiation, graphite monochromator, ω/2θꢀscanning
technique, θ ≤ 74.24°). The intensities of three check reflections
showed no decrease in the course of Xꢀray data collection.
The empirical absorption correction was applied (µ(Cu) =
27.26 cm–1). The structure was solved by direct methods using
the SIR program19 and refined first isotropically and then anisoꢀ
tropically with the use of the SHELXLꢀ97 program package.20
The coordinates of the hydrogen atoms were calculated based
on the stereochemical criteria and refined using a riding model.
The final R factors were R = 0.063, Rw = 0.166 based on 2051 reꢀ
flections with F 2 ≥ 4σ. All calculations were carried out with the
use of the WinGX program.21 The figures were drawn with the
use of the PLATON program.22
3
(t, H(13), JHH(13) = 7.0 Hz); 1.29 (s, H(17)). 13C NMR
1
(DMSOꢀd6), δ: 114.18 (ddt [d], C(3), JPC(3) = 170.9 Hz,
1JHC(3) = 160.1 Hz, 3JHC(9)CC(3) = 5.7 Hz); 151.83 (m [s], C(4));
3
122.40 (m [d], C(4a), JPCCC(4a) = 16.9 Hz); 121.67 (dd [s],
C(5), 1JHC(5) = 158.0 Hz, 3JHC(7)CC(5) = 7.5 Hz); 146.12 (m [s],
1
3
C(6)); 127.72 (dd [s], C(7), JHC(7) = 163.7 Hz, JHC(5)CC(7)
=
=
7.8 Hz); 122.29 (dm [d], C(8), 3JPOCC(8) = 6.7 Hz, 2JHC(7)C(8)
3
4.6 Hz); 144.60 (ddd [d], C(8a), JHC(7)CC(8a) = 8.6 Hz,
3JHC(5)CC(8a) = 8.6 Hz, 2JPOC(8a) = 6.5 Hz); 34.00 (tdm [s], C(9),
1JHC(9) = 125.9 Hz, 3JPCCC(9) = 17.9 Hz); 30.78 (m [s], C(10));
27.47 (tm [s], C(11), 1JHC(11) = 127.4 Hz); 21.78 (tm [s], C(12),
1JHC(12) = 125.2 Hz); 13.77 (qt [s], C(13), JHC(13) = 124.5 Hz,
1
2
3JHCCC(13) = 3.0—4.0 Hz, JHCC(13) = 3.0—4.0 Hz); 34.36
1
(m [s], C(16)); 30.81 (q.sept [s], C(17), JHC(17) = 125.9 Hz,
3JHCCC(17) = 4.7 Hz).
8ꢀtertꢀButylꢀ6ꢀchloroꢀ2ꢀhydroxyꢀ2ꢀoxoꢀ4ꢀpentylꢀ2Hꢀbenꢀ
zo[e][1,2]oxaphosphinine (17b). After the separation of the preꢀ
cipitate of oxaphosphinine 18b, compound 17b gradually preꢀ
cipitated from the hydrolyzed reaction mixture of phosphinines
14b—16b. The precipitate was filtered off, washed with diethyl
ether, and dried in air. The yield was 0.21 g (5%) (unoptimized),
m.p. 173—175 °C. Found (%): C, 59.17; H, 7.33; P, 8.79.
This study was financially supported by the Russian
Foundation for Basic Research (Project No. 07ꢀ03ꢀ
00180a) and the Council on Grants of the President of
the Russian Federation (Program for State Support of
Young Doctors, Grant MKꢀ1434.3.06).
C
17H24ClO3P. Calculated (%): C, 59.56; H, 7.01; P, 9.05. MS,
m/z: 344, 342 (C17H2435ClO3P) [M]•+, 327 [M – CH3],
286 [M – C4H8], 271 [M – C5H11]. 31P NMR (DMSOꢀd6,
36.48 MHz), δ: 5.6 (d, 2JPCH(3) = 18.4 Hz).
References
Reaction of quinone 1 with heptꢀ1ꢀyne in the presence of
phosphorus trichloride. The reaction was carried out analogously
to the reaction with phenylacetylene. Compounds 14b, 15b, and
16b were obtained in percentage of 57, 27, and 16%, respecꢀ
tively. Then the reaction mixture was treated analogously to that
obtained in the reaction of phosphole 5 with hexꢀ1ꢀyne.
Hydroxyphosphinines 17b and 18b were isolated in 27 and
5% yields, respectively.
1. V. F. Mironov, A. I. Konovalov, I. A. Litvinov, A. T.
Gubaidullin, R. R. Petrov, A. A. Shtyrlina, T. A. Zyablikova,
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Xꢀray diffraction study of compounds 8 and 9 was performed
on an automated fourꢀcircle EnrafꢀNonius CADꢀ4 diffractoꢀ
meter (MoꢀKα and CuꢀKα radiation). The unit cell parameters
were determined and the Xꢀray data collection and preliminary
processing were performed with the use of the MolEN program
package.18 Crystals of compound 8 (C19H20ClO3P) are colorless,
transparent, prismaticꢀshaped, monoclinic, space group P21/c.
At 20 °C, a = 8.859(2) Å, b = 15.672(7) Å, c = 13.005(7) Å,
β = 98.35(6)°, V = 1786(2) Å3, dcalc = 1.41 g cm–3, Z = 4. The
unit cell parameters and the intensities of 2679 independent
reflections, of which 812 reflections were with I > 3σ(I ), were
measured at 20 °C (λ(MoKα) radiation, graphite monochromaꢀ
tor, ω/2θꢀscanning technique, θ ≤ 24.63°). The intensities of
three check reflections showed no decrease in the course of
Xꢀray data collection. No absorption correction was applied
because of the low absorption coefficient (µ(Mo) = 4.6 cm–1).
The structure was solved by direct methods using the SIR proꢀ
gram19 and refined first isotropically and then anisotropically.
The hydrogen atoms were located in difference electron density
maps. Their contributions to the structure amplitudes were
taken into account in the final step of the refinement with fixed
positional and thermal parameters. The final R factors were
R = 0.086, Rw = 0.085 based on 737 independent reflections
with F 2 ≥ 3σ. All calculations were carried out on an Alpha
Station 200.

1910
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 9, September, 2007
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10. V. F. Mironov, V. K. Cherkasov, F. F. Alekseev, N. M.
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Sintez i vzaimnye prevrashcheniya monozameshchennykh
atsetilenov [Synthesis and Interconversions of Monosubstituted
Acetylenes], Izdꢀvo AN Kaz. SSR, AlmaꢀAta, 1976, 235 pp.
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Azancheev, F. F. Alekseev, T. A. Zyablikova, and R. Z.
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2002, 38 (Engl. Transl.)].
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Received June 5, 2007