2496
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 11, November, 2013
Artem´ev et al.
superbasic system KOH—DMSO (H O), which chemoꢀ
2ꢀ(4ꢀChlorophenyl)propylphosphine (2b). The yield was 1.5 g
2
1
(
(
18%), colorless liquid, b.p. 109—111 C (3 Torr). H NMR
and regioselectively led to the formation of antiꢀMarkꢀ
ovnikov adducts. The primary and secondary phosphines
synthesized can be further successfully used in organoꢀ
phosphorus synthesis and as ligands for design of catalytiꢀ
cally active metal complexes.19
3
CDCl ), : 1.36 (d, 3 H, Me, J
= 7.0 Hz); 1.85 (br.s, 2 H,
3
H,H
CH P); 2.34 (br.s, 1 H, PH); 2.77—2.87 (m, 2 H, CHC H ,
2
6
4
1
3
PH); 7.14—7.33 (m, 4 H, C H ). C NMR (CDCl ), : 22.6
d, CHC H ,
1.7 (d, CH P, J
31.9 (pꢀC
6
4
3
2
3
(
4
1
J
= 10.1 Hz); 22.9 (d, Me, J = 4.9 Hz);
P,C
6
4
P,C
1
= 3.6 Hz); 128.2 and 128.5 (o,mꢀC
);
C H
4
2
P,C
6
3
31
); 145.0 (d, ipsoꢀC
, J
C H
4
= 3.1 Hz). P NMR
C H
P,C
6
4
6
1
Experimental
(CDCl3), : –146.48 (t, JP,H = 195.4 Hz). Found (%): C, 57.87;
H, 6.40; P, 16.86. C H ClP. Calculated (%): C, 57.92; H, 6.48;
9
12
P, 16.70.
1H, 13C and 31P NMR spectra were recorded on a Bruker
DPXꢀ400 spectrometer (400.13, 101.61 and 161.98 MHz, reꢀ
spectively), using HMDS as an internal standard and 85% aqueꢀ
Bis[2ꢀ(4ꢀchlorophenyl)propyl]phosphine (3b). The yield was
1
4
.5 g (58%), colorless liquid, b.p. 235—238 C (3 Torr). H NMR
3
3
(
CDCl ), : 1.31 (dd, 6 H, Me, J
= 6.9 Hz, J
= 2.5 Hz);
31
3
H,H
P,H
ous H PO ( P NMR) as an external standard. 4ꢀChlorostyrene
3
4
1
.79 (br.s, 4 H, CH P); 2.79—2.90 (m, 2 H, CHC H );
2 6 4
and 4ꢀchloroꢀꢀmethylstyrene are commercial products (Aldꢀ
rich). All the experimental steps were carried out under argon.
A phosphineꢀhydrogen mixture was obtained according to the
method described earlier.13
13
7
.11—7.31 (m, 8 H, C H ). C NMR (CDCl ), : 23.2 (dd, Me,
6 4 3
3
2
JP,C = 6.9 Hz); 30.0 (d, CHC H , JP,C = 11.6 Hz); 38.5
6
4
1
(
(
(
d, CH P, J
= 10.8 Hz); 128.1 and 128.5 (o,mꢀC
); 131.8
2
P,C
C6H4
31
3
pꢀC
); 145.5 (d, ipsoꢀC
, J
C H
4
= 4.6 Hz). P NMR
C H
P,C
6
4
6
Hydrophosphination of 4ꢀchlorostyrene. A solution of
1
CDCl ), : –82.44, –82.29, –81.59 (all td, J
= 198.1, 198.9,
P,H
3
4
ꢀchlorostyrene (15.0 g, 108 mmol) in DMSO (10 mL) was addꢀ
199.7 Hz), the ratio intensities 1.4 : 1.9 : 1, respectively. Found (%):
ed dropwise over 2.5 h to a suspension of KOH•0.5H O (20.0 g,
2
C, 63.65; H, 6.21; P, 9.40. C H Cl P. Calculated (%): C, 63.73;
H, 6.24; P, 9.13.
18
21
2
3
6
08 mmol), DMSO (50 mL), and H O (12.0 mL) heated to
0 C and saturated with a phosphineꢀhydrogen mixture with
2
continuous bubbling of phosphine. Then, the mixture was cooled,
diluted with water (100 mL), and extracted with diethyl ether
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 12ꢀ03ꢀ31097ꢀ
mol_a) and the Council on Grants at the President of the
Russian Federation (Program of State Support for Leadꢀ
ing Scientific Schools of the Russian Federation, Grant
NShꢀ1550.2012.3).
(
30×3 mL). The extract was washed with water (40×2 mL) and
dried with K CO , the solvent was evaporated, the residue was
2
3
fractionally distilled in vacuo.
ꢀ(4ꢀChlorophenyl)ethylphosphine (2a). The yield was 1.85 g
2
1
(
(
10%), colorless liquid, b.p. 81—82 C (1 Torr). H NMR
CDCl ), : 1.70—1.79 (m, 2 H, CH P); 2.65 (dt, 2 H, PH,
3
2
1
JP,H = 195.0 Hz); 2.73—2.78 (m, 2 H, CH C H ); 7.06 (d, 2 H,
2
6
4
References
3
3
C H , JH,H = 8.3 Hz); 7.22 (d, 2 H, C H , J
= 8.3 Hz).
6
4
6
4
H,H
13
2
C NMR (CDCl ), : 15.6 (d, CH C H , J = 9.5 Hz); 38.2
3
2
6
4
P,C
1
(
(
(
d, CH P, J
pꢀC
= 2.5 Hz); 128.4 and 129.5 (o,mꢀC
); 131.8
JP,C = 4.4 Hz). P NMR
1. B. A. Trofimov, N. K. Gusarova, Mendeleev Commun., 2009,
19, 295.
2. N. K. Gusarova, S. N. Arbuzova, B. A. Trofimov, Pure Appl.
Chem., 2012, 84, 439.
2
P,C
C H
6
4
3
31
); 140.2 (d, ipsoꢀC
,
C H
6 4
C H
6
4
1
CDCl ), : –137.85 (t, J
= 195.0 Hz). Found (%): C, 55.51;
3
P,H
H, 6.01; P, 17.83. C H ClP. Calculated (%): C, 55.67; H, 5.84;
8
10
P, 17.95.
3. V. A. Milyukov, Yu. H. Budnikova, O. G. Sinyashin, Russ.
Chem. Rev. (Engl. Transl.), 2005, 74, 781.
Bis[2ꢀ(4ꢀchlorophenyl)ethyl]phosphine (3a). The yield was
1
1.3 g (67%), colorless liquid, b.p. 208—210 C (1 Torr), rapidly
4. B. A. Trofimov, S. N. Arbuzova, N. K. Gusarova, Russ.
Chem. Rev. (Engl. Transl.), 1999, 68, 215.
1
crystallizes to colorless needles (m.p. 40—42 C). H NMR
(
CDCl ), : 1.81—1.96 (m, 4 H, CH P); 2.73—2.81 (m, 4 H,
5. S. N. Arbuzova, N. K. Gusarova, B. A. Trofimov, Arkivoc,
2006, v, 12.
6. G. M. Bogolyubov, A. A. Petrov, Russ. J. Gen. Chem.
(Engl. Transl.), 1966, 36, 1510 [Zh. Obshch. Khim., 1966,
36, 1505].
3
2
1
CH C H ); 3.16 (d, 1 H, PH, J
= 199.4 Hz); 7.13 (d, 4 H,
2
6
4
P,H
3
3
C H , J
= 8.4 Hz); 7.28 (d, 4 H, C H , J
= 8.4 Hz).
6
4
H,H
6
4
H,H
13
2
C NMR (CDCl ), : 22.2 (d, CH C H , JP,C = 11.4 Hz);
3
2
6
4
1
3
1
(
3.9 (d, CH P, J
31.9 (pꢀC
= 10.9 Hz); 128.6 and 129.5 (o,mꢀC
);
C H
4
2
P,C
6
3
31
); 140.7 (d, ipsoꢀC
, J = 8.4 Hz). P NMR
C H
4
7. E. R. Bornancini, R. A. Alonso, R. A. Rossi, J. Organomet.
Chem., 1984, 270, 177.
C H
P,C
6
4
6
1
CDCl ), : –70.45 (d, J
= 199.4 Hz). Found (%): C, 61.63;
3
P,H
H, 5.46; P, 9.78. C H Cl P. Calculated (%): C, 61.75; H, 5.51;
P, 9.95.
Hydrophosphination of 4ꢀchloroꢀꢀmethylstyrene. A solution
of 4ꢀchloroꢀꢀmethylstyrene (7.0 g, 46 mmol) in DMSO (10 mL)
8. B. A. Trofimov, T. N. Rakhmatulina, N. K. Gusarova, S. F.
Malysheva, Russ. Chem. Rev. (Engl. Transl.), 1991, 60, 1360.
9. B. A. Trofimov, S. F. Malysheva, T. N. Rakhmatullina, A. V.
Gusarov, N. K. Gusarova, Zh. Obshch. Khim., 1991, 61, 1955
[Russ. J. Gen. Chem., 1991, 61 (in Russian)].
16
17
2
was added dropwise over 2 h to a suspension of KOH•0.5H O
2
(
20.0 g, 308 mmol), DMSO (50 mL), and H O (3.0 mL) heated
10. B. A. Trofimov, L. Brandsma, S. N. Arbuzova, S. F. Malyꢀ
sheva, N. K. Gusarova, Tetrahedron Lett., 1994, 35, 7647.
11. B. A. Trofimov, N. K. Gusarova, S. F. Malysheva, V. A.
Kuimov, B. G. Sukhov, S. I. Shaikhudinova, N. P. Tarasoꢀ
va, Yu. V. Smetannikov, O. G. Sinyashin, Yu. G. Budnikova,
T. I. Kazantseva, V. I. Smirnov, Zh. Obshch. Khim., 2005,
75, 1439 [Russ. J. Gen. Chem. (Engl. Transl.), 2005, 75, 1367.
2
to 70—75 C and saturated with a phosphineꢀhydrogen mixture
with continuous bubbling of phosphine. The reaction mixture
was cooled, diluted with water (100 mL), and extracted with
diethyl ether (30×3 mL). The extract was washed with water
(
40×2 mL) and dried with K CO , the solvent was evaporated,
2 3
the residue was fractionally distilled in vacuo.