Investigations of Allylic Phosphines, Arsines, and Stibines
heated to 80 °C and stirred for 1 h. Allylic dichloroarsines
J . Org. Chem., Vol. 63, No. 1, 1998 61
(m, 2H). 13C NMR (100 MHz, CDCl
120.9, 129.1.
, -30 °C): δ 27.0, 41.9,
3
3
e,f were then purified by distillation in vacuo. These
compounds can also be obtained by heating at 80 °C the
corresponding pure arsine precursor 3c,d .
(3-Meth yl-2-bu ten yl)d ich lor ostibin e (4f). Yield ≈ 35%
1
(crude). τ1 (5% in CDCl ) ≈ 10 min at rt. H NMR (400 MHz,
/2
3
2
2
2
-P r op en yld ich lor oa r sin e (3a ). Yield: 76%. Bp ) 116
3
CDCl , -30 °C): δ 1.81 (s, 3H), 1.88 (s, 3H), 3.10 (d, 2H, J )
13
1
°
5
1
C. H NMR (400 MHz, CDCl
3
): δ 3.26 (d, 2H, J ) 8.1 Hz),
.32 (ddt, 1H, J ) 16.9, 1.2, 1.2 Hz), 5.36 (dd, 1H, J ) 10.2,
.2 Hz), 5.96 (ddt, 1H, J ) 16.9, 10.2, 8.1 Hz). C NMR (100
): δ 48.8, 121.6, 128.1. HRMS: calcd for C
185.8985, found 185.899.
2-Meth yl-2-p r op en yl)d ich lor oa r sin e (3b). Yield: 70%.
Bp ) 138 °C (partially decomposed). H NMR (400 MHz,
CDCl ): δ 1.92 (br s, 3H), 3.32 (br s, 2H), 4.99 (br d, 1H, J )
.4 Hz), 5.06 (m, 1H, J ) 1.4, 1.4, 1.4 Hz) C NMR (100 MHz,
CDCl ): δ 24.7, 53.9, 116.2, 137.3. HRMS: calcd for C
As Cl : 199.9142, found 199.914.
1-Meth yl-2-p r op en yl)d ich lor oa r sin e (3c). Yield: 84%.
7.9 Hz), 5.43 (t, 1H, J ) 7.9 Hz). C NMR (100 MHz, CDCl
-30 °C): δ 18.6, 25.8, 43.5, 114.3, 137.8.
3
,
1
3
Allyla tion of Ben za ld eh yd e. Meth od A. Ad d ition of
Allyldich lor oph osph in e (2a), Allyldibr om oph osph in e (2b),
Allyld ich lor oa r sin e (3a ), Allyld ich lor ostibin e (4a ), or
Cr otylstibin es (4e,e′) on Ben za ld eh yd e. Compound 2a ,b,
3a , or 4a (1 mmol) was prepared as reported above and diluted
MHz, CDCl
3
3 5
H -
3
5
As Cl
2
(
1
in CH
2 2
Cl
(10 mL). The solution was cooled at -78 °C and a
3
1
3
1
solution of benzaldehyde (1 mmol) and CH
2
Cl (5 mL) was
2
H
7
-
slowly added. The mixture was stirred for 2 h at this
temperature and then hydrolyzed with saturated aqueous
NaHCO . 1-Phenyl-3-buten-1-ol (5) was purified by column
3
3
4
3
5
2
(
chromatography (hexane/ether). With phosphorus and arsenic
derivatives, the procedure was repeated at room temperature
and under reflux of the solvent. Similar experiments were also
performed starting from crotylstibines 4e,e′ and benzaldehyde.
Meth od B. Ad d ition of Allylsta n n a n e 1a on Ben za l-
τ
1/2 (5% in CDCl
Z)- and (E)-2-butenyldichloroarsines, 3e,e′). H NMR (400
3
) ≈ 18 h at rt (slowly rearranged at rt into
1
(
MHz, CDCl
3
): δ 1.57 (d, 3H, J ) 7.0 Hz), 3.17 (dqdd, 1H, J )
.0, 7.0, 0.9, 0.9 Hz), 5.32 (ddd, 1H, J ) 17.2, 0.9, 0.9 Hz),
.37 (ddd, 1H, J ) 10.4, 0.9, 0.9 Hz), 5.93 (ddd, 1H, J ) 17.2,
7
5
1
1
1
3
0.4, 7.0 Hz). C NMR (100 MHz, CDCl
3
): δ 14.3, 52.1, 119.5,
199.9142, found 199.914.
1,1-Dim eth yl-2-p r op en yl)d ich lor oa r sin e (3d ). Yield:
2%. Bp0.1 ) 37 °C. τ1/2 (5% in CDCl
) ≈ 10 h at rt (slowly
d eh yd e a n d P Cl
were introduced dry dichloromethane (10 mL); PCl
AsCl , or SbCl (1.2 mmol); and benzaldehyde (1.1 g, 1 mmol).
The flask was cooled at -78 °C and allyltributylstannane (1a )
1 mmol) in CH Cl (5 mL) was slowly added. The mixture
was stirred 2 h at this temperature and was then hydrolyzed
with saturated aqueous NaHCO . Purification was performed
3
, P Br
3
, AsCl
3
, or SbCl
3
. Into a 50 mL flask
3
5
34.2. HRMS: calcd for C
4
H
7
As Cl
2
3
, PBr ,
3
(
3
3
8
3
(
2
2
rearranged at rt into the (3-methyl-2-butenyl)dichloroarsine,
3
1
f) H NMR (400 MHz, CDCl
3
): δ 1.48 (s, 6H), 5.23 (d, 1H, J
)
17.4, 1.4 Hz), 5.38 (d, 1H, J ) 10.7, 1.4 Hz), 5.95 (dd, 1H, J
17.4, 10.7 Hz). C NMR (100 MHz, CDCl
3
1
3
by column chromatography (hexane/ether). With phosphorus
and arsenic derivatives, the procedure was reproduced at room
temperature and under reflux of the solvent.
)
3
): δ 21.9, 51.6,
3
5
1
2
18.2, 139.0. HRMS: calcd for C
13.930.
Z)- a n d (E)-2-Bu t en yld ich lor oa r sin es (3e,e′) (Z:E/30:
5 9 2
H As Cl 213.9298, found
1
-Phenyl-3-buten-1-ol (5) has never been observed in the
(
1
reactions with phosphorus compounds. Traces of alcohol 5
were detected with arsenic derivatives and using method A.
Compound 5 was obtained with antimony compounds in a 78%
(method A) and 68% yield (method B). Starting from stibines
4e,e′ and benzaldehyde, syn- and anti-1-phenyl-2-methyl-3-
butenol (6a ,b) were obtained in a 80/20 ratio in a 71% yield
(method A) and a 68% yield (method B). Attempts to detect
7
0). Yield: 67%. Bp 134 °C (partially decomposed), (Z) H
): δ 1.77 (dm, 3H, J ) 6.9 Hz), 3.32
dm, 2H, J ) 8.4 Hz), 5.63 (dt, 1H, J ) 10.5, 8.4 Hz), 5.78 (dq,
NMR (400 MHz, CDCl
(
1
3
1
3
H, J ) 10.5, ) 6.9 Hz). C NMR (100 MHz, CDCl
3
): δ 13.6,
1
4
3
3.6, 119.4, 131.0. (E) H NMR (400 MHz, CDCl ): δ 1.79 (dd,
3
H, J ) 6.5, 1.1 Hz), 3.22 (dm, 2H, J ) 7.8 Hz), 5.60 (dtq, 1H,
13
J ) 15.2, 7.8, 1.5 Hz), 5.78 (dqt, 1H, J ) 15.2, 6.5, 1.0 Hz).
C
(Z)- and (E)-1-phenyl-3-penten-1-ol (6c,c′) were unsuccessful.
NMR (100 MHz, CDCl ): δ 18.3, 48.2, 120.4, 133.1. HRMS:
3
3
5
Using BiCl as Lewis acid, crotylstannane 1c,c′, and ben-
calcd for C
4
H
7
As Cl
2
199.9142, found 199.914.
3
zaldehyde, the alcohols 6a ,b were obtained in a 81% yield and
with a 90:10 syn:anti ratio.
P r ep a r a tion of Allylic Ar sin es 8a -f. Gen er a l p r oce-
d u r e. The apparatus already described for the reduction of
alkynyl- and allenylarsines was used.23 The flask containing
the reducing mixture (30 mmol of LAH in tetraglyme or 90
(
3-Meth yl-2-bu ten yl)d ich lor oa r sin e (3f). Yield: 84%.
1
Bp0.1 ) 37 °C. H NMR (400 MHz, CDCl
3
): δ 1.79 (br s, 3H),
1
8
1
2
.84 (br s, 3H), 3.27 (d, 2H, J ) 8.4 Hz), 5.36 (t sept, 1H, J )
1
3
.0, 1.4 Hz). C NMR (100 MHz, CDCl ): δ 18.6, 26.0, 45.0,
35
3
13.4, 139.9. HRMS cald for C
13.930.
5 9 2
H As Cl 213.9298, found
3
mmol of Bu SnH in the presence of small amounts of duro-
P r ep a r a tion of Allylic Dich lor ostibin es 4a ,b,e-f for
NMR Ch a r a cter iza tion . Gen er a l P r oced u r e. In a NMR
tube were introduced SbCl (0.23 g, 1 mmol) and dry CDCl
quinone) was cooled at 0 °C, fitted on a vacuum line, and
degassed. The dichloroarsine 3a -f (10 mmol) diluted in
tetraglyme (10 mL) was then slowly added (10 min) at room
temperature with a syringe through the septum. During and
after the addition, the product was distilled off in vacuo from
the reaction mixture. A cold trap (-60 °C) selectively removed
the less volatile products and compound 8a -f was condensed
on a coldfinger (-196 °C) which was connected at the bottom
to a flask or a NMR tube. A cosolvent can be added at this
step. After disconnecting from the vacuum line by stopcocks,
the apparatus was filled with dry nitrogen; liquid nitrogen was
subsequently removed. The product was collected in a Schlenk
flask or a NMR tube and kept at low temperature (< -40 °C)
before analysis. The boiling points of arsines 8a -f have been
approximately determined ((5 °C) from their temperature of
condensation and revaporization in vacuo (0.1 mbar).
3
3
(
600 µL). The tube was cooled at -40 °C and allylic tributyl-
stannane 1a -d (1 mmol) was added. The tube was shaked a
few seconds and directly introduced in the cooled probe (-40
°
C) of the NMR spectrometer. On standing at room temper-
ature, allylic stibines gave insoluble brown-black materials.
2
-P r op en yld ich lor ostibin e (4a ). Yield ≈ 45% (crude).
1
τ
1/2 (5% in CDCl
3
) ≈ 20 min at rt. H NMR (400 MHz,
CDCl
3
): δ 3.53 (d, 2H, J ) 7.0 Hz), 5.35 (d, 1H, J ) 9.9 Hz),
.48 (d, 1H, J ) 17.0 Hz), 6.07 (ddt, 1H, J ) 17.0, 9.9, 7.0 Hz).
3
5
1
C NMR (100 MHz, CDCl ): δ 45.4, 122.4, 127.7.
3
(
2-Meth yl-2-p r op en yl)d ich lor ostibin e (4b). Yield ≈ 40%
1
3
(
crude). τ1/2 (5% in CDCl
) ≈ 20 min at rt. H NMR (400 MHz,
CDCl
3
, -30 °C): δ 1.96 (br s, 3H), 3.58 (br s, 2H), 5.10 (br s,
1
3
1
2
H), 5.17 (br s, 1H). C NMR (100 MHz, CDCl
4.2, 50.8, 110.6, 142.9.
3
, -30 °C): δ
P r ep a r a tion of Allylic Stibin es 9a ,b. The procedure is
similar to this one reported above for allylic phosphines and
arsines, but the crude mixture containing the precursor 4a ,b
(
Z)- a n d (E)-2-Bu ten yld ich lor ostibin es (4e,e′). Yield ≈
3
0% (crude). τ1/2 (5% in CDCl
3
) ≈ 10 min at rt. Two isomers
(E and Z) in a 5:1 ratio, the major isomer has not been
1
(22) Banks, C. K.; Morgan, J . F.; Clarck, R. L.; Hatlelid, E. B.;
Kahler, F. H.; Paxton, H. W.; Cragoe, E.; Andres, R. J .; Elpern, B.;
Coles, R. F.; Lawhead, J .; Hamilton, C. S. J . Am. Chem. Soc. 1947,
attributed. H NMR (400 MHz, CDCl
1
3
, -30 °C): δ (major)
.82 (m, 3H, J ) 5.8 Hz), 3.02 (d, 2H, J ) 6.6 Hz), 5.50-5.70
1
3
(m, 2H). C NMR (100 MHz, CDCl
3
, -30 °C): δ 18.6, 46.3,
21.7, 131.0. H NMR (400 MHz, CDCl , -30 °C): δ (minor)
.83 (d, 3H, J ) 3.6 Hz), 3.11 (d, 2H, J ) 7.6 Hz), 5.50-5.70
6
9, 927-930.
23) Lassalle, L.; Legoupy, S.; Guillemin, J .-C. Inorg. Chem. 1995,
35, 5694-5697.
1
1
1
3
(