Hydrolysis of bisphosphonium dihalides
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 3, March, 2010
563
1
The H and 31P NMR spectra of compound 5 fully agree
(0.3 g, 44%). Its 1H and 31P NMR spectra fully agree with those
of the authentic sample.
On the extraction with ether, the insoluble viscous resinous
mass contained in the water phase was separated and dried over
P2O5 to give resin (1.2 g).
with those for its sample obtained from salt 1a and aqueous
Na2CO3.
B. A solution of NaOH (0.31 g, 7.75 mmol) in water (2.8 mL)
was added to a suspension of salt 1a (5 g, 7.72 mmol) in water
(5 mL). The reaction mixture was stirred for 4 h and the product
was extracted with benzene. The benzene extracts were comꢀ
bined and dried with MgSO4. For detection of triphenylphosꢀ
phine, iodomethane (1.5 g, 10.5 mmol) was added and the soluꢀ
tion was left for 24 h. Formation of a precipitate virtually was not
observed. The benzene solution was filtered off and concentratꢀ
ed. The resulting waxy solid (2.3 g) was recrystallized from ethaꢀ
nol—chloroform to give triphenylphosphine oxide (1 g, 47%),
m.p. 154 °C. Its mixture with the authentic sample did not deꢀ
press the melting point. The mother liquor was concentrated
and the residue was dried to give a solid (1.3 g) consisting of
a ~9 : 1 mixture of isomeric 4ꢀdiphenylphosphorylꢀ4ꢀphenylꢀ
butꢀ2ꢀene (3) and 4ꢀdiphenylphosphorylꢀ4ꢀphenylbutꢀ1ꢀene (4)
(total yield 51%) (1H and 31P NMR).
The product from the aqueous layer was extracted with
chloroform; the extract was dried with MgSO4 and concentrated
to give the starting salt 1a (2.2 g, 44%). Its spectroscopic and
physicochemical parameters fully agree with those of the autheꢀ
ntic sample.
Reaction of 1,4ꢀbis(triphenylphosphonio)butaꢀ1,3ꢀdiene diꢀ
chloride (1a) with aqueous Na2CO3. A solution of Na2CO3 (1.3 g,
12.4 mmol) in water (30 mL) was added to a suspension of salt 1a
(2 g, 3.1 mmol) in water (20 mL). The reaction mixture was
stirred at 50—55 °C for 2 h and the product was extracted with
benzene. The benzene extract was dried with MgSO4 and conꢀ
centrated. The resulting viscous mass (1.2 g) was thoroughly
triturated with hexane. The hexane extracts were combined and
concentrated. The residue was dried in vacuo to give tripheꢀ
nylphosphine (0.4 g, 49%), m.p. 74—76 °C. Its mixture with the
authentic sample did not depress the melting point.
The hexaneꢀinsoluble residue was filtered off and dried to
give a solid (0.8 g), which was recrystallized from ethanol—chloroꢀ
form. The yield of triphenylphosphine oxide was 0.4 g (46%),
m.p. 154 °C. Its mixture with the authentic sample did not deꢀ
press the melting point. The mother liquor was concentrated to
give 1ꢀdiphenylphosphorylꢀ1ꢀphenylbutaꢀ1,3ꢀdiene (5) (0.4 g,
40%). H NMR (CDCl3), δ: 5.36 (m, 1 H, —CH=CH2); 5.53
(m, 1 H, —CH=CH2); 6.35 (dddd, 1 H, —CH=CH2, JP,H
= 1.8 Hz, J1 = 10.9 Hz, J2 = 16.9 Hz, J3 = 10.1 Hz); 7.07 (dd, 1 H,
—C(Ph)=CH—, 3JP,H = 18.9 Hz, JH,H = 10.9 Hz); 6.95—7.95
(m, 15 H, Ph2P(O)—C(Ph)=). 31P NMR (CDCl3), δ: 33.65 (s, 1 P).
The product from the aqueous layer was extracted with chloꢀ
roform. The starting salt (0.2 g, 0.3 mmol) was isolated from
the extract.
Reaction of 1,4ꢀbis(tributylphosphonio)butaꢀ1,3ꢀdiene dibroꢀ
mide (6) with aqueous Na2CO3. A solution of Na2CO3 (1.4 g,
13 mmol) in water (20 mL) was added to salt 6 (2 g, 3.2 mmol).
The reaction mixture was stirred under argon at 80—90 °C for
2 h and the product was extracted with benzene. The benzene
extracts were combined, dried with MgSO4, and kept with iodoꢀ
methane (0.5 g, 3.5 mmol) for 24 h. The precipitate that formed
was separated, thoroughly washed with ether, and dried to give
tributyl(methyl)phosphonium iodide (0.25 g, 0.73 mmol), m.p.
123 °C. Its mixture with the authentic sample did not depress the
melting point. The benzene solution was concentrated and the
residue was dried to give tributylphosphine oxide (0.3 g, 43%). The
product from the aqueous layer was extracted with chloroform; the
starting salt 6 (1 g, 1.6 mmol) was isolated from the extract.
The insoluble viscous resinous mass contained in the water
phase was separated and dried over P2O5 to give resin (0.5 g).
Reaction of 1,4ꢀbis(triphenylphosphonio)butaꢀ1,3ꢀdiene diꢀ
chloride (1a) with triethylamine. Triethylamine (1.2 g, 12 mmol)
was added to a suspension of salt 1a (2 g, 3.1 mmol) in anhydrous
DMF (30 mL). The reaction mixture was heated at 80—90 °C in
a sealed tube for 12 h. Then the tube was opened and the DMFꢀ
insoluble precipitate was separated, washed with ether, and dried
to give triethylamine hydrochloride (0.25 g, 58%), m.p. 253 °C.
Its mixture with the authentic sample did not depress the melting
point. The solution was concentrated and a resinous residue
(1.2 g) was thoroughly washed with ether. The ethereal extracts
were combined and concentrated to give triphenylphosphine
(0.6 g, 75%), m.p. 74—76 °C. Its mixture with the authentic
sample did not depress the melting point.
Reaction of 1,4ꢀbis(triphenylphosphonio)butaꢀ1,3ꢀdiene diꢀ
chloride (1a) N,NꢀdimethylꢀNꢀallylamine. N,NꢀDimethylꢀNꢀ
allylamine (2 g, 25 mmol) was added dropwise to a suspension of
salt (1a) (2 g, 3.1 mmol) in anhydrous DMF (30 mL). The reaction
mixture was heated at 80—90 °C in a sealed tube for 12 h and
subjected to the workꢀup described in the preceding entry. The
yield of triphenylphosphine was 0.5 g (61.3%).
1
Reaction of cisꢀ1,4ꢀbis(tributylphosphonio)butaꢀ1,3ꢀdiene diꢀ
bromide (cisꢀ1b) with triethylamine. A solution of the salt cisꢀ1b
(2 g, 3.2 mmol) in acetonitrile (15 mL) was added dropwise to
triethylamine (2.5 g, 25 mmol). The reaction mixture was stirred
for 5 h, kept for 24 h, and then concentrated. The residue was
washed with anhydrous ether, dried in vacuo, and recrystallized
from ethyl acetate to give transꢀ1,4ꢀbis(tributylphosphonio)butaꢀ
1,3ꢀdiene dibromide (1.7 g, 85%), m.p. 213 °C. Found (%):
4
=
3
1
Reaction of 1,4ꢀbis(tributylphosphonio)butaꢀ1,3ꢀdiene dibroꢀ
mide (6) with aqueous NaOH. A solution of NaOH (0.4 g,
10 mmol) in water (30 mL) was added to salt 6 (2 g, 3.2 mmol).
The reaction mixture was stirred under argon at 35—40 °C for
2 h; then the product was extracted with ether. The ethereal
extracts were combined, dried with MgSO4, and kept with iodoꢀ
methane (0.5 g, 3.5 mmol) for 24 h. The precipitate that formed
was separated, thoroughly washed with ether, and dried to give
tributyl(methyl)phosphonium iodide (0.3 g, 0.87 mmol), m.p.
123 °C. Its mixture with the authentic sample did not depress the
melting point. The mother liquor was evaporated to dryness and
the residue was dried in vacuo to give tributylphosphine oxide
Br, 26.32. C28H58Br2P2. Calculated (%): Br, 25.97. H NMR
(CDCl3), δ: 1.00 (t, 18 H, CH3, J = 6.9 Hz); 1.56 (m, 24 H,
CH2CH2CH3); 2.51 (m, 12 H, PCH2); 7.54 (dd, 2 H, CH=CH,
J1 = 18.5 Hz, J2 = 16.0 Hz); 8.43 (dd, 2 H, PCH=, J1 = 16.0 Hz,
J2 = 13.0 Hz). 31P NMR (CDCl3), δ: 32.8 (s, 2 P).
Reaction of cisꢀ1,4ꢀbis(tributylphosphonio)butaꢀ1,3ꢀdiene diꢀ
bromide (cisꢀ1b) with (N,Nꢀdimethyl)allylamine. A solution of
the salt cisꢀ1b (2 g, 3.2 mmol) in acetonitrile (15 mL) was added
dropwise to (N,Nꢀdimethyl)allylamine (2.12 g, 25 mmol). The
reaction mixture was stirred for 5 h, kept for 24 h, and subjected
to the workꢀup described in the preceding entry. The yield of
transꢀ1b was 1.6 g (80%).