REACTIONS OF BUT-2-YNE-1,4-DIYLBIS(TRIPHENYLPHOSPHONIUM) DIHALIDES
1045
anhydrous diethyl ether and anhydrous benzene, dried
in vacuum, and recrystallized from ethyl acetate–iso-
propyl alcohol mixture (4 : 1). Yield 0.76 g (66.7%),
mp 204–207°С. 1Н NMR spectrum, δ, ppm: 2.65–2.77
m (2Н, Р+CH2CH2), 3.67 d (2Н, СН2Ph, J = 1.3 Hz),
4.23–4.39 m (2Н, Р+CH2CH2), 5.37 d (2Н, Р+CH2C=N,
J = 14.3 Hz), 6.69 br.s (1Н, NНСН2Ph), 6.81–6.9 m
(2Н, Нo), 7.11–7.18 m (3Н, Нp,m), 7.54–8.0 m (30Н,
Ph3P+). 31Р NMR spectrum, δР, ppm: 28.23, 30.12.
Found, %: Р 6.79; I 26.92. С47Н44I2N2Р2. Calculated,
%: Р 6.51; I 26.68.
benzene and dried in vacuum to yield 0.7 g (77.8%) of
a mixture of compounds 17 and 18 in a ratio of 1 : 4.
2-(3,5-Dimethylpyrazol-1-yl)but-1-ene-1,4-diylbis-
(triphenylphosphonium) bromide (17). 1Н NMR
spectrum, δ, ppm: 1.9 s and 1.95 s (6Н, 2СН3), 3.18–
3.3 m (2Н, Р+CH2CH2), 4.27–4.48 m (2Н, Р+CH2CH2),
5.64 s (1Н-pyrazole), 6.31–6.4 m (1Н, Р+CH=), 7.56–
7.98 m (30Н, Ph3P+). 31Р NMR spectrum, δР, ppm:
26.41 d and 27.09 d (J = 12.5 Hz).
2-(3,5-Dymethypyrazol-1-yl)but-2-ene-1,4-diylbis-
1
(triphenylphosphonium) bromide (18). Н NMR spec-
b. 0.15 g (1.2 mmol) of benzylhydrazine was added
at 5°C to a solution of 1 g (1.2 mmol) salt 2 in 15 mL
of chloroform–methanol mixture. The reaction mixture
was stirred at 5°C during 8 h and then washed with
water. The organic layer was dried with CaCl2, and the
solvent was removed in vacuum. The residue was
sequentially washed with anhydrous diethyl ether and
anhydrous benzene and dried in vacuum to yield 0.62 g
(55.1%) of a mixture of compounds 15 and 16 in a
ratio of 1 : 1.
trum, δ, ppm: 1.79 s and 1.84 s (6Н, 2СН3), 5.12 d.d.d
1
2
3
(2Н, Р+CH2CH=, J = 16.1, J = 6.9, J = 5.2, Hz), 5.4
1
d.d (2Н, Р+CH2C=, J = 15.3, 2J = 2.4 Hz), 5.43 s (1Н-
pyrazole), 5.52–5.63 m (1Н, Р+CH2CН=), 7.56–7.98 m
(30Н, Ph3P+). 31Р NMR spectrum, δР, ppm: 25.56 d
and 27.92 d (J = 9.0 Hz). Found, %: Р 7.73; Br 19.61.
С45Н42Br2N2Р2. Calculated, %: Р 7.45; Br 19.23.
REFERENCES
1. Ovakimyan, M.Zh., Gasparyan, G.Ts., Bichakh-
chyan, A.S., Pogosyan, A.S., Kinoyan, F.S., Tama-
zyan, R.A., and Aivazyan, A.G., Russ. J. Gen. Chem.,
2014, vol. 84, no. 6, p. 1126. DOI: 10.1134/
S1070363214060127.
2. Plenat, F., Bennamara, A., Chiche, L., and Christol, H.,
Phosphorus, Sulfur, 1986, vol. 84, no. 26, p. 39. DOI:
10.1080/ 030866486080884568.
3. Ovakimyan, M.Zh., Movsisyan, M.L., Gasparyan, G.Ts.,
and Indzhikyan, M.G., Russ. J. Gen. Chem., 2011,
vol. 81, no. 2, p. 444. DOI: 10.1134/S1070363211020344.
4. Ovakimyan, M.Zh., Gasparyan, G.Ts., Pogosyan, A.S.,
Bichakhchyan, A.S., and Aivazya, A.G., Khim. Zh.
Armenii, 2013, vol. 66, no. 1, p. 63.
5. Ovakimyan, M.Zh., Gasparyan, G.Ts., and Bichakh-
chyan, A.S., Khim. Zh. Armenii, 2012, vol. 65, no. 4,
p. 574.
6. Cristau, H.J., Plenat, F., Duc, G., and Bennamara, A.,
Tetrahedron, 1985, vol. 41, no. 13, p. 2717. DOI:
10.1016/S0040-4020(01)96372-0.
2-(2-Benzylhydrzinyl)but-1-ene-1,4-diylbis(tri-
1
phenylphosphonium) iodide (16). Н NMR spectrum,
δ, ppm: 3.07–3.18 m (2Н, Р+CH2CH2), 4.05 s (2Н,
СН2Ph), 4.41–4.59 m (2Н, Р+CH2CH2), 4.72 br.s (2Н,
NНNНСН2Ph), 7.19–7.24 m (6Н, Р+CH=, СН2Ph),
7.64–8.1 m (30Н, Ph3P+). 31Р NMR spectrum, δР, ppm:
18.91, 30.8. Found, %: Р 6.35; I 27.12. С47Н44I2N2Р2.
Calculated, %: Р 6.51; I 26.68.
2-(3,5-Dimethylpyrazol-1-yl)but-1-ene-1,4-diylbis-
(triphenylphosphonium) bromide (17) and 2-(3,5-
dimethylpyrazol-1-yl)but-2-ene-1,4-diylbis(triphenyl-
phosphonium) bromide (18). A mixture of 0.8 g
(1.1 mmol) of but-2-yne-1,4-diylbis(triphenylphospho-
nium) dibromide and 0.1 g (1.1 mmol) of 3,5-di-
methylpyrazole in 15 mL of chloroform was stirred at
room temperature during 9 h. Chloroform was re-
moved in vacuum, and the residue was sequentially
washed with anhydrous diethyl ether and anhydrous
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 5 2016