112
VOLYNSKII, SHEVCHENKO
Table 3. Yields and physicochemical properties of 3-chloro-1-methoxyalkanes (2b–f)
Content
MRD,
found/calcd.
Empirical
formula
Bp,
°C/mmHg
n2D0
d240
Compound
Yield, %
of Cl, %
found/calcd.
28.90
------------
28.92
31.96
------------
31.82
3-Chloro-1-methoxybutane (2b)
3-Chloro-1-methoxyheptane (2c)
3-Chloro-1-methoxyoctane (2d)
3-Chloro-1-methoxynonane (2e)
47
35
42
42
C5H11ClO
C8H16ClO
C9H19ClO
C10H21ClO
C10H13ClO
124(760) 1.4141 0.9587
20.25
------------
21.58
45.67
------------
45.75
79(15)
94(15)
102(10)
95(4)
1.4334 0.9379
1.4365 0.9257
1.4385 0.9189
1.5165 1.0756
16.90
------------
19.90
50.52
------------
50.42
16.30
------------
18.40
55.10
------------
55.03
18.90
------------
19.20
51.89
------------
51.53
3-Chloro-1-methoxy-3-phenylpropane (2f) 92
mide in the trap. After the end of addition, the reaction trum, m/z (Irel, %): [M]+ 130(41), 115(5), 101(40),
mixture was cooled to room temperature, ice-cold 96(5), 87(100), 81(17), 73(20), 60(24), 55(5), 41(32).
water was added, the bottom organic layer was sepa-
1
2-Pentylthietane (4d). ç NMR, δ, ppm: α + α':
rated, and the aqueous layer was extracted with chloro-
3.25 (m) + 3.65 (tt, J1 = 7.3 Hz, J2 = 9.0 Hz, 1H); β: 2.53
form (3 × 50 ml). The extract was added to the main
(m, 1H) + 2.79 (m, 1H); γ: 2.85 (m, 1H) + 3.15 (m, J1 =
layer, dried with sodium sulfate, and distilled on a frac-
9.4 Hz, J2 = 8.0 Hz, 1H); 1: 1.7 (m, 1H) + 2.06 (m, 1 H);
tionating column (8 theoretical plates). 1-Bromo-3-
2–4: 1.00 –1.80 (m, 6H); 5: 0.85 (m, 3H). Mass spec-
chloroheptane 3c was obtained in a yield of 58 g
trum, m/z (Irel, %): [M]+ 144(45), 115(100), 101(40),
(Table 1).
87(88), 81(25), 73(42), 60(37), 55(56), 41(28).
2-Butylthietane (4c). A solution of KSH, which
1
2-Hexylthietane (4e). ç NMR, δ, ppm: α + α':
was prepared by the saturation of a solution of KOH
3.26 (m) + 3.66 (quintet, J2 = 7.5 Hz, 1H); β: 2.57 (m,
(14 g, 0.25 mol) in ethanol (150 ml) with hydrogen sul-
1H) + 2.81 (m, 1H); γ: 2.88 (m, 1H) + 3.15 (m, 1H);
fide at 0–6°ë, was placed in a 0.5-l flask equipped with
1: 1.84 (m, 1H) + 2.04 (m, 1H); 2–5: 1.00–1.80 (m,
a glass stirrer, a reflux condenser, a thermometer, and a
8H); 6: 0.85 (m, 3H). Mass spectrum, m/z (Irel, %): [M]+
dropping funnel. Then, 1-bromo-3-chloroheptane
158(18), 129(12), 115(12), 101(8), 87(100), 81(4),
(50.5 g, 0.24 mol) was added for 1 min with stirring and
67(8), 60(37), 55(4), 41(5).
cooling (during the addition, potassium bromide pre-
1
cipitated and the temperature in the flask spontaneously
2-Phenylthietane (4f). ç NMR, δ, ppm: α: 4.94
increased to 15°ë). The reaction mixture was stirred at
(t, 7.5 Hz, 1H); β: 3.02 (m, 1H) + 3.14 (m, 1H); γ: 3.14
40°ë for 45 min and then heated to boiling for 3 h, and
a solution of KOH (14 g, 0.25 mol) in water (150 ml)
was added dropwise. Refluxing and stirring were con-
tinued for 5 h, the mixture was cooled to room temper-
ature, and ice-cold water (150 ml) was added. Sulfide
was extracted with hexane (3 × 50 ml). Hexane was dis-
tilled off, and the residue was distilled on a rectification
column (8 theoretical plates). 2-Butylthietane was
washed with concentrated H3PO4, water, and a sodium
bicarbonate solution. 2-Butylthietane 4c was obtained
by distillation on a fractionating column (8 theoretical
plates) in a yield of 18.8 g (Table 2).
(m, 1H) + 3.38 (m, 1H); Ph: 7.10–7.60 (m, 5H). Mass
spectrum, m/z (Irel, %): [M]+ 150(100), 135(12),
122(62), 117(19), 104(88), 91(12), 78(20), 63(5),
51(8), 39(8).
2-Butylthietane 1-oxide (5c). 2-Butylthietane
(2.0 g, 0.015 mol) and glacial acetic acid (4 ml) were
placed into a 30-ml Erlenmeyer flask. Then, 1 ml of a
25% solution of an equimolar amount of hydrogen per-
oxide in 1 ml of acetic acid was added dropwise with
stirring for 30 min at 10°ë. The reaction mixture was
alkalized with a 15% NaOH aqueous solution,
extracted with chloroform (3 × 10 ml), and dried with
sodium sulfate. After the removal of chloroform by dis-
tillation, the residue was dissolved again in a minimum
1çNMR, δ, ppm: α + α': 3.07 (m) + 3.53 (tt, J1 = 7.5,
J2 = 7.3 Hz, 1H); β: 2.45 (m, 1H) + 2.66 (m, 1H); γ: 2.74
(q, J = 9.4 Hz, 1H) + 3.03 (q, J = 8.7 Hz, 1H); 1: 1.69 amount of chloroform, the resulting solution was fil-
(m, 1H) + 1.90 (m, 1H); 2–3: 0.9–1.65 (m, 4H); 4: 0.71 tered from mechanical admixtures, chloroform was dis-
(t, J1 = 7.3 Hz) + 0.74 (t, J1 = 6.5 Hz, 3H). Mass spec- tilled off, and the residue was stored in vacuum for 1 h.
PETROLEUM CHEMISTRY Vol. 47 No. 2 2007