DOUMANDJI ET AL.
5 of 6
CH ─C─), 1.56 (m, 2H, CH ─CH ─CH ), 1.64 (s, 3H,
the reaction, the solution obtained was filtered and was con-
centrated on a rotary evaporator to give purple oil corre-
sponding to acyl chloride of retinoic acid. This product was
solubilized in dry diethyl ether to completely eliminate pyri-
2
2
2
2
CH ─C), 1.93 (s, 3H, CH ─C), 1.95 (m, 2H, CH ─CH ─C),
3
3
2
2
2
.28 (s, 3H, CH ─C), 4.98 (m, 1H, CH ─CH─CH ), 5.67 (s,
3 3 3
1H, C─CH─C), 6.05 (d, 1H, CH─CH─C), 6.09 (s, 1H,
CH─CH─C), 6.18 (s, 1H, C─CH─CH), 6.23 (s, 1H,
CH─CH─C), 6.91 (t, 1H, CH─CH─CH). C NMR (CDCl3,
δC, ppm): 11.87, 12.79, 18.20, 20.98, 27.93, 28.68, 32.08,
dine hydrochloride, dried over MgSO , filtered and solubi-
lized in propionitrile.
4
1
3
To a stirred mixture of AgF (0.038 g, 0.3 mmol) in 5 ml
of propionitrile, trimethyl(trifluoromethyl)silane (0.053 g,
0.37 mmol) was added at room temperature. The mixture
was stirred for 30 min and copper powder (0.038 g, 0.6 mmol)
was added. The reaction mixture was stirred at room temper-
ature for 6 h. The corresponding acyl chloride to retinoic acid
was added and the reaction mixture was stirred for 48 h at
room temperature. The solution obtained was filtered and
concentrated on a rotary evaporator. Then, the solution was
solubilized in 10 ml of dry diethyl ether, filtered and concen-
trated on a rotary evaporator to give dark yellow oil corre-
sponding to our final product.
3
1
3.23, 38.58, 65.75, 118.14, 127.57, 128.51, 128.94,
29.70, 134.23, 136.25, 136.67, 138.37, 151.31, 165.70.
+
HRMS: m/z (%): 342.26 (100) M , 343.26 (75.5) [M − H],
3
+
+
44.26 (21) [M − 2H] , 371.30 (7.5) [M − C H ] .
2
5
4.3 | 1,1,1,3,3,3‐Hexafluoropropan‐2‐yl‐(2E,4E,6E,8E)‐
3,7‐dimethyl‐9‐(2,6,6‐trimethylcyclohex‐1‐en‐1‐yl)nona‐
2,4,6,8‐tetraenoate
To a flask containing a stirred mixture of retinoic acid
0.100 g, 0.33 mmol) and 4,4′‐azopyridine (0.072 g,
.4 mmol) in dry acetonitrile (3 ml) was added a solution of
(
0
−
1
IR (cm ): 3600–3200 w, 2959.84–2923.85–2854.31 s,
1758.28 s, 1670.33 m, 1584.48 m, 1435.68 m, 1379.15 m,
1258.10 m, 1171.79–1095.06–1033.45–984.11–911.78–
triphenylphosphine (0.104 g, 0.3 mmol) and 1,1,1,3,3,3‐
hexafluoro‐2‐propanol (73 mg, 0.4 mmol) in CH CN. The
3
1
reaction mixture was refluxed for 12 h. After completion of
the reaction, the pyridine hydrazine produced was filtered
and the solution was concentrated on a rotary evaporator to
give a viscous oil. After purification using a short column
of silica gel and cyclohexane as eluent, the product was
obtained as very bright yellow oil. Isolated yields and spectral
data for this compound are given below.
855.11–734.85 m. H NMR (CDCl , δ , ppm): 0.96 (s, 6H,
3
H
CH ─C─CH ), 1.40 (m, 2H, CH ─CH ─C─), 1.56 (m, 2H,
3
3
2
2
CH ─CH ─CH ), 1.65 (s, 3H, CH ─C), 1.95 (s, 3H,
2
2
2
3
CH ─C), 1.98 (m, 2H, CH ─CH ─C), 2.33 (s, 3H,
3
2
2
CH ─C), 5.76 (s, 1H, C─CH─C), 6.06 (d, 1H, CH─CH─C),
3
6.12 (s, 1H, CH─CH─C), 6.22 (m, 1H, C─CH─CH), 6.27
(m, 1H, CH─CH─C), 7.07 (t, 1H, CH─CH─CH).
−1
IR (cm ): 3100–3030 w, 2960.19–2928.39–2864.65 m,
738.32 m, 1577.48 m, 1434.72 w, 1385.42–1358.65 m,
288.16–1267.61 m, 1233.66–1199.38 m, 1110.15 s,
1
1
1
ACKNOWLEDGMENTS
The financial support of the French National Agency for
Environmental Safety, Food and Health (ANSES) is grate-
fully acknowledged (contract no. EST‐2012/2/64).
1
027.55 w, 950.58 m, 906.60 w,743.48–695.96 w. H NMR
(
CDCl , δ , ppm): 0.96 (s, 6H, CH ─C─CH ), 1.35 (s, 1H,
3 H 3 3
CF ─CH─CF ), 1.40 (m, 2H, CH ─CH ─C─), 1.56 (m,
3
3
2
2
2
H, CH ─CH ─CH ), 1.65 (s, 3H, CH ─C), 1.95 (s, 3H,
REFERENCES
2
2
2
3
CH ─C), 1.98 (m, 2H, CH ─CH ─C), 2.33 (s, 3H,
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3
2
2
CH ─C), 5.74 (m, 1H, C─CH─C), 6.06 (d, 1H, CH─CH─C),
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3
6
.12 (s, 1H, CH─CH─C), 6.22 (m, 1H, C─CH─CH), 6.27
1
3
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C
3
1
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19
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3
F
+
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(
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2
5
2179.
[
[
[
7] G. Duester, Cell 2008, 134, 921.
4
.4 | (3E,5E,7E,9E)‐1,1,1‐Trifluoro‐4,8‐dimethyl‐10‐
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[
[
[
11] N. Iranpoor, H. Firouzabadi, D. Khalili, S. Motavalli, J. Org. Chem. 2008,
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To a flask containing a stirred mixture of retinoic acid
7
(0.100 g, 0.33 mmol) and anhydrous pyridine (10 μl,
12] J. Wiedemann, T. Heiner, G. Mloston, G. K. Surya Prakashand, G. Olah,
0
.13 mmol) in dry CH Cl (20 ml), thionyl chloride (30 μl,
2
2
Angew. Chem. Int. Ed. 1998, 37, 820.
0.41 mmol) was added dropwise. The reaction mixture was
13] P. Singh Rajendra, C. Canfeng, R. I. Kirchmeier, J. M. Shreeve, J. Org.
Chem. 1999, 64, 2873.
stirred for 48 h at room temperature. After completion of