10.1002/chem.201902414
Chemistry - A European Journal
Dichloridobis(3-Methyl-2-butanone)beryllium(II) (5a): 21.3 µL 3-methyl-2-butanone (MIPK) (0.200
mmol) and 8.0 mg BeCl2 (0.100 mmol) were weighed into a J. Young NMR tube, which was
subsequently filled with CDCl3 by vacuum condensation. The solvent was removed in vacuo after two
weeks of storage. Single crystals of 5a were isolated from an oily brownish residue, which were suitable
for single crystal structure analysis. 1H NMR (500 MHz, CDCl3) δ = 1.09 (d, 3JHH =7.0 Hz, 6H, CH3), 2.13
(s, 3H, CH3), 2.58 (hept, 3JHH =6.9 Hz, 1H, CH). 9Be NMR (42 MHz, CDCl3) δ = 4.7 (ω1/2 =8.0 Hz). 13C NMR
(126 MHz, CDCl3) δ = 17.9 (CH3), 27.9 (CH3), 43.4 (CH), 231.8 (CO). FT-IR (cm−1): 2975.0 (w), 2937.0 (w),
2879.9 (w), 1650.0 (s), 1466.5 (m), 1391.0 (m), 1366.5 (m), 1270.7 (w), 1213.6 (m), 1154.4 (w), 1105.5
(m), 1105.5 (w),1105.5 (w), 764.8 (m), 634.3 (s), 556.8 (s), 522.1(s).
Bis(2,2-dimethylpropanal)bis(μ2-[1-iodo-2,2-dimethyl-propan-1-ol])diiododiberyllium(II) (6): 32.3
mg 2,4,6-tris-tertbutyl-1,3,5-trioxane (1a) (0.125 mmol) and 32.8 mg BeI2 (0.125 mmol) were weighed
into a J. Young NMR tube, which was subsequently filled with CDCl3 by vacuum condensation. The
solvent was removed in vacuo after two days of storage. Single crystals of 6 were isolated from an oily
brownish residue, which were suitable for single crystal structure analysis. 1H NMR (300 MHz, CDCl3) δ
= 1.08 (s, 9H, CH3), 1.26 (s, 9H, CH3), 6.71 (s, 1H, CHOI), 9.89 (s, 1H, C(O)H). 9Be NMR (42 MHz, CDCl3) δ
= 4.1 (ω1/2 =35.6 Hz). 13C NMR (126 MHz, CDCl3) δ = 24.1 (CH3), 26.5 (CH3), 43.8 (C((CH3)3), 71.5 (CCHOI),
226.0 (C(O)H). FT-IR (cm−1): 2967.9 (m), 2934.6 (w), 2905.0 (w), 2870.0 (w), 1662.4 (s), 1477.4 (m),
1462.3 (m), 1403.9 (m), 1382.7 (m), 1365.7 (m), 1309.6 (w), 1256.5 (w), 1210.8 (w), 1149.8 (w), 1104.3
(m), 1061.7 (s), 1014.3 (w), 941.5 (w), 891.0 (s), 776.4 (s), 721.8 (s), 679.0 (s), 600.0 (s), 553.8 (s), 526.5
(s).
Bis(μ2-[5-hydroxy-2,6,6-trimethylheptan-3-one])diiododiberyllium(II) (11): 10.8 mg 2,4,6-tris-
tertbutyl-1,3,5-trioxane (1a) (0.042 mmol) and 32.8 mg BeI2 (0.125 mmol) were weighed into a J. Young
NMR tube, which was subsequently filled with CDCl3 by vacuum condensation. The reaction mixture
was stored for 6 weeks and monitored weekly by NMR spectroscopy. Single crystals of 11 grew after 6
weeks as colourless blocks, which were suitable for single crystal structure analysis. 1H NMR (500 MHz,
CDCl3) δ = 1.04 (s, 9H, CH3), 1.25 (d, 3JHH =6.9 Hz, 3H, CH3), 1.31 (d, 3JHH =6.9 Hz, 3H, CH3), 2.71 (dd, 3JHH
=11.2 Hz, 2JHH =14.4 Hz, 1H, CHH), 3.04 (m, 1H, CH), 3.21 (dd, 3JHH =2.9 Hz, 2JHH =14.4 Hz, 1H, CHH), 4.15
(dd, 3JHH =2.9 Hz, 11.2 Hz, 1H, CH). 9Be NMR (42 MHz, CDCl3) δ = 3.0 (ω1/2 =10.7 Hz). 13C NMR (126 MHz,
CDCl3) δ =17.1 (iPr-CH3), 17.7 (iPr-CH3), 26.2 (tBu-CH3), 36.1 (tBu-C), 39.3 (CH2), 43.9 (CH), 233.9 (C(O)).
FT-IR (cm−1): 2972.2 (m), 2872.6 (w), 1631.6 (s), 1464.4 (m), 1388.9 (m), 1364.4 (m), 1311.4 (w), 1264.5
(w), 1213.5 (m), 1152.3 (w), 1078.9 (m), 1025.9 (m), 1011.6 (w), 993.3 (w), 960.6 (w), 921.9 (m), 852.5
(vw), 779.1 (s), 740.4 (s), 660.8 (s), 605.8 (m), 567.0 (w), 532.3 (m), 456.9 (w), 440.5 (vw).
2,4,6-Tris-isopropyl-1,3,5-trioxane (1b): 10 mg BeCl2 (0.125 mmol) was weighed into a J. Young
Schlenk tube and 5.0 mL isobutyraldehyde (54.78 mmol) was added under argon stream. The tube was
sealed and after a few hours of storage at ambient temperature rod shaped crystal grew from the solid
BeCl2. After one day the isobutyraldehyde was completely converted into a colourless crystalline solid.
Compound 1b was obtained in quantitative yield (3.95 g) after sublimation at 50 °C in vacuo. 1H NMR
(300 MHz, CDCl3) δ = 0.93 (d, 3JHH =6.9 Hz, 6H, CH3), 1.84 (dhept, 3JHH =5.5 Hz, 6.8 Hz, 1H, CH), 4.49 (d,
3JHH =5.5 Hz, 1H, C(O)2H). 1H NMR (300 MHz, C6D6) δ = 1.01 (d, 3JHH =6.9 Hz, 6H, CH3), 1.94 (dhept, 3JHH
=5.0 Hz, 6.8 Hz, 1H, CH), 4.39 (d, 3JHH =5.0 Hz, 1H, C(O)2H). 13C NMR (76 MHz, CDCl3) δ = 16.8 (CH3), 32.6
(CH), 104.9 (C(O)2H). 13C NMR (76 MHz, C6D6) δ = 16.8 (CH3), 32.9 (CH), 104.7 (C(O)2H). FT-IR (cm−1):
2980.5 (m), 2962.9 (m), 2923.7 (w), 2905.2 (w), 2875.2 (w), 1472.1 (m), 1457.8 (w), 1405.4 (w), 1378.4
(m), 1362.1 (m), 1302.4 (w), 1289.3 (w), 1190.3 (m), 1159.5 (m), 1133.7 (s), 1096.1 (m), 1046.8 (m),
1023.6 (w), 956.8 (m), 929.3 (w), 885.7 (w), 852.6 (w), 746.9 (w), 504.1 (w), 473.6 (m), 433.0 (w).
2-En-2-ethyl-1-hexanal (13): 2mL butyraldehyde (22.2 mmol), 2mL water and 40mg NaOH (1.00 mmol)
were heated to 120 °C for 2 hours inside a J. Young Schlenk tube. The reaction mixture was extracted
with ethyl acetate, the organic phase was dried with MgSO4 and filtered. Ethyl acetate was removed
in vacuo and 2-en-2-ethyl-1-hexanal, (13) was obtained as colourless liquid by subsequent distillation
at 180 °C. Yields were not determined. 1H NMR (300 MHz, CDCl3) δ = 0.95 (t, 3JHH =7.6 Hz, 3H, CH3), 0.97
(t, 3JHH =7.4 Hz, 3H, CH3), 1.53 (p, 3JHH =7.4 Hz, 2H, CH2), 2.25 (q, 3JHH =7.6 Hz, 2H, CH2), 2.33 (q, 3JHH =7.4
Hz, 2H, CH2), 6.41 (t, 3JHH =7.5 Hz, 1H, CH), 9.35 (s, 1H, C(O)H). 1H NMR (300 MHz, C6D6) δ = 0.70 (t, 3JHH
=7.4 Hz, 3H, CH3), 0.92 (t, 3JHH =7.5 Hz, 3H, CH3), 1.13 (p, 3JHH =7.4 Hz, 2H, CH2), 1.83 (q, 3JHH =7.6 Hz, 2H,
CH2), 2.19 (q, 3JHH =7.5 Hz, 2H, CH2), 5.79 (t, 3JHH =7.4 Hz, 1H, CH), 9.25 (s, 1H, C(O)H). 13C NMR (76 MHz,
This article is protected by copyright. All rights reserved.