RSC Advances
Page 4 of 12
DOI: 10.1039/C6RA06348A
(Cɣ,ɣ’), 86.0 (Cα), 103.0 (C2), 114.41 (C11), 136.4
(C1), 136.8 (C4), 138.9 (C10), 153.7 (C3).
catalyst (1-10 mol%) was added and the
reaction was stirred, under nitrogen, at 40 °C
for 4 h. Reaction was quenched with 1 mL of
THF and 4 drops of vinyl ethyl ether. Product
was concentrated and a sample was taken for
GPC analyses. The remainder was dissolved in
THF (1 mL) and precipitated in cold methanol
(50 mL).
Bis-Decene-O-syringaresinol (SYR-Dec)
5
O
3
γ
7
4
9
O
2
O
11
β
13
15
O
α
3
6
8
1
O
10
2
12
14
O
O
5
O
Polymer obtained from SYR-All (P1) (1 mol%
1
HG-II, 2 mol% 1,4-benzoquinone, 100 °C): H
Viscous oil (77%). FTIR (neat): νmax : 1502 (C=C
Ar). HRMS: (TOF MS, ES+): m/z calcd for
C42H62O8Na [MNa]+: 717.4342; found: 717.4351.
1H NMR (300 MHz, CDCl3, δ): 1.30 – 1.44 (m,
20H, H 8,9,10,11,12), 1.73 (qt, 4H, J = 7.8 Hz, H7),
2.02 (q, 4H, J = 7.1 Hz, H13), 3.1 (m, 2H, Hβ), 3.83
(s, 12H, H5), 3.92 (m, 6H, Hɣ,6), 4.29 (m, 2H, Hɣ’),
4,72 (d, 2H, J = 4.2 Hz, Hα), 4.89 – 5.28 (m, 4H,
H15), 5.75 (m, 2H, H14), 6.55 (s, 4H, H2). 13C NMR
(75 MHz, CDCl3, δ): 25.8 (C8), 28.9 – 30.1
(C7,9,10,11,12) , 33.8 (C13), 54.3 (Cβ), 56.1 (C5),
71.9(C6), 73.51 (Cɣ,ɣ’), 86.0 (Cα), 103.0 (C2), 114.1
(C15), 136.3 (C1), 136.9 (C4), 139.2 (C14), 153.7
(C3).
NMR (300 MHz, CDCl3, δ): 3.10 (m, 2H, Hβ), 3.84
(s, 12H, H5), 3.90 (m, 2H, Hɣ), 4.30 (m, 2H, Hɣ’),
4.49 (m, 4H, H6), 4.74 (m, 2H, Hα), 6.05 (m, 2H,
H7), 6.58 (s, 4H, H2). 13C NMR (75 MHz, CDCl3, δ):
54.7 (Cβ) , 56.6 (C5) , 72.3 (C6), 73.5 (Cɣ), 86.3
(Cα), 103.2 (C2), 130.2 (C7), 136.6 (C1) , 137.1
(C4) , 153.9 (C3).
Polymer obtained from SYR-But (P2) (1 mol%
1
HG-II, 2 mol% 1,4-benzoquinone, 100 °C): H
NMR (300 MHz, CDCl3, δ): 2.47 (m, 4H, H7), 3.10
(m, 2H, Hβ), 3.83 (s, 12H, H5), 3.95 (m, 6H, Hɣ,6),
4.29 (m, 2H, Hɣ’), 4.72 (d, 2H, J = 2.7 Hz, Hα),
5.60 (m, 2H, H8), 6.55 (s, 4H, H2). 13C NMR (75
MHz, CDCl3, δ): 34.4 (C7), 54.3 (Cβ), 56.2 (C5),
71.9 (C6), 72.9 (Cɣ), 86.0 (Cα), 102.9 (C2), 128,2
(C8), 136.6 (C4,1), 153.6 (C3).
General Procedure for ADMET polymerizations
Mass polymerizations
Monomer (500 mg) and p-benzoquinone (2 eq.
relative to Hoveyda-Grubbs II catalyst) were
stirred at 100 °C, under vacuum for 5 min.
Hoveyda-Grubbs II catalyst (0.1-10 mol%) was
added and the reaction was continued, under
vacuum, for 4 h at 100 °C. Reaction was
quenched with 1 mL of THF and 4 drops of vinyl
ethyl ether. Product was concentrated and
further dissolved in THF (1 mL) and precipitated
in cold methanol (50 mL).
Polymer obtained from SYR-Hex (P3) (1 mol%
1
HG-II, 2 mol% 1,4-benzoquinone, 100 °C): H
NMR (300 MHz, CDCl3, δ): 1.50 (m, 4H, H8), 1.71
(m, 4H, H7), 2.03 (m, 4H, H9), 3.10 (m, 2H, Hβ),
3.83 (s, 12H, H5), 3.95 (m, 6H, Hɣ,6), 4.29 (m, 2H,
Hɣ’), 4.73 (d, 2H, J = 3,9 Hz, Hα), 5.43 (m, 2H,
H10), 6.55 (s, 4H, H2). 13C NMR (75 MHz, CDCl3,
δ): 25.9 (C8), 29.7 (C7), 32.4 (C9), 54.4 (Cβ), 56.4
(C5), 72.0 (C6), 73.4 (Cɣ), 86.1 (Cα), 103.1 (C2),
130.4 (C10), 136.5 (C1), 137.0 (C4), 153.7 (C3).
Solvent polymerization
Monomer (1 eq.) and p-benzoquinone (2 eq.
relative to Hoveyda-Grubbs II catalyst) were
dissolved in dry DCM (2 M). Hoveyda-Grubbs II
Polymer obtained from SYR-Dec (P4) P4 being
slightly soluble, we were not able to get
acceptable 1H and 13C NMR spectrum.
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