M.M. Shmakov et al. / Journal of Organometallic Chemistry 899 (2019) 120889
7
F3) ¼ 16.4 Hz, 5J(F4, F6) ¼ 5.1 Hz, 6J(F4, F7) ¼ 1.2 Hz, 1F, F4), ꢀ140.1
(ddddd, 3J(F8, F7) ¼ 16.3 Hz, 5J(F8, F5) ¼ 15.9 Hz, 5J(F8, F2) ¼ 9.3 Hz,
6J(F8, F3) ¼ 3.4 Hz, 5J(F8, F4) ¼ 5.3 Hz, 1F, F8), ꢀ145.0 (dddddd, 4J(F5,
F4) ¼ 69.5 Hz, 3J(F5, F6) ¼ 18.2 Hz, 5J(F5, F8) ¼ 15.7 Hz, 5J(F5,
F3) ¼ 5.0 Hz, 6J(F5, F2) ¼ 4.8 Hz, 4J(F5, F7) ¼ 2.4 Hz, 1F, F5), ꢀ153.6
(ddddd, 3J(F7, F8) ¼ 17.0 Hz, 3J(F7, F6) ¼ 19.3 Hz, 7J(F7, F3) ¼ 9.0 Hz,
6J(F7, F4) 4.5 Hz, 4J(F7, F5) ¼ 2.3 Hz, 1F, F7), ꢀ155.0 (dddddd, 3J(F3,
F2) ¼ 22.2 Hz, 3J(F3, F4) ¼ 17.0 Hz, 7J(F3, F7) ¼ 8.6 Hz, 5J(F3,
F5) ¼ 5.3 Hz, 6J(F3, F6) ¼ 5.3 Hz, 6J(F3, F8) ¼ 3.0 Hz, 1F, F3), ꢀ155.2
(dddddd, 3J(F6, F7) ¼ 18.0 Hz, 3J(F6, F5) ¼ 16.4 Hz, 7J(F6, F2) ¼ 8.0 Hz,
allowed to warm to 20 ꢁC within 1 h and worked up as described
above to yield yellow oil (91 mg) contained 0.24 mmol (80%) of 5
(
19F NMR).
Analytically pure silylnaphthalene 5 was obtained by crystalli-
zation from ethanol.
4.6.4.1. 2-Trimethylsilylheptafluoronaphthalene 5. 1H NMR (ether):
d
¼ 0.45 (s, 9H). 19F NMR (ether):
d
¼ ꢀ102.0 (dd, 4J(F1, F8) ¼ 73.8 Hz,
5J(F1, F4) ¼ 20.1 Hz, 1F, F1), ꢀ124.3 (md, 3J(F3, F4) ¼ 19.2 Hz, 1F,
F3), ꢀ144.2 (dddddd, 4J(F8, F1) ¼ 73.8 Hz, 3J(F8, F7) ¼ 17.5 Hz, 5J(F8,
F5) ¼ 15.7 Hz, 5J(F8, F4) ¼ 4.1 Hz, 6J(F8, F3) ¼ 4.1 Hz, 4J(F8, F6) ¼ 2 Hz,
1F, F8), ꢀ147.6 (dddddd, 4J(F5, F4) ¼ 57.0 Hz, 3J(F5, F6) ¼ 17.3 Hz, 5J(F5,
F8) ¼ 15.7 Hz, 5J(F5, F3) ¼ 4.6 Hz, 5J(F5, F1) ¼ 2 Hz, 4J(F5, F7) ¼ 2 Hz, 1F,
F5), ꢀ151.3 (ddddd, 4J(F4, F5) ¼ 57.0 Hz, 3J(F4, F3) ¼ 20.1 Hz, 5J(F4,
F1) ¼ 19.1 Hz, 5J(F4, F6) ¼ 4.2 Hz, 5J(F4, F8) ¼ 4.1 Hz,1F, F4), ꢀ154.6 (m,
1F, F6), ꢀ157.6 (ddddd, 3J(F7, F6) ¼ 18.9 Hz, 3J(F7, F8) ¼ 17.3 Hz, 7J(F7,
F3) ¼ 7.5 Hz, 5J(F7, F1) ¼ 4.1 Hz, 4J(F7, F5) ¼ 1.3 Hz, 1F, F7). 1H NMR
5
6J(F6, F3) ¼ 6.4 Hz, J(F6, F4) ¼ 4.9 Hz, 4J(F6, F8) ¼ 3.2 Hz, 1F, F6).
4.4. Attempted reaction of C6F5H with EtMgBr
The solution of C6F5H (142 mg, 0.84 mmol) in ether (1 mL) was
treated with 0.42 M EtMgBr (2 mL, 0.84 mmol) at 22 ꢁC for 3 h. No
reaction occurred (19F NMR).
(CCl4):
d
d
¼ 0.45 (t, 5J(H, F1,3) ¼ 1.5 Hz, 9H). 19F NMR (CCl4):
4.5. Attempted reaction of C10F7H with EtMgBr
¼ ꢀ103.3 (dd, 4J(F1, F8) ¼ 73.8 Hz, 5J(F1, F4) ¼ 20.3 Hz, 1F,
F1), ꢀ125.0 (md, 3J(F3, F4) ¼ 18.6 Hz, 1F, F3), ꢀ144.2 (ddddd, 4J(F8,
F1) ¼ 73.8 Hz, 3J(F8, F7) ¼ 16.8 Hz, 5J(F8, F5) ¼ 16.8 Hz, 5J(F8,
F4) ¼ 3.3 Hz, 6J(F8, F3) ¼ 3.3 Hz, 1F, F8), ꢀ147.6 (dddd, 4J(F5,
F4) ¼ 57.0 Hz, 3J(F5, F6) ¼ 16.8 Hz, 5J(F5, F8) ¼ 16.8 Hz, 5J(F5,
F3) ¼ 4.5 Hz, 1F, F5), ꢀ151.3 (ddddd, 4J(F4, F5) ¼ 57.0 Hz, 3J(F4,
F3) ¼ 19.8 Hz, 5J(F4, F1) ¼ 19.8 Hz, 5J(F4, F6) ¼ 4.0 Hz, 5J(F4,
F8) ¼ 4.0 Hz, 1F, F4), ꢀ154.4 (m, 1F, F6), ꢀ157.6 (dddd, 3J(F7,
F6) ¼ 20.0 Hz, 3J(F7, F8) ¼ 16.8 Hz, 7J(F7, F3) ¼ 7.4 Hz, 5J(F7,
The solution of 1 and 2 (1:4) (82 mg, 0.32 mmol) in ether (1 mL)
was treated with 0.54 M EtMgBr (1 mL, 0.54 mmol) at 22 ꢁC for 5 h.
No reaction occurred (19F NMR).
4.6. Reaction of 2-heptafluoronaphthyllithium with ClSiMe3
4.6.1. A flame-dried flask equipped with a magnetic bar and septa
was charged with 2 (254 mg, 1.00 mmol) and flushed with dry argon
After the addition of ether (25 mL) the solution was cooled
to ꢀ70 ꢁC (bath) and stirred for 15 min. Then 2.5 M BuLi in hexanes
(0.5 mL, 1.25 mmol) was injected slowly and the solution was stir-
red for 4 h before the injection of ClSiMe3 (0.200 mL, 1.57 mmol).
After 10 min it was warmed up to 20 ꢁC within 20 min and hydro-
lyzed with 5% HCl (1 mL). The organic phase was separated, the
aqueous phase extracted with ether (2 ꢃ 3 mL), the merged extract
washed with brine and dried with MgSO4. The 19F NMR spectrum of
the extract showed the formation of 5 (0.80 mmol) that was ob-
tained by removing of volatiles on evaporator.
F1) ¼ 3.7 Hz, 1F, F7). 29Si{H} NMR (CDCl3):
d
¼ ꢀ0.92 (ddd, 4.5, 3.1
and 1.6 Hz). Found, %: C 48.0, H 2.78, F 40.6. C13H9F7Si. Calc. %: C
47.85, H 2.78, F 40.76.
4.7. Reaction of 1-H-heptafluoronaphthalene with BuLi and
ClSiMe3
The solution of 1 (254 mg, 1.00 mmol) in ether (25 mL) was
cooled to ꢀ70 ꢁC (bath) and stirred for 30 min. Then 2.5 M BuLi in
hexanes (0.5 mL, 1.25. mmol) was injected slowly. After
4 h at ꢀ70 ꢁC chlorotrimethylsilane (0.200 mL, 1.57 mmol) in ether
(1 mL) was injected, the solution was stirred for 10 min and
warmed up to 20 ꢁC within 20 min. It was treated with 5% HCl
(1 mL), the organic phase was separated, the aqueous phase
extracted with ether (2 ꢃ 3 mL), the merged extract washed with
brine (10 mL) and dried with MgSO4. Evaporation of the volatiles
gave yellow oil consisted of 1 (0.04 mmol), 1-H-3-C4H9eC10F6
(0.14 mmol), 1-H-6-C4H9eC10F6 (0.24 mmol), 1-H-7-C4H9eC10F6
4.6.2. The reaction was performed by the same manner using 1.6 M
t-BuLi in pentanes (1.12 mmol)
The 19F NMR spectrum of the extract showed the formation of 5
(0.84 mmol). After the solvent evaporation silylnaphthalene 5 was
isolated.
(0.38 mmol), and 1-H-3,7-(C4H9)2C10F5 (0.09 mmol) (GSMS and 19
NMR).
F
4.6.3. A reactor (see above) was charged with ether (10 mL) and
diisopropylamine (0.500 mL, 3.57 mmol)
The solution was cooled to ꢀ60 ꢁC (bath), stirred for 30 min, and
2.5 M BuLi in hexanes (1.4 mL, 3.5 mmol) was injected slowly and
stirred for 30 min. In another flask a solution of 2 (254 mg,
1.00 mmol) in ether (22 mL) was cooled to ꢀ60 ꢁC, and the solution
of LDA (3.1 mL, 1.1 mmol) was syphoned into it at ꢀ60 ꢁC under
pressure of dry argon. The reaction mixture was stirred at this
temperature for 4 h, treated with chlorotrimethylsilane (0.200 mL,
1.57 mmol), and the reaction mixture was worked up as described
above. The 19F NMR spectrum of the extract showed the formation
of 5 (0.94 mmol). After the solvent evaporation silylnaphthalene 5
was isolated.
4.7.1. 1-H-3-butylhexafluoronaphthalene 7
19F NMR (acetone):
d{
d
*}1 ¼ ꢀ112.3 {e113.3} (m, 1F, F2), ꢀ117.3
{e116.5} (dd, 4J(F4, F5) ¼ 61 Hz, 4J(F4, F2) ¼ 8 Hz, 1F, F4), ꢀ146.3
{e147.2} (ddd, 4J(F5, F4) ¼ 61 Hz, 3J(F5, F6) ¼ 16 Hz, 5J(F5, F8) ¼ 16 Hz,
1F, F5), ꢀ148.9 {e149.9} (dd, 5J(F8, F5) ¼ 16 Hz, 3J(F8, F7) ¼ 16 Hz, 1F,
F8), ꢀ157.5 {e157.5} (dd, 3J(F7, F6) ¼ 18 Hz, 3J(F7, F8) ¼ 16 Hz, 1F,
F7), ꢀ159.8 {e159.7} (dddd, 3J(F6, F7) ¼ 18 Hz, 3J(F6, F5) ¼ 16 Hz,
7J(F6, F2) ¼ 7 Hz, 4J(F6, F8) ¼ 4 Hz, 1F, F6).
4.7.2. 1-H-6-butylhexafluoronaphthalene 8
19F NMR (acetone):
d{d
*}1 ¼ ꢀ123.8 {e123.7} (dd, 4J(F5,
F4) ¼ 61 Hz, 5J(F5, F8) ¼ 19 Hz, 1F, F5), ꢀ131.1 {e131.5} (m, 1F,
F2), ꢀ139.5 {e140.0} (dd, 4J(F4, F5) ¼ 61 Hz, 3J(F3, F4) ¼ 17 Hz, 1F,
F4), ꢀ140.5 {e139.3} (d, 3J(F7, F8) ¼ 18 Hz, 1F, F7), ꢀ151.7 {e153.4}
4.6.4. 2.5 M BuLi in hexanes (0.4 mL, 0.34 mmol) was dissolved in
ether (2.5 mL) and injected into cold (ꢀ80 ꢁC) solution of 2-C10F7Br
(100 mg, 0.30 mmol) in ether (6.5 mL)
The reaction mixture was stirred for 1 h, a solution of chloro-
trimethylsilane (0.39 mmol) in 0.25 mL of ether was added. After
20 min cooling bath was removed, the reaction mixture was
1
d
* is chemical shift calculated according to the incremental scheme.