• Identification

  Reaxys ID:	4824909
  Chemical Names:	1,7-bis(4′-methyl-2,2′-bipyridyl-4-yl)heptane, 1,7bis-(4′-methyl-2,2′-bipyridyl-4-yl)heptane, 1,7-Bis(4′-methyl-2,2′-bipyrid-4-yl)heptane, 1,7-bis[4(4′-methyl-2,2′-bipyridyl)]heptane, bis[4-(4′-methyl-(2,2′-bipyridyl))]-1,7-heptane, bis[4(4′-methyl-2,2′-bipyridyl)]-1,7-heptane
  CAS Registry Number(s):	135804-29-4	Substance type:	heterocyclic
  Molecular Formula:	C29H32N4	Linear Structure Formula:	CH3C5H3NC5H3N(CH2)7C5H3NC5H3N(CH3)
  Molecular Weight:	436.6	No of references:	9
  InChIKey:	JPSDVMCWHMMGRO-UHFFFAOYSA-N

• Identification

  Reaxys ID:	17244404
  Chemical Names:	bis[4′-(4-methyl-2,2′-bipyridyl)]-1,12-dodecane, 1,12-bis-(4′-methyl-2,2′-bipyridyl-4-yl)dodecane, 1,12-bis[4-(4′-methyl-2,2′-bipyridyl)]dodecane, bis[4-(4′-methyl-(2,2′-bipyridyl))]-1,12-dodecane, bis[4(4′-methyl-2,2′-bipyridyl)]-1,12-dodecane
  CAS Registry Number(s):	144290-33-5	Substance type:
  Molecular Formula:	C34H42N4	Linear Structure Formula:	CH3C5H3NC5H3N(CH2)12C5H3NC5H3N(CH3)
  Molecular Weight:	506.734	No of references:	11
  InChIKey:	KCCVTPNQXUKKEL-UHFFFAOYSA-N

• Identification

  Reaxys ID:	21115756
  Chemical Names:	bis[4′-(4-methyl-2,2′-bipyridyl)]-1,16-hexadecane, bis[4-(4′-methyl-(2,2′-bipyridyl))]-1,16-hexadecane, bis[4(4′-methyl-2,2′-bipyridyl)]-1,16-hexadecane
  CAS Registry Number(s):	1269508-96-4	Substance type:
  Molecular Formula:	C38H50N4	Linear Structure Formula:	CH3C5H3NC5H3N(CH2)16C5H3NC5H3N(CH3)
  Molecular Weight:	562.842	No of references:	6
  InChIKey:	KMKDQZOLRUIKIB-UHFFFAOYSA-N

需要以下3个不同碳链长度的化合物各2g     n=7,12,16

参考文献

The syntheses of the linking ligands bbn (n = 7, 12 and 16; A) were performed in a
similar manner to that reported in the literature with several modifications.5,6 To prepare
mono-lithiated 4,4′-dimethyl-2,2′-bipyridine (Me2bpy), Me2bpy (1.6 g, 8.7 mmol,
Sigma-Aldrich) was dissolved in dry THF (50 mL) under an inert atmosphere (N2) and
cooled to -78 ºC. A solution of lithium diisopropylamide (LDA, 4.8 mL, 9.6 mmol, 2.0
M solution, Sigma-Aldrich) in THF (10 mL) was added dropwise over the course of 30
min, and the mixture stirred for a further 1.5 h at -78 ºC, during which time the colour
turned from white to dark brown-red. This mixture was then brought to -10 ºC over the
course of 30 min.
For bb7, 1,5-dibromopentane (0.59 mL, 4.3 mmol, Sigma-Aldrich) was added dropwise
to a mono-lithiated Me2bpy (27 mmol) suspension at room temperature, and stirred for
20 h. The solution was quenched with methanol and neutralized with methanol-HCl,
then diluted with water (100 mL) and extracted with dichloromethane (DCM). The
extract was dried with MgSO4 and evaporated. The residue was placed on a silica-gel
column and eluted with a mixture of CH2Cl2-acetone (9:1, v/v) to give a white solid.
Recrystallization from ethanol yielded 0.43 g (61%) product. 1H NMR (CDCl3 = 8.53
(dd, 4H), 8.21 (s, 4H), 7.13 (d, 4H), 2.68 (t, 4H), 2.44 (s, 6H), 1.68 (q, 4H), 1.37 (m, 6H)

For bb12 and bb16, 1,10-dibromodecane and 1,14-dibromotetradecane (4.3 mmol),
respectively, was injected into the suspension of mono-lithiated Me2bpy. The reaction
was brought to room temperature and left to stir under an inert atmosphere (N2). Within
the first 2 h of the reaction, a colour change from dark-red to dark-green to grey-green
then to cream was observed. After a further 24 h the reaction was quenched with water
(10 mL), and the product extracted into diethyl ether (3 × 80 mL) and DCM (1 × 80
mL). The organic layers were combined, washed with water (1 × 50 mL), dried over
anhydrous Na2SO4, filtered, and then evaporated to dryness in vacuo to yield a fluffy
white powder in each case.
The crude product was dissolved in a minimal volume of DCM and then loaded onto a
silica gel column (230 400 mesh, 3 cm diam. × 10 cm). The unreacted dibromoalkane
(pale yellow band) and Me2bpy (yellow band) were eluted using DCM. Bb12 (yellow
band) and side products (yellow brown band, suspected to be due to the di-lithiation of
Me2bpy) were gradient-eluted using a 1 10% (v/v) methanol-DCM mixture. The purity
and contents of each fraction was determined by TLC using methanol-DCM (3:17, v/v)
as the mobile phase. The purest fractions were combined and the solvent was removed
in vacuo to yield 1.54 g (34%) fluffy white solids. 1H NMR (CDCl3) = 8.55 (dd, 4H),
8.22 (s, 4H), 7.13 (dd, 4H), 2.69 (t, 4H), 2.44(s, 6H), 1.26 1.69 (m, 20H). Bb16 was
recrystallized from boiling DCM after extraction to yield 0.38 g (16%) product. 1H
NMR (CDCl3) = 8.58 (dd, 4H), 8.32 (s, 4H), 7.19 (dd, 4H), 2.71 (t, 4H), 2.47 (s, 6H),
1.25 1.70 (m, 28H).