Synthesis of Oxygen Absorbing Crystal (from cobalt)

relevant username much?! don't make me regret this


Edit(woelen): Cmos6667 asked me to remove downloadable file, due to copyright issues.

[Edited on 16-6-15 by woelen]

Quote: Originally posted by cmos6667

right, that's what I thought! but seriously though, this could be useful for making inert environment for reactions

Here's what you could do: you know how cigarettes have a lot of tar and ash? That's because of incomplete combustion - increase the oxygen and voilà, low tar cigarettes

Quote: Originally posted by cmos6667

Here's what you could do: you know how cigarettes have a lot of tar and ash? That's because of incomplete combustion - increase the oxygen and voilà, low tar cigarettes

Supa Villan, a more detailed documentation of synth is on the last two pages of document. Here is the beginning of it. You are going to need bpbpH which I think stands for bipyrrolidine, but I am not 100% sure. You could easily look it up, after all you have access nearly infinite information right at your fingertips!

Sorry I can't login as SupaVillain, password issues and not receiving emails within temp password....

anyways I've found the synthesis for bpbpH,(aka Hbpbp?) which is necessary for pretty much all the syntheses.


bpbpH SYNTHESIS

2,6-Bis{[bis(2-pyridylmethyl)amino]methyl}-4-tert-butylphenol,
Hbpbp
4-tert-Butylphenol (1.994 g, 0.0133 mol) and p-formaldehyde
(1.55 g, 0.0517 mol) were suspended in ethanol (25 cm3
). A
solution of N,N-bis(2-pyridylmethyl)amine (10.0 g, 0.0503 mol)
in H2O (50 cm3
) was added and the slightly yellow suspension
was stirred at reflux temperature for 3 d. The two-phase reaction
mixture was allowed to cool to room temperature and was
then partitioned between CH2Cl2 (200 cm3
) and H2O (100 cm3
).
The aqueous phase was extracted with CH2Cl2 (3 × 50 cm3
) and
the combined organic phase dried over anhydrous Na2SO4.
After removal of the solvent, the resulting brown oil was chromatographed
on a silica gel column using acetone as eluent
affording the crude product (5.86 g, 77% yield) as a slightly
yellow solid (m.p. = 122–126 8C). Recrystallization from diethyl
ether–light petroleum resulted in the pure product as white
crystals (60% relative to the crude product, m.p. = 123 8C). 1
H
NMR (250 MHz): d 1.27 (s, 9 H), 3.82 (s, 4 H), 3.90 (s, 8 H),
7.08 (m, 4 H), 7.19 (s, 2 H), 7.48–7.61 (m, 8 H), 8.52 (m, 4 H),
10.80 (s, 1 H). 13C-{1
H} NMR (62 MHz): d 31.57 (s), 33.85 (s),
55.12 (s), 59.88 (s), 121.81 (s), 122.84 (s), 123.16 (s), 125.85 (s),
136.33 (s), 140.79 (s), 148.83 (s), 153.43 (s), 159.39 (s) (Found:
C, 75.49; H, 7.04; N, 14.67. Calc. for C36H40N6O: C, 75.23; H,
6.96; N, 14.48%). FAB mass spectrum: m/z 572 (0.5, M1), 93
(100%, C5H4NCH2
1)

(from "Dinuclear iron(III)–metal(II) complexes as structural core models for
purple acid phosphatases †"
Morten Ghiladi, Christine J. McKenzie, Anke Meier, Annie K. Powell, Jens Ulstrup, and Sigrid Wocadlo
J. Chem. Soc., Dalton Trans., 1997, Pages 4011–4018)

@halogen; I didn't have any picoline at the time I started though I was keeping an eye open for it and still am but I did track down some picolinamide which is rare, the 3 carboxamide is nicotinamide but is no use in this case. Another problem with the chloromethyl group to amine is getting the right amine! You can get the mono amine by using the Delepine or the K-phthalamide reactions but getting the the secondary amine is more difficult, you tend to get mixture which then has to be separated. The advantage of the enamine route was that it only gives a secondary amine (in theory). So while you are right about pyridylmethyl chloride being a simpler route to the monoamine, the secondary amine I am less sure about and I also have other uses for pyridine-2-carboxaldehyde (I have already posted the preparation of pyridoin and I am now trying to convert it to 2-pyridil (the pyridine analogue of benzil)) so it made sense to purchase some when the opportunity arose.

It may be possible to separate the mixture of pyridylmethyl amines that results from the interaction of ammonia and the pyridylmethyl chloride in a manner similar to that used to separate aniline, methylaniline and dimethylaniline but that's more research and experimentation.

As with most amateurs the route I choose is to a large extent dictated by what is available to me! If only we could still pick up the Sigma A or TCI catalogue and just buy what we need ... Ahhhh Dreams

An interesting material however i dont think equipment is the issue.

http://pubs.rsc.org/en/content/articlepdf/2014/sc/c4sc01636j...




This i think it bpbpH, to which i estimated the structure based on the following paper:
https://www.sciencedirect.com/science/article/pii/S002016930...

It is this compound that i think is the troublesome part.
Co(BF4)2.6H2O i think could be prepared by reacting hydrofluoric acid with boric acid to form fluoroboric acid, which could then be neutralized with cobalt hydroxide and then worked up.

I originally tried to draw the entire {(bpbp)Co2II(NO3)}2(NH2bdc)2.2H2O ligand complex on chemsketch however it turned into a bit of an illogical mess and while it does resemble the compound from the paper, i think the structures in the paper do a much better job of illustrating it .


[Edited on 23-1-2018 by Assured Fish]