Explosive & Strained Molecular Cubes: Azahomocubane: Organic Chemistry Cubane Synthesis & Mechanisms
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- Опубліковано 1 чер 2024
- 💣 In this video, we dissect the synthesis and properties of azahomocubane, a recently synthesized homocubane 'azalogue'. Is it as unstable or explosive as the malevolent octanitrocubane? Watch to find out!
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00:00 Cube time: Azahomocubane and friends
01:12 Broke some glassware? CELL supplies!
01:57 Cubane and octanitrocubane synthesis (Eaton)
05:01 Azahomocubane synthesis
08:29 X-ray, DFT, computations, hypohomodesmotic reaction analysis
References:
- Azahomocubane: pubs.rsc.org/en/content/artic...
- Cubanes in Medicinal Chemistry: Synthesis of Functionalized Building Blocks pubs.acs.org/doi/10.1021/ol50...
- Hepta- and Octanitrocubanes: doi.org/10.1002/(SICI)1521-37...
Some recommended books on organic synthesis:
- Clayden, Greeves, Warren; Organic Chemistry (basic organic chemistry knowledge)
- Wyatt, Warren; Organic Synthesis: The Disconnection Approach (excellent introduction to retrosynthesis)
- Kurti, Czako; Strategic Applications of Named Reactions in Organic Synthesis (extensive toolkit of functional group reactions and applications thereof with common conditions)
- Nicolaou et al; Classics in Total Synthesis 1-3 (the ultimate total synthesis trilogy)
- Nicolaou; Molecules That Changed the World (the world's most important molecules and their impact on everyday life)
- Carreira, Kvaerno; Classics in Stereoselective Synthesis (compilation of the groundbreaking methods of stereoselective synthesis and application to synthesis of stereochemically complex structures) - Наука та технологія
You know you are working with some serious stuff when almost every step comes with precaution of compounds being explosive and 'gentle evaporation' over 8 months
Who's here from CELL?
Awesome channel!
smoking weed watching total synthesis, perfect evening
Watch cubane boy next
Hi Total Synthesis,
Nice video.
The ONC has a lower density than expected or predicted; so does VOD (velocity of detonation that is based on H°form and H°combustion and density; on the other hand hepta-NO2-cubane has a higher density than expected and thus a higher density than theoricized :o)
For the rest, the exchange of a N atom in place of a (°:)C-H should increase the density by at least 14/13 for that atom (MMN /(MMC+MMH) for a very close atomic volume).
Any increase of 0,1g/ccm can increase the VOD by about 350-450 m/s.
The case of adamantane (C6H12C4H4 / C10H16 / (-CH2-)6(CH)4) and hexamethylenetetramine (C6H12N4 / (-CH2-)6N4) comes to mind as analogous chemical subject.
There is of course question of an hypothetical octa-nitrogen as a special form of solid or liquid N2; what should be hell unstable and powerful High Explosive (HE)
N8 (s) --> 4 N2(g) + heat
The intermediary tetraaza-cubane could be an interesting backbone for density start, but stability calls for non adjacent N-atoms; so no hydrazine (RR1N-N-R2R3) or triazane-like or terazane-like into the structure; instead a cubane with on each 6 side (face) two N atoms and two CH (C4H4N4); that way it would optimise the separation of the N atoms into space and make them "identical" by rotation of the cube; it will also improve a bit the molecuar stability.
As a matter of facts; it would be as if H-C#N (hydrogen cyanide) was polymerized...
4 H-C#N --> (HC)4N4
This polymer might be highly endothermic from its elements (thus high chance of non existance); cyanhydric acid being highly toxic, but also, unstable, liable to detonate back to its elements, and burning with one of the hottest flames...
The later sequence of compounds burning with a flame temperature into oxygen starting above 3200°C up to 4900°C
H-C#C-H < H-CC#N < NC#C-C#N < H-C#C-C#C-H < N#C-C#C-C#N
Such linear polymers tends to becomes less stable with lenght and (hyper-)conjugated tripple bonds...acetylen must be pressurized with aceton for example to allow for a safer use of blow troch.
This gives an idea of the energy stored into the chemical links (or into this very example of cubane into the strain).
Just as a side note pagodane (C20H20) what is also a hydrocarbon has already a density of 1,629 g/ccm (cubane is at 1,29 g/ccm); and we were all told that hydrocarbons float onto water ;o);
Pagodane has almost the density of TNT (1,654 g/ccm) while it is "only" an hydrocarbon: nitrating it will of course push its density to higher grounds.
Now simply by making a little arithmetic from cubane that is at 1,29 g/ccm but that can go up close to 2,00 g/ccm when octanitro nitrified; this makes a density increase of 2,00/1,29= 1,55; so pagodane if fully nitrated could go to 2,52 g/ccm what would mean a VOD into the range of 12,625 km/s leaving TNT, PETN, ETN, MHN, RDX, HMX, ONC far behind.
Kind regards.
PHZ
(PHILOU Zrealone from the Science Madness forum)
Thanks for all that info! And damn, I never thought of nitrated pagodane
@@totalsynthesis
So much unexplored possibilities ;o)
@@totalsynthesis
I could have added this comment to your pagodane YT tread that I viewed yesterday; but I rather leave it down here closer to my comment here a little up :o)
Pagodane is C20H20; if fully nitrated; it would lead to C20(NO2)20 and would belong to the POB (perfect oxygen balanced High Energetic Materials family; with OB = 0; thus displaying the best energetical output for H2O (inexistant here thus not "tempering the heat of explosion"), N2(g) and CO2(g) while burning); family in which there are also hexanitrobenzen, trinitro-sym-triazine, octanitrocubane...
C6(NO2)6 --> 6 CO2(g) + 3 N2(g) + heat
C3N3(NO2)3 --> 3 CO2(g) + 3 N2(g) + heat
C8(NO2)8 --> 8 CO2(g) + 4 N2(g) + heat
C20(NO2)20 --> 20 CO2(g) 10 N2(g) + heat
ONC and HNB have densities in the range of 2,00 g/ccm and VOD of 10.000 m/s (yes 10km/s)
Dodecanitropagodane should be up by a bit (I could use more pushed calculations for its density and VOD; but what I wrote muste be close enough without that).
A tiny note for pagodane;
It is a caged structure; pretty undeformable molecularly speaking; but when looking at the structure, it is a reflection image of various planes within the molecule (so the molecule is superimposable by rotations and the result is an identical molecule despite not the same C or H atom.
When looking at the central square; one could imagine a 90° twist to make another type of pagodane (a bit like hands joined for prayer and hand ready for clapping at a concert).
About cubane, it can be also made to be a cubane-oct-ol (C8(-OH)8) thus displaying only "tertiary alcohol"; and theorically it could be nitrated (certainly not by conventional ways) to make C8(ONO2)8.
The compound would be overoxygenated like NG, ETN, XPN, MHN, SHN.
C8(ONO2)8 --> 8 CO2(g) + 4 N2(g) + 2 O2(g) + heat (positive OB)
This extra O2 can be used to burn fuel and maximize energy output (heat and gas).
Further pushing the theory; one could imagine an octa-perchloric ester because I have the feeling that tertiary alcohols may stabilise perchloric esters vs secondary or primary what often decompose under the slightest stimulus; probably has it to do with the presence of C-H; see the stability and organic chemistry use of (CH3)3C-OCl
(CH3)2CH-OCl --> (CH3)2C=O + HCl(g) + heat (explosion risk for no apparent reason)
CH3-OCl --> CH2=O(g) + HCl(g) + heat (explosion risk for no apparent reason)
This is even more dramatic for methyl perchlorate or isopropyl perchlorate
So here C8(OClO3)4 could be a target molecule, but with a too positive OB that needs to be maximized by conterbalancing fuel (polymer, C(s), (CN)n or negative OB HE)
C8(OClO3)8 --> 8 CO2(g) + 4 Cl2(g) + 8 O2(g) + heat
Regards,
PHZ
(PHILOU Zrealone from the Science Madness forum)
Some of the most elegant chemistry I've ever seen for a moderately basic compound.. Very easy to see the molecules/reaction schemes very easy to follow 👍
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Correction to 4:20 (nice timing btw): Just noticed I drew this one incorrectly - that bridged cyclobutanone is the most typical intermediate but it's only real for a normal ring contraction (typical Favorskii rearrangement). In the cubane case however, the alpha position is not enolizable (the double bond at bridge head violates Bredt's rule) so instead the mechanism proceeds via a "quasi Favorskii" rearrangement where hydroxide addition occurs first, and triggers migration of the alkyl group to displace the halide.
I finally got around to watching... , Awesome!
You getting your PhD soon?
And ,
What is NIt3? (In the decarboxylation step)
Thanks! Sorry which step exactly? No PhD pursuit here :)
Sorry meant NEt3 , on the 6th minute .
Sorry if this is a silly question, but does the Me from the molecule in the beginning stand for something special or is it just an abbreviation of methyl?
Just methyl
I tried stabilizing this structure by QM/MM energy minimization. My computer exploded.
😂
1:22 Yes, I have....but not THAT one!
my mind got stuck too long for comfort on PEE A TON resercher :/
How much mj/kg is it?
Where Hamilton?
The point is not to know but to understand. And you make allot jump out the screen and understandworthy
Arrgh!! You showed a direct displacement at a carbonyl instead of a tetrahedral intermediate!
Drawing all arrows is a nuisance!
@@totalsynthesis Just draw a double-headed arrow from the carbon to the oxygen of the carbonyl and all will be well!
First!
🔥🔥🔥
CL-20 is a heterocyclic, but it's a pretty amazing compound. It too has a good synthesis. Also, I wonder if aminocubane has antiviral effects like aminoadanatine?
en.wikipedia.org/wiki/Hexanitrohexaazaisowurtzitane
Ye thats a nice one! And quite short synthesis!