Syntese av TADBIW : 2,6,8,10-tetraacetyl-4,10-dibenzyl-2,4,6,8,10,12-heksaazaisowurtzitane
FFI-Report
2008
This publication is only available in Norwegian
About the publication
Report number
2008/02328
ISBN
978-82-464-1480-5
Size
2.8 MB
Language
Norwegian
TADBIW (2,6,8,12-tetraacetyl-4,10-dibenzyl-2,4,6,8,10,12-hexaazaisowurtzitane) have been
synthesized from HBIW (2,4,6,8,10,12-hexabenzyl-2,4,6,8,10,12-hexaazaisowurtzitane) by
hydrogenation in acetic acid anhydride catalyzed by palladium catalyst. In addition has bromobenzene
been used as catalyst and in most cases N, N-dimethylformamide (DMF) as co-solvent.
Different methods to produce TADBIW have been studied as by using different co-solvent in
addition to acetic acid anhydride. In the first experiments where acetic acid anhydride was used
both as reagent and solvent gave satisfactory yields. However, since TADBIW is soluble in acetic
acid anhydride it was difficult to isolate and produce pure TADBIW. By using the co-solvent
DMF TADBIW together with the Pd catalyst can be isolated from the reaction mixture by
filtration. This gives a purer product and a material that is easier to work with. The last solvent
that was tried was 1-methyl-2-pyrrolidone (NMP). In addition to moderate yield gave NMP the
same problems to isolate TADBIW as acetic acid anhydride, since TADBIW is soluble in NMP.
Three different Pd catalysts have been used in the hydrogenation of HBIW. Introductorily water
wet Pd and PdOH2 catalysts on activated carbon from Sigma-Aldrich were used. Both catalysts
gave satisfactory yields, however since we needed large amount of the catalyst was the 10 g units
that Sigma-Aldrich could offer to expensive, and we did change to Degussa as supplier. They
deliver catalyst in kilogram quantities to a cost not significant different from the cost of SigmaAldrich
10 g quantity. The catalyst supplied by Degussa had the trade name: water wet Palladium
catalyst 5-10 % Pd on activated carbon, E 101 NE/W 10 %.
Pure TABDIW from the syntheses performed in DMF was obtained by repeatedly extractions
with chloroform of the solid fraction after filtering the reaction mixture. The extractions were
repeated until only black catalyst remained in the filter.
For production of TADBIW to be used for producing CL-20 is isolation of pure TADBIW not
necessary. A product containing TADBIW and Pd catalyst can be used directly in the synthesis of
TADFIW (2,6,8,12-tetraacetyl-4,10-diformyl-2,4,6,8,10,12-hexaazaisowurtzitane) after poisoning
compounds for the catalyst have been removed. By making a slurry of the solid mixture of
TADBIW/Pd catalyst by adding either DMF or ethanol and perform a new filtration followed by
drying, is a product obtained that can be hydrogenated in formic acid to TADFIW with out
problems.
A large number of syntheses in 270 g scale have been performed in a 2-litre Parr glass reactor. As
co-solvent has DMF been used giving a yield of TADBIW/ Pd catalyst after purification and
drying that was stable and on average 79 %.
synthesized from HBIW (2,4,6,8,10,12-hexabenzyl-2,4,6,8,10,12-hexaazaisowurtzitane) by
hydrogenation in acetic acid anhydride catalyzed by palladium catalyst. In addition has bromobenzene
been used as catalyst and in most cases N, N-dimethylformamide (DMF) as co-solvent.
Different methods to produce TADBIW have been studied as by using different co-solvent in
addition to acetic acid anhydride. In the first experiments where acetic acid anhydride was used
both as reagent and solvent gave satisfactory yields. However, since TADBIW is soluble in acetic
acid anhydride it was difficult to isolate and produce pure TADBIW. By using the co-solvent
DMF TADBIW together with the Pd catalyst can be isolated from the reaction mixture by
filtration. This gives a purer product and a material that is easier to work with. The last solvent
that was tried was 1-methyl-2-pyrrolidone (NMP). In addition to moderate yield gave NMP the
same problems to isolate TADBIW as acetic acid anhydride, since TADBIW is soluble in NMP.
Three different Pd catalysts have been used in the hydrogenation of HBIW. Introductorily water
wet Pd and PdOH2 catalysts on activated carbon from Sigma-Aldrich were used. Both catalysts
gave satisfactory yields, however since we needed large amount of the catalyst was the 10 g units
that Sigma-Aldrich could offer to expensive, and we did change to Degussa as supplier. They
deliver catalyst in kilogram quantities to a cost not significant different from the cost of SigmaAldrich
10 g quantity. The catalyst supplied by Degussa had the trade name: water wet Palladium
catalyst 5-10 % Pd on activated carbon, E 101 NE/W 10 %.
Pure TABDIW from the syntheses performed in DMF was obtained by repeatedly extractions
with chloroform of the solid fraction after filtering the reaction mixture. The extractions were
repeated until only black catalyst remained in the filter.
For production of TADBIW to be used for producing CL-20 is isolation of pure TADBIW not
necessary. A product containing TADBIW and Pd catalyst can be used directly in the synthesis of
TADFIW (2,6,8,12-tetraacetyl-4,10-diformyl-2,4,6,8,10,12-hexaazaisowurtzitane) after poisoning
compounds for the catalyst have been removed. By making a slurry of the solid mixture of
TADBIW/Pd catalyst by adding either DMF or ethanol and perform a new filtration followed by
drying, is a product obtained that can be hydrogenated in formic acid to TADFIW with out
problems.
A large number of syntheses in 270 g scale have been performed in a 2-litre Parr glass reactor. As
co-solvent has DMF been used giving a yield of TADBIW/ Pd catalyst after purification and
drying that was stable and on average 79 %.
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