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The Magic of Cubane!

By DR ANTHONY MELVIN CRASTO

Cubane[1]

Pentacyclo[4.2.0.02,5.03,8.04,7]octane CAS 277-10-1 Cubane (C8H8) ! a !ynt"et c "y#$oca$bon %olecule t"at con! !t! o& e '"t ca$bon ato%! a$$an'e# at t"e co$ne$! o& a cube, ( t" one "y#$o'en ato% attac"e# to eac" ca$bon ato%. A !ol # c$y!tall ne !ub!tance, cubane ! one o& t"e Platon c "y#$oca$bon!. )t (a! & $!t !ynt"e! *e# n 1+,4 by P" l - .aton, a -$o&e!!o$ o& c"e% !t$y at t"e /n 0e$! ty o& C" ca'o.[2] 1e&o$e .aton an# Cole2! (o$3, $e!ea$c"e$! bel e0e# t"at cub c ca$bon-ba!e# %olecule! coul# not e4 !t, becau!e t"e unu!ually !"a$- +0-#e'$ee bon# n' an'le o& t"e ca$bon ato%! (a! e4-ecte# to be too " '"ly !t$a ne#, an# "ence un!table. 5nce &o$%e#, cubane ! 6u te 3 net cally !table, #ue to a lac3 o& $ea# ly a0a lable #eco%-o! t on -at"!. 7"e ot"e$ Platon c "y#$oca$bon! a$e #o#eca"e#$ane an# tet$a"e#$ane.

Cubane an# t! #e$ 0at 0e co%-oun#! "a0e %any %-o$tant -$o-e$t e!. 7"e +0-#e'$ee bon# n' an'le o& t"e ca$bon ato%! n cubane %ean! t"at t"e bon#! a$e " '"ly !t$a ne#. 7"e$e&o$e, cubane co%-oun#! a$e " '"ly $eact 0e, (" c" n -$ nc -le %ay %a3e t"e% u!e&ul a! " '"-#en! ty, " '"-ene$'y&uel! an# e4-lo! 0e! (&o$ e4a%-le, octan t$ocubane an# "e-tan t$ocubane). Cubane al!o "a! t"e " '"e!t #en! ty o& any "y#$oca$bon, &u$t"e$ cont$ but n' to t! ab l ty to !to$e la$'e a%ount! o& ene$'y, (" c" (oul# $e#uce t"e ! *e an# (e '"t o& &uel tan3! n a $c$a&t an# e!-ec ally $oc3et boo!te$!. 8e!ea$c"e$! a$e loo3 n' nto u! n' cubane an# ! % la$ cub c %olecule! n%e# c ne an# nanotec"nolo'y.

Synthesis
7"e o$ ' nal 1+,4 cubane o$'an c !ynt"e! ! ! a cla!! c an# !ta$t! &$o% 2cyclopentenone (co%-oun# 1.1 n scheme 1)9[2][3]

8eact on ( t" N-b$o%o!ucc n % #e n ca$bon tet$ac"lo$ #e -lace! an allyl c b$o% ne ato% n 1.2 an# &u$t"e$ b$o% nat on ( t" b$o% ne n -entane -%et"ylene c"lo$ #e ' 0e! t"e t$ b$o% #e 1.3. 7(o e6u 0alent! o& "y#$o'en b$o% #e a$e el % nate# &$o% t" ! co%-oun# ( t" # et"yla% ne n # et"yl et"e$ to bromocyclopentadienone 1.4

)n t"e !econ# -a$t (scheme 2), t"e !-ontaneou! : el!-Al#e$ # %e$ *at on o& 2.1 to 2.2 ! analo'ou! to t"e # %e$ *at on o& cyclo-enta# ene to # cyclo-enta# ene. ;o$ t"e ne4t !te-! to !uccee#, only t"e en#o !o%e$ !"oul# &o$%< t" ! "a--en! becau!e t"e b$o% ne ato%!, on t"e $ a--$oac", ta3e u- -o! t on! a! &a$ a(ay &$o% eac" ot"e$, an# &$o% t"e ca$bonyl '$ou-, a! -o!! ble. )n t" ! (ay t"e l 3e-# -ole nte$act on! a$e % n % *e# n t"e t$an! t on !tate &o$ t" ! $eact on !te-. 1ot" ca$bonyl '$ou-! a$e -$otecte# a! acetal! ( t" et"ylene 'lycol an# ptoluene!ul&on c ac # nben*ene< one acetal ! t"en !elect 0ely #e-$otecte# ( t" a6ueou! "y#$oc"lo$ c ac # to 2.3 )n t"e ne4t !te-, t"e en#o !o%e$ 2.3 (( t" bot" al3ene '$ou-! n clo!e -$o4 % ty) &o$%! t"e ca'e-l 3e !o%e$ 2.4 n a -"otoc"e% cal [2=2] cycloa## t on. 7"e b$o%o3etone '$ou- ! con0e$te# to $ n'-cont$acte# ca$bo4yl c ac # 2.5 n a ;a0o$!3 $ea$$an'e%ent ( t" -ota!! u% "y#$o4 #e. >e4t, t"e t"e$%al #eca$bo4ylat on ta3e! -lace t"$ou'" t"e ac # c"lo$ #e (( t" t" onyl c"lo$ #e) an# t"ete$t-butyl -e$e!te$ 2.6 (( t" t-butyl "y#$o-e$o4 #e an# -y$ # ne) to 2.7< a&te$(a$#, t"e acetal ! once %o$e $e%o0e# n 2.8. A !econ# ;a0o$!3 $ea$$an'e%ent ' 0e! 2.9, an# & nally anot"e$ #eca$bo4ylat on ' 0e! 2.10 an# 2.11.

7"e cube %ot & occu$! out! #e o& t"e a$ea o& o$'an c c"e% !t$y. P$e0alent non-o$'an c cube! a$e t"e [;e4-S4] clu!te$! &oun# -e$0a! 0ely $on-!ul&u$ -$ote n!. Suc" !-ec e! conta n !ul&u$ an# ;e at alte$nat n' co$ne$!. Alte$nat 0ely !uc" no$'an c cube clu!te$! can o&ten be 0 e(e# a! nte$-enet$ate# S4 an# ;e4 tet$a"e#$a. ?any o$'ano%etall c co%-oun#! a#o-t cube !t$uctu$e!, e4a%-le! be n' (C-;e)4(C5)4, (C-@8u)4Cl4, (P"3PA')4)4, an# (CH3A )4.

)t (a! %ent one# -$e0 ou!ly t"at cubane (a! & $!t -$e-a$e# n 1+,4 by :$. P" l - .. .aton. He (a! -a$tne$e# by 7"o%a! B. Cole an# to'et"e$ t"ey !ucce!!&ully co%-lete# t"e & $!t !ynt"e! !, !"o(n !c"e%at cally belo(9

7" !, "o(e0e$, (a! !oon ! %-l & e# by >.1.C"a-%an ("o con#en!e# t"e -$oce!! to ' 0e cubane-1,4-# ca$bo4yl c ac # n & 0e !te-! an# !o cubane n ! 49

)n 1+,, C C 1a$bo$a3 et al # !co0e$e# yet anot"e$ ne( !ynt"e! ! o& cubane. )t (a! !l '"tly uncon0ent onal n t"e &act t"at t ut l !e# cyclobuta# ene a! a 3ey !ub!tance to t"e -$oce!!. 1e&o$e t" !,cyclobuta# ene (a! u!ually una0a lable &o$ t"e -u$-o!e! o& o$'an c c"e% !t$y #ue to t2! n!tab l ty. 7"e !"o$te$ !ynt"e! ! ! !"o(n belo(9

Since the synthesis of the cubane-1,4-dicarboxylic acid has become shorter and easier, a new decarboxylation method has also devised to give increased yields of the final cubane product. This has allowed the scale of production reach multikilogram batches in places (Fluorochem in California and EniChem Synthesis in Milan) eventhough cubane and its derivatives remain expensive to purchase. Cuneane %ay be -$o#uce# &$o% cubane by a %etal- on-cataly*e# D-bon# $ea$$an'e%ent.[4][5]

Cubane ! a un 6ue %olecule &o$ t! e4t$ao$# na$y C8 ca'e, 0e$y " '" !y%%et$y,e4ce-t onal !t$a n an# unu!ual 3 net c !tab l ty. 7"e -a$t cula$ a--eal o& cubane,$e&e$$e# to a! a lan#%a$3 n t"e (o$l# o& %-o!! ble co%-oun#!, !te%! &$o% t"e$e"yb$ # *at on o& t"e ca$bon ato%! a(ay &$o% t"e canon cal !-3 con& 'u$at on,t"at ! $e6u $e# to boun# to'et"e$ e '"t CH un t! n a cub c &$a%e(o$3. 7"e$e ! no( a $e0 0al o& nte$e!t on t"e c"e% !t$y o& cubane an# t! &unct onal *e# #e$ 0at 0e!,t$ ''e$e# by -otent al a--l cat on! a! " '"-ene$'y &uel!, e4-lo! 0e! an# -$o-ellant!an# nte$%e# ate! n -"a$%aceut cal-$e-a$at on!.Aet u! no( # !co0e$ t"e !ynt"e! ! an# -$o-e$t e! o& t" ! lan#%a$3 %olecule o& %-o!! ble c"e% !t$y

Cubanehas the highest strain energy (166kcal/mol) of any organiccompounds available in multi gram amount. It is a kineticallystable compound and only decomposite above 220 elsius !egree.It is also one of the most dense hydrocarbons ever kno".#o"ever$ although many physical properties of cubane have been measured$ in1%&0 and before$ cubane "as considered 'ust a laboratory curiosity of interest only to academics.It changed$ in early 1%&0s "hen (ilbert of ).* +rmy+rmament and !evelopment ommand (no" +,!- ) pointed out that cubane.svery high heat of formation and its e/ceptionally high density could make certain cubanederivatives important

e/plosives. 0he effectiveness of an e/plosive is dependent on the energentics of the decomposition reaction$ the number of moles and molecular "eight of the gaseous products and also the density. 0he more mols of of an e/plosive that can be packed into the limited volume the better. . #ighly nitrated cubanes can be predicted to be very dense and very po"erful e/plosives. 1ctanitrocubane is calculated to be 123405more po"erful than #67.

Cubane$ "hich + inde/ name is 8entacyclo9:.2.0.02$2.04$&.0:$;<octane (; I$& I$% I)$has e/ceptional structure$ strain and

symmetry and it is a benchmark in organic chemistry.It has been studied e/tensively and much of its properties has been published.*ome of the physical properties are given at right hand table.

7"e C-C bon# len't" ! a b t lon'e$ t"an obta ne# n t"e o$ ' nal E-$ay !t$uctu$e #ete$% nat on by ;le !c"e$ n 1+,4. 7"e$e ! not %uc" # &&e$ence bet(een t" ! bon# len't" an# t"e C-C bon# len't" n a ! %-le cyclobutane.

SF>7H.S)S 7"e cubane !y!te% (a! & $!t !ynt"e! *e# o0e$ 35 yea$! a'o by P" l - .aton an# 7o% Cole. )t ! a " '"ly !y%%et$ c cub c ca'e !t$uctu$e "a0 n' ca$bon ato%! at t"e 0e$t ce! o& a cube. 7"e !ynt"e! ! nee#! to 'o t"$ou'" b$o%b$o%ocyclo-enta# enone # %e$ ) an# cubane-1,4,# ca$bo4yl c ac #. )t ! a %a$0el !c"e%e o& econo%y an# ! %-l c ty. B t" only % no$ %o# & cat on, t" ! -$oce#u$e $e%a n! to t" ! #ay t"e be!t a0a lable %et"o# &o$ la$'e-!cale !ynt"e! ! o& cubane-1,4,# ca$bo4yl c ac #.

7"e !te$eo!-ec & c n ! tu [4 = 2] (: el!-Al#e$) cyclo# %e$ *at on o& 4-b$o%ocyclo-enta# enone ! t"e 3ey n t" ! 3 net cally cont$olle# !ynt"e! !. Ho(e0e$, t ! !t ll a t$ c3y %atte$ an# a &e( yea$! late$ a&te$ t" ! !ynt"e! ! ! -ubl !"e#, >.1.C"a-%an et al n .n'lan# &ollo( n' ut" ! (o$3 an# %-$o0e# t" ! !ynt"e! !.
Why cubane is stable?

7"e $ea!on &o$ t" !, una--$ec ate# at t"e t %e o& t"e ea$ly -$e# ct on! o& n!tab l ty, ! t"at t"e$e a$e no 3 net cally 0 able -at"! alon' (" c" cubane can $ea$$an'e t"e$%ally. 5n one "an#, o$b tal !y%%et$y con! #e$at on! $a !e t"e ene$'y o& conce$te# t(o-bon# $ n' o-en n' $eact on!. 5n t"eot"e$, t"e$e ! l ttle to be 'a ne# by b$ea3 n' Gu!t one bon# a! t"e$e ! conco% tantly only a !%all c"an'e n 'eo%et$y, an# t"e $e!ult n' b $a# cal ! !t ll 0e$y !t$a ne#.

Functional g ou! t ans"o #ation


=unctional groups on the cubane system generally behaves very "ell.=unctional group transformation can be applied successfully.=or e/ample$ the preparation of 1$:>dinitrocubane from cubane>1$:>dicarbo/ylic acid.(0he mechanism is provided on the right hand side.) lassical methodology is used here.

Sub!t tut on on t"e cubane &$a%e(o$3 ! &a $ly ea!y #one by t"e cubyl $a# cal. Ho(e0e$, t"e -$oble% ! !uc" t"at a % 4tu$e o& -$o#uct! a$e obta ne#. 7"u!, to ac" e0e cont$olle# !ub!t tut on on t"e cubane &$a%e(o$3, (e nee# to ca$e&ully !tu#y t"e c"e% !t$y o& t"e cubane !y!te%.

$he i#! o%e#ent in synthesis o" cubane&1'4&(ica bo)ylic aci(

7" ! ! t"e %-$o0e# !ynt"e! ! by >.1 C"a-%an et al n .n'lan#. 1a! cally t"e %-$o0e%ent ! !uc" t"at t"e 2-b$o%ocyclo-enta# enone coul# be %a#e ea! ly an# un#e$'oe! !-ontaneou! # %e$ *at on. 7"e $e!t o& t"e $eact on ! t"e !a%e a! t"e o$ ' nal one.

7" ! !ynt"e! ! no( ! !cale# u- an# ! con#ucte# n !%all - lot -lant! by ;lu$oc"e% n Cal &o$n a an# .n C"e% Synt"e! ! n ? lan.

7" ! %et"o# ! %uc" %o$e !u-e$ o$ t"an t"e ol# %et"o#. )t ! nt$o#uce# by

:e$e3 1a$ton et al an# u!e t"e $a# cal- n#uce# #eco%-o! t on o& # e!te$ (" c" can be -$e-a$e# ea! ly &$o% cubane-1,4-# ca$bo4yl c ac #. )?P85H.?.>7 7" ! %et"o# ! %uc" %o$e !u-e$ o$ t"an t"e ol# %et"o#. )t ! nt$o#uce# by :e$e3 1a$ton et al an# u!e t"e $a# cal- n#uce# #eco%-o! t on o& # e!te$ (" c" can be -$e-a$e# ea! ly &$o% cubane-1,4-# ca$bo4yl c ac #

)8

Cubane ! a colo$le!! !ol #. )t %elt! at 130- 131IC, an# #eco%-o!e! abo0e t"e %elt n' -o nt. )t ! !oluble n CS2, CC14, CHC13, an# ben*ene. S-ect$a (e$e obta ne# &$o% 400 to 3,00 c%-l ( t" a 1ec3%an )8-12 !-ect$o-"oto%ete$. 7"e lo(e$ l % t (a! !et by J1$ cell ( n#o(!. )n a## t on a t" c3 #e-o! t o& #o (a! %ea!u$e# #o(n to 200 c%-l n a C!l cell. S nce no n&$a$e# ban#! (e$e &oun#, t"e $an'e 200-400 c%-l (a! not e4a% ne# &o$ t"e ot"e$ co%-oun#!. 7"e !-ect$al !l t ( #t"! (e$e 1-2 c%-l n all ca!e!. )n t"e n&$a$e# !-ect$u%, t"e$e a$e only not ceable ab!o$-t on! n t"e $e' on &$o% 4000 to ,,0 c%-1a--ea$ at 300,1231, an# 851 c%-1.

Kene$ally, &o$ ! n'le-l ne -$oton %a'net c $e!onance !-ect$u%, t"e one an# only ab!o$-t on a--ea$! at c"e% cal !" &tL,.0--%. 5$ ' nally t"e$e (a! #oubt ("et"e$ cubane #oe! e4 !t. 7"e 'eo%et$y at eac" ca$bon ato% ! &a$ &$o% tet$a"e#$al. 5nly late$, (e &oun# out t"at t"e$e ! no 3 net cally 0 able -at"! e4 !t &o$ t"e t"e$%al $ea$$an'e%ent o& cubane. At !a%e t %e, o$b tal !y%%et$y con! #e$at on! !"o(! t"at t"e ene$'y o& conce$te# t(obon# $ n'-o-en n' $eact on! ! 0e$y " '". 7"e$e ( ll be 0e$y l ttle 'a n n ene$'y by b$ea3 n' Gu!t one bon#, a! t"e conco% tant c"an'e n 'eo%et$y ! !%all, an# t"e $e!ult n' b $a# cal ! !t ll 0e$y !t$a ne# )n 1+,4 ;le !c"e$ !"o(e# t"at cubane &o$%! a !table !ol # at $oo% te%-e$atu$e ( t" a

c$y!tall ne !t$uctu$e co%-o!e# o& cubane %olecule! occu-y n' co$ne$! o& t"e $"o%bo"e#$al -$ % t 0e un t cell (!-ace '$ou- 83). 7"e cub c %olecula$ 'eo%et$y ' 0e! t"e !ol # %any unu!ual elect$on c,!t$uctu$al, an# #yna% cal -$o-e$t e! co%-a$e# to t"e ot"e$ "y#$oca$bon!. ;o$ e4a%-le, !ol # cubane "a! a $elat 0ely " '" %elt n' -o nt te%-e$atu$e about 405 JM an# a0e$y " '" &$e6uency &o$ t"e lo(e!t-ly n' nt$a%olecula$ 0 b$at onal %o#e (,17 c%1). 8ecent (o$3 $elate# to cubane "a! &ocu!e# on !ol # cubane an# cubane ba!e# #e$ 0at 0e!.1ecau!e o& $elat 0ely (ea3 nte$%olecula$ nte$act on t"e co"e! 0e ene$'y $elat 0e to t"e con!t tuent C8H8 ! e4-ecte# to be !%all, an# %o!t o& t"e -"y! cal -$o-e$t e! o& !ol # cubane a$e #o% nate# by t"e -$o-e$t e! o& t"e C8H8%olecule.

*ha #aceutical as!ect o" cubane


1ecau!e t"e cubane &$a%e ! $ ' #, !ub!t tuent "a0e -$ec !e !-at al $elat on!" -! to eac" anot"e$.

7"e # !tance ac$o!! t"e cubane (t"e bo#y # a'onal) ! al%o!t t"e !a%e a! t"at bet(een t"e -a$a -o! t on! o& t"e ben*ene $ n'. 5n cubane, on can a## !ub!t tuent! n t"e Nben*ene -laneN, a! (ell a! abo0e an# belo( t, !o to !-ea3. 7" ! o&&e$! &a!c nat n' -o! t on -o!! b l t e! &o$ t"e !ynt"e! ! o& ne( -"a$%aceut cal!. A nu%be$ o& cubane #e$ 0at 0e! "a0e al$ea#y been obta ne# (" c" !"o(! nte$e!t n' act 0 ty n ant -A):S an# ant -tu%o$ !c$een!. Alt"ou'" t"e act 0 ty o$ t"e to4 c ty balance o& cubane ! yet not 3no(, t"e cubane !y!te% ! not n"e$ently to4 c. ?o!t o& cubane! a$e b olo' cally nnocuou!. 7"e $e!ea$c" o& cubane -"a$%aceut cal "a! Gu!t be'an. At lea!t no(, cubane ! a b olo' cally !table, l -o-" l c -lat&o$% on (" c" t"e c"e% !t can n!tall a ( #e $an'e o& !ub!t tuent! n a 0a$ ety o& (ell #e& ne# !-ec al $elat on!" -!. :e0elo-%ent! n #$u' #e! 'n -$o'$a%! !"oul# allo( t"e Gu# c ou! c"o ce.

: - 0aloylcubane9 a cubane #e$ 0at *e# ( t" 3eto, cyano, an# a% #e '$ou-!, !"o(n on t"e le&t- e4" b t! %o#e$ate act 0 ty a'a n!t "u%an %%uno#e& c ency 0 $u! (H)H), (" c" cau!e! A):S, ( t"out %-a $ n' "ealt"y cell!.

*oly#e s o" cubane+


5-t cally t$an!-a$ent cubane! an# cubylcubane! "a0e been -$o-o!e# a! bu l# n' bloc3! &o$ $ ' # l 6u #-c$y!tal co%-oun#!. /H act 0e cubane!, &o$ e4a%-le cubyl 3etone!, a$e $ea# ly t$an!&o$%e# -"otoc"e% cally nto colou$e# cyclooctatet$aene!<t" ! t$an!&o$%at on can be u!e# to -e$%anent n&o$%at on !to$a'e. Anot"e$ e4a%-le o& /H act 0e cubane, (" c" can be u!e# to !ynt"e! ! l 6u # c$y!tal!.

Poly%e$! ( t" cubane n t"e bac3bone o$ a! a -en#ant '$ou- alon' a -oly%e$ c"a n ! &ocu!e# no(. 7"e cubane !ubun t! n t"e!e -oly%e$! can be $ea$$an'e# ea! ly to cycloctatet$aene!. )t ! e4-ecte# t"at -olycyclooctatet$a can be con0e$te# n to -olyacetylene! by

t"e (ay o& $ n'-o-en n' %etat"e! ! -oly%e$ *at on. 7"e -olyacetylene! ( ll "a0e -$o-e$t e! (" c" a$e en"ance# by t"e c"a n be n' nt$ n! cally -a$t o& anot"e$ -oly%e$. 7"e!e -$o-e$t e! nclu# n' !tab l ty an# e4t$u#ab l ty an# etc. A e4a%-le ! !"o(n belo(9

ubane derivative could be the structural basis for a class of intrinsic small gap polymers.0he small gap polymer could present intrinsic good conductivity "ithout doping$good nonlinear optical and photoelectric properties.Investigation of oligamers "ith up to si/ units of a con'ugated unsaturated cubane derivative$"here all the hydrogen "ere removed$ is carried out.0he table belo" sho"s that the gap values in e? by -#0 and 864.0hese values suggest to us that these structures could be used to design a ne"class of polymers "ith very small gap.

,)!losi%e an( "uels+


)n t"e ea$ly 1+80! .0e$ett K lbe$t o& t"e /.S. A$%y A$%a%ent 8e!ea$c" an# :e0elo-%ent Co%%an# (no( A8:.C) -o nte# out t"at t"e n t$oca$bon octan t$ocubane (5>C), t"en un3no(n, "a! a -e$&ect o4y'en balance, an# n l '"t o& t"e -$o-e$t e! o& t"e -a$ent "y#$oca$bon cubane !"oul# "a0e a 0e$y " '" "eat o& &o$%at on -e$ C>52 un t an# an e4ce-t onally " '" #en! ty a! (ell. H ! collea'ue! Cac3 Al!te$, 5!ca$ San#u! an# >o$%an Sla'' at A8:.C -$o0 #e# t"eo$et cal !u--o$t &o$ K lbe$t2! b$ ll ant n! '"t an# e!t %ate# t"at 5>C (oul# "a0e a #etonat on -$e!!u$e ! 'n & cantly '$eate$ t"an H?E. Aate$, bot" !tat !t cal an# co%-utat onal a--$oac"e! -$e# cte# a #en! ty o& 2.1 O 2.2 ' Pc%3 &o$ octan t$ocubane, '$eate$ t"an any ot"e$ C, >, 5 co%-oun#.

-s Cubane a eally goo( e)!losi%es?


Quant tat 0e e0aluat on o& t"e -otent al o& a can# #ate e4-lo! 0e be&o$e !ynt"e! ! ! 0e$y # && cult. Cu$$ently, e!t %at on o& ene$'et c -$o-e$t e! $el e! on t"e e%- $ cally #e$ 0e# Ja%let an# Cacob! e6uat on!9

)n t"e!e e6uat on! t"e "eat $elea!e# by t"e #eco%-o! t on, t"e nu%be$ o& %ole! o& 'a! -$o#uce#,

an# t"e %olecula$ (e '"t o& t"e!e 'a!e! a$e all c$ t cal &acto$!. :en! ty too ! c$uc al. 5b0 ou!ly, t"e %o$e %olecule! o& a " '"-ene$'y %ate$ al t"at can be -ac3e# nto t"e l % te# 0olu%e o& a !"ell o$ $oc3et t"e bette$. Ae!! ob0 ou!, but %o$e %-o$tant, #en! ty a&&ect! t"e #etonat on 0eloc ty o& an e4-lo! 0e. 7" ! ! a !-ec al *e# Nl nea$N $ate o& $eact on t"at $an'e! &$o% 5 to 10 3%P! n e4-lo! 0e! an# a&&ect! t"e %a4 %u% #etonat on -$e!!u$e, a # $ect %ea!u$e o& t"e -o(e$ o& an e4-lo! 0e. ;o$ a ' 0en e4-lo! 0e, t"e #etonat on -$e!!u$e ! -$o-o$t onal to t"e !6ua$e o& t! #en! ty, !o '$eat e&&o$t ! %a#e to obta n t"e " '"e!t #en! ty &o$% o& any -a$t cula$ e4-lo! 0e. Quant tat 0e e0aluat on o& t"e -otent al o& a can# #ate e4-lo! 0e be&o$e !ynt"e! ! ! 0e$y # && cult. Cu$$ently, e!t %at on o& ene$'et c -$o-e$t e! $el e! on t"e e%- $ cally #e$ 0e# Ja%let an# Cacob! e6uat on!9

)n t"e!e e6uat on! t"e "eat $elea!e# by t"e #eco%-o! t on, t"e nu%be$ o& %ole! o& 'a! -$o#uce#, an# t"e %olecula$ (e '"t o& t"e!e 'a!e! a$e all c$ t cal &acto$!. :en! ty too ! c$uc al. 5b0 ou!ly, t"e %o$e %olecule! o& a " '"-ene$'y %ate$ al t"at can be -ac3e# nto t"e l % te# 0olu%e o& a !"ell o$ $oc3et t"e bette$. Ae!! ob0 ou!, but %o$e %-o$tant, #en! ty a&&ect! t"e #etonat on 0eloc ty o& an e4-lo! 0e. 7" ! ! a !-ec al *e# Nl nea$N $ate o& $eact on t"at $an'e! &$o% 5 to 10 3%P! n e4-lo! 0e! an# a&&ect! t"e %a4 %u% #etonat on -$e!!u$e, a # $ect %ea!u$e o& t"e -o(e$ o& an e4-lo! 0e. ;o$ a ' 0en e4-lo! 0e, t"e #etonat on -$e!!u$e ! -$o-o$t onal to t"e !6ua$e o& t! #en! ty, !o '$eat e&&o$t ! %a#e to obta n t"e " '"e!t #en! ty &o$% o& any -a$t cula$ e4-lo! 0e. >u%e$ou! n t$o co%-oun#! a$e e%-loye# co%%only a! % l ta$y an# co%%e$c al e4-lo! 0e!.

7"e$e ! a cont nu n' !ea$c" &o$ %o$e -o(e$&ul an# le!! !"oc3-!en! t 0e e4a%-le!. Suc" %ate$ al! a$e al!o !ou'"t a! -otent ally u!e&ul &uel! an# -$o-ellant!. ?o!t nte$e!t ! &ocu!e# on " '"-#en! ty o$'an c co%-oun#! t"at conta n all o& t"e ele%ent! nee#e# &o$ co%bu!t on to 'a!eou! -$o#uct! n t"e ab!ence o& a $. > t$ocubane! ca$$y n' & 0e o$ %o$e n t$o '$ou-! conta n enou'" o4y'en to o4 # *e all con!t tuent ca$bon an# "y#$o'en ato%! to 'a!eou! C5, C52, o$ H25. .ac" o& t"e!e, alon' ( t" >2, Ne4-lo#e!N &$o% t"e !ol # to 12 'a!eou! %olecule!. 7"e e4-an! on &$o% t"e #en!e !ol # to a lot o& 'a! (%uc" e4-an#e# by t"e $elea!e# "eat) -$o#uce! t"e #e! $e# e&&ect n -$o-ellant! an# e4-lo! 0e!. 5>C "a! a N-e$&ectN o4y'en balance an# (oul# -$o#uce ((e$e t"e #etonat on co%-letely e&& c ent) e '"t %olecule! o& ca$bon # o4 #e an# &ou$ o& # n t$o'en. A! 5>C "a! no "y#$o'en, no (ate$ &o$%! ("en t bu$n!< ("en u!e# a! -$o-ellant! !uc" *e$o-"y#$o'en co%-oun#! lea0e l ttle o$ no 0 ! ble !%o3e (!tea%) n t"e -lu%e be" n# t"e $oc3et< !uc" Nlo(-! 'natu$eN $oc3et! a$e # && cult to t$ac3.

5n a--l cat on o& t"e Ja%let an# Cacob! e6uat on! le# A8:.C to -$e# ct t"at octan t$ocubane (oul# be a 0e$y %uc" bette$ e4-lo! 0e (7able 1) t"an t"e cla!! c C-n t$o co%-oun# t$ n t$otoluene (7>7), -e$"a-! 15O30R bette$ t"an t"e n t$a% ne H?E (t"e %o!t -o(e$&ul, co%%only u!e# % l ta$y e4-lo! 0e), an# at lea!t co%-et t 0e ( t" (an# -e$"a-! le!! !"oc3-!en! t 0e t"an) t"e ne(e!t e4-e$ %ental e4-lo! 0e CA-20

SYNTHESIS:(1)

0he high strain that the cubane frame"ork is under has already been highlighted. 0he researchers had to very cautiously attach a nitro group to each of the corners of the cube in order to make the desired product. 0he insertion of the first four nitro groups could be done by manipulating functional groups@

0he key intermediate$ cubane>1$4$2$;> tetracarbo/ylic acid (0A )$ "as obtained by clever application of the Bro"n>Charasch photochlorocarbonylation to cubane mono>acid. 0he addition of four further nitro groups proved far more difficult and ne" methodologies had to be developed$ specifically the process of interfacial nitration. 0his method "as used successfully to convert the sodium salt of 0A to pentanitrocubane (8A ) and then he/anitrocubane (#A )$ both are stable materials. Interfacial nitration$ ho"ever$ proved deficient for further nitration of #A and again ne" e/perimental methodology had to be developed for its successful conversion to heptanitrocubane (#pA )@

+ddition of e/cess A1 l to a solution of the lithium salt of #pA ;&D gave the long>sought 1A @

in dichloromethane at >

.-FF $/*,S

;o$ t"e la!t -lanne# -o!t n %y /nnatu$al P$o#uct! !e$ e!, )S% 'o n' to ($ te about .atonS! 1+81 !ynt"e! ! o& -enta-$ !%ane.[A] At t"e t %e, unnatu$al "y#$oca$bon! (e$e "ot ta$'et!, an# a! t"e ne4t la$'e!t -$ !%ane on t"e l !t t" ! ta$'et (a! t"e !ubGect o& %uc" $e!ea$c" by '$ou-! a$oun# t"e (o$l#. Pe$"a-! .aton2! b ''e!t $ 0al! (e$e t"e '$ou-! o& Pa6uette an# Pet t, an# n &act all t"$ee "a#, at 0a$ ou! t %e!, !ynt"e! !e# "y-o!t$o-"ene a! an nten#e# -$ecu$!o$ to t"e ta$'et.

/n&o$tunately, t"e Tob0 ou!S [2 = 2] # !connect on &$o% -enta-$ !%ane tu$ne# out to be a #ea# en# an# t"e -"otoc"e% cal $ n' clo!u$e (a! un!ucce!!&ul. 7"e 1+70! an# ea$ly

1+80! !a( t"e -ubl cat on o& a nu%be$ o& ot"e$ ! % la$ly c$eat 0e, but !a#ly ll-&ate#, a--$oac"e! ba!e# on 0a$ ou! $ n' cont$act on!, an# t"e co%-oun# 'a ne# a (ell-ea$ne# $e-utat on &o$ e4t$ao$# na$y !ynt"et c nacce!! b l ty. .atonS! $oute be'an, a! ( t" t"e cubane an# #o#eca"e#$ane !ynt"e!e! -$e0 ou!ly co0e$e# n t" ! !e$ e!, ( t" a : el!-Al#e$ $eact on. 7"e # ene u!e# (a! t"e 3no(n tet$ac"lo$ocyclo-enta# enone acetal !"o(n t"at u-on "eat n' neat ( t" ben*o6u none -$o#uce# t"e en#o a##uct !"o(n n e4cellent y el#. >e4t, an e0en " '"e$ y el# n' -"otoc"e% cal [2 = 2] $eact on (a! u!e# to clo!e t"e ca'e-l 3e !t$uctu$e by cyclobutane &o$%at on. 7$eat%ent ( t" l t" u% n l 6u # a%%on a ! %ultaneou!ly $e#uce# bot" 3etone! an# $e%o0e# all &ou$ c"lo$ ne ato%!. 7"e $e!ult n' # ol (a! con0e$te# to t"e # to!ylate, (" c", un#e$ ca$e&ully cont$olle# con# t on! ( t" !o# u% o# #e n H?PA, un#e$(ent a %ono-; n3el!te n $eact on to ' 0e t"e o#oto!ylate !"o(n. B"en t" ! (a! t$eate# ( t" t-1uA "alo'en-l t" u% e4c"an'e, &ollo(e# by an e4t$ao$# na$y &$a'%entat on, 'a0e a # ene $e% n !cent o& "y-o!t$o-"ene !"o(n abo0e. Ho(e0e$, t"e e4t$a ca$bon ato% n t"e !3eleton %a#e all t"e # &&e$ence, an# unl 3e t"e -a$ent co%-oun#, t" ! # # un#e$'o a [2 = 2] cycloa## t on ("en e4-o!e# to /H l '"t. ; nally, acetal "y#$oly! ! 'a0e "o%o-enta-$ !%ane n 34R y el# &$o% ben*o6u none, -utt n' t"e '$ou- a ! n'le $ n' cont$act on &$o% 0 cto$y.[1]

B t" ! 'n & cant a%ount! o& "o%o-enta-$ !%anone n "an#, t"e '$ou- no( nten#e# to e%-loy t"e t$an!&o$%at on t"at "a# been t"e co$ne$!tone o& t"e $ cubane !ynt"e! ! U t"e ;a0o$!3 $ea$$an'e%ent. /n&o$tunately, t" ! $e6u $e# t"e nt$o#uct on o& a lea0 n' '$ou- n t"e 3etone V--o! t on, a t$an!&o$%at on %a#e nc$e# bly # && cult #ue to t"e !t$a ne# !y!te% an# 1$e#tS! $ule, (" c" -$e0ente# enol !at on.[C] .0entually a ! 4-!te!e6uence (M) to nt$o#uce a to!ylo4y '$ou- (a! #e0 !e#, be' nn n' ( t" a 1aeye$-H ll 'e$ $eact on u! n' m-CP1A. A $e%a$3able CH o4 #at on ( t" 8u54, 'ene$ate# in situ, t"en 'a0e t"e "y#$o4ylactone. 7$eat%ent o& t" ! ( t" # a*o%et"ane 'a0e t"e co$$e!-on# n'

W-3etoe!te$ n al%o!t 6uant tat 0e y el#. 7"e '$ou- t"en $e&o$%e# t"e !ta$t n' no$bo$nane-l 3e b$ #'e t"$ou'" u!e o& an unu!ual acylo n ty-e $eact on e&&ecte# by t$eat%ent ( t" !o# u% n l 6u # a%%on a. ; nally, o4 #at on o& t"e !econ#a$y alco"ol an# to!ylat on 'a0e t"e ;a0o$!3 -$ecu$!o$, a--a$ently -$e-a$able n %ut -'$a% 6uant t e!.

7$eat%ent ( t" a6ueou! -ota!! u% "y#$o4 #e !olut on e&&ecte# ;a0o$!3 $ea$$an'e%ent n e4cellent y el#, e!-ec ally con! #e$ n' t"at t" ! (a! t"e & $!t t %e t"e elu! 0e -enta-$ %ane $ n' !y!te% "a# been -$e-a$e#. ; nally, .aton u!e# t"e t"$ee-!te#eca$bo4ylat on "e "a# #e0elo-e# &o$ cubane to $e%o0e t"e e4t$aneou! ac # an# ' 0e -enta-$ !%ane n 18 !te-!. A(e!o%e.[:]

0e"e ences an( suchli1e 1. A J. Am. Chem. Soc., 1+81, 103, 2134. ?uc" l 3e .atonS! !e% nal cubane -a-e$, t"e t tle ! a ! n'le (o$#, TPenta-$ !%aneS. ) lo0e t"e lac3 o& "y-e. 2. 1 Alt"ou'" Pet t "a# -$e-a$e# t" ! co%-oun# a &ull #eca#e ea$l e$, " ! a--$oac" $el e# on a cycloa## t on o& t"e # && cult to -$e-a$e cyclobuta# ene $on t$ ca$bonyl ( t" t"e acetal o& t$o-one, an# -$o0e# # && cult to !cale u-. )n &act, n " ! o(n -a-e$ .aton $at"e$ # $ectly #e!c$ be# t a! Tconce-tually &a!c nat n' [but] u!ele!! !ynt"et callyS. 3. C .aton u!e! t"e -"$a!e T n0a! on at t"e b$ #'e"ea#S, (" c" ) & n# #el '"t&ully e0ocat 0e. ?a3e! t !oun# l 3e a !econ# (o$l# (a$ ca%-a 'n. A--a$ently t"e

'$ou- n t ally -lanne#, n !- te o& 1$e#tS! $ule, to #e-$otonate t"e b$ #'e"ea# -o! t on, $ely n' on inductive !tab l !at on o& t"e an on $at"e$ t"an enolate &o$%at on, but (e$e unable to #o !o. 4. : Penta-$ !%ane ! t"e %o!t $ecent o& t"$ee -$ !%ane! !ynt"e! !e# to #ate, t"e ot"e$ t(o be n' cubane, an# t$ -$ !%ane. Alt"ou'" ) t" n3 t$ -$ !%ane loo3! 6u te ! lly, t (a! actually !ynt"e! !e# !o%e 8 yea$! -$e0 ou!lyby 7. C. Jat* n &a$ &e(e$ !te-!. Ko & 'u$e.

$he 2#i(e 2cti%ating 3 ou!

7"e 0e$y & $!t !te- o& cubane &$a%e !ub!t tut on ( ll be t"e act 0at on o& t"e cubane &$a%e. 7" ! can be #one by a% #e!. 7"e #ea ! #e$ 0e# &$o% t"e ! % la$ t e! bet(een cubane an# a$ene!. 1ot" o& t"e% "a0e C-H bon#! ( t" en"ance# ! c"a$acte$ ( !ee !t$uctu$e), an# n bot" t"e a#Gacent (o$t"o) !ub!t tuent! a$e &o$ce# to be co-lana$. A %o$e !-ec & c e4a%-le ! t"e cubane->,>-# !o-$o-yl ca$bo4a% #e $eact! ( t" e4ce!! l t" u% tet$a%et"yl- -e$ # #e (A 7?P) n 7H; !ol0ent. About 3R o& t"e #eute$ at on -$o#uct! obta ne#. 7"e # !o-$o-yl a% #e act 0at n' '$ou- ! u!e# becau!e t ! ne$t to t"e a% #e ba!e! e%-loye# &o$ o$t"o %etalat on. Alt"ou'" t"e$e ! a -$oble%, t"e$e ! # && culty n "y#$oly*e# t t"e co$$e!-on# n' ca$bo4yl c ac #. 7"e -$oble% ! & nally !ol0e# by u! n' bo$ane $e#uct on &ollo(e# by t"e o4 #at on o& t"e a% ne !o -$o#uce# ( t" # %et"yl# o4 $ane o$ -ota!! u% -e$%an'anate ( n la$'e !cale). 7$an!%etalat on ! t"e ba! ! o& a co%-lete !ynt"et c %et"o#olo'y &o$ t"e -$e-a$at on

o& a '$eat 0a$ ety o& t"e !ub!t tute# cubane!. )n o$#e$ to %a3e t"e !ub!t tut on -$o#uct 0ely, a (ay %u!t be &oun# to %a3e u!e o& t"e !%all a%ount o& an on n t"e e6u l b$ u% ( t" t"e !ta$t n' %ate$ al. ?e$cu$y !alt ! u!e# "e$e a! an e&&ect 0e an on t$a- an# 0e$y l ttle !ta$t n' %ate$ al $e%a n un$eacte#. 7"e %e$cu$y &o$ l t" u% t$an!%etalat on $e!ulte# n nea$ly co%-lete con0e$! on o& t"e !ta$t n' %ate$ al by #$a( n' t"e l t" at on e6u l b$ u% to t"e $ '"t.

7"e a% #e '$ou- ! %-o$tant n !tab l * n' t"e nte$%e# ate l t" ate# cubane, but not t"e %e$cu$ ate# co%-oun#. 5nce t"e l t" u% ! $e-lace# by %e$cu$y, t"e a% #e '$ou- ! a'a n able to a!! !t $e%o0al o& anot"e$ o$t"o-"y#$o'en ato%. )n t"e en#, t"e co%-le4 o$t"o-%e$cu$ate# -$o#uct % 4tu$e obta ne# (a! ! %-l & e# by t$eat%ent ( t" ele%ental o# ne.

7"e o# ne clea0a'e o& t"e ca$bon-%e$cu$y bon#! 2- o#o an# 2,,-# o#o #e$ 0at 0e! o& t"e !ta$t n' a% #e n72R an# 15R $e!-ect 0ely

Cubyl 3 igna ( 0eagents


;$o% t$an!%etalat on, a $e0e$!e t$an!%etalat on (a! al!o #e0elo-e#, (" c" ! ba! cally a## n' K$ 'na$# $ea'ent to t"e %e$cu$ ate# cubane n!tea# o& t"e o# ne. Ho(e0e$, t"e!e -$oce!!e! "a0e a '$eat %a n # !a#0anta'e, t"e %e$cu$y ! " '"ly to4 c. 7"u!, !cale u- o& t" ! %et"o# (a! l % te#. )n 1+88, 1a!" $-Ha!"e% nt$o#uce# t$an!%etalt on ( t" %a'ne! u% !alt! an# t"e$eby -$o0 #e# ea!y acce!! to cubyl %ono-an# b !-K$ 'na$# $ea'ent!. )t ! a $eact on o& cubane # a% #e ( t" an e4ce!! o& A 7?PP?'182 n 7H; an# 6uenc" n' ( t" )2 'a0e # o#ocubane # a% #e o& 72R y el#.

$he e""ect o" the ! esence o" elect on 4ith( a4ing g ou!

& Cyani(e

B"en elect$on ( t"#$a( n' '$ou- !uc" a! cynate -$e!ent, t"ey !tab l *e bot" nte$%e# ate l t" ate# cubane! 0e$y (ell. A! a $e!ult, only a !%all a%ount o& A 7?P ! nee# to ac" e0e &a $ly co%-lete #e-$otonat on e0en at -78IC.

7"e n#uct 0e e&&ect o& t"e cyano '$ou- clea$ly en"ance! t"e $eact on. Ho(e0e$, t"e a## n' o& cyano '$ou-! $e!ult! n co%-et t 0e l t" at on an# a % 4tu$e o& -$o#uct!. Ho(e0e$, t" ! -$oble% can be (ell t$ac3le# by a## n' ?'1$2.7"e -$o#uct $at o (a! %-$o0e# to +91 &a0o$ n' ca$bo4yl at on o$t"o to t"e a% #e &unct on. 2 #i)tu e o" ! o(uct "o #e(.

-nc ease( selecti%ity by a((ing 5g6

Since t"e $eact 0 ty o& cubane %etalat on ! en"ance# '$eatly ( t" -$e!ence o& cyano '$ou-!, t ! -o!! ble to !ub!t tute all t"$ee -o! t on! o$t"o to t"e a% #e n a ! %-le $eact on. ;o$ n!tance, 4-cyanocubana% #e can be con0e$te# # $ectly nto t"e t$ (te$tbutylca$bonyl)#e$ 0at 0e a! !"o(n belo(. 7"$ou'" 1aeye$-H ll 'e$ o4 #at on, te$-butyl cuybl 3etone! can be con0e$te# ea! ly to t"e -olyca$bo4yl ate# cubane.

PH.>FA C/1A>.

;$o% t"e ba! ! #ea o& cubyl K$ 'na$# 8ea'ent, -"enyl cubane can be !ynt"e! !e#. 7"e $eact on o& cubane # a% #e ( t" 10 e6u 0 o& A 7?P an# 4.0 e6u 0alent! o& ?'1$2 et"e$ate n 7H; at 0IC &ollo(e# by t"e a## t on o& 10.0 e6u 0 o& b$o%oben*ene, 'a0e # -"enylcubane # a% #e n 53R y el#.

7"e %ec"an !% ! !"o(n belo(9

7"e ben*yne nte$%e# ate (a! &o$%e# n ! tu &$o% t"e $eact on o& e4ce!! o& A 7?P ( t" b$o%oben*ene. ;o$ a ! % la$ $eact on, ?e?'1$ ! u!e# an# ' 0e 30R y el# o& b$o%o-"enylcubane # a% #e, t"e & $!t cubane #e$ 0at 0e conta n n' 3 # &&e$ent !ub!t tuent!.
7o4' let us loo1 the #ain conce n o" the cubane (e i%ati%es&&the nit ocubanes.

> t$ocubane! a$e !ou'"t to be -o(e$&ul, !"oc3- n!en! t 0e, " '"-#en! ty e4-lo! 0e!. 7"ey a$e !table co%-oun#! ( t" #eco%-o! t on -o nt! abo0e 200IC. S %-le n t$ocubane can be %a#e &$o% ! %-le o4 #at on o& a% ne!( See ;unct onal K$ou7$an!&o$%at on.) )& (e (ant to a## %o$e n t$o '$ou-! nto t"e cubane nucleu!, (e cannot #o t t"ou'" t$an!%etalat on becau!e t"e$e ! un!to--able ca'e clea0a'e $eact on! ("en %a3e a#Gacent n t$o '$ou-!. 7"e ab n t o calculat on "a! con& $%e# t" ! #e!tab l ! n' e&&ect. Be a$e 'o n' to # !cu!! "o( to %a3e %o$e an# %o$e !ub!t tute# n t$ocubane unt l octan t$ocubane(5>C), t"e ult %ate -o(e$ "ou!e, ! !ynt"e! !e#.

1'3'5 t init ocubane an( 1'3'5'7 tet anit ocubane8$7C9

A! (e %ent on ea$ly, a## t on o& n t$o '$ou-! cannot be #one t"$ou'" # $ect t$an!%etalat on. 7"u!, (e nee# &oun# !o%e n# $ect $oute. 7" ! ! #one by nt$o#uc n' a !ub!t tuent on eac" o& 3 o$t"o ca$bon! an# $e%o0e t"e o$t"o-act 0at n' '$ou- n t"e en#.

1y a## n' a elect$on-( t"#$a( n' '$ou- !uc" a! a cyano '$ou- ( ll "el- t"e ca!e "e$e. 7" ! c"o ce o& o$ ' nal !ub!t tuent ! %-o$tant "e$e an# ("en cyano '$ou- ! c"o!en, t act 0ate! t"e cubane nucleu! ( t"out a&&ect n' t"e o$t"o # $ect n' by t"e # a% #e (&o$ #eta l! -lea!e $e&e$ to elect$on-( t"#$a( n' '$ou--cyan te). B"en t"e # cyano a% #e (a! t$eate# ( t" 7?P?'1$ n 7H; an# 6uenc"e# ( t" C52. 7"e o$t"o (to a% #e) ca$bo4yl c ac # (a! t"e only -$o#uct. .0en ("en t"e %uc" act 0ate# t$ cyanoa% #e ! t$eate# ( t" 7?P?'1$ an# C52 ,a'a n, t"e o$t"o -o! t on ( to a% #e) ca$bo4yl c ac # (a! &o$%e#.

7"e $e%o0al o& t"e ca$bo4a% #o '$ou- ! #one t"$ou'" a !%a$t yet te# ou! -$oce!!. 7"e cyano '$ou- ! con0e$te# to ac # '$ou- & $!t. 7"en, t ! $e#uce# to alco"ol by l t" u% alu% n u% "y#$ #e. At !a%e t %e, t"e ca$bo4a% #o ! $e#uce# to a% notet$ol. 7"e alco"ol! a$e -$otecte# a! acetate! an# a% no tet$ol ! con0e$te# to ca$bo4yl c ac #. 7"e ca$bo4yl c ! t"en $e%o0e# t"$ou'" 1a$ton :eca$bo4ylat o. A #eta l %ec"an !% ! -$o0 #e# belo(.

7"e cubane-1,3,5,7-te$aca$bo4yl c ac # ! con0e$te# to 7>C on t"e %ec"an !% a! &ollo(9

7"e ("ole -$oce!! ! 0e$y cle0e$, but t ! 0e$y lon'. 7"u!, n 1++7, a %-$o0e# !ynt"e! ! %et"o# &o$ 7>C (a! -$o-o!e# by %a3 n' u!e o& t"e -"otoc"e%! t$y.

-#! o%e( synthesis "o $7C


-n 1993' 6ashi &:ashe#i sho4e( the cubane&1'3'5'7&tet aca bo)ylic aci( chlo i(e can be "o #e( by a!!lying !hotoche#ically in(uce( chlo oca bonyl cation8 the ;ha asch<6 o4n 0eaction9.

;o$ a &a!t $eact on, a " '" -o(e$ Hano0 a o& 450 (att!, %e# u% -$e!!u$e H' (a! u!e#. 7"e &a0ou$e# -$o#uct! a$e cubane tet$aac # c"lo$ #e !"o(n on t"e $ '"t "an# ! #e. 7"e & $!t one, cubane-1,3,5,7-tet$aca$bo4yl c ac #, %a#e u- 30R o0e$all. 7" ! $eact on con0en ently -$e-a$e u! t"e %-o$tant 0e$!at le nte$%e# ate . A #eta l con0e$! on -$oce!! ! -$o0 #e# belo(9

A cataly!t 7?S>3 ! u!e# n con0e$t n' tet$aac # c"lo$ #e to tet$acyla* #e. 7"e $e!t ! t"e !a%e a! t"e o$' nal $eact on.

7>C ! a t"e$%o#yna% c -o(e$"ou!e but $e%a$3ly !table 3 net cally. ; 'u$e 1 !"o(! t"at $a- # t"e$%al #eco%-o! t on #oe!not !ta$t unt l o0e$ 250IC.

7"e l te$atu$e (a! un!u--o$t 0e o& t" ! o-t % !t c 0 e(. Poo$ $e!ult! (e$e al!o obta ne# n t ally ( t" n t$at n' a'ent !uc" a! >521;4, acetyl n t$ate, a%yl n t$ate etc. 7et$an t$ocubyl!o# u% can be &o$%e# # $ectly on t$eat%ent o& 7>C ( t" !o# u% b !(t$ %et"yl! lyl) a% #e n 7H; at -75IC. )t can $eact ( t" elect$o-" le! to -$o0 #e a u!e&ul an# con0en ent (ay to ac" e0e &u$t"e$ &unct onal *at on o& cubane nucleu!.

5o e substitute( nit ocubanes& *entanit ocubane8*7C9 an( :e)anit ocubane8:7C9


P>C

6ase on the ! o!e ty o" tet anit ocubylso(iu#' nit yl chlo i(e87=2Cl9 4as use( to "u the nit ate the cubane nucleus. $ eat#ent o" 7=2Cl 4ith tet anit ocubylso(iu# in $:F at &75>C 4o 1s out

10&15? yiel( o" !entanit ocubane8*7C9. $he yiel( inc ease( to 30? 4hen the solution 4as " o@en to& 180>C an( allo4e( to 4a # slo4ly. $his is calle( the inte "acial nit ation ! ocess. -t is suggeste( that 7=2Cl o)i(i@e( tet anit ocubylso(iu# to a a(ical' 4hich #a(e the 4hole eaction 4o 1e(.

1a!e on t"e -$o-e$ty o& >52Cl , >254 !"oul# be a bette$ c"o ce. 7"e $e!ult! !"o(e# t"at t ! actually a bette$ ( t" ,0940 P>C to 7>C $at o. 7"e $eact on ! e4t$e%ely clean. P>C ! colou$le!! an# " '"ly c$y!tall ne. )t ! t"e & $!t n t$ate# cubane to conta n a#Gacent n t$o '$ou-!. )t be"a0e! Gu!t 7>C an# ot"e$ n t$ocubane!, $e%a$3ly !table 3 net cally.

:7C
Alt"ou'" H>C can be -$e-a$e# t"e !a%e (ay a! P>C, but t"e !e-a$at on bet(een P>C an# H>C ! e4t$e%ely # && cult.

Ho(e0e$, & 7)PS-!ub!t tute# P>C( by >254 n t$at on &$o% 7)PS-!ub 7>C) $eact ( t" -ota!! u% ba!e (J(7?S>)2an# t"e n t$at on ( t" >254 'a0e a % 4tu$e o& (t$ !o-$o-yl) H>C an# P>C n ,0940 $at o. 7" ! !te- ! %-o$tant an# c$uc al. 7"e !e-a$at on ! no( -o!! ble by colu%n c"$o%ato'$a-"y on ! l ca 'el. 30R !olate# y el# o& P/8. H>C coul# be obta ne# ("en &u$t"e$ t$eate# ( t" S 52.

Synthesis "o the last t4o nit o cubanes& he!tanit ocubane an( octanit ocubane
)nte$&ac al n t$at on ! not !u&& c ent to &u$t"e$ n t$at on &o$ "e-tan t$ocubane. Al t"ou'" t ! 0e$y 'oo# n #ee#, (e nee# to & n# !o%et" n' (" c" can !ucce!!&ully con0e$t "e-tan t$ocubane (H->C).

:!7C

)n t" ! -$oce#u$e 7>C (a! t$eate# ( t" at lea!t 4 e6u 0alent! o& t"e ba!e >a>(7?S)2 (("e$e 7?S L t$ %et"yl! lyl) at O78 -C n 191 7H;P?e7H;. A&te$ t"e %ono !o# u% !alt "a# &o$%e#, t"e !olut on (a! coole# to bet(een O125 an# O130I-C ' 0 n' a clea$, but 0e$y 0 !cou! &lu #. 7" ! (a! !t $$e# 0 'o$ou!ly a! e4ce!! >254 n col# !o-entane (a! a##e#. A&te$ one % nute, t"e ba!e (a! 6uenc"e#, an# t"e ("ole % 4tu$e (a! a##e# to (ate$. 7" ! $e!ulte# $e-$o#uc bly n al%o!t co%-lete con0e$! on o& 7>C (1 ' !cale) to H->C (+5R by >?8), !olate# c$y!tall ne n 74R y el#M

=7C
Ho(e0e$, e0en n t"e -$e!ence o& e4ce!! n t$at n' a'ent (>254 o$ %any ot"e$!) no n# cat on o& any &o$%at on o& 5>C (a! e0e$ !een. )t ! !u!-ecte# t"at an on n t$at on ( t" >254 -$ocee#! by o4 #at on o& t"e ca$ban on to t"e co$$e!-on# n' $a# cal.Pe$"a-! t"e an on o& H->C ! too !tab l *e# &o$ t" ! to occu$. (H->C ! ! 'n & cantly on *e# n neut$al %et"anol.) 7" ! conce-t le# to t"e u!e o& t"e %o$e -o(e$&ul o4 #ant n t$o!yl c"lo$ #e. A## t on o& e4ce!! >5Cl to a !olut on o& t"e l t" u% !alt o& H->C n # c"lo$o%et"ane at 78I -C &ollo(e# by o*onat on at 78I -C 'a0e t"e lon'-!ou'"t 5>C n 45O55R !olate# y el# on % ll %ole !cale. 7"e nte$%e# ate -$o#uct -$ o$ to o4 #at on ! t"ou'"t to be n t$o!o"e-tan t$ocubane.

; nally, t"e %a' c %olecule, t"e !o calle# t"e %-o!! ble %olecule, octan t$ocubane (a! !ynt"e! !e#. 1ut, "o( 'oo# a$e t"ey an# "o( u!e&ul a$e t"eyX Aet u! # !cu!! about t n t"e &ollo( n' !ect on.

* o!e ties o" nit ocubane+


>e t"e$ H->C no$ 5>C ! #etonate# by "a%%e$ blo(!M 1ot" "a0e #eco%-o! t on -o nt! (ell abo0e 200 -C. 5ctan t$ocubane !ubl %e! unc"an'e# at at%o!-"e$ c -$e!!u$e at 200 -C. H->C &o$%! beaut &ul, colo$le!!, !ol0ent-&$ee c$y!tal! ("en t! !olut on n &u% n' n t$ c ac # ! # lute# ( t" !ul-"u$ c ac #. S n'lec$y!tal E-$ay analy! ! con& $%e# t"e a!! 'ne# !t$uctu$e an# -$o0 #e# an accu$ate #en! ty at 21 -C o& 2.028 ' c%O3, %-$e!! 0ely " '" &o$ a C, H, >, 5 co%-oun#. Alt"ou'" octan t$ocubane catc"e! t"e %a' nat on ( t" t! !y%%et$y, "e-tan t$ocubane cu$$ently ! ! 'n & cantly ea! e$ to %a3e t"an 5>C. )t ! #en!e$, an# t %ay be a %o$e -o(e$&ul, !"oc3- n!en! t 0e e4-lo! 0e t"an any no( n u!e. Acco$# n' to -a'e 41 o& a 2004 )/PAC 'u #e, cubane ! t"e N-$e&e$$e# )/PAC na%e.N 1. 2 2Cubaneand Thomas W. Cole. Philip . aton and Thomas W. Cole J. Am. Chem. Soc.! 1964! "#$1%& pp '1%( - '1%"! doi)1*.1*21+,a*1*#-a*.1. 2. The Cubane System P" l - .. .aton an# 7"o%a! B. Cole C. A%. C"e%. Soc.< 1964< 8,(5) -- +,2 - +,4< #o 910.1021PGa0105+a072 3. ? c"ael 1. S% t", Ce$$y ?a$c", /arch0s Advanced 1r2anic Chemistry, 5 t" .#., Co"n B ley Y Son!, )nc., 2001, -. 145+. )S1> 0-471-5858+-0 4. J. J n#le$, J. AZ"$!, Chem. 3er., 0ol. ++, 1+,,, -. 227.

.aton Cubane Synt"e! ! [ SynA$c" 0e.co% Cubane c"e% !t$y at )%-e$ al Colle'e Aon#on

1a!3etane 5ctaa*acubane 5ctan t$ocubane

.i#ethyl cubane&1'4&(ica bo)ylate

(i#ethyl 1'4&cubane(ica bo)ylateA 1'4&cubane(ica bo)ylic aci( (i#ethylBeste A


#ethyl 4&8#etho)yca bonyl9!entacycloC4.2.0.0D2'5E.0D3'8E.0D4'7EFoctaneca bo)ylate *entacyclo84.2.0.082'59.083'89.084'799octane&1'4&(ica bo)ylic aci( (i#ethyl este

C2S 29412&62&2
6olecular Eeight@ 220.2214

6olecular =ormula@

12#121:

!ensity@

1.6&:g/cm4

Boiling 8oint()@

2;0D

at ;60 mm#g

=lash 8oint()@

141.4D

refractiveFinde/@

1.;0:

An nte$e!t n' 5P8: -a-e$ on t"e !cale u- o& # %et"yl cubane -1,4-# ca$bo4ylate.

7"e (o$3 a--ea$e# n 5$'an c P$oce!! 8e!ea$c" an# #e0elo-%ent, 2013, #o .o$'P10.1021Po-400181' . )t (a! ca$$ e# out by an Au!t$al an '$ou-, Co"n 7!ana3t! # !, ? c"ael ;al3 ne$, Stua$t A ttle$, Jennet" ?c8ae an# Paul Sa0a'e &$o% CS)85an# &eatu$e! a la$'e-!cale -"otoc"e% cal $eact on (" c" ! 0e$y unu!ual to !ee n a !cale# c"e% cal -$oce!!. .4ten# n' t"e $ -$e0 ou! (o$3 &$o% 1++7, t"ey !cale# t"e &ollo( n' $eact on.

A! ! t"e no$% ( t" !uc" $eact on! t"e $eact on $e6u $e! " '" # lut on to be !ucce!!&ul. )n t" ! ca!e t"ey u!e# a ta lo$ %a#e -"otoc"e% cal $eacto$. A !olut on o& 1 n %et"anolP(ate$ (a! -u%-e# t"$ou'" t"e $eacto$ at 4 AP% nute an# t"e con0e$! on o& 1 to 2 (a! note# a! 1'P4 % nute! o& $$a# at on.

7" ! %eant a total t %e o& 173 "ou$!. ;u$t"e$ -$oce!! n' o& 2 t"$ou'" t"e #ouble ;a0ou$!3 $ n' cont$act on $e6u $e# ! 'n & cant #e0elo-%ent but e0entually #el 0e$e# t"e # -!o# u% !alt co$$e!-on# n' to t"e # -e!te$ o& cubane. 5ne nee#! to be ca$e&ul ( t" t"e!e cubane! a! t"ey a$e, #ue to t"e " '"ly !t$a ne# natu$e o& t"e !y!te% 6u te ene$'et c %ate$ al!, t"e #o-ac # an# e!te$ be n' %o$e !table t"an t"e -a$ent "y#$oca$bon. Ho(e0e$ t"e ene$'y $elea!e# u-on (a$% n' abo0e t"e %elt n' -o nt ! not n! 'n & cant. 7" ! -a-e$ $e-$e!ent! a 'oo# #e%on!t$at on o& t"e !cale-u- o& !e0e$al 0e$y # && cult c"e% cal $eact on!, nclu# n' e4cellent #e!c$ -t 0e -a$a'$a-"! o& t"e -$oble%! an# !olut on!. 7"ey a$e to be con'$atulate# on a 0e$y n ce - ece o& (o$3.
See below

A !calable -$oce!! &o$ t"e -$e-a$at on o& " '" -u$ ty # %et"yl 1,4-cubane# ca$bo4ylate (3) ! $e-o$te#. 7"e (o$3 #e!c$ be# "e$e n bu l#! on -$e0 ou! !ynt"et c (o$3 &$o% t" ! an# ot"e$ labo$ato$ e!, to -$o0 #e a $el able -$oce!! t"at can be u!e# to -$e-a$e %ult '$a% 6uant t e! o& 3 n a -a$t ally tele!co-e#, 8 !te- -$oce!!, ( t" % n %al -u$ & cat on o& nte$%e# ate!.

*ilot&Scale * o(uction o" .i#ethyl 1'4&Cubane(ica bo)ylate


? c"ael C. ;al3 ne$ , Stua$t B. A ttle$ , Jennet" C. ?c8ae , K. Paul Sa0a'e , an# Co"n 7!ana3t! # ! @ CS)85 ?ate$ al! Sc ence Y .n' nee$ n', )an Ba$3 Aabo$ato$y, 1ay0 e( A0enue, Clayton H cto$ a 31,8,Au!t$al a 1r2. Process 4es. 5ev., 2013, 17 (12), -- 1503U150+ .=-+ 10.1021Po-400181' Publ cat on :ate (Beb)9 >o0e%be$ 8, 2013

"tt-9PP-ub!.ac!.o$'P#o P&ullP10.1021Po-400181'X-$e0Sea$c"LcubaneY!ea$c"H !to$yJeyL

Sc"e%e 5. P lot-Scale Synt"e! ! o& : %et"yl 1,4-Cubane# ca$bo4ylate (3)

; 'u$e 1. Cubane nucleu!. Ste- 5 A #$y 100 A 'la!! $eacto$ (a! c"a$'e# ( t" t"e c$u#e # ac # 2 (1287 '), #$y %et"anol (3, A), an# :o(e4 on-e4c"an'e $e! n 50BE8U100 (17, ') t"at (a! -$e(a!"e# ( t" 1 A o& %et"anol. 7" ! % 4tu$e (a! t"en !t $$e# (150 $-%), an# "eate# un#e$ $e&lu4 &o$ 18 " un#e$ an at%o!-"e$e o& n t$o'en. 7"e % 4tu$e (a! t"en coole# to $oo% te%-e$atu$e an# & lte$e# to $e%o0e t"e $e! n. 7"e %et"anol !olut on % 4tu$e (a! t"en e0a-o$ate# to #$yne!! u! n' a $ota$y e0a-o$ato$ (45 IC at 45 %%H') lea0 n' be" n# t"e c$u#e

# e!te$ 3 (8,3 ') a! a #a$3 b$o(n !ol #. Pu$ & cat on by !ubl %at on (100U120 ICP0.01 %%H'), &ollo(e# by $ec$y!tall *at on &$o% aceton t$ le &u$n !"e# t"e # e!te$ 3 (5,0 ', 30R), a! a colo$le!! !ol #, %- 1,4.5 IC (l t. 1,1U1,2 IC).(47) 1H >?8 W9 3.7, !, ,H 4.24, !, ,H, $ n' -$oton!. 13C >?8 W9 47.03, 51.55, 55.77, 171.8+.

...................................... "tt-9PPc!t-(((.n$l.na0y.% lPlatt ceP!t$u3Pc8"8."t%l. "tt-9PP(((.c". c.ac.u3PlocalP-$oGect!Pb\%u $P.nte$."t%l. "tt-9PP(((.!c ence# $ect.co%. "tt-9PP(((.!c encene(!.o$'P. "tt-9PP(((.( nb%#o.co%P. 1a!" $-Ha!"e% , A., >e( #e0elo-%ent! n cubane c"e% !t$y9 -"enylcubane!.

G. 2#. Che#. Soc.A1988A1108219A7234&7235' 110(21), 7234-7235. :.S.Cal0ao, -. %. 0. b. 1. A. C. C. a., 7"eoo$et cal C"a$acte$ *at on o& ol 'ocubane. Synthetic 5etals 102 819999 1410. .. B. :ella, .. ;. ?., H. J. Patney,Ke$al# A. Cone!,< ? lle$, a. ;. A., H b$at onal S-ect$a o& Cubane an# ;ou$ o& )t! :eute$ate# :e$ 0at 0e!. Gou nal o" the 2#e ican Che#ical Society H 101.25 H .ece#be 5' -979'7441& 7457. Kala!!o, H., 7"eo$et cal !tu#y o& !-ect$o!co- c -$o-e$t e! o& cubane. Che#ical *hysics 184 819949 107&114. J $ ll A. Au3 n, C. A., P" l - .. .aton,@,>obu" $o Jano%ata,Cu $'en Ha n,.$ c Pun*alan,an# 8 c"a$# K la$# , Synt"e! ! an# C"e% !t$y o& 1,3,5,7-7et$an t$ocubane )nclu# n' ?ea!u$e%ent o& )t! Ac # ty, ;o$%at on o& o-> t$o An on!, an# t"e ; $!t P$e-a$at on! o& Pentan t$ocubane an# He4an t$ocubane. G. 2#. Che#. Soc.' Iol. 119' 7o. 41' 1997'9592&9602. P....aton, Cubane!9 !ta$t n' ?ate$ al! ;o$ t"e c"e% !t$y o& 1++0! an# t"e >e( Centu$y. G. 2#. Che#. Soc.A1992A31A1421&1436' 31, 1421-143,. P" l - .. .aton, t. F. E., t an# 8 c"a$# K la$# @, Sy!te%at c Sub!t tut on on t"e Cubane >ucleu!. Synt"e! ! an# P$o-e$t e! o& 1,3,5-7$ n t$ocubane an# 1,3,5,7-7et$an t$ocubane

. G. 2#. Che#. S=C.1993'115' 10195&10202. P" l - .. .aton, 8. A. K.< ]"an', a. ?.-E., Polyn t$ocubane!9 A#0ance# H '"-:en! ty, H '"-.ne$'y ?ate$ al!@@. 2(%. 5ate . 2000' 12' 7o. 15' 2ugust 2. P" l - .. .aton, Cubane9 Sta$t n' ?ate$ al! &o$ t"e c"e% !t$y o& t"e 1++0! an# t"e ne( centu$y. 2nge4.Che#.-nt.,(.,ngl.1992'31'1421&1436. P" l - .. .aton, t. F. E., t an# 8 c"a$# K la$# @, Sy!te%at c Sub!t tut on on t"e Cubane >ucleu!. Synt"e! ! an# P$o-e$t e! o& 1,3,5-7$ n t$ocubane an# 1,3,5,7-7et$an t$ocubane. G. 2#. Che#. S=C.' Iol. 115' 7o. 22' 1993'10196&10202. 7. F)A:)8)?, P. ?. K., :. A. >./?A>>, P. .. .A75>C an# T7. .?8)CJS, S5A): C/1A>.9 A 18).; 8.H).B. Ca bon Iol. 36' 7o. 5&6' !!. 809&815'1998. ]"an', P. .. .. a. ?.-E., 5ctan t$ocubane9 A >e( > t$oca$bon. * o!ellants' ,)!losi%es' *y otechnics 27' 1 & 6 820029. C5?P)A.: 1F

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