Generation and cycloaddition reactions of the 1,2,3-triazole analogue of o-quinodimethane

Article abstract of DOI:10.1016/S0040-4039(00)60120-X

4,5-Dihydro-4,5-dimethylene-1-phenyl-1,2,3-triazole (4), the 1,2,3-triazole analogue ofσ-quinodimethane, can be generated in situ from 4,5-bis(bromomethyl) derivative (3) by sodium iodide induced 1,4-elimination process. By trapping the 1,4-dimethylene-tr

Full text of DOI:10.1016/S0040-4039(00)60120-X

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Generation and Cycloaddition Reactions
of t he
of o- Qui nodi met hane
Ge or ge E. Me r t z a nos , J ul i a St e pha ni dou- St e pha na t ou*, Cons t a nt i nos A. Ts ol e r i di s
a nd Ni c hol a s E.
Che mi s t r y
De pa r t me nt
,
La bor a t or y
of
Or ga ni c
Che mi s t r y,
Uni ve r s i t y of The s s a l oni ki , The s s a l oni ki 54006, Gr e e c e
o- Qui nodi me t ha ne ;
Di e l s - Al de r Cyc l oa ddi t i ons , AM1
words:
Ca l c u l a t i o n s
Abs t r act :
t he
a na l ogue of o- qui nodi me t ha ne , c a n be ge ne r a t e d i n s i t u f r om
va t i ve ( 3) by s odi um i odi de i nduc e d pr oc e s s . By t r a ppi ng t he
de r i -
t hyl e ne - t r i a z ol e wi t h s ymme t r i c a l l y a nd uns ymme t r i c a l l y s ubs t i t ut e d di e nophi l e s t he
Di e l s - Al de r c yc l oa dduc t s we r e i s ol a t e d i n mode r a t e t o l ow yi e l ds ; i n t he pr e s e nc e of
a c t i va t e d mol e c ul a r
s i e ve s
t he yi e l ds
a r e ma r ke dl y i mpr ove d.
The ge ne r a t i on of o- qui nodi me t ha ne s
f r om a r oma t i c s ys t e ms a nd t he i r Di e l s - Al de r
t r a ppi ng r e a c t i ons pr ovi de d powe r f ul me t hod f or t he pr e pa r a t i on of pol yc yc l i c
a
t e r ns . 1 Al t hough r e c e nt l y i nt e r e s t ha s be e n t ur ne d t o t he he t e r oc yc l i c a na l ogue s of
t he i r s ynt he t i c pot e nt i a l ha s be e n e s pe c i a l l y de mons t r a t e d i n t he
As
s ynt he t i c i nve s t i ga t i ons on t he
s ul t s c onc e r ni ng t he ge ne r a t i on a nd t he i nt e r mol e c ul a r c yc l oa ddi t i on r e a c t i ons of t he
a
f ur t he r s t udy on he t e r oc yc l i c
a nd i n c ont i nua t i on of our
r e -
we wi s h t o di s c l os e our
hi t he r t o unknown
Our a ppr oa c h, s hown i n t he Sc he me , ut i l i z e s t he unknown
whi c h c a n be s ynt he s i z e d f r om t he
a z ol e - 4, 5- di c a r boxyl a t e (1) i n t wo s t e ps . Sodi um bor ohydr i de
a f f or de d t he c or r e s pondi ng ( mp
wi t h phos phor ous t r i br omi de ga ve t he bi s br omi de
( 4) .
1- phe nyl - 1, 2, 3- t r i -
of t he di e s t e r
nyl - 1, 2, 3- t r i a z ol e
1
2
70% yi e l d) , whi c h upon
3
( mp
78% yi e l d) .
By 1, 4- e l i mi na t i on of br omi ne , a c hi e ve d by t r e a t me nt of
3
s odi um i odi de i n DMF a t
4499

4 5 0 0
Sc he me
a bs .
X
X
t he n
a q.
Ph
3
2
1
Me
Me
XCH2
a
-
-
9
4
mp
1 1 % [ a ]
mp
5 0 %
‘N- N’
8
7
6
oi l
2 0 % [ a ]
mp
mp
2 7 % [ a ]
4 5 %
[ a ] Yi e l ds i n t he pr e s e nc e of mol e c ul a r s i e ve s ( 41) .
Al l Di e l s - Al de r
ha d a na l yt i c a l a nd s pe c t r os c opi c da t a i n a gr e e me nt wi t h t he
pr opos e d
s t r uc t ur e .

4501
t he
4 wa s
a c c or di ng t o t he r e por t e d pr oc e dur e
ge ne r a t e d a nd wa s t r a ppe d a s i t s Di e l s - Al de r
5- 9. Whe n t he l e s s r e a c t i ve
phi l e s me t hyl vi nyl ke t one a nd me t hyl a c r yl a t e we r e us e d ve r y l ow yi e l ds 2% a nd 4% of
t he c or r e s pondi ng c yc l oa dduc t s a nd we r e i s ol a t e d, a l t hough t he s e di e nophi l e s we r e
i n t he pr e s e nc e of hi ghl y a c t i va t e d mol e c ul a r
8
9
i n l a r ge e xc e s s Howe ve r ,
t he r e a c t i on yi e l ds we r e i mpr ove d t o 20% a nd 11% r e s pe c t i ve l y. The poor yi e l ds of
Di e l s - Adl e r
5- 9 mi ght be e xpl a i ne d c ons i de r i ng t ha t
4
i s
a mor e r e a c t i ve i nt e r me -
o - q u i n o d i me t h a n e s
l e a di ng t hus t o t he f or ma t i on
di a t e c ompa r e d t o ot he r he t e r oc yc l i c
of
s e ve r a l
The
pol yme r
by- pr oduc t s .
c yc l oa ddi t i on be t we e n
4
a nd di e nophi l e s wa s a l s o e xa mi ne d c ons i de r i ng t he
c a r r i e d out on c ompound
of t he r e a c t i ng s pe c i e s . On t he ba s i s of AM1
4, me t hyl a c r yl a t e a nd N- me t hyl ma l e i mi de i t i s c onc l ude d t ha t t hi s c yc l oa ddi t i on, i n
s pi t e of t he pr e s e nc e of t he t r i a z ol e r i ng, i s HOMO- di e ne c ont r ol l e d ( Fi gur e ) l i ke ot he r
nor ma l Di e l s - Al de r
e
- 2
- 0 . 5 8
-1 .1 4
- 4
- 6
= 7. 52
= 10. 44
-8.66
= 9. 93
N
- 8
1 0
a 2
-10.51
-11.02
1 0
12
‘ N- Me
( b)
4
0.12
6
Fi gur e .
HOMO- LUMO i nt e r a c t i ons be t we e n di e ne 4 a nd t he di e nophi l e s me t hyl a c r yl a t e
( a )
a nd N- me t hyl ma l e i mi de ( b)
a f t e r
AM1 c a l c ul a t i ons .
I n r e s pe c t wi t h t he r e gi os e l e c t i vi t y of t he c yc l oa ddi t i on of
4
wi t h me t hyl a c r yl a t e
i t i s pr e di c t e d a f t e r e xa mi na t i on of t he or bi t a l c oe f f i c i e nt s ( Fi gur e ) t ha t t he
f a vor e d r e gi o- pr oduc t 10 s houl d be t he pr e domi na nt i s ome r . Howe ve r , t he s t r uc t ur e
of t he i s ol a t e d
On t he ot he r ha nd, t he e ne r gy di f f e r e nc e AE =
t i on of 4, i s e qua l t o 8. 08
r e a c t i on wi t h N- me t hyl ma l e i mi de , but l owe r t ha n f or t he r e a c t i on of
9
a s we l l a s t ha t of
8
i s unde r f ur t he r c ons i de r a t i on.
f or
a
va l ue whi c h i s hi ghe r t ha n t he a l l owe d pr oc e s s f or t he
wi t h me t hyl
4

4 5 0 2
l a t e a nd t hi s mi ght be t he r e a s on f or t he l ow yi e l d of t he c or r e s pondi ng Di e l s - Al de r
References and Notes
1.
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M. M.
2.
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1991, 32, 7609. c ) J a c ks on, P. M. ; Moody,
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S. ;
Per&in Trans.
1
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Ch e m.
P
Kni ght , D. W.
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9.
Sodi um bor ohydr i de i mpr ove s t he r e por t e d i n r e f .
whe r e t he l i t hi um a l umi num hydr i de wa s us e d.
6 r e duc t i on yi e l d f r om 26% t o
Ca va , M. P. ;
A. A. ; Mut h, K. J. Am. Chem.
1 9 5 9 ,
6 4 5 8 .
Ha be r , M. ; Pi ndur , U. ,
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11.
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(Received in UK 22 May 1992)