J. Chem. Sci. (2 0 2 0 ) 13 2: 65
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le nt in te ra ct io ns ( NCIs) were analy zed th ro ugh eval- 80 °C ) e lua te s, R
u at ion o f the B3LYP/6 -3 1G(d ) mon odet er minanta l ( 60- 80 °C )
wav e fun ctio ns o f the l ocat ed tr an si tion states by using mꢀ = 30 77( w) , 167 0 ( s) , 15 20 ( s) , 134 7( s) , 1251 ( s ),
= 0.5 1 ( sil ic a ge l, pe tr ol eu m e the r
be nz e ne = 1: 1) , I R( c m ) ( KB r ) :
f
-1
:
3
6
1
M u l t i w f n p r og ra m . ELF b asin analysi s was performed 827 ( m) , 75 2 ( s) , 692 ( s) , H NMR ( 30 0M Hz ,
wit h a hig h-q ua lity gr id wit h sp acin g of 0.0 6 Bohr. ELF C DCl ,) :d 5.5 8 ( 1H,d, J = 7.0 Hz , H3) , 4.0 3 ( 1H ,dd,
b as in s a nd a ttra ctors were vi su al ized b y using VMD J = 7.0 , 9.2 Hz , H4) , 5.4 6 ( 1H,d, J = 9.2 Hz , H 5) , 6.88
3
3
7
38
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( 3H, m H2,4 ,6 ( A) ), 7.0 8- 7.31 ( m, H3,5 (A) , H2,3,5 ,6
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C N MR
3
(
75.5 MHz , C DCl ,) : d 74. 28 ( C3 ), 69 .20 ( C4 ) , 84.78
3
2
. 1 Experimental methods
( C5 ), 151 .32 ( C1 (A) ) , 114 .42 ( C2 ,6( A) ), 127.9 2
C3 ,5( A) ), 12 2.30 ( C4 (A) ) , 136 .33, 13 6.89 ( C 1( B ),
C 1( C) ) , 13 3.15( C 4( B) , 12 6.77 ( C3 ,5( C) ) ,128.95
C4 (C ) ) , 12 8.77, 128 .68, 128 .43 ( C2 ,6( B) , ( C 3,5( B ) ,
C 2,6( C )) , 196 .20 ( C= O) , 27. 42 ( - CH ) ; MS : m/z377
(
Ni t ro n e 1 wa s p re pa re d by r eflu xi n g p hen yl h ydr ox y-
l a m in e (p re p a re d f ro m ni t r ob enz en e u si ng zi nc a nd
am m on i um ch lo ri d e) a nd 4 -c h l o ro b e nz al d eh yde in
e t ha n o l in wa te r ba t h f or 2 h. Ni tr o ne 1 se pa ra te d a s
wh i te c ry s ta ls wh ic h wer e t he n r ecr ys t al li z ed in e tha -
n o l . Be n z y li d e n e ac et on e 2 was ob t ai ne d f r om th e
m i x e d a ld o l c o n d en sa ti o n o f be nz al de h yd e a nd a ce -
t o n e. Re a c ta n ts 1 an d 2 wer e o bt ai ne d i n pu re f or m
a n d c o n fi rme d by I R an d NM R st u di es . F or th e
c y c lo a d d i ti o n re a c t io n, 0. 00 44 mo l of r eac t an t 1 wa s
(
3
?
(
(
1
C H NO C l, M ) , 24 2 ( C H OC l), 231
2 3 2 0 2 1 5 1 1
?
C H NOC l) , 21 6 ( C H NC l) , 13 1 ( C H O ) ,
1 3 1 0 1 3 1 1 9 7
?
1 1 ( C H C l ) , 91 ( C H ?) .
6 4 7 7
3
9
2.1 b (3a,4a,5b)-3-(4-chlorophenyl)-4-oxomethyl-2,5-
Diphenyl-isoxazolidine (4, C H ClNO ): W hite
a mo rp hous sol id, 0.1 2 gm ( 7%) , is ola te d f r om 20%
2
3
20
2
3
a l lo we d to re a c t w it h 0. 00 66 mo l o f r eac t ant 2 in 5 c m
be nz e ne in pe tr ol eu m e the r ( 60- 80 °C ) e lua te s ,
re fl u x in g d ry th i o ph en e- fr ee t ol ue ne un d er a n itr o gen
a t m o s p h e re fo r 1 6 h. Th e cy cl o ad di ti o n was mon ito re d
b y th e e x a mi n a ti on of r eac t io n al i qu ot s at r eg ula r
i n t e rv a ls o f ti me by t hi n- l ay er ch ro ma to gr ap hy ( usi ng
b e n z e n e -et h y l a c et at e ( 4: 1) so l ve nt sy st e m an d si lic a
R = 0.6 0 ( sil ic a ge l, pe tr ol eu m e the r ( 60- 80 °C ) :
f
-
1
be nz e ne = 1: 1) , I R( c m ) ( KBr ) : mꢀ = 304 5( w) , 1677
1
s) , 159 4 ( s) , 14 87 ( s) , 825 ( m) , 755 ( s) , 695( s ) , H
(
NMR ( 300 MHz , C DCl ,) :d 5.3 5 ( 1H,d, J = 1 0.3 H z,
3
H3) , 4.9 7 ( 1H,dd , J = 10. 3, 9.1 Hz , H4) , 6.5 1( 1H, d,
J = 9.1 Hz , H5) , 6.9 3 ( 3H, m H2,4 ,6 ( A) ), 7.10- 7. 36
1
g e l a d s o rb e n t) a n d 3 00 M Hz H sp ec tr o sco py . Af te r
c o mp le tio n o f th e r un t im e, ex ce ss t ol ue n e wa s
re mo v e d fro m t he p ost - re ac ti o n mi xt u re s un der
re d u c e d p re s s u re us i ng a r ot ar y ev ap or at o r. C yc loa d-
d u c ts we re is o l a ted f ro m t he cr ud e r eac t io n mi xt ur e by
c o l um n c h ro ma t o g ra ph y o ver n eut r al al u min a ( Ac tiv-
i t y I-I I, M e rc k ) us i ng pe t ro le um et h er an d be nz e ne
m i x tu re s a s th e el u en ts . Th e co l umn was in iti al ly
e l ut e d wi th p e tr o leu m et h er ( bp t: 60 - 80 °C) a nd th en
p ro g re s s iv e ly , th e p ro po rt io n of be nz en e was i n cr e a se d
i n th e e lu e n t. Al l st a rt i ng ma te ri a ls an d so l ve n ts use d
fo r re a c ti o n s a n d ch ro ma to grap hi c se pa ra ti on we r e
d i s t il le d b e fo re us e. I R sp ec tr a o f t he cy cl o a dduc ts
we re re c o rd e d us i ng a Pe rk i n- El mer RX- 9 F T- IR
(
(
(
(
(
m, H3,5 (A) , H2,3 ,5,6 ( B) , H2,3 ,4,5, 6 ( D) ), 7.33- 7. 39
1
3
m, H2,3 ,4,5, 6 ( C) ) , 2.1 8 ( s, C H 3) ;
C N MR
75.5 MHz , C DCl ,) : d 73. 48 ( C3 ), 67 .30 ( C4 ) , 84.75
3
C5 ), 149 .07 ( C1 (A) ) , 115 .58 ( C2 ,6( A) ), 127.9 0
C3 ,5( A) ),1 22.3 0 ( C4 (A) ) , 13 6.13, 13 6.92 (C 1( B ) ,
C 1(C )), 1 33.30 (C4 (B ),1 26.85 (C3 ,5 (C )), 12 8.8 5( C4( C) ) ,
1 28 .78 , 12 8.6 8, 12 8.3 3 (C 2, 6(B) , (C 3, 5(B ), C 2, 6( C) ),
1
97 .59 (C =O), 2 7.5 8 (-C H3) ; MS : m/z3 77
?
C H N O C l , M ) , 242 ( C H O C l ) , 2 31
(
23
2 0
2
15 11
?
C H N OCl ), 2 1 6 (C H NC l) , 1 31 ( C H O ), 111
(
13 1 0 13 1 1 9 7
?
C H C l ), 91 (C H ?).
(
6
4
7
7
1
1
3
s p e c tro p h o to m e t er . H an d C NM R sp ec tr a of th e
c y c lo a d d u c t s a n d cr ud e r eac t io n mi xt u re s wer e r ec or -
d e d b y a Br u k e r AV- 30 0 NM R sp ec tr o met er a t 30 0
a n d 7 5 . 5 M Hz , res pe ct i ve ly . Sp ec tr a wer e r eco r de d in
3
. Results and Discussion
3.1 Experimental findings for 32CA reaction
between 1 and 2
C D Cl s o lv e n t. Ch emi ca l sh i ft s f or NM R ar e re por t ed
3
i n p p m, d o wn fi el d f ro m TM S . M as s sp ect r a a re
re c o rd e d u s in g a JE OL JM S 60 0 H ma ss sp ec tr om e te r .
3
2C A r ea c ti on be twe e n 1 a nd 2 a ff o rd ed a dia s te r e -
om e ri c m ixt ur e of meta c yc loa dd uc ts 3 a nd 4
Sc he m e 1 ) in th e r at io 87: 13 wit h th e to ta l y ie ld of
5% . S tr uc tur e e luc id at ion wa s a cc om pl ishe d by
(
7
2
Diphenyl-isoxazolidine (3, C H ClNO ): W hi te
.
1
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3
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4
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5
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spe c tr os cop y ( pa r tic ul ar l y NMR ) a nd m as s spe ct r om-
1
e tr y. 300 MHz H NMR spe c tr um of th e m aj or pr oduc t
a m or p h o us s o li d , M .p .: 12 2 °C, 0 .96 gm ( 58%) ,