Diphenyl phosphate creatine immobilized on magnetite nanoparticles: an efficient and recyclable catalyst for Aza-Michael reaction

Article abstract of DOI:10.1007/s12039-019-1721-7

Abstract: In this paper, diphenyl phosphate creatine was successfully immobilized on Fe₃O₄ nanoparticles and used as the highly efficient catalyst for the aza-Michael reaction of 5-substituted tetrazole and α,β-unsaturated carbonyl.

Full text of DOI:10.1007/s12039-019-1721-7

J. Chem. Sci. ( 2 0 2 0 ) 1 3 2 : 3 0
Ó I n d ia n A c a d e m y o f S c i en c es
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REGULAR ARTICLE
Diphenyl phosphate creatine immobilized on magnetite
nanoparticles: an efficient and recyclable catalyst for Aza-Michael
reaction
F A R Z A N E P A Z O K I , F A H I M E H M O H AM M AD P A N A H , A R E F E S A L A M A T M A N E S H,
*
J A M S H I D A Z A R N IA M E H R A B A N a n d A K B A R H E Y D A R I
D e p ar t m e n t o f C h e m i c a l , F a c u l t y o f S c i e n c e s , T a r b ia t M o d a r e s U n iv e r s i ty , T e h r a n 1 4 1 1 7 - 1 3 1 1 6 , I r a n
E - m a i l : H E Y D AR _ A @ m o d a r e s . a c . i r
T h i s a r t i c l e i s d e d i c a t e d t o t h e m e m o r y o f M o h a m m a d - l i R a j a i.
M S r e c e i v e d 1 4 J u l y 2 01 9 ; r e v i s e d 6 S e p t e m be r 2 0 1 9; a c c e p t e d 1 9 S e p t e m be r 2 0 1 9
Abstract. I n t h i s p a p e r, d i p h e n y l p h o s p h a t e c r e a t in e w a s s u c c e s s f u l l y i m m o b i li z e d o n F e O n a n o p a r t ic l es
4
3
a n d u s e d a s t h e h i g h l y e f fi c i e n t c a t a ly s t f o r t h e a z a - M i c h a e l r e a c t io n o f 5 - s u b s t it u t e d t e t r a z o l e a nd a, b-
u n s at u r a t e d c a rb o n y l . T h e p r e p a r e d n a n o c a t a l y s t w a s f u ll y a n a ly z e d b y v a r io u s t e c h n i q u e s s u c h a s F o u r i er -
t r a n s f o r m I n f r a r e d S p e c t r o s c o p y ( FT - I R ) , F i e ld E m i s s io n S c a n n i n g e l e c t r o n m i c r o s c o p e ( F E - S E M ) , V ib r a t i ng
S a m p l e M a g n e t o m e t e r ( VS M ) , T h e r m a l G r a v i m e t r i c A n a l y s i s ( T G A ) a n d X - r a y D i f f r a c t i o n ( X RD ). T h i s
p r o c e d u r e p o s s e s s e s n u m e r o u s a d v a n t a g e s s u c h a s s i m p l e w o r k - u p , h i g h y i e l d a n d s h o r t r e a c ti o n t im e s .
Keywords. A z a - M i c h a e l r e a c t i o n ; D i p h e n y l p h o s p h a t e C r e a t i n e ; T e t r a z o l e s ; H e t e r o g e n e o u s C a t a ly s t .
1 7 ,1 8
c at al y s i s . T h e s u r f a ce o f m ag n e t i c n a n o p a r t i c l e s
c an b e f u n c t i o n a l i ze d w i t h v a r i o u s k i n d s o f o r g a n i c
1. Introduction
1
9
T e t ra z o l e s a r e a cl as s o f i m p o r t a n t he t e r o c y cl ic c o m -
p o u n d s b e c au s e t h e s e c o m p o u n d s h a v e b e e n a p p l i e d i n
m a j o r a r e a s o f s c i e n c e , s uc h a s m e d i c i n e , c h e m i s t r y a n d
m a t e r i a l s c i e n c e s . T h u s , m a n y s y n t h e t i c m e t h o d s h a v e
c o m p o u n d . H e n c e, m o d i fi e d m ag n e t i t e n a n o p a r t i c l e s
h a v e a t t r a c t e d a s c at a l y t i c s y s t e ms i n v a r i o u s o r g a n i c
r e ac t i o n s . T h e y h a v e n u m e r o u s b e n e fi t s i n v o l v i n g t h e i r
e as e s e p a r at i o n , r ec y c l a b i l i t y , e x c el l e n t c h e mi c a l s t a -
b i l i t y , g o o d a cc e s s i b i l i t y , h i g h s u r f a ce , s i mp l e p r e p a -
r a t i o n , r e as o n a b l e p r i c e a n d a b i l i t y t o b e
1
–
5
b e e n r e p o r t e d f o r t h e s y n t h e s i s o f t e t r a z o l e s . N -f u n c -
t i o na li z a t i on o f te t r a z o le s is a n a p p r o a c h f o r t h e s y n t h e s i s
6
o f v a r i o u s t e t r a z o l e d e r i v a t i v e s . T h e a z a - M i c h a e l a d d i t i o n
2
0
–
2
3
f u n c t i o n a l i ze d .
d e v e l o p s i mp l e p r o t o c o l s f o r t h e s y n t h e s i s o f t e t r a -
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o f t h e s e t e t r a z o l e s t o a, b- u n s a t u r a t e d c a r b o n y l c o m p o u n d s
i s a co nv e n i e n t a nd p ow e rf u l m e t h o d t o f u n c ti o na l i z e
t e t r az o l e s. T h er e a r e f e w r e p o r t s f o r t h is m e t h o d .
P h o s p h o r am i d e s p l a y a n i m p o rt a nt r o l e i n m an y
b i o l o g i c a l p r o c e s s e s .
a n d p h o s p h a t e c r e a t in e p la y a k e y r ol e i n fl u c t u a t i n g
e n e r g y d e ma n d s , e n e r g y t ra n s du c t io n i n t i s s u e s .
C o n si d e r i n g t h e s e f a c t s , d i p h e n y l p h o s p h a t e c re a t i n e
c an a c t a s c h e m i c a l a n d b i o c h e m i c a l c a t a l ys ts d u e t o
D i p he n y l p h o s p h a t e c r e a t in e i s a t yp e o f P h o s p h o -
r a m i d e s w i t h s u b s t i tu t io n o f c r e a t in e .
N a n o m a gn et i c m a te ri a ls h a v e a t t e n de d g r e a t a t t e n -
t i o n o w i n g t o t h e i r s e v e ra l a p pl i c a ti o n s i n s y n t h e s i s a n d
2
4
z o l e s a n d c o n s i d e ri n g t h e i m p o r t an ce o f t h e c a t a l y t i c
a ct i v i t y o f d i p h e n y l p h o s p h at e c r ea t i n e , h e r e i n , w e
r e p o r t s u c c e s s f u l l y s y n t h e s i s o f d i p h e n y l p h o s p h a t e
c r ea t i n e a n d F e O @ D i p h en y l p h o s p h a t e c r e at i n e
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O n t h e o t h e r h a nd , c r ea t i n e
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n a n o p ar t i c l e s a s a g r e en c at a l y s t . I n a d d i t i o n , t h e c a t -
a l y t i c p e r fo r ma n c e o f s y n t h e s i ze d n a n o p ar t i c l e s h a s
b e e n i n v e s t i g at ed i n a za - M i c h a el r ea c t i o n o f 5 - s u b -
s t i t u t e d t e t r a z o l e w i t h a, b- u n s at u r at e d c ar b o n y l w h i c h
o b t a i n e d p r o d u ct s i n g o o d y i el d s . T h e s e m ag n e t i c a l ly
r et r i e v a b l e n a n o p ar t i c l e s a re h i g h l y e ffi c i e n t , e n v i r o n -
m en t a l l y f r i e n d l y a n d n o v el h e t e r o g e n e o u s c a t a l y s t .
1
6
T h e
F e O @ D i p h en y l
3
p h o s p h at e
c r e at i n e
4
* F o r c o r re s p o n d e n c e
Electronic supplementary material: The online version of this article (https://doi.org/10.1007/s12039-019-1721-7) contains
supplementary material, which is available to authorized users.

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w a s a d d e d t o t h i s m i x t u r e . T h e r e s u lt a n t n a n o p a r t i c l es w e re
s t ir r e d f o r 1 h a t 2 5 °C a n d t h e m i x t u r e w a s h e a te d f or 5 h a t
8 0 °C . T h e fi n a l p r o d u c t w a s s e p a r a t e d b y a n e xt e rn a l
m a g n e t a n d w a s h e d w i t h d e i o n iz e d w a t e r a n d e t h a n o l t hr e e
t im e s a n d d r i e d a t 6 0 °C f o r 1 2 h .
n a n o p a r t i c l e s c a n b e e a s i l y s e p a ra t e d b y a n e x t e r n a l
m a gn e t a n d t h e i r c a t a l y t i c a c t iv it y r e m a in s u n a l t e r e d
a f t e r 6 c o n s e cu ti v e c y c l e s . T h e s t r uc t u r e o f t h e
n a n o p a r t i c l e s w a s f ul l y c h a r a c t e ri z e d b y u s e f u l a n a l y -
s e s . T h e F e O @ D i p h e n y l p h o s p h a t e c r e at i n e
3
4
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A
r o u n d - b o t t o m e d fl a s k ( 2 5 m L ) w a s c h a r g e d w i t h 5 - s u bs t i -
t u t e d t e t r a z o l e d e r iv a t i v e s ( 2 .0 m m o l ) , a, b- u n s a t ur a te d
c a r b o n y l ( 2 .0 m m o l ) a n d t h e c a t a l y s t ( 5 0 .0 m g ) i n m e t h an ol
( 1 0 m L ) . T h e m i x t u r e w a s s t ir r e d a t 6 5 °C t o r e a c t i on c om -
p l e t i o n . A f t e r c o m p le t i o n , t h e m a g n e t i c n a n o c a t a l ys t w a s
e a s i l y c o l l e c t e d b y a n e x t e r n a l m a g n e t . T h e n , t h e p r o d u c t w a s
p u r i fie d b y c o l u m n c h r o m a t o g r a p h y , a f t e r t h e p r o du c t w a s
w a s h e d w i t h h e x a n e a n d d i e t h y l e t h e r t h r e e t im e s .
t h e a z a- M i c h e al r e a c t io n b e t w e e n 5 -s u b s t it u te d t e t r a -
z o l e d e r i v a t i v es a n d a, b- un s a tu r a te d c a rb o n y l t o s y n -
t h e s i z e t e t r a z o l e d e ri v a t iv e s i n g o o d y i e ld s ( S c h e me 1) .
2. Experimental
2 . 1 General considerations
C h emi ca l m a t er i al s we re p u rc ha se d fro m Si g m a -Al d ri ch or
M e r c k . T h e mo n i t o r i n g o f r e act i on pr og r es s w as ca rr i e d o ut b y
a na l y t i c a l T h i n L a y e r C h r om at ogr a ph y ( T LC ) on M e r c k
0 .2 m m of si l i c a g e l 60 F - 2 54 A l- p l a t e s . F T - I R w a s d e t e r m i n e d
o n a S h i ma d z u F T - IR -8 4 00 S s p e c t r om e t e r b y us i n g the K B r
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2 . 3 a Diphenyl phosphate creatine Y i e l d : 7 3 % . M . p . : 1 4 °C ;
3
1
P N M R ( 2 0 2 . 4 6 M H z , d 6 - D M SO , p p m ) : d - 1 1 . 24 ( s ) .
1
1
H N M R ( 5 0 0 . 1 3 M H z , d 6 - D M SO , p p m ) : d 1 3 . 3 ( s , 1 H ,
O H ) , 7 . 6 2 ( s , 2 H , N H a m i n e ) , 6 . 9 7 ( t, 3 J H H = 9 . 5 H z ,
p l a t e te c h ni q ue . H N M R ( 50 0 M H z ) s p e ct ra w e r e o b t a i n e d o n
B r u k e r D R X -50 0 A d v a n c e sp ec t r om e te r s w i th C H Cl a s s o l -
3
2 H Ph ) , 7 . 1 2 ( d , 3 J H H = 5 H z , 4 H Ph ) , 7 . 1 9 ( t , 3 J H H =
1 3
v e n t a t a m b i e n t te m p er a t ur e u s ing T M S a s t he in te rn a l st a n da r d.
X RD w a s c a r r i e d o u t b y a P h i l i p s X - P e r t 1 7 1 0 d i f f r a ct o m e t er
a nd al s o S E M w a s pe r fo r me d on Z e i s s -S i g m a V P 5 00 . Th e
m agn e ti c m e a s u re m e n t s e xp e ri m e n t s w e r e o bt a i n e d b y us i n g a
v i b r a ti n g ma g n e t om e te r/ a l t e r na ti ng g r a d ie nt fo rc e m a g n e -
t o m e t e r (M D C o . , I ra n, w w w. m d k -m a g n e t i c. c o m ) .
7 . 4 H z , 4 H Ph ) , 4 . 1 3 ( s , 2 H , C H ) , 2 . 4 8 ( s , 3 H , C H ) .
2
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1 2 2 .9 4 , 1 2 9 .9 , 1 4 . 2 1 ( C i p s o ) , 1 7 . 8 7 ( C= N ) , 1 9 . 8 3 ( C = O )
p p m . I R ( K Br , c m -1 ) : 3 3 6 7 ( V s ) , 3 1 8 5 ( v s , N – H ) , 1 71 8( s ,
C = O ) , 1 6 6 7 ( s ) , 1 6 0 8 ( s ) , 1 4 0 7 ( m ) , 1 2 1 1 ( v s , P = O ) , 1 10 0
( m , P – N ) , 8 5 4 ( m ) , 6 0 0 ( m ) .
2 . 3 b Phenyl-1H-tetrazol-1-yl) cyclohexenone (compound 4)
1
W h it e s o l i d . M . p . : 1 8 6 – 1 8 9 °C ; H N M R ( 3 0 0 M H z ,
2
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C h l o r o f o r m - d ) d 2 . 0 – 2 .1 6 ( m , 2 H ) , 2 . 3 2 – 2 .4 6 ( m , 2 H ),
2 . 4 8 – 2 .5 5 ( m , 2 H ) , 2 . 9 6 – 3 .2 2 ( m , 2 H ) , 5 . 1 5– 5. 3 0
2 . 2 a Synthesis of diphenyl phosphate creatine T h e m e t h y l -
g u an id o a ce t ic a ci d ( 1 5 m m o l ) a n d t r i e t h y l a m i n e ( E t N ,
3
( t t , J = 9 . 5 , 4 . 8 H z , 1 H ) , 7 . 4 3 – 7 .5 2 ( m , J = 4 . 1 , 1 . 6 H z , 3 H ),
1 3
1 5 m m o l ) w e r e d i s s o l v e d i n a c e t o n i t ri l e s o l v e n t a t -8 °C .
T h e n , 1 5 m m ol o f t h e d i p h e n y l p h o s p h i n i c c h l o ro p h o s p h a te
w a s a d de d d r o p b y d r o p t o t h e m i x t u r e f o r 3 0 m i n . N e x t , t h e
m ix tu r e w a s s t ir r e d f o r 8 h a t 2 5 °C . F i n a l l y , t h e fi n a l
p ro d u c t w a s e x tr ac t e d b y w a t e r a n d e t h y l a c e t a t e .
8 . 0 9 – 8 .2 1 ( m , 2 H ) . C N M R ( 7 5 M H z , C D C l ) d 2 1, 3 1,
3
4 0 , 4 , 1 , 1 2 . 8 , 1 2 7 , 1 2 9 , 1 3 0 , 1 , 2 0 . I R ( K Br ) c m -1 : 3 06 3
( C H ) , 1 7 1 7 ( C = O ) , 1 5 2 7 ( N = N ) . H R M S ( E S I ) ( [ M ?H ] ?)
C a l c d . F o r C 1 3 H 1 4 N 4 O :2 4 2 . 2 8 , F o u n d : 2 4 3 .2 .
2 . 3 c benzo[d] [1, 3] dioxol-6-yl)-1H-tetrazol-1-yl) cyclo-
hexenone (compound 6) W h i t e s o l i d . M . p . : 1 9 4 – 1 95 °C ;
2 . 2 b Synthesis of Fe3O4@Phenyl phosphate creatine F e O
3
4
2 5
w a s p r e p a r e d b y c o p r e c i p i t a t i o n t e c h n i q u e .
F e C l . 4 H O ( 0 . 0 2 1 6 m o l )) a n d F e C l . 6 H O ( 0 . 0 1 0 8 m o l )
T h u s,
1
H N M R ( 3 0 0 M H z , C h l o r o f o r m - d) d 1 . 8 9 – 2 .1 7 ( m , 2 H ),
2
2
3
2
2 . 2 8 – 2 .6 1 ( m , 4 H ) , 2 . 8 6 – 3 .2 6 ( m , 2 H ) , 5 . 1 7– 5. 2 8
( t t , J = 9 . 7 , 4 . 9 H z , 1 H ) , 5 . 9 6 – 6 .1 4 ( s , 2 H ) , 6 . 9 1– 7. 0 1
( d , J = 8 . 1 H z , 1 H ) , 7 . 5 5 – 7 .6 6 ( d , J = 1 . 6 H z , 1 H ),
7 . 6 9 – 7 .8 1 ( d d , J = 8 . 1 , 1 . 7 H z , 1 H ) . I R ( K Br ) c m -1 : 1 67 6
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A f t e r w a r d s , 1 0 m L o f 2 5 % N H O H s o l u t i o n w as a d d e d
d ro p b y d r o p t o t h e s t i rr i n g s u s p e n s i o n a t 2 5 °C ( u n ti l
p H = 1 1 ) . T h e n , d i p h e n y l p h o s p h a t e c r e a t i n e ( 2 . 5 m m o l )
4
Scheme 1. C a t a l y t i c a p p l i c a b i l it y o f t h e F e O @ P h e n y l p h o s p h a t e c r e a ti n e .
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a nd t he p ea k o bs er ve s at 5 93 cm- d u e t o t he F e– O
v ib ra tio n. It a ls o s ho ws t ha t th e F e O @Di ph en yl
( C = O ) , 1 5 9 9 ( N =N ) , 1 4 5 1 ( C = C ) , 1 3 8 3 ( C = N ). H R M S ( E S I )
( [M ?H ] ?) C al c d . F o r C H N O : 2 8 6 . 1 1 , F o u n d : 2 8 6 .1
1
4
1
3
4
3
3
4
p ho sp ha te c re at in e na nop ar tic le s ha ve th e sa me
st ru ct ur e af te r 6 c yc le s an d th is th e st ru ct ur e is st ab le .
A l l t h e s y n th e s iz e d c o m p o u n d s (1– 9) w e r e c h a r a c te r i z e d
1
1 3
b y H , C , N M R a n d I R s p e c t r o s c o p y ( s e e s u p p l e m e n t a r y
i n f o r m a ti o n ) .
T h e s i ze a n d s t ru ct u r e o f t h e F e O @ Di p h e n y l
3
4
p h o s p h at e c r ea t i n e a r e e s t i ma t e d b y u s i n g a n F E - S E M
( Fi g u r e 2) . T h i s i m a g e s h o w ed t h at p r e p a r e d
n a n o p ar t i c l e s h a v e a n e a r l y s p h er i ca l m o r p h o l og y a n d
t h e F e O @ D i p h en y l p h o s p h at e c re a t i n e n a n o p a r t i c l e s
3. Results and Discussion
3
4
F i g u r e 1 s h o w s t h e F T -I R o f t he d ip he ny l p h o s p h a t e
c r e a t i n e ( b l ac k c u r v e ), F e O ( re d c u rv e ) a n d F e
O @ D i p h e n y l p h o s p h a t e c r e a t in e b e fo re ( b l ue c u r v e )
h a v e a d i am e t e r o f a b o u t 1 0 0 n m .
3
4
3
-
T h e m ag n e t i c p r o p er t i es o f F e O @ Di p h e n y l
3
4
4
p h o s p h at e c re a t i n e w e re c h a ra c t e r i z e d b y V SM a t
r o o m t e m p e ra t u r e ( Fi g u r e 3 ) . T h e s a t u ra t i o n m a g n e -
t i za t i o n o f F e O @ D i p h en y l p h o s p h at e c re a t i n e i s
a n d a f t e r r e a c t i o n ( y e ll o w c u rv e ) . T h e F T -I R s p e ct r a o f
d i p h e n y l p h o s p h a t e c r e a t in e ( b l a c k c u r v e ), t he p e a k a t
-
1
3
4
1
7
1
8
c
m
c
a
n
b
e
a
t
t
r
i
b
u
t
e
d
t
o
C
=
O
s
t
r
e
t
c
h
i
n
g
a r o u n d 6 6 . 1 e mu / g w h i ch a cc o u n t s f o r e as y r e c o v e r y
o f t h i s c at al y s t a n d t h e m ag n e t i z a t i o n c u r v e d e m o n -
s t ra t e t h at t h es e F e O @ D i p h en y l p h o s p h a t e c r e at i n e
v i b r a t i o n . T h e p e a k s a t 1 6 7 3 . 9 c m- , 1 5 9 6 . 7 c m-
c an b e a t t r i b ut e d t o C = N s t r e t c h in g v i b ra t io n a n d t h e
1
1
-
1
3
4
p
e
a
k
s
a
t
t
h
e
n
e
a
r
r
e
g
i
o
n
f
r
o
m
3
3
0
0
c
m
t
o
n a n o p ar t i c l e s h a v e s u p er p ar a ma g n et i c p r o p e r t i e s .
T h e X R D d i ag ra m s o f t h e D i p h e n y l p h o s p h a t e
c re a t i n e ( Bl ac k c u r v e ), F e O ( Re d c u r v e ) a nd F e
1
3 4 0 0 c m- a r e a s s i g n e d t o v i b ra t io ns c h a r a c te r i s t i c o f
-
1
t
h
e
c
a
r
b
o
x
y
l
i
c
a
c
i
d
.
T
h
e
p
e
a
k
a
t
1
1
0
0
c
m
c
a
n
b
e
3
4
3 -
a t tr i b ut e d t o t h e P – O v i b ra t io n, t he s e r e s u l ts c o n fi r m
t h e f o r m a t i o n o f p h o s p h a te c r e a t in e .
I n t h e c a s e o f F e O ( re d c u r v e ), t he p e a k a t t h e n e a r
O @ D i p h en y l p h o s p h a t e c r ea t i n e ( Bl u e c u r ve ) a r e
4
g i v e n i n F i g u re 4. T h e X R D p a t t er n o f F e O @ -
3
4
3
4
D i p h e n y l p h o s p h a t e c re a t i n e r ev ea l e d fi v e r e fl ec t i o n
p e a k s ( 2 h = 3 5 . 2 3°, 4 1 . 5 9°, 5 0 . 7 9 °, 6 7 . 7 1°, 7 4 . 5 5°)
t h at i n d e x e d a s { 3 1 1 } , { 4 0 0 } , { 4 2 2 } , { 5 1 1 } a n d { 4 4 0 }
t h e X R D p e a k s a r e i n g o o d a g r ee m en t w i t h c ry s t a l l i n e
s t ru ct u r e o f F e O a n d t h es e c o n fi r me d t h e f o r m a t i o n
1
1
r e g i on f r o m 3 4 0 0 c m - t o 3 4 1 0 c m- i n t he c u r v e i s
a s s i g n e d t o O - H v i br a t i o n s o f w a t e r a n d t he a b s o r p t i o n
1
p e a k o b s e r v e s a t 5 7 8 c m- d u e t o t he F e – O v i b r at i o n
r e l a t e d t o t h e F e O s a m p le . T h i s r e s u l t s t r o n g l y s u p -
3
4
2
6
3
4
p o r t s t h e a s s i g n m e n t o f t he s y nt h e s i z e d F e O .
3
4
F e O p h a s e ( J C PD S 1 9 -6 2 9 ) . A n d t h e a mo u n t o f
3
4
I n th e c as e of F e O @D ip hen yl p ho sp ha te c re at in e
3
4
D i p h e n y l p h o s p h a t e c re a t i n e s u p p o r t e d o n m ag n e t i c i s
l i t t l e t h er e f o r e w e s h o w n o o b v i o u s p e a k s o f D i p h e n y l
p h o s p h a t e c r ea t i n e i n X R D d i ag ra m s o f F e O @ -
(b lu e c ur ve ), p eak s at 16 43 cm- , 1 58 9 c m- c a n b e
a ssi gn ed to C =N str et ch in g vi br at io n, th e ab sor pt ion
1
1
1
p ea k a t 11 00 cm- c or re sp on ds to t he P– O vi br at ion
3
4
D i p h e n y l p h o s p h at e c r ea t i n e .
Figure 1. F T - I R s p e c t r a o f D i p h e n y l p h o s p h a t e c r e a t i n e ( b la c k c u r v e ) , F e O ( r e d c u r v e ) a n d F e O @ D i p h e n y l p h o s p h a t e
3
4
3
4
c r e a t i n e b e f o r e ( b l u e c u rv e ) a n d a f t e r r e a c t i o n ( y e l l o w c u r v e ) .

3
0
P
a
g
e
4
o
f
9
J. Chem. Sci. ( 2 0 2 0 ) 1 3 2 : 3 0
Figure 5. T G A o f F e O @ D i p h e n y l p h o s p h a t e c r ea t i ne .
3
4
Figure 2. F E - S E M m i c ro g r a p h s o f F e O @ D ip h e n y l
3
4
p
h
o
s
p
h
a
t
e
c
r
e
a
t
i
n
e
.
T h e r m o g r a v i m e t r i c a n a l y s i s o f t h e n a n o p a r t i c l e s
w a s u s e d f o r i n v e s t i g at i o n o f t h e p e r c en t o f o r g a n i c
f u n c t i o n a l g r o u p s c h e mi s o r b e d o n t o t h e s u r f ac e o f
F e O @ Ph en y l p h o s p h a t e c r ea t i n e . T h e T G A c u r v e o f
3
4
t h e F e O @ D i p h en y l p h o s p h a t e c r ea t i n e i s s h o w n i n
3
4
F i g u re 5. T h e s a m p l e l o s t 3 . 8 % w e i g h t a t b e l o w
1 3 0 °C t h at r el a t e d t o t h e l o s s o f t h e a d s o r b e d w at er .
T h e T G A c u r v e o f t h e F e O @ D i p h en y l p h o s p h a t e
3
4
c r ea t i n e s u b s t r a t e s h o w s w e i g h t l o s s b e t w e e n 1 3 0 °C
a n d 4 0 0 °C w h i ch a t t r i b u t e d t o t h e d e c o m p o s i t i on o f
c o v a l e n t l y b o n d e d t h e o r g a n i c g r o u p s ( a b o u t 2 4 . 1 % ) .
T h u s , t h e T G A c u r v e p r o v e s t h e F e O f u n c t i on al i z e d
3
4
Figure 3. H y s t er e s i s l o o p s o f F e O @ Di p h e n y l p h o s -
3
p h at e c r ea t i n e.
4
w i t h P h e n y l p h o s p h a t e c r ea t i n e .
T h e n i t r o g e n a d s o r p t i o n - d e s o r p t io n i s o t h e r m s o f
D i p h e n y l p h os p ha t e c re a t i n e ( c u r v e 1 ) , F e O ( c u r v e 2 )
3
4
Figure 4. X R D p a t t e r n s o f D i p h e n y l p h o s p h a t e c r e a t in e ( B l a c k c u r v e ) , F e O ( R e d c u r v e ) a n d F e O @ D i ph e ny l
3
4
3 4
p h o s p ha t e c r ea t i n e ( B l u e c u rv e ) .

J. Chem. Sci. ( 2 0 2 0 ) 1 3 2 : 3 0
P a g e 5 o f 9 3 0
Figure 6. N i t r o g e n a d s o r p t i o n - d e s o r p t i o n i s o t h e r m s o f D i p h e n y l p h o s p h a t e c r e a ti n e ( c u r v e 1 ) , F e O ( c u r v e 2 ) a nd
3
4
F e O @ D i p h e ny l p h o s p h a t e c r e a t i n e ( c u r v e 3 ) .
3
4
Table 1. O p t i m i z a t i o n o f t h e r e a c t i o n t e m p e r a t u r e a n d t h e c a t a l y s t a m o u n t s .
E
n
t
r
y
T
e
m
p
e
r
a
t
u
r
e
(
°
C
)
A m o u n t o f c a t a l y s t ( m g )
Y
i
e
l
d
(
%
)
a
1
2
3
4
5
6
7
8
2 5
5 0
6 5
7 0
6 5
6 5
6 5
6 5
5 0
5 0
5 0
5 0
–
3 0
4 0
6 0
3 5
6 0
7 0
7 0
3 0
6 0
6 5
7 0
a
a
a
b
b
b
b
a
5 - s u b s t i t u t e d t e t r a z o l e d e r iv a t i v e s ( 2 m m o l ) a n d a, b- u n s a t u r a t e d c a r -
b o n y l ( 2 m m o l ) i n m e t h a n o l ( 1 0 m L ) a n d t h e c a t a l y s t ( 5 0 m g ) a t d i f f e r e n t t e m p e r a t u r e .
R ea ct i o n c o n d i t i o n s :
b
R ea ct i o n c o n d i t i o n s : 5 - s u b s t i t u t e d t e t r a z o l e d e r iv a t i v e s ( 2 m m o l ) a n d a, b- u n s a t u r a t e d c a r -
b
o
n
y
l
(
2
m
m
o
l
)
i
n
m
e
t
h
a
n
o
l
(
1
0
m
L
)
a
n
d
a
d
i
f
f
e
r
e
n
t
a
m
o
u
n
t
o
f
t
h
e
c
a
t
a
l
y
s
t
a
t
6
5
°
C
.
Table 2. S c r e e n i n g o f t h e c a t a l y s t s .
E n t r y
C a t a l y s t
T i m e ( m i n u t e )
Y i e l d ( % )
1
2
3
4
–
F e O
F e O @ C r e a t i n e
3
6 0
6 0
6 0
6 0
3 5
4 5
4 5
7 0
3
4
4
F e O @ Di p h e n y l p h o s p h a t e c r e a ti n e
3
4
R ea c t i o n c o n d i t i o n s : 5 - s u b s t i t u t e d t e t r a z o l e d e r iv a t i v e s ( 2 m m o l ) a n d a, b- u n s a t u r a t e d c a r b o n y l
( 2 m m o l ) i n m e t h a n o l ( 1 0 m L ) a n d t h e c a t a l y s t ( 5 0 m g ) a t 6 5 °C .
3 . 1 Investigation of catalytic activity
of Fe3O4@Diphenyl phosphate creatine in the Aza-
Michael reaction
a n d F e O @ D i p he n y l p h o s p h a t e c r e a t in e ( c u rv e 3 ) a re
3
4
e x h i b i t e d i n F i g u r e 6. T h e c o r re s p o n d i n g p a r a m et er s
i n c l u d i n g B E T s ur f a c e a r e a o f t he F e O @ D i p h en y l
p h o s p h a t e c r e a t i n e , D i p h e n y l p h o s p h a te c r e a t i n e a n d
3
4
2
1
2
1
2
1
F e O i s 4 9. 0 6 m g- , 1 . 1 33 4 m g- a nd 1 06 . 73 m g-
T h e c at a l y t i c p o t e n t i al o f t h e F e O @ D i p h en yl p h o s -
3
4
3
4
p h a t e c re a t i n e a f t e r p r e p a r at i o n a n d c h a r ac t e r i za t i o n
w a s p r o b e d i n t h e a za - M i c h ae l r ea c t i o n . I n i t i a l l y , t h e
b l an k e x p e r i m en t w a s o p t i m i z e d u s i n g t h e r e a c t i o n
b e t w e e n 5 - ( 4 - n i t r o p h e n yl ) - 1 H - t e t r a z o l e a n d c y c l o h e x -
re sp ecti ve ly . Th is o bs er va tio n su gge st s t ha t w ith co n-
v er tin g o f h omo gen ou s c at al ys t to he te ro ge neo us ca ta -
ly st , th e B ET s pe ci fic su rfa ce ar ea of t he ca ta ly st i s
si gn ifi can tly i nc re as ed .

3 0 P a g e 6 o f 9
J. Chem. Sci. ( 2 0 2 0 ) 1 3 2 : 3 0
Table 3. F e O @ D i p h e n y l p h o s p h a t e c r e a t i n e c a t a ly z e d t h e a z a - M i c h a e l r e a c ti o n .
3
4
Compound 3,
Compound 1,
Compound 2,
70% yield, 180 min
55% yield, 95 min
70% yield, 60 min
Compound 5, 70%
yield, 85 min
Compound 6, 65%
yield, 80 min
Compound 4, 85%
yield, 60 min
Compound 8,
Compound 9, 55%
yield, 85 min
Compound 7, 85%
yield, 70 min
20% yield, 130 min
Compound 10, 65%
yield, 90 min
R e a c ti o n c o nd it i on s : 5 - s u b s t i t u t e d t e t r a z o l e d e ri v a t i v e s ( 2 m m o l ) a n d a, b- u n s a t u r a t e d c a r b o n y l ( 2 m m o l ) i n m e t h an ol
( 10 m L ) a n d t h e c a t a l y s t ( 5 0 m g ) a t 6 5 °C .

J. Chem. Sci. ( 2 0 2 0 ) 1 3 2 : 3 0
P
a
g
e
7
o
f
9
3
0
Scheme 2. M ec h a n i s m f o r t h e r e a c t i o n b e t w e e n 5 - s u b s t it u t e d t e t r a z o l e s a n d a, b- u n s a t u r a t e d c a r b o n y l i n t h e p r e s e nc e o f
F
e
O
@
D
i
p
h
e
n
y
l
p
h
o
s
p
h
a
t
e
c
r
e
a
t
i
n
e
c
a
t
a
l
y
s
t
.
3
4
Figure 7. C a t a l y s t r e u s a b i l i t y .
Figure 8. L e a c h i n g t e s t f o r c a t a l y s t d u r i n g a c at a ly t i c
r e a c ti o n .
2 - e n o n e a s a m o de l r e a c t io n i n t he p re s e n c e o f F e
O @ P h e n y l p h o s p h a te c r e a t in e . T h e r e a c t io n p ar a m e-
3
-
p r o d u c t y i el d c an b e i m p r o v ed f u r t h e r ( T a b l e 1 , E n t r y
3 ) . S cr e e n i n g t h e a mo u n t o f c at al y s t i n d i c a t e d t h a t t h e
r e ac t i o n i n 3 0 a n d 4 0 m g w a s s l u g g i s h t o a ff o r d t h e
d e s i re d p r o d u ct ( T a b l e 1 , E n t r y 6 a n d 7 ) . B u t i t w as
f o u n d t h at 5 0 m g o f F e O @ D i p h en y l p h o s p h a t e c r e -
4
t e r s i n cl u d i n g v a r i o us c a t a l ys t a m ou n t a n d t e m p e ra t u r e
w e r e i n v es t i ga t e d t o o b t a i n m a xi m u m o f t h e y i el d
( T a b l e 1) . T h e c o rr e s p o n d in g a z a - M i c h e a l r e a c t i o n w a s
o b t a i n e d a t 3 5 % y i e ld a t r o o m t e m p e r a t u r e ( Ta b l e 1 ,
E n t r y 1 ) a n d b y r a i s in g t he t e m p e r a t u re t o 6 5 °C t h e
3
4
a t i n e g i v e s t h e d e s i re d p r o d u c t . T h e m o d e l r ea c t i o n w as
c ar r i e d o u t w i t h F e O , F e O @ D i p h en y l p h o s p h a t e
3
4
3
4

3
0
P
a
g
e
8
o
f
9
J. Chem. Sci. ( 2 0 2 0 ) 1 3 2 : 3 0
c r e a t i n e a n d i n t h e a b s e n c e o f t he c a t a l y s t. T h i s r ea c t i o n
h a s l o w y i e l d i n t h e p re s e n c e o f F e O a n d F e O @ -
A v a r i e t y o f 5 - s u b s t i t u t ed t e t r a z o l e s r ea c t e d w i t h a, b-
u n s at u r a t e d c ar b o n y l i n t h e p r e s e n c e o f t h e c a t a l y s t
a f fo rd i n g t h e p r o d u c t s i n g o o d y i el d s . T h e m a g n e t i c
o r g a n o c a t a l y s t i s e as i l y p r e p a r ed a n d h i g h s p e ci fic
s u r f a ce , h i g h s t ab i l i t y , n o n - t o x i ci t y , l o w -c o s t, m a g -
n e t i ca l l y s e p a r at i o n , e as y r ec o v er a b i l i t y a n d r e u s a b i l -
i t y a r e t h e m ai n a d v a n t a g e s o f t h i s u n i q u e
n a n o c a t a l y s t .
3
4
3
4
C r e a t i n e a n d n o p r o du c t i n t h e a b s e n c e o f t he c at a l y s t
( T a b l e 2, E n t r y 1 a n d 2 ) .
W e e x p l o r e d t he c a t a l yt ic a c t iv i ty o f F e O @ -
3
4
D i p h en y l p h o s p h a t e c r e a t in e f or t he a z a - M i c h ae l r e ac -
t i o n u n d e r t h e o p t i m iz e d r e a c t io n c o nd i ti o n s . T h e
r e a c t i o ns w e r e p e r f o r m e d b y u s i n g d if fe re n t t y p e s o f
5 - s u b s t i t u t e d t e t r a z o l e a n d a, b- u n s a t u ra t e d c ar b o n y l
a n d t h e r e s u l t s a r e s u m m a ri z e d i n T a b l e 3 . I t i s o b s e r v e d
t h a t r e a c t i o n s b e t w e e n a, b- un s a tu r a te d c a rb o n y l a n d
5 - p h e n y l -2 H - t et r a z o l e o r 5 - ( n a p h t h a l e n - 2- y l ) - 2 H - t e -
t r a z o l e w e r e p r o v i de d i n g o o d y i e ld s ( T a b l e 3 , E n t r y 4
a n d 7 ) . B u t r e a c t i o n a, b- u n s a t u ra t e d c a rb o n y l b et w e en
5 - ( 4 - n i t r op h e n y l )- 2 H -t e t ra z o l e o r 5 -( 4- c h l o r o p he n y l )-
2 H - t et r az ol e g i v es m o d e ra t e y i e ld s ( T a b l e 3, E n t r y 2
a n d 3 ) . A p r o b a b l e m e c h a n is m f o r t h e a z a - M i c h a e l
r e a c t i o n c a t a l yz e d w i th F e O @ D ip he ny l p h o s p h a t e
Supplementary Information (SI)
1
1 3
H N M R , C N M R , a n d m a s s c h a r a c t e r i z a t io n d at a a re
a v a il a b l e a t w w w . ia s . a c .i n / c h e m s c i .
Acknowledgements
T h e a u t h o r s g r a te f u l l y a c k n o w l e d g e t h e F a c u l t y o f C h e m -
i s tr y o f T a r b i a t M o d a r e s U n iv e r s i ty f o r s u p p o r t i n g t hi s
w o r k .
3
4
c r e a t i n e h a s b e e n s u g g e s t e d i n S c he m e 2 .
A t fi r s t , t h e r e a c t io n o f 5 -s u b s t it u te d t e t ra z o l e w i t h
F e O @ D i p he ny l p h o s p h a te c r e a t in e i s e x p e c t e d t o
f o r m t h e i n t e r m o l e c u l a r h y d ro g e n - b o n d e d i nt e r m e d i a t e
( a ) . T h e n n i t r o g e n o f t e t r a z o l e a t t a c k e d t o d o u b l e b o n d
o f t h e a, b- u n s a t u r a te d c a rb o n y l ( b ) fi n a l l y p r o du ct w a s
f o r m e d w i t h t h e r e g e n e ra ti o n o f t he c a t a l ys t ( d ) .
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D i p h en y l p h o s p h a te c r e a t in e a s a h ig hl y e f fi c i e n t c at - 1 0 . G a n d e l m a n M a n d J a c o b s e n E N 2 0 0 5 H i g h l y e na n-
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