synthesis of the bidentate organophosphorus compounds with an urea substituents
TRANSCRIPT
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Synthesis of the BidentateOrganophosphorus Compoundswith an Urea SubstituentsShi-Kang Xi a b & Yu-Fen Zhao a ba Institute of Chemistry, Academia Sinica , Beijing,Chinab Whei Oh Lin and Marcos Costa de Souza Secaode Quimica, Institute Militar de Engenharia Rio deJaneiro , BrasilPublished online: 24 Oct 2006.
To cite this article: Shi-Kang Xi & Yu-Fen Zhao (1990) Synthesis of the BidentateOrganophosphorus Compounds with an Urea Substituents, Synthetic Communications:An International Journal for Rapid Communication of Synthetic Organic Chemistry,20:21, 3295-3301
To link to this article: http://dx.doi.org/10.1080/00397919008051562
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SYNTHETIC COMMUNICATIONS, 2 0 ( 2 1 ) , 3295-3301 (1990)
SYNTHESIS O F THE BIDENTATE ORGANOPHOSPHORUS
COMPOUNDS W I T H AN UREA SUBSTITUENTS
* 1 Shi -Kang X i , Yu-Fen Zhao
I n s t i t u t e of C h e m i s t r y , Academia S i n i c a , B e i j i n g , C h i n a
Whei Oh L i n a n d Marcos C o s t a de S o u z a
S a c a o de Q u i m i c a , I n s t i t u t o M i l i t a r de E n g e n h a r
R i o de J a n e i r o , B r a s i l
ABSTRACT:Thiourea. S - a l k y l i s o t h i o u r e a a n d guan r e a c t w i t h d i i s o p r o p y l p h o s p h i t e ( 2 ) a n d c a r b o n t e t r a - c h l o r i d e i n t h e a q u e o u s b a s i c c o n d i t i o n e a s i l y t o g i v e t h o n h n s n h n r i r l z t o r i n r n i i i i r t 7 q - o t h v l i c n t h i n i i r e n i c 2
r’LVUr.LVLI L y c - u rLuy”’ L . ., .,. AIVcI.Lvuc-u L y ” v e r y good p e r c u r s o r f o r t h e s y n t h e s i s of t h e d e r i v a t i v e s of t h e p h o s p h o r y l g u a n i d i n e 5 .
I t i s known t h a t t h e b i d e n t a t e o r g a n o p h o s p h o r u s
compounds w i t h a d i a l k o x y l p h o s p h i n y l a n d a c a r b o n y l
g r o u p s w e r e p o w e r f u l e x t r a c t a n t s for t r i v a l e n t l a n t h a -
n i d e s a n d a c t i n i d e s a n d a l k a l i m e t a l s 2 I 3 . An a l t e r n a t i o n
of the m o l e c u l a r s t r u c t u r e s m i g h t improve t h e e x t r a c t a n t
s t r e n g t h . I t i s o n t h i s p u r p o s e t h a t t he o r g a n o p h o s p h o r u s
compounds w i t h a n u r e a , t h i o u r e a , g u a n i d i n e and a l k y l
g u a n i d i n e s u b s t i t u e n t s a r e p r e p a r e d . The 0 , O - d i a l k y l p h o s -
p h o r y l u r e a c o u l d n o t be s y n t h e s i z e d d i r e c t l y f rom p h o s -
p h o r y l a t i o n of t h e u r e a l a by t h e Zhao m e t h o d , w h i c h had
a
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3295
Copyright 0 1991 by Marcel Dekker, Inc.
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XI ET AL. 32 96
been s u c c e s s f u l l y a p p l i e d f o r t h e N-phosphoryla t ion of
t h e amino a c i d s i n t h e b a s i c aqueous a l c o h o l i c s o l u t i o n . The g u a n i d i n e lb was phosphory la t ed i n t h e sodium hydro-
x i d e aqueous s o l u t i o n i n 80 % y i e l d (Scheme 1 ) . And t h e
f i n a l p roduc t 3b i s s o l u b l e i n water which was n e u t r a l
PH as i n d i c a t e d by l i t m u s i n d i c a t o r .
4 -6
0 II
H 2 N C N H 2
la
NH II
H 2 N C N H . H C 1 2
lb
S 0 NaOH, H 2 0
EtOH, C C 1 4 H 2 N C N H 2 I I + ( P ~ % ) ~ P H -
25 "C,4-5h. lc 2
SEt I
H N C = N H . H B r 2
Id
SMe 1
H N C = N H * H I 2
le
No Reac t ion
0 SH 11 I
2PNHC=NH
3c
0 SEt
2PNHC=NH II I
3d
0 SMe ( P r i 0 ) 2 P N H C = N H If I
3e
Scheme 1
The t h i o u r e a lc w a s a l s o e a s i l y phosphory la t ed i n
t h e same sys tem, b u t t h e p roduc t 3c i s n o t w a t e r s o l u b l e ,
an a l c o h o l i c aqueous s o l u t i o n was s l i g h t l y a c i d i c . The
n o v e l chemica l p r o p e r t y of t h e phosphory la t ed S - e t h y l
i s o t h i o u r e a i s t h e amino group rep lacement for t h e
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BIDENTATE ORGANOPHOSPHORUS COMPOUNDS 3297
m e r c a p t a n e m o l e c u l e i n it. A s t h e d i e t h y l amine o r t h e
c y c l o h e x y l amine w e r e r e f l u x e d w i t h 3d r e s p e c t i v e l y ,
a s t r o n g rnercaptane s m e l l w a s e v o l v e d (Scheme 2). The UV
spectra s t u d y showed t h a t t h e s e compounds had s t r o n g
c h e l a t i n g p o t e n t i a l f o r Cu , P b + + , N i i o n e s b u t n o t
f o r t h e a l k a l i metal i o n e s . T h e e x t r a c t i n g a b i l i t y of
t h e s e compounds f o r t h e r a r e - e a r t h metal i s u n d e r f u r t h e r
i n v e s t i g a t i o n .
++ ++
H N E t 2
4a 5a
0 S E t
0 NH ___c i II I ( P r 0)2PNHC=NH +
II II 3d % N O ( PriO)2PNHCNHC) + E t S H
4b 5b
Scheme 2
From t h e r e s u l t s o b t a i n e d , i t i s c o n c l u d e d t h a t
t h e g u a n i d i n e , t h i o u r e a , S - e t h y l i s o t h i o u r e a c o u l d b e
p h o s p h o r y l a t e d i n t h e aqueous bas ic c o n d i t i o n e a s i l y .
The S - e t h y l i s o t h i o u r e a is a v e r y good p r e c u r s o r f o r t h e
s y n t h e s i s of t h e d e r i v a t i v e s of the p h o s p h o r y l g u a n i d i n e
which a re i m p o r t a n t b i o l o g i c a l a c t i v e compounds, s u c h a s
t h e p h o s p h o r y l c r e a t i n e .
EXPERIMENTAL
M e l t i n g p o i n t w e r e u n c o r r e c t e d . 'H NMR and l3C NMR
s p e c t r a w e r e t a k e n on JEOL FX-100 s p e c t r o m e t e r , w i t h TMS
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as the internal standard in CDC13. Positive ion FAB-MS
were obtained on KYKY ZHP-5 double focussing mass
spectrometer (Scientific Instrument Factory, Beijing,
China) equipped with a standard KYKY fast atom gun.
Elemental analyses were performed by the analytical
Laboratory of the Institute. IR spectra were obtained
on a Perkin-Elmer 782 spectrometer using KBr tablets.
31P NMR were recorded on J E O L FX-100 machine, with 8 5 %
H3P04 as external references in CDCl
0,O-diisopropylphosphoryl guanidine (3b):
3'
A solution of guanidine hydrochloride (0.01 mole,
0.96 9) in NaOH (0.02 mole, 0 .80 g), H20 ( 5 m L ) and
EtOH (2 mL) was cooled to 0°C. A solution of diisopro-
pylphosphite (0.01 mole, 1.66 9) in CC14(5 m L ) was added
dropwise and the mixture was stirred at 25°C for 4h.then
diluted with H20 (3 mL), and extracted with CHC13.The
combined organic layers were dried and evaporated.
Crystallization from CHC13gave 1.78 g (80 % ) of 3b, mp
126-128°C. 'H NMR: s 1.31 (12H, d), 4.54 (2H,
(4H, br). l3C NMR: 8 23.60 (d, J=5.8 Hz), 69.8
Hz), 159.53 (d, J=7.3 Hz). 31P NMR: 5.87. IR
3420, 3290, 3150, 1635, 1190 ern-'. Anal. calc. for C H N 0 P: C, 37.67; H, 8.13;
Found: C, 37.70; H, 7.98; N, 19.13.
0.0-diisopropylphosphoryl thiourea (3c):
FAB-MS (M
7 1 8 3 3
m), 5.94
(d, J=5.9
( KBr) :
1).f 224. N, 18.83
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BIDENTATE ORGANOPHOSPHORUS COMPOUNDS 3299
To a s t i r r e d suspension of t h iou rea (O.Olmole,
0.769) i n NaOH (0.01 mole, 0.40 g),H20(5 m L ) and EtOH
(2 m L ) was added dropwise a s o l u t i o n of d i i s o p r o p y l -
phosphi te ( 0 . 0 1 mole, 1.66 g ) and CC14 (5 mL) a t 0°C.
The mixture was s t i r r e d for 5 h . a t 25 "C and d i l u t e d
w i t h H20 (
phases w e r e washed with H 0, and d r i e d (MgS04). The 2 s o l v e n t was then removed and the m a t e r i a l r e c r y s t a l l i z e d
from CHC13-EtOAc t o g ive 1 . 1 0 g ( 4 5 % ) of 3c a s a c o l o r -
l e s s c r y s t a l , mp 146-148"C.'H NMR: & 1.40 (12H,d),4.68 (2H, m), 6.96(1H, br), 7.50 (1H. br), 8.60 (lH,br).
l3 C NMR: 2 23.39 ( d , J=4.4 Hz), 73.67(d, J=5.9Hz),
184.36 ( d , J=2.9 Hz). 31P NMR: 2-6.72. IR (KBr): 3250,
3330, 3160, 1610 cm-l.FAB-BS 241 (M + 1): Anal. c a l c .
f o r C7H17 2 3 C.35.00; H, 7.20; N, 11.46.
0,O-diisopropylphosphoryl S-e thy l i s o t h i o u r e a (3d) :
5 mL ) then e x t r a c t e d with CHC13. The organic
N 0 PS: C,34.99; H, 7.13; N, 11.66. Found:
According t o t h e procedure of 3b, t h e so lven t was
removed t o g ive v i scous o i l . I t was kept i n r e f r i g e r a t o r
ove rn igh t , g iv ing 2.23 g (83 % ) of c o l o r l e s s s o l i s , m p
34-36°C. 'H NMR: 3 1.30 (3H. t), 1.34(.12H, d ) , 2.94(2H,
q), 4,46 (2H, m ) , 6,70 (2H, b r ) , 13C NMR: $14.76, 23,69
( d , J=4.4Hz), 25.23, 70.63 (d, J=5.9 Hz), 168.74(d,
J=2.9 Hz). 31P NMR:
1620 cm-l FAB-MS 269 (M + 1): Anal. c a l c . for
C9H21N203PS: C,40.28; H, 7.89; N, 10.44. Found:
C, 40.28; H, 7.55; N, 10.53.
2.60. IR (KBr): 3330, 3260, 3130,
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3300 XI ET AL.
0,O-diisopropylphosphoryl S - m e t h y l i s o t h i o u r e a ( 3 e ) :
T o t h e m i x t u r e o f d i i s o p r o p y l p h o s p h i t e ( 0 . 0 2 m o l e ,
3 . 3 2 g ) , S -me thy l i s o t h i o u r e a h y d r o i o d i d e ( 0 . 0 2 m o l e ,
4 .36 g ) , H 2 0 ( 4 m L ) , E t O H ( 4 m L ) w a s added d r o p w i s e a
s o l u t i o n o f NaOH ( 0 . 0 4 mole, 1 .60 g ) i n H 2 0 ( 6 m L ) a t
0 ° C . The r e a c t i o n m i x t u r e w a s s t i r r e d f o r 4h. a t room
t e m p e r a t u r e , t h e n e x t r a c t e d w i t h C H C 1 3 t o g i v e o i l . I t
w a s k e p t i n r e f r i g e r a t o r , g i v i n g 2.10 g ( 4 0 0 ) o f s o l i d .
m p 38-40 O C . 'H NMR:
( 2 H , m ) , 7.10 (2H, b r ) . FAB-MS 255 ( M + 1)'.
0,O-diisopropylphosphoryl N , N - d i e t h y l g u a n i d i n e (5a):
1 . 2 8 (12H, d ) , 2 . 3 3 ( 3 H , s ) , 4.50
The s o l u t i o n of 3d ( 0 . 0 0 1 mole, 0.27 g ) and d i e t h y l
arnine (0.01 mole, 0 .73 g ) i n t o l u e n e ( 5 mL) w a s r e f l u x e d
f o r 24 h. The e x c e s s d i e t h y l amine and s o l v e n t w e r e
removed t o g i v e s e m i - s o l i d . P u r i f i c a t i o n of t h e c r u d e
p r o d u c t by column ch romatography ( s i l i c a g e l , C H C 1 3 ) and
r e c r y s t a l l i z a t i o n f rom p e t . e t h e r g a v e 0 .24 g ( 8 2 % ) of
c r y s t a l , m p 55-57 "C. 'H NMR: 2 1 . 1 0 (6H, t ) , 1 . 2 3 ( 1 2 H , d )
3 .30 ( 4 H , q), 4.43 ( 2 H , m ) , 6 .07 (2H, b r ) . I 3 C NMR:
1 3 . 0 7 , 23 .71 , 41 .62 , 69 .35 , 156 .45 ( d , J = 8 . 8 H z ) . ~ I P NMR:
3 6 .54 . I R ( K B r ) : 3429, 3321, 1 5 9 5 , 1 5 6 2 , 1 1 9 8 , 994 an-'.
FAB-MS 280 ( M + 1 ) + . A n a l . calc . f o r C11H26N303P: C , 47.30
H , 9 .38 ; N, 15 .04 . Found: C , 47.24; H , 10.07: N,14.48
0.0-diisopropylphosphoryl N - c y c l o h e x y l g u a n i d i n e 5b:
The s o l u t i o n of 3d (0 .002mole , 0 . 5 4 9 ) a n d c y c l o h e x y l
amine ( 0 . 0 0 4 m o l e , 0 . 4 0 9 ) i n t o l u e n e ( 5 m l ) w a s r e f l u x e d
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BIDENTATE ORGANOPHOSPHORUS COMPOUNDS 3301
f o r 24h . The e x c e s s c y c l o h e x y l a m i n e a n d s o l v e n t w e r e
removed t o g i v e s e m i - s o l i d . R e c r y s t a l l i z a t i o n f r o m pe t .
e ther ( 3 0 6OoC ) g a v e 0 .52g ( 8 5 % ) o f 5 b , m p 96 -98 C .
'H-NMR
6 .08 (3H,m . C-NMR: 2 3 . 8 0 ( d , J = 4 . 4 H z ) , 2 4 . 7 6 , 2 5 . 5 8 , 3 3 . 0 7 ,
4 9 . 2 8 , 6 9 . 7 3 ( d , J = 7 . 3 ) , 1 5 7 . 3 5 ( d , J = 8 . 8 H z ) . 31p-NMR: 6 - 3 6 .
0
1 2 8 ( 1 8 H , m ) , 1 . 7 0 ( 4 H , m ) , 3 . 5 5 ( 1 H , b r ) , 4 . 5 0 ( 2 H . m ) ,
1 3
I R ( K B r ) : 3 3 6 4 , 3 2 3 2 , 1 6 5 1 , 9 9 4 ~ m ~ ' . FAB-MS 306 (M+1). A n a l .
c a l c . f o r C H N 0 P: C , 5 1 . 1 3 : H . 9 . 2 4 ; N ,13 .76 . Found:
C , 5 1 . 3 9 ; H , 9 . 0 0 ; N ,13 .50 .
1 3 2 8 3 3
Acknowledgemen t :
W e t h a n k C h i n e s e N a t i o n a l S c i e n c e F o u n d a t i o n a n d C o n s e l h o N a c i o n a l de P e s q u i s a D e s e n v o l v i m e n t o C i e n t i f i c o (CNPq) o f B r a s i l f o r f i n a n c i a l S u p p o r t .
REFERENCES AND NOTES:
1. D e p a r t m e n t o f C h e m i s t r y , T s i n g h u a U n i v e r s i t y , B e i j i n g
1 0 0 0 8 4 , C h i n a .
2 . T . H . S i d d a l l I I , J . I n o r g . Nucl.Chem. 1 9 6 3 , 2 5 , 8 8 3 .
3 . G . P e t r o v , I . V e l i n o v a n d M . k i r i l o v , M o n a t s h e f t e F u r
C h e m i e 1 9 7 3 , 1 0 4 , 1 3 0 1 .
4 . Gai-J iao J i , Chu-Biao Xue , J i a - N i n g Zeng, Fu-Fen Zhao,
S y n t h e s i s , 1 9 8 8 , 6 , 4 4 4 .
5 . Yu-Fen Zhao , Sh i -Kang X i , A i -Teng S o n g , a n d Ga i - J i ao J i ,
J . O r g . Chem., 1 9 8 4 , 4 9 , 4 5 4 9 .
6 . J . N . Zeng, C . B . Xue , Q . W . Chen a n d Y.F. Zhao , B i o o r g a n i c
C h e m . , 1 9 8 9 , 1 7 , 4 3 4 .
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