synthesis of the bidentate organophosphorus compounds with an urea substituents

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This article was downloaded by: [130.132.123.28] On: 01 October 2014, At: 08:28 Publisher: Taylor & Francis Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry Publication details, including instructions for authors and subscription information: http://www.tandfonline.com/loi/lsyc20 Synthesis of the Bidentate Organophosphorus Compounds with an Urea Substituents Shi-Kang Xi a b & Yu-Fen Zhao a b a Institute of Chemistry, Academia Sinica , Beijing, China b Whei Oh Lin and Marcos Costa de Souza Secao de Quimica, Institute Militar de Engenharia Rio de Janeiro , Brasil Published online: 24 Oct 2006. To cite this article: Shi-Kang Xi & Yu-Fen Zhao (1990) Synthesis of the Bidentate Organophosphorus 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 PLEASE SCROLL DOWN FOR ARTICLE Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and are not the views of or endorsed by Taylor & Francis. The accuracy of the

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Page 1: Synthesis of the Bidentate Organophosphorus Compounds with an Urea Substituents

This article was downloaded by: [130.132.123.28]On: 01 October 2014, At: 08:28Publisher: Taylor & FrancisInforma Ltd Registered in England and Wales Registered Number: 1072954Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH,UK

Synthetic Communications: AnInternational Journal for RapidCommunication of SyntheticOrganic ChemistryPublication details, including instructions forauthors and subscription information:http://www.tandfonline.com/loi/lsyc20

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

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all theinformation (the “Content”) contained in the publications on our platform.However, Taylor & Francis, our agents, and our licensors make norepresentations or warranties whatsoever as to the accuracy, completeness,or suitability for any purpose of the Content. Any opinions and viewsexpressed in this publication are the opinions and views of the authors, andare not the views of or endorsed by Taylor & Francis. The accuracy of the

Page 2: Synthesis of the Bidentate Organophosphorus Compounds with an Urea Substituents

Content should not be relied upon and should be independently verified withprimary sources of information. Taylor and Francis shall not be liable for anylosses, actions, claims, proceedings, demands, costs, expenses, damages,and other liabilities whatsoever or howsoever caused arising directly orindirectly in connection with, in relation to or arising out of the use of theContent.

This article may be used for research, teaching, and private study purposes.Any substantial or systematic reproduction, redistribution, reselling, loan,sub-licensing, systematic supply, or distribution in any form to anyone isexpressly forbidden. Terms & Conditions of access and use can be found athttp://www.tandfonline.com/page/terms-and-conditions

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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

d i n e 1

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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Page 5: Synthesis of the Bidentate Organophosphorus Compounds with an Urea Substituents

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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Page 6: Synthesis of the Bidentate Organophosphorus Compounds with an Urea Substituents

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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Page 8: Synthesis of the Bidentate Organophosphorus Compounds with an Urea Substituents

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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