Some Preparative and Mechanistic Aspects of the Chemistry of

Ic : amine = 1:1 i n the presence of ROH only dial- kyldithiophosphate i s produced, while at a ratio of. Ic : amine « 1:2 a mixture of esteramide an...
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32 Some Preparative and Mechanistic Aspects of the Chemistry of Phosphoric Acid and Thiophosphoric Acid Chloride Betaines M. MEISEL, C. DONATH, and H. GRUNZE

Downloaded by MONASH UNIV on July 25, 2013 | http://pubs.acs.org Publication Date: November 11, 1981 | doi: 10.1021/bk-1981-0171.ch032

Zentralinstitut für Anorganische Chemie der Akademie der Wissenschaften der DDR, DDR-1199 Berlin-Adlershof, Rudower Chaussee, GDR

Phosphoric a c i d c h l o r i d e and thiophosphoric a c i d c h l o r i d e pyrididium betaines (I) which are e a s i l y prepared by reacting PO , POS and PS , respect i v e l y , with phosphorus oxychloride or phosphorus t h i o c h l o r i d e i n the presence of p y r i d i n e (1), are of i n t e r e s t for the synthesis of s u b s t i t u t e d phosphates and thiophosphates. 4

10

4

6

4

4

10

During n u c l e o p h i l i c attack on the P-atom of I both the Ρ-Cl and the P-N bond may be broken and three p o s s i b l e reaction types may r e s u l t : type A : Nu- +

Py•PX Cl 2

-->Py•PX Nu 2

type B : Nu- +

Py•PX Cl

-->NuPXCl-

type C : 2Nu- +

Py•PX Cl

-->NuPXNu-

Nu = n u c l e o p h i l e ;

2

2

2

2

+

Cl-

+ Py

(1) (2)

+ Cl- + Py (3)

Py = p y r i d i n e

A t y p i c a l example for a type A reaction i s the "halosilane condensation", i.e. the reaction of the betaines I with t r i m e t h y l s i l y l d e r i v a t i v e s with l i b e ­ r a t i o n of t r i m e t h y l s i l y l c h l o r i d e . This reaction i s e s p e c i a l l y smooth with I c : Py•PS Cl

+ Me SiY

2

3

-->

Py•PS Y + 2

Me SiCl 3

(4)

(Y = e.g. NCS, OR, NRR') The amido d e r i v a t i v e s can a l s o be prepared by reac­ t i n g Py•PS Cl with amines at a molar r a t i o of Ic : amine = 1:2. 2

0097-6156/81/0171-0161$05.00/0 © 1981 American Chemical Society In Phosphorus Chemistry; Quin, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1981.

162

PHOSPHORUS CHEMISTRY

Py-PSpCl ( I c ) r e a c t s a c c o r d i n g t o type A w i t h NaF i n d r y a c e t o n i t r i l e y i e l d i n g PyPSJF ( 2 ) . The ana­ l o g o u s r e a c t i o n w i t h P y * P 0 C 1 ( l a ) does not t a k e p l a c e * Only when s t r o n g e r f l u o r i n a t i n g a g e n t s l i k e A s F a r e e m p l o y e d , t h e C l - F exchange o c c u r s and the f o r m a t i o n of the f l u o r i d e b e t a i n Py^PCUF i s o b s e r ­ ved ( 3 ) . * The i n t e r m e d i a r y f o r m a t i o n of a monometaphosp h a t e " ( c f . ( 4 ) ) i n a t y p e A r e a c t i o n i s i n d i c a t e d by t h e h y d r o l y s i s of Py·Ρ0 01. The r e a c t i o n of l a w i t h e q u i m o l a r amounts of w a t e r i n n i t r o m e t h a n e y i e l d s a p o l y p h o s p h a t e m i x t u r e , whereas i n a c e t o n i t r i l e c y c l i ­ z a t i o n of t h e Γ Ρ Ο 3 ] " - a n i o n s t o t r i m e t a p h o s p h a t e i s o b s e r v e d . The r e a c t i o n can be f o r m u l a t e d as an S 1 ( P ) ( e l i m i n a t i o n - a d d i t i o n ) as f o l l o w s : 2

3

M

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2

N

0 P y - ρ - 0Θ

0

W

H0

+

Py - Ρ

2

1

:

CI

J

-

,Θ ο

>

+ HCl

I

ή - 0 [pyH]

0

-

·—

P'

i

[PyH] [po ] n

3

(5)

n

η

I n c o n t r a s t , d u r i n g the r e a c t i o n ot P y * P S C l ( I c ) w i t h water p o l y m e r i c thiophosphates a r e never found. The r e a c t i o n w i t h s a t u r a t e d aqueous NH.F a l s o i n d i c a t e s t h e d i f f e r e n t b e h a v i o u r of l a and I c (5)· F o r Py.POpCl ( l a ) t h e p r o d u c t c o n s i s t s of m o n o f l u o r o p h o s p h a t e (75 %) and monophosphate (25 % ) . I t i s p r o b a b l e t h a t i n i t i a l l y formed L P O 3 I " ( c f . e q . ( 5 ) ) r a p i d l y r e a c t s w i t h F" t o [ P 0 3 F ] ^ ~ (S 1 ( P ) ) . The r e a c t i o n of Py»PS Cl ( I c ) w i t h aqueous NH .F, however, l e a d s t o d i f l u o r o a i t h i o p h o s p h a t e (40 %) m o n o f l u o r o d i t h i o p h o s p h a t e (5 %) and m o n o t h i o p h o s p h a t e (35 % ) . Here t h e f i r s t s t e p most l i k e l y i s an a t t a c k of t h e two c o m p e t i n g n u c l e o p h i l e s w h i c h s h o u l d y i e l d t h e i n t e r m e d i a t e s P y . P S F and P y # P S ( 0 H ) . The s u b s e ­ quent s t e p s of t h e r e a c t i o n p r o b a b l y c o r r e s p o n d t o an S 2 ( P ) mechanism. R e a c t i o n s of the b e t a i n e s I w i t h i n i t i a l c l e a v a g e of t h e P-N bond ( t y p e B) a r e r a r e l y o b s e r v e d . One example i s t h e r e a c t i o n w i t h h y d r o g e n h a l i d e s l e a d i n g t o d i h a l o g e n o p h o s p h a t e s and - t h i o p h o s p h a t e s : 2

2

9

2

2

N

Py.PX Cl 2

(Hal

+ H [Hal]

-[PyH][HalPX Cl] 2

= halide)

In Phosphorus Chemistry; Quin, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1981.

(6)

32.

MEISEL E T A L .

Phosphoric

Acid

Chloride

163

Betaines

#

T h i s type o f r e a c t i o n was f i r s t d e s c r i b e d f o r P y P b p F w h i c h r e a c t s w i t h HC1 t o f l u o r o c h i o r o d i t h i o p h o s p h a t e (2)· The c h l o r i d e b e t a i n e s l a and I c r e a c t w i t h HCi q u a n t i t a t i v e l y t o the r e s p e c t i v e d i c h l o r o p h o s p h a t e s ( 6 ) . Py#PObCl ( l b ) r e a c t s , a s has been f o u n d , t o o , w i t h o t h e r n u c l e o p h i l e s , under p a r t i a l d i s m u t a t i o n , and a m i x t u r e o f ΓΡ0 01 ] " , T P O S C l J " and [ P b C I J ~ i s o o t a i n e d . The r e a c t i o n o t H y * P S C l ( I c ) w i t h HBr c e r ­ tainly at t i r s t yields [BrPS Cl]~ according to ( 6 ) . W i t h an e x c e s s of HBr a l s o C l - B r exchange under f o r m a t i o n o f i P S B r l takes p l a c e . The r e a c t i o n s o f c h l o r i d e b e t a i n e s o f type C p r o c e e d e a s i l y and w i t h h i g h y i e l d s . A l i p h a t i c a l c o ­ h o l s , p h e n o l s , ammonia and p r i m a r y o r s e c o n d a r y a m i ­ nes c a n be used a s t h e c o r r e s p o n d i n g n u c l e o p h i l e s ( 7 ) · S t u d i e s of t h e r e a c t i o n o f Py«PS Cl w i t h a l c o h o l s i n d i f f e r e n t m o l a r r a t i o s show t h a t i n c o n t r a s t to what has been r e p o r t e d ( 2 ) t h i s r e a c t i o n does n o t p r o c e e d under p r i m a r y c l e a v a g e o f t h e P-N bond ( t y p e B) v i a t h e i n t e r m e d i a t e [ R 0 P S C 1 ] ~ , b u t r a t h e r v i a Py»PS 0R ( t y p e A ) . However, i n most c a s e s , t h e s e c o n d s t e p , i . e . c l e a v a g e o f t h e P-N b o n d , i s s o f a s t , that a simultaneous r e a c t i o n of I c c o r r e s p o n ­ ding t o type C r e s u l t s . An i n t e r e s t i n g example f o r t h e t y p e C r e a c t i o n i s the simultaneous r e a c t i o n of I with alcohol/amine m i x t u r e s . I n t h e c a s e o f I c t h e r e a c t i o n c a n be c o n ­ t r o l l e d i n such a way, t h a t p r a c t i c a l l y e x c l u s i v e l y the esteramide of the d i t h i o p h o s p h o r i c a c i d i s f o r ­ med (c3 ) : 2

2

2

2

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2

2

2

2

2

P y P S C l + ROH + 3 RR·NH — * [ R R Ν Η ] [ R 0 P S ( N R R )] β

2

β

£

2

Φ [ R R N H ] C l + Py f

2

(7)

A study of the r e a c t i o n (7) a t d i f f e r e n t a l c o h o l / amine r a t i o s has r e v e a l e d t h a t a p p a r e n t l y a t f i r s t t h e a l c o h o l r e a c t s under f o r m a t i o n o f t h e e s t e r b e t a i n e Py«PS 0R. T h u s , a t a m o l a r r a t i o o f I c : amine = 1:1 i n t h e p r e s e n c e o f ROH o n l y d i a l k y l d i t h i o p h o s p h a t e i s produced, w h i l e a t a r a t i o of I c : amine « 1:2 a m i x t u r e o f e s t e r a m i d e and d i a l k y l e s t e r r e s u l t s . Only a t a molar r a t i o of I c : amine « 1 : 3 t h e e s t e r a m i d e i s formed a l m o s t exclusively (cf. eq. ( 7 ) ) . I t was f o u n d t h a t P y # P 0 C l i s an e x c e l l e n t p h o s ­ p h o r y l a t i o n agent f o r n u c l e o t i d e s y n t h e s e s (9)· When l a r e a c t s w i t h an OH group o f a n u c l e o s i d e art e s t e r b e t a i n e i s formed a c c o r d i n g t o t y p e A a s d e m o n s t r a 2

2

In Phosphorus Chemistry; Quin, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1981.

164

PHOSPHORUS

CHEMISTRY

t e d by NMR. T h i s i n t e r m e d i a t e b e t a i n e r a p i d l y r e a c t s w i t h n u c l e o p h i l i c a g e n t s l i k e [ P 0 3 ~, [ P 0 ] " R OH and p r o d u c e s i n r e l a t i v e l y h i g h yields the r e s p e c t i v e n u c l e o s i d e p h o s p h a t e s and d i n u c l e o s i d e phosphates : 4

4

[

Ρ

Λ

2

]

4

?

1

#

" R 0

/ P y P 0 C l + ROH — ~ P y P O g O R - /

P

[ - 3°9

]

(8)

2

Ρ

Υ

\ ^ R OH

R0-P0 -0R

e

2

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β

ROH = p r o t e c t e d and u n p r o t e c t e d

nucleosides

β

R 0H= ROH; o t h e r a l c o h o l s T h i s s y n t h e s i s c a n be p e r f o r m e d a s an one-pot reaction. The r e a c t i o n s o f t h e b e t a i n e s I d e m o n s t r a t e t h e g r e a t v a r i e t y o f a p p l i c a t i o n s o f t h e s e compounds f o r t h e p r e p a r a t i o n o f s u b s t i t u t e d p h o s p h o r i c and t h i o p h o s p h o r i c a c i d d e r i v a t i v e s , and t h e y open new r o u t e s f o r t h e s y n t h e s i s o f new o r d i f f i c u l t t o p r e p a r e compounds.

Literature Cited 1. Meisel, M . ; Grunze, H. Z.anorg.allg.Chem. 1968, 360, 277 and unpublished results respectively. 2. Fluck, E.; Retuert, P.J.; Binder, H. Z.anorg.allg. Chem. 1973, 397, 225. 3. Donath, C h . ; Cernik, M . ; Meisel, M . ; Dostal, K . ; Grunze, H. unpublished results. 4. Ramirez, F.; Marecek, J.F. Pure and Appl.Chem. 1980, 52, 1021. 5. Meisel, M . ; Donath, Ch. Chemiedozententagung, Freiberg, 1979. 6. Meisel, M . ; Donath, C h . , to be published. 7. Meisel, M . ; Donath, C h . ; Wolf, G . - U . DDR Pat. WP C 07 F/213 416 (6.6.79). 8. Meisel, M . ; Donath, Ch. DDR Pat. WP C 07 F/205 560 (31.10.78) 9. Bauschke, E . ; Meisel, M . ; Brankoff, T . DDR Pat. WP C 07 H/223 311 (14.8.80). RECEIVED

July 7, 1981.

In Phosphorus Chemistry; Quin, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1981.