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

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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.